9th Australasian Symposium on Ionic Liquids
Abstract Booklet
1st-2nd December 2020
Tuesday 1 December - Day 1 Sessions
Sydney time Perth time Auckland time Speaker Title 9:30 - 10:00 am 6:30 - 7:00 am 11:30 - 12:00 pm A/Prof Ekaterina (Katya) Pas Welcome - Panel #1-1
Prof Tom Welton, Imperial College, Connecting Ion Structure and Flexibility with the Transport 10:00 - 10:30 am 7:00 - 7:30 am 12:00 - 12:30 pm London, UK Properties of Ionic Liquids - Panel #1-1
Electrochemical Sensor Development for Explosives Detection 10:30 - 10:45 am 7:30 - 7:45 am 12:30 - 12:45 pm Catherine Hay, Curtin University Using Ionic Liquids - Panel #1-1 Reconsidering Intermolecular Interactions in Surface Active Jhonatan Soto Puelles, Deakin 10:45 - 11:00 am 7:45 - 8:00 am 12:45 - 13:00 pm Ionic Liquids as Steel Corrosion Inhibitors – A Modelling Study University - Panel #1-1 11:00 - 11:30 am 8:00 - 9:30 am 13:00 - 13:30 pm Coffee break Designing Novel Solid State Electrolytes based on Karolina Biernacka, Deakin 11:30 - 11:45 am 8:30 - 8:45 am 13:30 - 13:45 pm Hexamethylguanidinium Organic Ionic Plastic Crystal for University Sodium Batteries - Panel #1-2 Quantitative Determination of Protein Solubility in Ionic 11:45 - 12:00 pm 8:45 - 9:00 am 13:45 - 14:00 pm Stuart Brown, RMIT University Liquids - Panel #1-2
Dr. Karolina Matuszek, Monash 12:00 - 12:15 pm 9:00 - 9:15 am 14:00 - 14:15 pm Thermal Energy Storage in Ionic Liquids - Panel #1-2 University Dr. Cameron Weber, The Seeking Solvation: How do Solutes Affect the Amphiphilic 12:10 - 12:30 pm 9:15 - 9:30 am 14:15 - 14:30 pm University of Auckland, Nanostructure of Ionic Liquids? - Panel #1-2 New Zealand Formation of SEI on Sodium Metal Electrodes in Shammi Ferdousi, Deakin 12:30 - 12:45 pm 9:30 - 9:45 am 14:30 - 14:45 pm Superconcentrated Ionic Liquid Electrolytes and the Effect of University Additive Water - Panel #1-2 Microbiologically Influenced Corrosion (MIC); Discovering 12:45 - 13:00 pm 9:45 - 10:00 am 14:45 - 15:00 pm Mahdi Ghorbani, Deakin University Inhibitors and their Mechanisms - Panel #1-2 Ambient Energy Dispersion and Stabilisation of Large 13:00 - 13:15 pm 10:00 - 10:15 am 15:00 - 15:15 pm Justin Freeman, University of WA Graphene Sheets from Graphite Using a Surface Energy Matched Ionic Liquid - Panel #1-2 Effect of Hydrogen Bonding between Ions of Like Charge on 13:15 - 13:30 pm 10:15 - 10:30 am 15:15 - 15:30 pm Dr. Hua Li, University of WA the Boundary Layer Friction of Hydroxy-Functionalized Ionic Liquids - Panel #1-2 13:30 -14:30 pm 10:30 - 11:30 am 15:30 - 16:30 pm Lunch time Versatile Task-specific Sodium Iongels by Fast UV Dr. Luca Porcarelli, Deakin 14:30 - 14:45 pm 11:30 -11:45 am 16:30 - 16:45 pm Photopolymerization for Emerging Solid State Energy Storage University Applications - Panel #1-3 Revealing the Liquid Structure of Cholinium Argininate Bio- 14:45 - 15:00 pm 11:45 - 12:00 pm 16:45 - 17:00 pm Manuel Brunner, University of WA Ionic Liquids via Small-Angle Neutron Diffraction - Panel #1-3
Single Atom Catalysts with Nanoconfined Ionic Liquids for 15:00 - 15:15 pm 12:00 - 12:15 pm 17:00 - 17:15 pm Qian Sun, University of NSW Enhanced CO2 Electroreduction - Panel #1-3
Laura Garcia-Quintana, Deakin Highly Homogeneous Sodium Superoxide Growth in Na−O2 15:15 - 15:30 pm 12:15 -12:30 pm 17:15 - 17:30 pm University Batteries Enabled by a Hybrid Electrolyte - Panel #1-3
Shurui Miao, The University of Unexpected Origin of Nanostructure in Choline 15:30 - 15:45 pm 12:30 - 12:45 pm 17:30 - 17:45 pm Sydney Phenylalaninate, a Biocompatible Ionic Liquid - Panel #1-3
Predicting Reaction Outcomes through Physical 15:45 - 16:00 pm 12:45 - 13:00 pm 17:45 - 18:00 pm Daniel Morris, University of NSW Measurements of Ionic Liquids - Panel #1-3
16:00 -16:30 pm 13:00 - 13:30 pm 18:00 - 18:30 pm Coffee break 16:30 - 17:30 pm 13:30 -14:30 pm 18:30 - 19:30 pm Poster session Prof. Hiroyuki Ohno, Tokyo 17:30 - 18:00 pm 14:30 - 15:00 pm 19:30 - 20:00 pm University of Agriculture and Iconic Liquids - Panel #1-4 Technology, Japan Panel #1-1 – Chair: Tam Greaves and Katya Pas, Judge: Doug MacFarlane; https://monash.zoom.us/j/85994557177?pwd=VldWYXVSaUtEb0hTMzhraW1jbXNKUT09 Panel #1-2 – Chair: Nathan Martens and Saffron Bryant, Judge: Katya Pas; https://monash.zoom.us/j/85284664352?pwd=cDVISEI5a1V5aERPVnpSK0UxRWIzZz09 Panel #1-3 – Chair: Mega Kar and Kaycee Low, Judge: Debbie Silvester-Dean; https://monash.zoom.us/j/85121071598?pwd=bWFucTdvYkQvMElIU2p2M1poSlBpQT09 Panel #1-4 – Chair: Tam Greaves and Katya Pas; https://monash.zoom.us/j/86396285770?pwd=ZDNkZ3dkM1lIcVR1cjFsRjNGKzB1dz09 Wednesday 2 December - Day 2 Sessions
Sydney time Perth time Auckland time Speaker Title Protic Ionic Liquids: How Structure in the Liquid Phase is Dr. Małgorzata Swadźba-Kwaśny, 10:00 - 10:30 am 7:00 - 7:30 am 12:00 - 12:30 pm Reflected in Macroscopic Properties and Queen’s University, Belfast, UK Performance in Catalysis - Panel #2-1 Oxazolidinium-based Ionic Electrolytes: The Effect of Ether 10:30 - 10:45 am 7:30 - 7:45 am 12:30 - 12:45 pm Dr. Colin Kang, Deakin University Functionality in the Ring - Panel #2-1
Effect of Humidity on Electrochemical Gas Sensing in Ionic 10:45 - 11:00 am 7:45 - 8:00 am 12:45 - 13:00 pm Simon Doblinger, Curtin University Liquid-based Electrolytes - Panel #2-1
11:00 - 11:30 am 8:00 - 9:30 am 13:00 - 13:30 pm Coffee break
The Effects of Ionic Liquids as Solvents: Reactions that 11:30 - 11:45 am 8:30 - 8:45 am 13:30 - 13:45 pm Alyssa Gilbert, University of NSW Proceed through Carbocation Intermediates - Panel #2-2 Investigating Specific-ion Effects on the Nanostructure of Kasimir Gregory, University of 11:45 - 12:00 pm 8:45 - 9:00 am 13:45 - 14:00 pm Propylammonium Nitrate via Molecular Dynamics Newcastle Simulations - Panel #2-2
12:00 - 12:15 pm 9:00 - 9:15 am 14:00 - 14:15 pm Dr. Mega Kar, Monash University Ionic Liquids for Rechargeable Metal Batteries - Panel #2-2
Nathan Martens, Monash 12:10 - 12:30 pm 9:15 - 9:30 am 14:15 - 14:30 pm Ionic Liquids in Electric Fields - Panel #2-2 University
Dr. Binayak Roy, Monash Fluoroalkylborate [B(ORF)4]- Anions for High-voltage LiBs 12:30 - 12:45 pm 9:30 - 9:45 am 14:30 - 14:45 pm University - Panel #2-2 Synthesis, Electrochemical and Spectroscopic Study of Novel 12:45 - 13:00 pm 9:45 - 10:00 am 14:45 - 15:00 pm Rory McCallum, CSIRO Boronium Ionic Liquid based Electrolyte Systems for High Energy Density Lithium Batteries- Panel #2-2 Parametrisation of Polarisable Force Fields through 13:00 - 13:15 pm 10:00 - 10:15 am 15:00 - 15:15 pm Peter Halat, Monash University Incorporation of Many-body Effects in Ionic Liquids - Panel #2-2 The Effect of Bisimidazolium-based Ionic Liquids on A 13:15 - 13:30 pm 10:15 - 10:30 am 15:15 - 15:30 pm Kenny Liu, University of NSW Bimolecular Substitution Process. Are Two Head(group)s Better Than One? - Panel #2-2 13:30 -14:30 pm 10:30 - 11:30 am 15:30 - 16:30 pm Lunch time
Jonathon Clarke-Hannaford, RMIT Boronium Cation-based Ionic Liquid Electrolytes for Li-Metal 14:30 - 14:45 pm 11:30 -11:45 am 16:30 - 16:45 pm University Batteries - Panel #2-3
14:45 - 15:00 pm 11:45 - 12:00 pm 16:45 - 17:00 pm Dr. Saffron Bryant, RMIT University Deep Eutectic Solvents for Cryopreservation - Panel #2-3
Dr. Shern Tee, The University of Fully Periodic Constant Potential Simulations of Electric 15:00 - 15:15 pm 12:00 - 12:15 pm 17:00 - 17:15 pm Queensland Double Layers - Panel #2-3
Investigating the Effects of Mixtures of Ionic Liquids on 15:15 - 15:30 pm 12:15 -12:30 pm 17:15 - 17:30 pm Matthew Taylor, University of NSW Reaction Outcome - Panel #2-3
The Effect of Ionic Liquids on Lysozyme and Green 15:30 - 15:45 pm 12:30 - 12:45 pm 17:30 - 17:45 pm Dr. Hank (Qi) Han, RMIT University Fluorescent Protein: A Multi-technique Approach - Panel #2-3
Anjali Gaur, JNCASR, Bangalore, 15:45 - 16:00 pm 12:45 - 13:00 pm 17:45 - 18:00 pm Stabilization of Fluoride Ions in Ionic Liquids - Panel #2-3 India
16:00 -16:30 pm 13:00 - 13:30 pm 18:00 - 18:30 pm Coffee break 16:30 - 17:00 pm 13:30 -14:00 pm 18:30 - 19:00 pm Poster session
Kateryna Goloviznina, ENS de Lyon, Polarisable Force Field for Protic Ionic Liquids and Deep 17:00 - 17:15 pm 14:00 - 14:15 pm 19:00 - 19:15 pm France Eutectic Solvents - Panel #2-4
Dr. Luke Wylie, ENS de Lyon, Ionic Liquids as Stabilising Agents for Nitroxide Redox Flow 17:15 - 17:30 pm 14:15 - 14:30 pm 19:15 - 19:30 pm France Batteries - Panel #2-4
Prof. Margarida Costa Gomes, Low Pressure Carbon Dioxide Capture and Utilisation using 17:30 - 18:00 pm 14:30 - 15:00 pm 19:30 - 20:00 pm CNRS, Lyon, France Porous Ionic Liquids - Panel #2-4
Panel #2-1 – Chair: Cameron Weber and Alyssa Gilbert, Judge: Debra Bernhardt; https://monash.zoom.us/j/89479110819?pwd=RVJrUmloelJwUzJxcGRrVFZmRFZ4UT09 Panel #2-2 – Chair: Sachini P and Karolina Matuszek, Judge: Rob Atkin; https://monash.zoom.us/j/85018189434?pwd=dUtWMTNZQTZCSmc5Z0kyYWdsMmdPUT09 Panel #2-3 – Chair: Peter Halat and Hua Li, Judge: Maria Forsyth; https://monash.zoom.us/j/85602067453?pwd=VFd0SXhSb1pMdUh3UnUrZzVkQnk0QT09 Panel #2-4 – Chair: Stuart Brown, Hank Han and Tam Greaves, Judge: Jenny Pringle; https://monash.zoom.us/j/89846988162?pwd=QzdJTlBMOTJmV3RabW1tOE1PdHBNQT09
Poster Session Tuesday Day 1: https://unsw.zoom.us/j/81397803927 Wednesday Day 2: https://unsw.zoom.us/j/87376379866
Presenter Judge Title
Yunxiao Zhang, 1 Mega Kar Potential-Dependent Superlubricity of Ionic Liquids on Graphite Surface University of WA Lucas Wong, 2 Mega Kar Chain Dimensions of Polymeric Ionic Liquids through Small-Angle Neutron Scattering University of WA
Joshua Buzolic, 3 Mega Kar Interfacial Nanostructure of Amphiphilic Deep Eutectic Solvents University of WA
Dale Duncan, Temperature-dependant Solubility Determination of Sodium Salts for Sodium-ion Secondary 4 Hua Li Monash University Batteries The An Ha, Understanding the Discharge Products Formation in Ionic Liquids 5 Hua Li Deakin University Based Na-O 2 batteries and Strategy to Limit Side Reactions Jeffrey Black, 6 Christina Pozo-Gonzalo Chemical Transformations by Thermomechanical Stresses Revealed by TOF-SIMS Analysis University of NSW Nikhil Kumar, Investigating the Solubility of Petroleum Asphaltene in 7 Christina Pozo-Gonzalo IIT Guwahati, India Deep Eutectic Solvents and their Interaction using COSMO-RS Nikhil Avula, 8 Christina Pozo-Gonzalo A Bespoke Force Field for DEME-TFSI Ionic Liquid JNCASR, India Maxwell Coney, 9 Christina Pozo-Gonzalo Investigating the Effects of An Ionic Liquid on the Nucleofugality of Chloride University of NSW Sachini Kadaoluwa 10 Pathirannahalage, RMIT Luke O’Dell Effect of Surfactant Ionicity on Critical Micelle Concentration in Aqueous Ionic Liquid Mixtures University Wade Millar, 11 Luke O’Dell Graphite Infused Ionic Liquid Greases University of WA Dhirendra Kumar Mishra, 12 Luke O’Dell Ionic Liquid Based Deep Eutectic Solvents Aided Thermal Dehydrogenation of Chemical Hydrides IIT Guwahati, India Longkun Xu, 13 Australian National Christina Pozo-Gonzalo Ordered Solvents and Ionic Liquids Can be Harnessed for Electrostatic Catalysis University Combined Experimental and Simulation Understanding of Structure, Dynamics and Nanditha Sirigiri, 14 Hua Li Temperature Dependent Phase Transitions in Novel Ammonium based Organic Ionic Plastic Deakin University Crystals Faezeh Makhlooghiazad, Improved High Temperature Cycling Sodium Vanadium 15 Hua Li Deakin University Phosphate Cathodes using NaFSI Rich Organic Ionic Plastic Crystal Electrolyte Sneha Malunavar, Study of Ion Gel Electrolytes for Na-battery Application Comprising of OIPC/Na-salt/Electrospun 16 Cameron Webber Deakin University PVDF Nanofiber Kalani Periyapperuma, Towards Sustainable Nd Recovery: An Electrochemical Approach Using Fluorine-Free Ionic Liquid 17 Cameron Webber Deakin University Electrolytes Fernando Ramos, 18 Luke O’Dell Solid Ionic Composite Membranes for CO2 Separation Deakin University Andrew Hsieh, 19 Luke O’Dell Investigating the Effects of Ionic Liquids on Cyclisation Reactions University of NSW Samantha Piper, 20 Cameron Webber Thermal Energy Storage in Ionic Liquids/Organic Salts Monash University Anna Warrington, 21 Cameron Webber Development of New Ionic Electrolytes with Ethoxy Side Chains Deakin University Shanika Abeysooriya, 22 Cameron Webber Development of Mixed Organic Ionic Plastic Crystal Electrolytes for Energy Storage Deakin University Frederick Nti, 23 Mega Kar Insights into the anion originated interactions in OIPC/PVDF composites Deakin University Keynote Speaker
Prof. Tom Welton Imperial College London Sustainable or Green Chemistry aims to make the chemicals and related industries both environmentally and economically sustainable. I am interested in using an exciting class of solvents - ionic liquids - to improve chemical processes. I have worked with ionic liquids throughout my research career. Recently, interest from both academic and commercial chemists in these has increased dramatically. I hope that my work has made a significant contribution to this change in attitude. My research covers a broad range of the chemical sciences and I have been the author of papers in all three of the traditional branches of the subject (Inorganic, Organic and Physical). I am particularly interested in clean synthesis and catalysis. The central academic aim of my research is to understand the role that the immediate chemical environments in which reacting species find themselves influence the reaction process. I also aim to use this understanding to provide more effective chemical processes by the matching of the reaction with the optimum reaction environment. The principal foci of my investigations are the reactions themselves and how they change in rate, product distributions etc. My group correlates our synthetic results with calculated values (e.g. gas phase acidities) and physical measurements (e.g. the spectra of probe dye molecules).
Keynote Presentation: Connecting Ion Structure and Flexibility with the Transport Properties of Ionic Liquids
The transport properties of ionic liquids result from a complex mixture of effects, such as ion size, shape and interactions. Recently it has been suggested that the generally good transport properties of ionic liquids containing the bis(trifluoromethylsulfonyl)imide ion results from its flexibility. We have combined theoretical approaches with the synthesis of ions that are as close as possible in all other regards, but differing in flexibility to explore the significance of this effect. I will report the results of these studies here. Keynote Speaker
Prof. Hiroyuki Ohno Tokyo University of Agriculture and Technology
Prof. Hiroyuki Ohno is known as one of the leading scientists in the field of ionic liquids. He has been working on designing functional ionic liquids for more than 20 years. He has published nearly 500 original papers as well as 200 reviews, book chapters, and notes. He received his PhD. from Waseda University (Japan) in 1981. He was invited to Tokyo University of Agriculture and Technology (TUAT) as an associate professor in 1988 and in 1997, he was promoted to be a full professor. He was elected as a vice dean in 2007, then dean in 2013, and president of TUAT from 2017 to 2020.
Keynote Presentation: Iconic Liquids
The most attractive characteristic of ionic liquids is the diverse ion structure and accordingly designable properties. This widely designable properties is very iconic for liquids. In my talk, I will introduce a few interesting properties and component ions to design functional ionic liquids. Expanded application area will be inspired by coupling ionic liquids with molecular liquids. As this example, I will introduce unique phase transition of ionic liquid/water mixture driven by temperature change. Keynote Speaker
Dr. Gosia Swadźba-Kwaśny Queen’s University, Belfast
Dr Gosia Swadźba-Kwaśny received her MSc Eng in Chemical Technology from the Silesian University of Technology (Poland) in 2005, and her PhD in Chemistry from the Queen’s University Belfast (UK) in 2009. Her PhD studies were carried out in the QUILL Research Centre, under the supervision of Professor Kenneth R Seddon. After several years of post-doctoral work at QUILL, in 2015 she secured a Queen’s University Research Fellowship in Green Chemistry (a tenure-track position) and established her own research group. In 2019 she was tenured as a Lecturer in inorganic chemistry, followed by a promotion to Senior Lecturer the same year. Gosia has been associated with the QUILL Research Centre throughout her career at Queen’s, and in 2018 she became the director of QUILL. Gosia’s current research interests are: (i) fundamental structural studies of the liquid phase (liquid structure, speciation of metals); (ii) development of new acidic ionic liquids and their applications in catalysis, including frustrated Lewis pair catalysis; (iii) the use of acidic ionic liquids to valorise waste polymers. Gosia is a Member of the Royal Society of Chemistry and American Chemical Society. She is also a member of Editorial Advisory Board of ACS Sustainable Chemistry & Chemical Engineering and sits on the Disordered Materials Panel for ISIS Neutron and Muon Source at the STFC Rutherford Appleton Laboratory. Keynote Presentation: Protic Ionic Liquids: How Structure in the Liquid Phase is Reflected in Macroscopic Properties and Performance in Catalysis
Protic ionic liquids are a very appealing family of ionic liquids. Easy synthesis through a simple acid-base neutralisation offers a route to the cheapest ionic liquids available to a chemist. Non- stoichiometric reactions lead to Brønsted acidic or basic systems, which can be used as proton- conducting electrolytes or as Brønsted acidic catalysts. When weak acids are used, non-complete proton transfer results in interesting dynamic equilibria that are keenly studied by physical and theoretical chemists.
In my talk, I will present our neutron scattering studies on protic ionic liquids formulated with weak and strong acids and demonstrate how the liquid phase structure is reflected in macroscopic properties and performance in acid catalysis. Keynote Speaker
Prof. Margarida Costa Gomes CNRS and ENS Lyon, France
Margarida Costa Gomes is a Chemical Engineer that obtained her PhD in Experimental Thermodynamics in Lisbon, Portugal. She started her career as research associate at Imperial College in London before moving to the Blaise Pascal University in France as a post-doctoral fellow. In France, she joined the CNRS in 1998 and became a CNRS Research Professor in 2010. She was awarded the CNRS Bronze Medal in 2003 and in 2004 she passed her Habilitation. Margarida was an invited researcher in 2008 at the Institute of Chemical and Biological Technology, Portugal and in 2014-15 was a visiting scholar at the Massachusetts Institute of Technology, USA, where she maintains a position as research affiliate. Margarida moved from the Institute of Chemistry in Clermont-Ferrand to the ENS Lyon in 2018 as a Fellow of the IDEX Lyon.
Margarida works on molecular thermodynamics of alternative solvents and environmentally friendly liquids, her research concerning chemistry, engineering and environmental aspects. She is driven by challenging scientific questions at the intersection of these fields, especially where they have relevance to societal outcomes or to innovative applications. Her current research covers two major topics: the solvation in ionic media aiming to engineer and design sustainable solvents, and the interactions of materials with ionic liquids motivated by the development of new processes and devices. Her research is funded by French and European research agencies as well as by industrial partners.
Keynote Presentation: Low Pressure Carbon Dioxide Capture and Utilisation using Porous Ionic Liquids
Porous ionic liquids are non-volatile materials capable of absorbing high quantities of gases. In order to improve the capacity and selectivity of carbon dioxide absorption, we prepared porous ionic liquids based on ZIF-8 – a zinc based metal organic framework – and acetate or levulinate phosphonium salts. Because carbon dioxide can reversibly react with the ionic liquids, the capacity of the porous ionic liquid thus formed is considerably enhanced when compared with the porous solid or the pure ionic liquids. We have also used porous ionic liquids to convert CO2 into cyclic carbonates by its coupling with epoxides. The use of pure ionic liquids as organocatalysts for this reaction is well documented but the use of porous ionic liquids represents a new approach never explored before and we will show how it offers the possibility of using milder and safer conditions of reaction. Presentation Electrochemical Sensor Development for Explosives Detection Using Ionic Liquids Catherine Hay, Junqiao Lee, Debbie Silvester-Dean School of Molecular and Life Sciences, Curtin University Email: [email protected]
The ability to detect and quantify explosives on scene is crucial to reducing the imminent threat of improvised explosive devices [1]. Electrochemical methods provide a viable, portable alternative to traditional methods, as explosive compounds possess reducible nitro groups that give rise to a current signal. [2] The impure nature of IEDs creates selectivity issues as the nitro groups of different explosives may show overlapping signals or interact with each other. The non-volatile nature and minute volume requirements of room temperature ionic liquids (RTILs) in conjunction with planar electrode surfaces offers a miniaturised setup for portable sensing. Furthermore, the ability to tailor the properties of RTILs through selection of ion combination presents RTILs as an ideal solvent for explosive separation and detection. This presentation focusses on understanding the anion and cation effect on the mechanisms and electrochemical behaviour of a range of commonly found explosives including 1,3,5,7- tetranitro-1,3,5,7-tetrazoctane (HMX), 1,3,5-Trinitro-1,3,5-triazinane (RDX), Pentaerythritol tetranitrate (PETN). The implications of this on detection ability of a sensor is examined. The non-aromatic nature of these compounds has resulted in more complex voltammetry than that observed for nitro-aromatic compounds such as 2,4,6-trinitrotoluene (TNT) and 2,4- dinitrotoluene (DNT). Voltammetry observed in RTILs containing the bulky perfluoroalkylphosphate ([FAP]−) anions result in more well definied peaks compared to − − bis(trifluoromethanesulfonyl)imide ([NTf2] ), tetrafluoroborate ([BF4] ) or − + hexaflurorophosphate ([PF6] ). A single centre, diethylmethylsulfonium ([S2,2,1] ]) also presented less defined peaks for cyclic analytes such as HMX and RDX yet similar behaviour was observed for PETN. This presentation will also discuss our recent work towards the development of a simple and robust, low-cost electrochemical device for the detection of trace solid TNT from a non- porous surface.[3] Low-cost disposable electrodes are utilised in this work in combination with room temperature ionic liquids (RTILs). Different collection substrates were investigated to sample explosive residue including a bare thin-film electrode, glass microfiber filter paper, a gel polymer electrolyte (GPE) made from RTIL and polymer additive, and a GPE-filter paper composite with a simple “swabbing” technique employed as a field portable sampling method. The effect of oxygen, moisture and temperature is explored by carrying out experiments in simulated and real environments, and the portability of the technique is enhanced by using a hand-held portable potentiostat. Ultimately, the RTIL selected for this sensor ([P14,6,6,6][NTf2]) showed distinct separation between the peak corresponding to the electrochemical reduction of oxygen and the reduction of TNT. The portability, ease of use and low-cost of the sensor device makes this a viable platform for the rapid onsite detection of explosives. References [1] G. Ulrich, V. Winfried, Z. Jens, Measurement Science and Technology 2009, 20, 042002. [2] a)H. Yu, D. DeTata, S. Lewis, D. Silvester, TrAC Trends in Analytical Chemistry 2017, 97; b)J. Wang, Electroanalysis 2007, 19, 415-423. [3] C. E. Hay, J. Lee, D. S. Silvester, Journal of Electroanalytical Chemistry 2020, 114046. Presentation Intermolecular Interactions in Surface Active Ionic Liquids as Steel Corrosion Inhibitors – A Modelling Study Jhonatan Soto Puelles a, Mahdi Ghorbani a, Fangfang Chen a, Maria Forsyth a, Anthony Somers a a Institute of Frontier Materials, Deakin University, Burwood VIC 3125 Australia Email: [email protected]
The present work focuses on high quality molecular modelling as applied to an ionic liquid formed by the cationic surfactant cetrimonium and the aromatic counterion 4OH-cinnamate (commonly found in beans, tomatoes, carrots, basil and garlic). Previously we have reported that this inhibitor possesses multifunctional characteristics, hindering corrosion of mild steel in saline solutions and being able to control bacteria commonly associated with microbiologically influenced corrosion (MIC). As a result of these properties it is proposed to be a solution for replacing harmful inhibitors such as hexavalent chromates and tributyltins. The modelling studies carried out in the National Computational Infrastructure show us with an atomic resolution an encapsulation event in solution, where the aromatic anion is being integrated in the outer shell of the cetrimonium micelles. Interestingly such a synergy mechanism has not been previously considered in corrosion science, although it is well documented in other fields such as cancer research, where hydrophobic drugs are delivered to tumor cells by “smart” micelles. The model is consistent with NMR experiments and will be validated by comparing its predicted small x-ray scattering pattern with its experimental counterpart. In addition, the interaction between the inhibitor molecules and a hydrated iron oxide layer, 훼 Fe2O3, was also modelled, showing that the morphology of the adsorbed aggregates on the oxide layer is affected by the inhibitor concentration and ionic strength. At lower inhibitor concentrations, it was observed that spherical micelles adsorbed on the oxide substrate and as the concentration increased, there was a transition from spherical to wormlike aggregates. Finally, the addition of sodium chloride in the system promotes coalescence between the absorbed aggregates due to an electrostatic screening effect, increasing surface coverage. By increasing the apparent solubility of active hydrophobic compounds this new synergy mechanism could have profound implications in the development of inhibitors, as we are no longer constrained to hydrophilic compounds , thus widening the list of potential substitutes for toxic inhibitors. Presentation Designing Novel Solid State electrolytes based on Hexamethylguanidinium Organic Ionic Plastic Crystal for Sodium Batteries Karolina Biernacka, Faezeh Makhlooghiazad, Jenny Pringle, Maria Forsyth Deakin University, Institute for Frontier Materials 221 Burwood Highway, Victoria, 3125, Australia Email: [email protected] Current battery storage relies on unsustainable mining of global reserves of lithium and cobalt that could potentially become constrained and expensive. In addition, battery technologies have safety issues, particularly at elevated temperatures. Sodium based batteries are emerging as a viable beyond Li-ion battery technology for future energy storage. Sodium has certain advantages such as greater abundance than lithium, better intrinsic safety and potentially a relatively high energy density. Currently, much research is focussed on the electrode materials (hard carbon anodes and new cathodes) however the electrolyte component is an important enabler of the technology. Ionic liquids and organic ionic plastic crystals (OIPCs) have been shown to be good electrolyte candidates for Na batteries, enabling Na metal anodes.[1] Organic ionic plastic crystals (OIPCs) are purely ionic solid state electrolyte materials that are increasingly drawing attention due to their unique combination of properties such as negligible volatility, non-flammability and increased safety in contrast to electrolytes based on organic, flammable solvents that are typically used in electrochemical cells. Additionally, many of them are characterized by high thermal and electrochemical stability that makes them an attractive candidate for many electrochemical device applications. Tailoring the materials properties can be achieved by pairing various anions and cations. In order to enable use of OIPCs in sodium batteries a source of Na+ needs to be added to the neat plastic crystal. Addition of sodium salt significantly changes their properties and understanding the effect of incorporation of a second component on the materials properties and battery performance is crucial for designing new electrolytes. Based on a recently reported promising new OIPC - hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) and prior work showing its favourable electrolyte properties after Li salt addition (good transport properties and reversible deposition and stripping of lithium),[2] this material was chosen to be studied for sodium battery applications. In this work we focus on [HMG][FSI] and the effect of doping with different concentrations of sodium salt (NaFSI) on the material properties. All the electrolytes and the neat OIPC were evaluated in terms of thermal properties, solid state structures, ionic conductivities, ion diffusion and electrochemical properties. Interesting and usual conductivity behaviour was observed for [HMG][FSI] and low sodium salt concentrated mixtures. All compositions of OIPC with NaFSI resulted in promising solid-state electrolytes, and a phase diagram where the eutectic point was determined is proposed.
References
[1] F. Makhlooghiazad, D. Gunzelmann, M. Hilder, D. R. MacFarlane, M. Armand, P. C. Howlett, M. Forsyth, Adv. Energy Mater. 2017, 7, DOI 10.1002/aenm.201601272. [2] K. Biernacka, D. Al-Masri, R. Yunis, H. Zhu, A. F. Hollenkamp, J. M. Pringle, Electrochim. Acta 2020, 357, 136863. Presentation Quantitative Determination of Protein Solubility in Ionic Liquids Stuart Brown, Tamar Greaves, Calum Drummond College of Science, Engineering and Health, RMIT University Australia Email: [email protected]
Proteins are often utilised for a range of applications in the pharmaceutical, biological, chemical and food industries1-2. The ideal solvent for hydrophilic proteins is usually buffered water due to its minimal cost, and ability to mimic the native environment of proteins. However, many proteins are hydrophobic and have poor solubility in water. Because of this, organic solvents have been investigated as alternative solvents for biocatalysis3 and protein extraction4, but often have detrimental effects on the protein stability and structure. We propose to use ionic liquids (ILs) as an alternative solvent, or as an additive in aqueous solutions, to control the solubility and stability of proteins. In this project, we will quantify the protein solubility in IL solutions and measure the stability. Initially the model protein lysozyme will be tested in ILs from highly dilute to neat. A novel, high throughput method has been developed to quantitatively determine the solubility of lysozyme. The aim is to explore specific-ion effects and how these differ for concentrated IL solutions compared to conventional dilute salts. A variety of techniques including UV/vis spectroscopy, Fourier- transformation infrared spectroscopy, circular dichroism and small angle x-ray scattering will be used to describe the stability and structure of the protein, and to gain insight into its interactions with ILs. Further studies will be extend this work to compare variations in the specific ion effects to other proteins, and to begin building a database of quantified protein solubility and stability in ILs.
References 1. Egorova, K. S.; Gordeev, E. G.; Ananikov, V. P., Biological Activity of Ionic Liquids and Their Application in Pharmaceutics and Medicine. Chemical Reviews 2017, 117 (10), 7132-7189. 2. van Rantwijk, F.; Sheldon, R. A., Biocatalysis in Ionic Liquids. Chemical Reviews 2007, 107 (6), 2757-2785. 3. Klibanov, A. M., Improving enzymes by using them in organic solvents. Nature 2001, 409 (6817), 241-246. 4. Hyde, A. M.; Zultanski, S. L.; Waldman, J. H.; Zhong, Y.-L.; Shevlin, M.; Peng, F., General Principles and Strategies for Salting-Out Informed by the Hofmeister Series. Organic Process Research & Development 2017, 21 (9), 1355-1370. Presentation Thermal Energy Storage in Ionic Liquid Karolina Matuszek, Ranganathan Vijayaraghavan, Mega Kar, Douglas R. MacFarlane School of Chemistry, Monash University, Clayton, VIC 3800, Australia Email: [email protected]
Renewable energy has the ultimate capacity to resolve the environmental and scarcity challenges of the world’s energy supplies. However, the utility of these sources and the economics of their implementation are strongly limited by their intermittent nature. To overcome this issue an inexpensive means of energy storage needs to be part of the whole design. Among storage technologies, thermal energy storage utilizing phase change materials (PCM) is particularly suitable for renewable energy storage.[1] PCM technology can offer many benefits including low cost, low environmental impact, good reliability and is highly scalable. PCMs are classified as materials in which heat is absorbed when the material undergoes a phase transition, usually melting, and the heat can be released upon crystallization or solidification. The amount of energy needed to melt the material, the heat of fusion (ΔHf), is one of the primary properties of PCMs, while its melting point determines the application.[2] The most suitable temperature range that the PCM should melt to store renewable energy is between 100 and 220 ̊C. PCMs have been known for the past few decades but the temperature range between 100 and 220 ̊C has been rather neglected. Among studied materials are salt hydrates, sugar alcohols and polymers. Nevertheless, each of these materials suffers specific drawbacks (volatility, flammability, low thermal conductivity, phase separation etc.) Recently, researchers are focusing on improving some of the required properties of a PCM or to develop new families of materials. Ionic liquids, due to their properties such as non- flammability, chemical and thermal stability, low volatility and good heat transfer properties may offer a promising PCM alternative. Moreover, a wide variety of possible combination of cations and anions offer the opportunity to tune the melting point and ΔHf of these salts for suitable applications. Recently in our group, certain protic ionic liquids have been shown to exhibit high ΔHf, making them excellent candidates as PCMs in the desired temperature range (100 – 220 °C). It is proposed that hydrogen bonding, in protic ionic liquids plays a key role in obtaining the high heat of fusion, enabling them to absorb large amounts of energy. Here, we investigate the ionic liquids at the molecular level, to gain an understanding on the role of the cation, anion and certain functional groups present.
References
[1] K. Matuszek, R. Vijayaraghavan, C. M. Forsyth, S. Mahadevan, M. Kar, D. R. MacFarlane, Chemsuschem 2020, 13, 159-164; bK. Matuszek, R. Vijayaraghavan, M. Kar, D. R. MacFarlane, Cryst Growth Des 2020, 20, 1285- 1291. [2] C. Zhou, S. Wu, International Journal of Energy Research 2019, 43, 621-661. Presentation Seeking Solvation: How do Solutes Affect the Amphiphilic Nanostructures of Ionic Liquids? Cameron C. Weber,1 Dilek Yalcin,2 Ivan D. Welsh,1 Bhavana Kapila,3 Emma L. Matthewman,1,3 Paul Jun,1 Mikkaila McKeever-Willis,4 Iana Gritcan,3 Tamar L. Greaves2 1 The University of Auckland, Auckland, New Zealand 2 RMIT University, Melbourne, Australia 3 Auckland University of Technology, Auckland, New Zealand 4 Imperial College London, London, United Kingdom Email: [email protected] The ability of ionic liquids (ILs) containing at least one amphiphilic ion to form nanostructures with well-defined polar and non-polar domains is becoming increasingly well understood.1-3 There is evidence that the existence of these nanostructures can influence the outcomes of processes where ILs are used as solvents, including for material and chemical synthesis, separations and purifications, as well as for energy and electrochemical applications.4, 5 In many of these applications, the IL is diluted by reactants, catalysts or co-solvents and yet there have been surprisingly few investigations of the partitioning of solutes within these nanostructures and on the effect of this dilution on the existence of amphiphilic nanostructures.
This presentation will describe our combined computational and experimental investigations into the effect of solutes on the amphiphilic nanostructures of a series of imidazolium ILs.6 The effect of the solute, alkyl chain length and IL anion on the stability of the IL amphiphilic nanostructure and the partitioning of solutes will be discussed. The consequences of these findings on the ability to control solute partitioning through the appropriate selection of IL ions will be presented and an example of the effect of this on the kinetics of dehydration reactions will be discussed.
References
1. Y. Wang and G. A. Voth, J. Am. Chem. Soc., 2005, 127, 12192-12193. 2. J. N. A. Canongia Lopes and A. A. H. Padua, J. Phys. Chem. B, 2006, 110, 3330-3335. 3. R. Hayes, G. G. Warr and R. Atkin, Chem. Rev., 2015, 115, 6357-6426. 4. H. J. Jiang, R. Atkin and G. G. Warr, Curr. Opin. Green Sust. Chem., 2018, 12, 27-32. 5. C. C. Weber, A. F. Masters and T. Maschmeyer, Green Chem., 2013, 15, 2655-2679. 6. D. Yalcin, I. D. Welsh, E. L. Matthewman, S. P. Jun, M. McKeever-Willis, I. Gritcan, T. L. Greaves and C. C. Weber, Phys. Chem. Chem. Phys., 2020, 22, 11593-11608. Presentation Formation of SEI on Sodium Metal Electrodes in Superconcentrated Ionic Liquid Electrolytes and the Effect of Additive Water Shammi A. Ferdousi1*, Maria Forsyth1,, Luke A. O’Dell, Patrick C. Howlett1,* 1Institute for Frontier Materials, Deakin University, Burwood, Victoria 3125, Australia *Email [email protected]; [email protected]
Designing and developing water-tolerant electrolytes for future battery technologies using materials that are feasible from a commercial point of view is critical to enable advances in energy storage to address pressing demands for energy efficiency and renewable storage1–3. Therefore, this research investigates water as a unique and promising electrolyte additive for sodium battery electrolyte applications. The study will systematically examine surface morphology and chemistry of the metal/electrolyte interface after the addition of different amounts of water to the electrolytes. Present energy demand is hard to sustain due to increasing energy consumption. Thus new energy storage and supply technologies are required, which are reliable, safe, inexpensive, and show high energy and power densities. Among various battery chemistries, Na based batteries have been identified as potential efficient stationary energy storage technologies. Electrolytes are an integral component of a sodium battery with ionic liquid-based electrolytes attracting considerable interest due to their safety and stability. The use of additives during electrolyte preparation is often carried out to achieve better transport performance, tune the composition of the solid electrolyte interphase (SEI) and alter other characteristics. Recently, electrolyte additives for Na batteries are an emerging area of investigation. We have already reported4–6 water addition (~1000 ppm) to a N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3mpyrFSI) superconcentrated ionic liquid electrolyte (50 mol% NaFSI) showing formation of a favourable SEI and enhanced cycling stability. The current study reports the characterization of Na-metal anode surfaces cycled with these electrolytes containing different water concentrations (up to 5000 ppm). The average cycling efficiency (ACE) was enhanced by water addition; up to ~99 % for the 1000 ppm cell compared to ~98% for the dry cell. Post cycling morphological and spectroscopic characterization showed that water addition greatly influences the formation of the SEI, and that ~1000 ppm of water promoted the formation of an active and more uniform deposit, with larger quantities of SEI species (S, O, F, N) present. Water addition to the electrolyte system is also proposed to promote the formation of a new complex denoted as Na2[SO3-N-SO2F].nH2O (n= 0 to 2) between the FSI anions, water molecules and sodium cations along with NaF and Na2O components. This study has demonstrated that water not only enhances the intrinsic electrolyte properties but also that the presence of water can support (and even improve) performance for practical battery applications. These compositions are now being tested at the BatTRI-hub pouch cell prototyping facility, located at Deakin University. This research can open a new pathway for practical application of an extensive scale energy storage system, which is environmentally more sustainable and ultimately cheaper.
References 1. Lee, B., Paek, E., Mitlin, D. & Lee, S. W. Chem. Rev. 119, 5416–5460 (2019) 2. Zhao, Y., Adair, K. R. & Sun, X. Energy Environ. Sci. 11, 2673–2695 (2018) 3. Sun, B. et al. Adv. Mater. 32, 1903891 (2020) 4. Ferdousi, S. A. et al. ChemSusChem 12, 1700–1711 (2019) 5. Basile, A. et al. J. Power Sources, 344–349 (2018) 6. Rakov, D. A. et al. Nat. Mater. 4–10 (2020) Presentation Microbiologically Influenced Corrosion (MIC): Discovering Inhibitors and Their Mechanisms Mahdi Ghorbani*, Anthony Somers, Maria Forsyth Institute of Frontier Materials, Deakin University, Burwood VIC 3125 Australia Email: [email protected]
Carbon steel is one of the most commonly utilised construction materials and makes up the largest part of steel production in the world1. However, its limited corrosion resistance along with Microbiologically Influenced Corrosion (MIC) leads to enormous economic losses to replace or maintain corroded structures. The global economic cost of corrosion is US$ 2.5 trillion, of which US$ 0.5 trillion is estimated to be a result of MIC2. Reviewing current corrosion p rotection systems shows that corrosion inhibitor technologies are efficient, practical and economical pathways. Chromate-based compounds have demonstrated high efficacy corrosion protection (abiotic corrosion inhibitor), but are highly toxic and carcinogenic3. Furthermore, there is concern for the biocides that have been used for combating MIC, as they are highly toxic chemicals4. This highlights the significance of developing new corrosion protection technologies to maintain metallic structures in a variety of service environments. Hence, highly efficient, eco-friendly, novel MIC-inhibitors with multiple functionality that can protect against both abiotic and microbial corrosion of mild steel is much needed. This research project aims to design and underpin new environmentally friendly chemical structures to develop highly efficient, novel MIC-inhibitors for mild steel AS1030 grade. The project is a joint project with Deakin and Curtin universities to examine the anti-microbial properties in addition to the abiotic corrosion properties of the new inhibitors that have been developed. A novel series of cetrimonium cinnamate compounds have been designed and synthesised. The preliminary results show that CTA-4OHcinn, and CTA-4Etocinn are excellent abiotic corrosion inhibitors at neutral conditions, which are important for marine and offshore systems, while CTA-4Butcinn is a powerful inhibitor for acidic conditions. Potentiodynamic polarization (PP) studies combined with immersion in aqueous chloride solutions demonstrated the high inhibition efficiency of the combination of ions and NMR pfg- diffusion measurements revealed behaviour consistent with micellar formation that was concentration and pH dependent. The NMR data suggest that speciation changes occur in the solution that correlate strongly with enhanced corrosion inhibition efficiency at higher pH and at concentrations above the critical micelle concentration (CMC) of the compound (CTA- 4OHcinn)2. This new contribution may provide a rational molecular design towards delivering corrosion inhibitors to a metal surface through controlled speciation in solution.
References
1. A. L. Chong, J. I. Mardel, D. R. MacFarlane, M. Forsyth and A. E. Somers, ACS Sustainable Chemistry & Engineering, 2016, 4, 1746-1755. 2. M. Ghorbani, J. Soto Puelles, M. Forsyth, R. A. Catubig, L. Ackland, L. Machuca, H. Terryn and A. E. Somers, The Journal of Physical Chemistry Letters, 2020, DOI: 10.1021/acs.jpclett.0c02389, 9886-9892. 3. J. Sinko, Progress in organic coatings, 2001, 42, 267-282. 4. A. Moghe, S. Ghare, B. Lamoreau, M. Mohammad, S. Barve, C. McClain and S. Joshi-Barve, Toxicological Sciences, 2015, 143, 242-255. Presentation Ambient Energy Dispersion and Stabilisation of Large Graphene Sheets from Graphite Using a Surface Energy Matched Ionic Liquid Justin S. Freeman,a Kateryna Goloviznina,b Hua Li,a,c Martin Saunders,a,c Gregory G. Warr,d Agilio A. H. Pádua,b Rob Atkina,*
aSchool of Molecular Sciences, The University of Western Australia, Perth, WA 6009, Australia. bLaboratoire de Chimie, École Normale Superieure de Lyon & CNRS, 69364 Lyon, France. cCentre for Microscopy, Characterisation and Analysis, The University of Western Australia, Perth, Western Australia 6009, Australia dSchool of Chemistry and University of Sydney Nano Institute, The University of Sydney, Sydney, NSW 2006, Australia. * [email protected]
Keywords: graphene, ionic liquids, exfoliation, ambient energy, monolayer
Liquid phase exfoliation (LPE) is the most promising method for scalable graphene production, but conventionally requires significant energy input to break apart layers in the bulk material, introducing defects and limiting production of large, few-layer sheets. In this work, we exfoliated graphene under ambient conditions with minimal external energy input using the surface energy matched ionic liquid 1-ethyl-3-methylimidazolium acetate, then isolated and characterised the exfoliated material. This method produced large, thin, graphene sheets with size up to 3 μm. Monolayer sheets were identified in samples that had been left undisturbed for 6 months prior to sampling, meaning the graphene sheets suspended in the ionic liquid are stabilized against restacking. Energy Dispersive X-Ray Spectroscopy shows that ionic liquid remains adsorbed to graphene sheets even after washing. This, combined with molecular dynamic simulations, reveals the most likely reason for long-term stability is ion adsorption to the graphene nanosheets. Ambient energy exfoliation using ionic liquids offers simple, energy efficient method for producing large, high quality graphene sheets, with long-term stability in the ionic liquid. Presentation Effect of Hydrogen Bonding between Ions of Like Charge on the Boundary Layer Friction of Hydroxy-Functionalized Ionic Liquids
Hua Li,1, 2,* Thomas Niemann,3,4 Ralf Ludwig,3,4,5 Rob Atkin,1 1School of Molecular Sciences, The University of Western Australia, Perth, Western Australia 6009, Australia 2Centre for Microscopy, Characterisation and Analysis, The University of Western Australia, Perth, Western Australia 6009, Australia 3Universität Rostock, Institut für Chemie, Abteilung für Physikalische Chemie, Dr.-Lorenz- Weg 2, 18059, Rostock, Germany 4Department LL&M, University of Rostock, Albert-Einstein-Str. 25, 18059, Rostock, Germany 5Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany Email: [email protected]
Atomic force microscopy (AFM) has been used to measure the lubricity of a series of ionic liquids (ILs) at mica surfaces in the boundary friction regime. A previously unreported cation bilayer structure is detected at the IL-mica interface due to the formation of H-bonds between the hydroxy-functionalized cations ((c-c) H-bonds), which enhances the ordering of the ions in the boundary layer and improves the lubrication. The strength of the cation bilayer structure is controlled by altering the strength of (c-c) H-bonding via changes in the hydroxyalkyl chain length, cation charge polarizability and the coordination strength of the anions. This reveals a new means of controlling IL boundary nanostructure via H-bonding between ions of the same charge, which can impact diverse applications including surface catalysis, particle stability and electrochemistry, etc. Presentation Versatile Task-specific Sodium Iongels by Fast UV Photopolymerization for Emerging Solid State Energy Storage Applications
Luca Porcarelli,1,2 Preston Sutton,2 The An Ha,2 Cristina Pozo-Gonzalo,2 David Mecerreyes,1 Maria Forsyth2
1 POLYMAT University of the Basque Country UPV/EHU, Donostia–San Sebastin, Spain 2 ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, Australia
Email: l.porcarelli@deakin,edu,au
In recent years, there has been growing interest in ionic liquids (ILs) electrolytes since their superior thermal and electrochemical stability with respect to conventional organic electrolytes [1]. The need of incorporating ionic liquid into solid state energy storage applications has led to the development of iongels materials. This novel class of materials combines the unique electrolyte properties of ILs with the superior mechanical properties of polymers [2]. In this work, a simple method to prepare a mechanically robust iongel films is demonstrated. Fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide was employed to prepare versatile task- specific iongel electrolytes for application in two emerging solid state energy storage devices: namely sodium metal batteries and sodium oxygen batteries. The iongel electrolytes showed high ionic conductivity at room temperature (≥10–3 S cm–1) and tuneable storage modulus (104 – 107 Pa). The high salt concentration of the gel electrolyte (42% mol) was beneficial for battery performance, Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g–1 at 0.1C and 120 mAh g–1 at 1C with good capacity retention after 300 cycles. In addition, preliminary results in sodium oxygen batteries showed remarkable capacity of 0.285 mAh cm–2 at a discharge current of 0.1 mA cm–2. These results suggest the feasibility of solid state design based on iongel materials for next–generation energy storage and conversion applications based on sodium metal electrodes.
References [1] A. Fdz De Anastro, L. Porcarelli, M. Hilder, C. Berlanga, M. Galceran, P. Howlett, M. Forsyth, D. Mecerreyes, ACS Applied Energy Materials 2019, 2 (10), 6960-6966.
[2] M. Forsyth, L. Porcarelli, X. Wang, N. Goujon, D. Mecerreyes, Accounts of Chemical Research 2019, 52 (3), 686-694. Presentation Revealing the Liquid Structure of Cholinium Argininate Bio-Ionic Liquids via Small-Angle Neutron Diffraction Manuel Brunnera, Silvia Imbertib, Gregory G. Warrc, Rob Atkina
aSchool of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Perth, WA, 6009, Australia bSTFC, Rutherford Appleton Laboratory, Didcot OX11 0QX, U.K. cSchool of Chemistry and University of Sydney Nano Institute, The University of Sydney, Sydney, NSW 2006, Australia
Email: [email protected]
Choline amino acid ionic liquids are an interesting class of eco-friendly solvents, especially cholinium argininate (Ch[Arg]) aqueous solutions showed outstanding performance in biomass dissolution and extraction studies.1-4 Here we use small-angle neutron diffraction experiments to probe the liquid nanostructure of three Ch[Arg] solutions mixed with water, namely Ch[Arg]/water = 1:3, Ch[Arg]/water = 1:10 and with added 2-methoxyphenol (guaiacol) Ch[Arg]/water/guaiacol = 1:10:0.5. Empirical Potential Structure Refinement was used to fit a structure model onto the scattering data. In all three ILs a segregation of water rich and IL rich domains was observed including a continuous cation-anion network throughout the bulk liquid with integrated water domains of variable size. In agreement with previous studies cation-anion electrostatic interactions are complemented by a multitude of hydrogen bond interactions between all involved species. Intramolecular radial distribution functions showed that arginine exists in closed ring conformation. While the concentrated 1:3 Ch[Arg]/water system had an arginine ring content of 17% the addition of water lead to the formation 38% arginine in ring conformation. We hypothesis that this increase is caused by favourable IL-IL electrostatic and hydrogen bond interactions (opposed to IL-water) and the increased significance of attractive intramolecular interactions of arginine in the more dilute system. Addition of guaiacol notably reduced argininate in ring conformation to 6%. The presence of argininate in ring conformation in Ch[Arg] agrees with previous computational studies which predict that this ring conformation is crucial for strong hydrogen bonding with hydrogen bond donors, explaining its high performance in biomass pre-treatment experiments.5
References 1. To, T. Q.; Shah, K.; Tremain, P.; Simmons, B. A.; Moghtaderi, B.; Atkin, R., Treatment of lignite and thermal coal with low cost amino acid based ionic liquid-water mixtures. Fuel 2017, 202, 296-306. 2. Brunner, M.; Li, H.; Zhang, Z.; Zhang, D.; Atkin, R., Pinewood pyrolysis occurs at lower temperatures following treatment with choline-amino acid ionic liquids. Fuel 2019, 236, 306-312. 3. Hou, X.-D.; Smith, T. J.; Li, N.; Zong, M.-H., Novel renewable ionic liquids as highly effective solvents for pretreatment of rice straw biomass by selective removal of lignin. Biotechnology and Bioengineering 2012, 109 (10), 2484-2493. 4. Chua, E. T.; Brunner, M.; Atkin, R.; Eltanahy, E.; Thomas-Hall, S. R.; Schenk, P. M., The Ionic Liquid Cholinium Arginate Is an Efficient Solvent for Extracting High-Value Nannochloropsis sp. Lipids. ACS Sustainable Chemistry & Engineering 2019, 7 (2), 2538-2544. 5. Karton, A.; Brunner, M.; Howard, M. J.; Warr, G. G.; Atkin, R., The High Performance of Choline Arginate for Biomass Pretreatment Is Due to Remarkably Strong Hydrogen Bonding by the Anion. ACS Sustainable Chemistry & Engineering 2018, 6 (3), 4115-4121. Presentation Single Atom Catalysts with Nanoconfined Ionic Liquids for Enhanced CO2 Electroreduction Qian Sun, Yong Zhao and Chuan Zhao * School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia * Corresponding author. E-mail: [email protected]
Ionic liquids (IL) are effective electrolyte additives that can enhance the electrochemical performances of metallic catalysts for CO2 reduction reaction (CO2RR) over. ILs deliver much higher CO2 solubility than aqueous electrolytes, which can increase the local CO2 concentration and facilitate CO2 transportation to the single active site. Besides, ILs can form interaction with CO2 molecules, lowering the energy barrier for the formation of the key intermediate CO2*. However, ILs typically suffer from high viscosity and expensive costs, leading to slow mass transfer and low conductivity of the electrolytes. Using large quantity of bulk viscous ionic liquids in industrial for CO2RR electrolyser is impractical.
Here we show a nanoconfined strategy for using ionic liquids for CO2RR. We confine a hydrophobic ionic liquid (BmimPF6) into a nickel-nitrogen-carbon (Ni-N-C) single atom catalyst (SAC) to develop a Ni-N-C/ILs nanocomposite catalyst for direct use in aqueous electrolytes for CO2RR. The synergistic effect between the ILs co-catalyst and Ni-N active sites lead to excellent CO2RR performances in pure CO2 and diluted CO2. The fabricated Ni- N-C/BmimPF6 exhibited higher CO Faradaic efficiency (FECO) and partial current densities (jCO) than those of Ni-N-C SAC in pure and diluted (10%, 50%) in a wide potential range from -0.5 to -1.0 V vs RHE (Figure 1). A high FECO of 98% and a large CO partial current 2 density of 37 mA/cm were achieved in pure CO2 on the composite catalyst. This work lay solid foundations for future applications of ionic liquids for industrial CO2RR and many other important electrochemical reactions such as oxygen reduction reactions, water splitting and nitrogen reduction and beyond.
Figure 1. (a) FECO, (b) jCO, and (c) LSV of Ni-N-C and Ni-N-C/BmimPF6 at different potentials and CO2 concentrations.
References [1] S. Chen, K. Kobayashi, Y. Miyata, N. Imazu, T. Saito, R. Kitaura, H. Shinohara, J. Am. Chem. Soc. 2009, 131, 14850. [2] S. Zhang, J. Zhang, Y. Zhang, Y. Deng, Chem. Rev. 2017, 117, 6755. [3] D. Vasilyev, E. Shirzadi, A. V. Rudnev, P. Broekmann, P. J. Dyson, ACS Appl. Energy Mater. 2018, 1, 5124. [4] W. Ren, X. Tan, W. Yang, C. Jia, S. Xu, K. Wang, S. Smith, C. Zhao, Angew. Chem. Int. Ed. Engl. 2019, 58, 6972. Presentation
Highly Homogeneous Sodium Superoxide Growth in Na−O2 Batteries Enabled by a Hybrid Electrolyte Laura Garcia-Quintana,a Nagore Ortiz-Vitoriano,b,c Iciar Monterrubio,b Juan Miguel Lopez del Amo,b Fangfang Chen,a Teofilo Rojo,b,d Patrick C. Howlett,a Maria Forsyth,a,c and Cristina Pozo-Gonzaloa aARC Centre of Excellence for Electromaterials Science, Institute for Frontier Materials, Deakin University, Geelong, Victoria 3200, Australia bCenter for Cooperative Research on Alternative Energies, CIC energiGUNE, 01510 Vitoria-Gasteiz, Spain cIkerbasque, Basque Foundation for Science, 48013 Bilbao, Spain dDepartamento de Quimica Inorganica, Universidad del Pais Vasco UPV/EHU, 48080 Bilbao, Spain Email: [email protected]
Metal-O2 batteries have emerged as a great candidate in the substitution of Li-ion batteries as energy storage technology for the future. Among the different chemistries available for oxygen batteries, Na-O2 are of special importance due to the high theoretical energy density (1105 Wh kg-1), high abundance of Na on the earth crust and lower overpotential when compared to Li-O2 (<0.7V vs >1V), coming from the different discharge products obtained [1] (NaO2 vs Li2O2). The nature of the electrolyte has been demonstrated to be intimate related to the performance of Na-O2 batteries. On one hand, organic solvents such as glyme-ether based electrolytes have been studied, showing a relationship between the length of the glyme and the discharge products morphology and, in turn, the battery performance.[2] Thus, the discharge capacity decreases upon alkyl chain length, related to the interactions between the electrolyte and the electrogenerated species in the bulk. On the other hand, ionic liquids (IL) have also been studied due to their interesting properties, such as low volatility, low flammability, and wide electrochemical window, among others. In our group, we have previously studied the concentration effect in the N-butyl-N- methyl pyrrolidinium bis(trifluoromethanesulfonyl) imide ([C4mpyr][TFSI]) IL, showing that the discharge capacity increases upon the concentration of Na salt, which again was related to the interactions between the species present in the bulk of the electrolyte.[3] In order to further increase the concentration of Na+ in the IL, and reduce the flammability of the glyme solvents, here we used the [C4mpyr][TFSI]:diglyme hybrid electrolyte with two different NaTFSI concentrations. In these electrolytes, the presence of the IL has been proven to enhance the cyclability of the battery when compared to the electrolyte with glyme only (ca. 20 vs 5 respectively). Additionally, the IL has been demonstrated to decrease the generation of side products typically found in glyme-based electrolytes, responsible for the lower reversibility. Furthermore, a relationship between the battery performance, the discharge products deposition and the physicochemical properties has been found, where the presence of free glyme leads to larger deposits delaying the failure of the battery.[4]
References [1] H. Yadegari, X. Sun, Accounts of chemical research 2018. [2] L. Lutz, W. Yin, A. Grimaud, D. Alves Dalla Corte, M. Tang, L. Johnson, E. Azaceta, V. Sarou-Kanian, A. Naylor, S. Hamad, The Journal of Physical Chemistry C 2016, 120, 20068-20076. [3] Y. Zhang, N. Ortiz-Vitoriano, B. a. Acebedo, L. O’Dell, D. R. MacFarlane, T. f. Rojo, M. Forsyth, P. C. Howlett, C. Pozo-Gonzalo, The Journal of Physical Chemistry C 2018, 122, 15276-15286. [4] N. Ortiz-Vitoriano, I. Monterrubio, L. Garcia-Quintana, J. M. López del Amo, F. Chen, T. Rojo, P. C. Howlett, M. Forsyth, C. Pozo-Gonzalo, ACS Energy Letters 2020, 5, 903-909. Presentation Unexpected Origin of Nanostructure in Choline Phenylalaninate, a Biocompatible Ionic Liquid Shurui Miao1, Haihui Joy Jiang1, Jared Wood,1 Silvia Imberti2, Rob Atkin3, Gregory Warr1 1The University of Sydney, Sydney, Australia 2Rutherford Appleton Laboratory, Harwell, United Kingdom 3University of Western Australia, Perth, Australia Email: [email protected], [email protected]
Recently, a number of choline amino-acid salts have been reported to form ionic liquids (ChILs), creating the possibility of biocompatible ILs with a sustainable production cycle.[1,2] Since their discovery, these designer solvents have proven useful across many applications, including drug synthesis and delivery, electrochemistry, biomass processing and CO2 capture, often in mixtures with water.[3] However, little is still known about how the structure of their constituent ions determines properties and performance of both the pure IL and its solutions, limiting the capacity to design task-specific ILs and optimise for large scale applications. In this study, we investigate choline DL-phenylalaninate (ChPhe) using time-of- flight neutron diffractionand modelled its structure with simulations. Our aim is to understand how its amphiphilic liquid nanostructure arises from atomic correlations. Surprisingly, we discovered the aromatic moieties of the phenylalaninate anion form distinct, small clusters or non-polar domains, but with no evidence for pi-pi stacking. Detailed analysis of the atomic correlations reveals that inter-anion hydrogen bonds are the main stabilisation factor of these non-polar clusters. This is the first example of self-assembled ionic liquid nanostructure not of solvophobic origin. The unusual suite of interactions also explains its water miscibility but inability to retain nanostructure upon water dilution,[4] as well as its poor performance for biomass pretreatment (relative to other nanostructured ChILs),[5] and provides a new strategy by which to engineer and tune ionic liquid nanostructure for the design of application- specific, renewable solvent systems.
References [1] K. Fukumoto, M. Yoshizawa, and H. Ohno, Journal of the American Chemical Society 127, 2398 (2005). [2] Q.-P. Liu, X.-D. Hou, N. Li, and M.-H. Zong, Green Chemistry 14, 304 (2012). [3] L. Gontrani, Biophysical reviews 10, 873 (2018). [4] S. Miao, R. Atkin, and G. G. Warr, Physical Chemistry Chemical Physics 22, 3490 (2020). [5] X. D. Hou, T. J. Smith, N. Li, and M. H. Zong, Biotechnology and Bioengineering 109, 2484 (2012). Presentation Predicting Reaction Outcome through Physical Measurements of Ionic Liquids
Daniel C. Morris1,2,* Stuart W. Prescott1 and Jason B. Harper2 1School of Chem. Eng., UNSW Sydney, NSW 2052, Australia 2School of Chemistry, UNSW Sydney, NSW 2052, Australia *E-mail: [email protected] Ionic liquids have been investigated as a potential replacement for molecular solvents due to their unique properties and customisability.1 Despite this, common application remains inaccessible due to their often unpredictable effects on reaction outcome.2 The reaction between pyridine and benzyl bromide has been investigated in mixtures of acetonitrile and different ionic liquids in the 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C2n+2C1im][NTf2], n = 0-5) homologous series (Fig. 1a). Unique behaviours as a function of mole fraction were seen in each ionic liquid, along with a consistent trend where longer alkyl chain substituents result in lower values of k2 (Fig. 1b).
Figure 1. a) (left) the reaction of benzyl bromide and pyridine, performed in the presence of the [C2n+2C1im][NTf2] homologous series of ionic liquids (n=0-5). b) (right) mole fraction dependence of the bimolecular rate coefficient (k2) for the reaction of benzyl bromide and pyridine at 22.2°C in mixtures containing different proportions of either 3 [C2C1im][NTf2] (◆), [C4C1im][NTf2] (◆), [C6C1im][NTf2] (◆), [C8C1im][NTf2] (◆), or [C12C1im][NTf2] (◆) with acetonitrile, and in acetonitrile (—). Errors are reported as the standard deviation of at least triplicate results. Some errors fall within the size of the markers used.
Solvent relaxation NMR measurements are sensitive to both molecular motion and solvent structuring, with entropic differences such as increases in structuring having a large influence on the value of the spin-spin relaxation time (T2). Since the observed increase in k2 is entropically influenced, T2 of the homologous series of ionic liquids was investigated. Correlation of T2 and k2 allows quantitative prediction of rate coefficients in various solvent mixtures. These data, along with associated activation parameters, indicate that solvent structuring plays an important part when understanding the microscopic origins of rate enhancement for these ionic liquid systems. References 1. Hallett, J. P.; Welton, T. Chem. Rev. 2011, 111, 3508–3576. 2. Hawker, R. R.; Harper, J. B. Adv. Phys. Org. Chem. 2018, 52, 49–85. 3. Schaffarczyk McHale, K. S.; Hawker, R. R.; Harper, J. B. New J. Chem. 2016, 40, 7437–7444. 4. Yau, H. M.; Croft, A. K.; Harper, J. B. Faraday Discuss. 2012, 154, 365– 371. Presentation Oxazolidinium-based Ionic Electrolytes: The Effect of Ether Functionality in the Ring a,bColin S. M. Kang, aRuhamah Yunis, aHaijin Zhu, bOliver Hutt, aJenny Pringle aInstitute for Frontier Materials, Deakin University, Burwood, Victoria 3125, Australia bBoron Molecular, Noble Park, Melbourne, Victoria, Australia Email: [email protected]
The advancement of safer, long-lasting energy storage technologies is paramount for the transition into a clean renewable energy economy and sustainable future. To envision this approach, at least in part, relies on the development of new electrolytes that i) are safe and reliable, and ii) can support next-generation battery technologies that have higher energy densities (e.g. alkali metal, metal-air batteries); both of these requirements are necessary to sustain the ever-growing demand for energy usage, that today’s Li-ion batteries cannot solely achieve. Whilst current battery electrolytes utilise organic solvents that are volatile and flammable, both ionic liquids (ILs) and organic ionic plastic crystals (OIPCs) are promising electrolyte candidates as they exhibit negligible vapour pressure, non-flammability, and are thermally stable at high temperatures. OIPCs, very similar to ILs in structure, differ in that they are solid-like materials at above ambient temperatures with plastic-like mechanical properties, yet exhibit appreciable ionic conductivities.[1] To further enhance the development, and thus utilisation, of these electrolytes depends on increasing our fundamental understanding of the structure and dynamics of emerging cation/anion families. This work describes the synthesis and characterisation of a range of dimethyloxazolidinium + - - - ([C1moxa] )-based ILs and OIPCs, that contain various anions such as [FSI] , [NTf2] , [BF4] + etc. The analysis of thermal behaviour reveals that some of these [C1moxa] -based OIPCs are + highly disordered and exhibit a wide conductive phase. Interestingly, the [C1moxa] -based OIPCs studied have been found to exhibit higher ionic conductivities than their equivalent + pyrrolidinium counterparts. On the contrary, [C4moxa] -based ILs have conversely been shown to exhibit lower ionic conductivities.[2] In other words, the presence of ether functionality in the ring may affect the solid-state ionic conductivity of OIPCs differently to the liquid-state ionic conductivity of ILs. Lastly, we probe the ion transport dynamics of the cation/anion species through solid-state NMR experiments.
+ + [C1moxa] [C2moxa] + + Figure 1: Molecular structure of [C1moxa] and [C2moxa] cations investigated in this study.
References [1] J. M. Pringle, P. C. Howlett, D. R. MacFarlane, M. Forsyth, J. Mater. Chem. 2010, 20, 2056–2062. [2] Z. Bin Zhou, H. Matsumoto, K. Tatsumi, Chem. Eur. J. 2006, 12, 2196–2212. Presentation Effect of Humidity on Electrochemical Gas Sensing in Ionic Liquid- based Electrolytes Simon Doblinger, Taylor J. Donati, Junqiao Lee, Debbie S. Silvester-Dean Curtin Institute for Functional Molecules and Interfaces, School of Molecular and Life Sciences, Curtin University, Perth, WA 6845, Australia Email: [email protected]
Room-temperature ionic liquids (RTILs) are known to have promising characteristics such as low volatility, good conductivity, wide electrochemical windows (EWs) and high chemical and thermal stability, especially when employed as electrolytes in electrochemical gas sensors. However, the ionic nature of RTILs results in highly hygroscopic properties. It has been shown by various researchers that the presence of water significantly alters the physicochemical properties of RTILs[1], including the electrochemical window, i.e. the operation range of an electrolyte, which is significantly reduced in water saturated ionic liquids[2]. Also, the electrochemical reaction mechanism of an analyte can be different in a water-free and a water- saturated electrolyte. For oxygen gas, a one-electron reduction is observed in a ‘dry’ RTIL, whereas a two- or four-electron reduction is observed in ‘wet’ RTILs.[3] Our recent studies have shown that RTILs form alternating cation and anion layers close to a charged electrode. Depending on the exact chemical structures, a highly hydrophobic and therefore water repellent or a more hydrophilic innermost layer is formed. We have studied RTIL layering in the EDL via atomic force microscopy and indirectly monitored the presence of water close to the electrode via the electrochemical oxygen reduction reaction in RTILs with various different structures.[4] We also studied the EWs of RTILs in a systematic way over a wide humidity range, showing that at the maximum relative humidity of 95 RH%, all RTILs have similar EWs of approximately 2 V, i.e. comparable to aqueous electrolytes, regardless of the cation or anion structure. In ‘dry’ conditions, structure dependent EWs between 4.3 – 6.5 V were observed. We then studied the impact of the narrowing of the EW on the response of two analytes, i.e. decamethylferrocene and ammonia gas. We concluded that the presence of water not only changes the transport properties of the electrolyte due to reduced viscosity, but the narrowing EW may also contribute to the current response at the same redox potential of the analyte.[5] The outcomes of these studies demonstrate that the effect of water has to be considered when RTILs are used as electrolytes in ‘open’ environments, especially where water absorption is unavoidable. References [1] a) E. P. Grishina, L. M. Ramenskaya, M. S. Gruzdev, O. V. Kraeva, J. Mol. Liq. 2013, 177, 267-272; b) J. G. Huddleston, A. E. Visser, W. M. Reichert, H. D. Willauer, G. A. Broker, R. D. Rogers, Green Chem. 2001, 3, 156-164. [2] A. M. O’Mahony, D. S. Silvester, L. Aldous, C. Hardacre, R. G. Compton, J. Chem. Eng. Data 2008, 53, 2884-2891. [3] A. Khan, X. Lu, L. Aldous, C. Zhao, J. Phys. Chem. C 2013, 117, 18334-18342. [4] S. Doblinger, J. Lee, D. S. Silvester, J. Phys. Chem. C 2019, 123, 10727-10737. [5] S. Doblinger, T. J. Donati, D. S. Silvester, J. Phys. Chem. C 2020, 124, 20309-20319.
r Presentation The Effects of Ionic Liquids as Solvents for Reactions that Proceed through Carbocation Intermediates Alyssa Gilbert,1 Ronald S. Haines1 and Jason B. Harper1 1School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia [email protected]
Ionic liquids have been shown to affect reaction outcomes, including rate enhancements and increased selectivity, differently to molecular solvents.1, 2 Extensive efforts have been made to explore these effects and the microscopic interactions that cause them, particularly for 2 SN2 processes. Comparatively few studies have investigated these effects in unimolecular substitution reactions,3, 4 often due to slow reaction rates and competing side reactions. This work uses ionic liquids as solvents for reactions that proceed through unimolecular substitution processes in an effort to understand how they affect reactions of this mechanism. Understanding how ionic liquids interact with species along the reaction coordinate is explored through variation of the constituent ions and use of multivariate regression analysis to correlate reaction outcome with Kamlet–Taft solvent parameters (e.g., see Figure 1). Understanding key interactions between ionic liquids and species along the reaction coordinate has the potential to allow for rational selection of an ionic liquid for reactions of this mechanism to give a desired reaction outcome.
Figure 1. The relationship between the natural log of the unimolecular rate constant (k1) and a combination of the Kamlet Taft α and β parameters for the unimolecular reaction between xanthenyl acetate 1 and indole 2 in a number of ionic liquids at a mole fraction of 0.20. References 1. J. P. Hallett and T. Welton, Chem. Rev., 2011, 111, 3508-3576. 2. H. M. Yau, S. T. Keaveney, B. J. Butler, E. E. L. Tanner, M. S. Guerry, S. R. D. George, M. H. Dunn, A. K. Croft and J. B. Harper, Pure Appl. Chem., 2013, 85, 1979. 3. B. Y. W. Man, J. M. Hook and J. B. Harper, Tetrahedron Lett., 2005, 46, 7641-7645. 4. H. M. Yau, S. A. Barnes, J. M. Hook, T. G. A. Youngs, A. K. Croft and J. B. Harper, Chem. Commun., 2008, 3576-3578. Presentation Investigating Specific-ion Effects on the Nanostructure of Propylammonium Nitrate via Molecular Dynamics Simulations Thomas Burke, Kasimir P. Gregory, Alister J. Page University of Newcastle, Australia Email: [email protected]
Specific-ion effects (SIEs) induce or influence physicochemical phenomena in a way that is determined by the identity of the ions present, and not merely by their charge or concentration. Such effects have been known for 130 years since the seminal work of Hofmeister and are often categorised according to the well-known Hofmeister series.[1] Examples are ubiquitous throughout the chemical, biological, environmental and material sciences, and are traditionally explained in terms of the influence ions have on the structure of water. However, this explanation is unsatisfactory as it is unable to adequately explain and predict frequently- observed series reversals and anomalies, nor does it account for SIE in the absence of water, such as non-aqueous solvents and ionic liquids (ILs). The distinct nanostructure of ILs represent an ideal medium to study these effects. The effects of dissolved monovalent salts in the IL propylammonium nitrate (PAN) were investigated via molecular dynamics simulations. These effects were observed for both a propylammonium halide anion series (F⁻,Cl⁻, Br⁻, I⁻) and alkali metal nitrate cation series (Li+, Na+, K+, Rb+) dissolved in PAN. The anions conform to the Hofmeister series in terms of predicting nanostructure changes, whilst the cations include more points of nuance. In general, anions were shown to increases the probability of hydrogen bonding within propylammonium nitrate, whereas cations would decrease the probability. These effects were most prominent at the high 50 mol% concentrations of dissolved salt.
References [1] W. Kunz, J. Henle, B. W. Ninham, Curr. Opin. Colloid Interface Sci. 2004, 9, 19–37. [2] N. Schwierz, D. Horinek, U. Sivan, R. R. Netz, Curr. Opin. Colloid Interface Sci. 2016, 23, 10–18. [3] V. Mazzini, G. Liu, V. S. J. Craig, J. Chem. Phys. 2018, 148, 222805. [4] M. Senske, D. Constantinescu-Aruxandei, M. Havenith, C. Herrmann, H. Weingärtner, S. Ebbinghaus, Phys. Chem. Chem. Phys. 2016, 18, 29698–29708. [5] Y. Zhang, P. S. Cremer, Proc. Natl. Acad. Sci. 2009, 106, 15249–15253. Presentation Ionic Liquids for Rechargeable Metal Batteries
Mega Kar, Douglas R MacFarlane Monash University, Wellington Road, Clayton, Victoria, 3800, Australia *Email address: [email protected]
The current demand for alternative energy storage technologies has inspired many researchers to investigate rechargeable batteries based on low cost, highly abundant and safe metals such as magnesium (Mg). However, one main challenge lies in designing a stable and compatible electrolyte to achieve reduction/oxidation of (Mg) in rechargeable Mg batteries (RMBs). Recently we have reported the synthesis of a weakly-coordinating closo-boron-cluster-based room temperature ionic liquid (RTIL), [N2(20201)(20201)(20201)][CB11H12], with high oxidative stability (Figure 1a), which supports Mg deposition/stripping,[1] making them immensely attractive for high-voltage cathodes and the development of high-energy density RMBs.
The ongoing challenge of common impurities, such as water, which can have a significant effect on the cycle life of Mg, is also addressed in our recent publications.[2] Herein we demonstrate the use of trace amounts of a dehydrating agent, Mg[BH4]2, to achieve stable magnesium deposition/stripping in a mixture of RTIL/organic solvents (Figure 1b).[2]
Figure 1: Cyclic Voltammetry illustrating a) Anodic stability of [N2(20201)(20201)(20201)][CB11H12] (Substrate: Glassy carbon)[1] and b) Mg deposition/stripping from a mixture of RTIL/organic [2] solvent in the presence of Mg[BH4]2 (Substrate: Platinum). Reference [1] M. Kar, O. Tutusaus, D.R. MacFarlane, R. Mohtadi, Energ. Environ. Sci. 2019, 54, 566-571. [2] Z. Ma, D.R. MacFarlane, M. Kar*, Green Energ. Environ., 2019, 4, 146-153
. Presentation Ionic Liquids in Electric Fields Nathan Martens, Ekaterina I Izgorodina School of Chemistry, Monash University, Wellington Rd, Clayton VIC 3800, Australia
Email: [email protected]
Electric fields are commonplace in many modern-day devices such as batteries and capacitors, arising from the separation of electrical potential or point charges in space. Consequently, electric fields are typical within chemical systems, and have recently been realised as a potential alternative to traditional chemical catalysis methods, offering green, sustainable and tuneable catalysis.1 Such catalysis methods have been studied extensively theoretically, and recent experimental work has acted as a proof of concept2, yet any meaningful and scalable experimental realisation of such methods has not been achieved. This work proposes the use of ionic liquids as a promising means of realising the full potential of electric field mediated catalysis. Ionic liquids are a relatively new class of tuneable, green solvents comprised of low melting point organic salts, and being comprised of formally charged ions, interact significantly with electric fields.
The interactions of ionic liquids within external electric fields has been studied via a variety of computational and experimental techniques including ab initio quantum mechanical calculations, molecular dynamics simulations and cyclic voltammetry.
It is revealed that interaction energy is seen to decrease within two ion pair clusters by as much as 200 kJ/mol, while inter-ionic spacing increases significantly. Despite this shift, the ratio of electrostatic to correlation energy components remains constant, implying an enhancement of correlation interactions and a dampening of electrostatics. This result is reflected in a newly developed experimental strategy, utilising cyclic voltammetry to measure reduction and oxidation potentials of ionic liquids. In this fashion, it was observed that ionic liquids exhibit less energetic redox processes and increased ion mobility following the application of an external electric field. Finally, polarisable molecular dynamics simulations of a number of ionic liquids where conducted under varying external electric field conditions. These simulations show good agreement with both the
References [1] S. Shaik, R. Ramanan, D. Danovich and D. Mandal, Chemical Society Reviews, 2018, 47, 5125–5145.
[2] A. C. Aragonès, N. L. Haworth, N. Darwish, S. Ciampi, N. J. Bloomfield, G. G. Wallace, I. Diez-Perez and M. L. Coote, Nature, 2016, 531, 88–91. Presentation F - Fluoroalkylborate [B(OR )4] Anions for High-voltage LiBs Binayak Roy, Mega Kar, Douglas R. Macfarlane School of chemistry, Monash University Email: [email protected]
Our recent work has focussed on a novel family of perfluourinated alkyl borate anions for use in ionic liquid and solvent based electrolytes for batteries and supercapacitors. The conventional fluorophosphate and sulfonylimide based lithium (Li) salts show high moisture sensitivity and limited oxidative stability at voltages higher than 4.5V vs Li. In this work we F - explore a new class of fluoroalkyl borate salts [B(OR )4] of lithium, based on different fluorine substituted alkyl ligands (-ORF, trifluoroethyl, hexafluoroisopropyl and nonafluoro tert-butyl) to address the instabilities of conventional salts and discuss their applicability in high density energy storage devices. The high atmospheric and electrochemical stability (>5 V vs. Li) of these fluoroalkylborate salts and their Li plating-stripping behaviour suggest that Lithium (tetra) 1,1,1,3,3,3-hexafluoro-isopropyl borate (LiBHFip) (fig. 1) is an excellent candidate among other salts in its class.
Figure 1: The structure of LiBHFip salt Presentation Synthesis, Electrochemical and Spectroscopic Study of Novel Boronium Ionic Liquid based Electrolyte Systems for High Energy Density Lithium Batteries Rory McCalluma,b, Marzieh Barghamadia, Anthony F. Hollenkampa, Peter Mahon b, Thomas Rüthera a CSIRO, Research Way, Clayton VIC 3168, Australia b Swinburne University, John Street, Hawthorn Victoria 3122 Australia
E-mail: [email protected]
There are two broad areas in which lithium battery technology draws ionic liquid electrolytes (ILELs) into consideration. First, contemporary lithium-ion technology is plagued by concerns about the thermal instability, vapor pressure and flammability of the organic carbonate/Li[PF6] electrolyte systems which makes cooling of lithium-ion batteries mandatory in most new applications. The second, and arguably more significant, area of impact is in the domain of next generation batteries that use lithium metal anodes, notably lithium-sulfur[1] and lithium air (oxygen)[2] batteries, along with on-going interest in replacing the graphite anode in lithium-ion with metallic lithium. There is enormous potential for the discovery and application of new ILELs that may offer significant improvements. However, the properties of ILs vary enormously as a function of the structure of their constituent ions. Despite considerable effort has been devoted to identifying and understanding those that have superior properties in battery application, there are currently few cation families (essentially cyclic and non-cyclic ammoniums, phosphoniums) stable enough when paired with TFSI or FSI anions to sustain efficient and long-term lithium battery cycling. For relatively unexplored binary and ternary ILEL systems based on the unique boronium cation[3], we present a comprehensive study of their physicochemical properties, the crystal structure of a respective isolated Li-salt and their cyclability in LFP Li and Li Li cells. According to the cycle studies, the boronium IL systems perform equally or better than the commonly employed pyrrolidinium ILEL systems.
References [1] M. Barghamadi, A. S. Best, A. I. Bhatt, A. F. Hollenkamp, M. Musameh, R. J. Rees, T. Rüther, Energy & Environmental Science 2014, 7, 3902-3920. [2] J. Christensen, P. Albertus, R. S. Sanchez-Carrera, T. Lohmann, B. Kozinsky, R. Liedtke, J. Ahmed, A. Kojic, Journal of the Electrochemical Society 2011, 159, R1. [3] T. Rüther, T. D. Huynh, J. Huang, A. F. Hollenkamp, E. A. Salter, A. Wierzbicki, K. Mattson, A. Lewis, J. H. Davis, Chemistry of Materials 2010, 22, 1038-1045. Presentation Parametrisation of Polarisable Force Fields through Incorporation of Many-body Effects in Ionic Liquids Peter Halat, a Nathan Martens, a Thomas Mason, a Ekaterina I Izgorodina a a School of Chemistry, Monash University, Wellington Rd, Clayton VIC 3800, Australia
Email: [email protected]
Drude-oscillator polarisable force fields are emerging as the standard for ionic liquids, where thorough parametrisation offers accurate dynamic and structural properties, simultaneously.1 Presently, non-bonded parameters for classical, non-polarisable simulations are tweaked to be used in Drude-oscillator simulations, since Drude-oscillators account of induction in ionic liquids, bringing the risk of double counting. To counter this, it is suggested to scale non-bonded parameters by the ratio of induction and dispersion forces, effectively eliminating the risk of double counting of induction interactions. In this work, large-scale ionic liquids cluster calculations are performed to parametrise polarisable force fields. These calculations involve the Fragment Molecular Orbital (FMO) method and its accompanying Pair Interaction Energy Decomposition Analysis (PIEDA),2 incorporating many-body effects, especially polarisation which is yet to be considered when calculating scaling factors. A convergence study on ionic liquids [C4mim][dca] and [C4mim][Cl] indicates that extracting eight-ion-pair clusters from non-polarisable simulations are sufficient to calculate scaling factors, which are then applied to polarisable simulations. The scaling factors provided by FMO-PIEDA calculations are successful in recreating structural and dynamic properties of ionic liquids. From this, we present a workflow of calculations which can be applied to any ionic liquid or mixture, giving parameters for polarisable force field simulations from non-polarisable simulations.
References [1] K. Goloviznina, J. N. Canongia Lopes, M. Costa Gomes and A. A. Padua, J. Chem. Theory Comput., 2019, 15, 5858–5871.
[2] D. G. Fedorov and K. Kitaura, J. Comp. Chem., 2007, 28, 222–237. Presentation The effect of Bisimidazolium-based Ionic Liquids on a Bimolecular Substitution Process. Are Two Head(group)s Better Than One? Kenny Liu1,*, Ronald S. Haines1 and Jason B. Harper1 1School of Chemistry, The University of New South Wales, NSW 2052, Australia *E-mail: [email protected]
Ionic liquids have been studied as potential alternatives to molecular solvents, with particular interest taken in how they affect reaction outcome.1, 2 Previous studies have explored the effects of ionic liquids on substitution processes, with a focus on the microscopic interactions that cause these changes in reaction outcome.
Previous studies have demonstrated that the Menshutkin reaction (Scheme 1) is accelerated in 3, 4 the presence of [bmim][N(SO2CF3)2] 4 in the reaction mixture; in general, the greater the proportion of the salt in the reaction mixture, the greater the rate constant. These changes were primarily attributed to interactions of the cationic component of the ionic liquid 4 with the nitrogen heteroatom of pyridine 1.5, 6
Scheme 1. The reaction of pyridine 1 with benzyl bromide 2 to form 1-benzylpyridinium bromide 3, which is accelerated in the presence of [bmim][N(SO2CF3)] 4. The work described here investigates the effect of a homologous series of bisimidazolium- based ionic liquids 5 (Figure 5) on the reaction described above. The effects of the salts 5 on the rate constant of the reaction were compared to those observed from ionic liquid 4, demonstrating the significance of the structure of the cationic component of ionic liquids in determining their effect on the reaction described above, particularly regarding potential co-operativity between the charged centres of the cationic component of the salts.
Figure 1. The bisimidazolium ionic liquids 5, where n = 1, 3-12.
References 1. J. P. Hallett and T. Welton, Chem. Rev., 2011, 111, 3508-3576. 2. C. Dai, J. Zhang, C. Huang and Z. Lei, Chem. Rev., 2017, 117, 6929-6983. 3. H. M. Yau, A. G. Howe, J. M. Hook, A. K. Croft and J. B. Harper, Org. Biomol. Chem., 2009, 7, 3572-3575. 4. K. S. Schaffarczyk McHale, R. R. Hawker and J. B. Harper, New J. Chem., 2016, 40, 7437-7444. 5. H. M. Yau, A. K. Croft and J. B. Harper, Faraday Discuss., 2012, 154, 365-371. 6. E. E. L. Tanner, H. M. Yau, R. R. Hawker, A. K. Croft and J. B. Harper, Org. Biomol. Chem., 2013, 11, 6170-6175. Presentation Boronium Cation-based Ionic Liquid Electrolytes for Li Metal Batteries Jonathan Clarke-Hannaforda,b, Michael Breedonb, Thomas Rütherc, Michelle J.S. Spencera aSchool of Science, RMIT University, GPO Box 2476, Melbourne, VIC 3001, Australia bCSIRO Manufacturing, Private Bag 10, Clayton South, VIC 3169, Australia cCSIRO Energy, Private Bag 10, Clayton South, VIC 3169, Australia Email: [email protected]
Rechargeable Li metal batteries (LMBs) can provide the high energy densities required for next generation energy storage systems. However, there are safety and long cycle life issues associated when using a pure Li metal anode with conventional organic solvent-based electrolytes. Utilising ionic liquid-based electrolytes (ILEL) can mitigate these concerns due to their low vapour pressure, low flammability and ability to stabilise the Li metal anode during repetitive charge/discharge cycles. The boronium cation based ionic liquid (trimethylamine)(dimethylethylamine)dihydroborate bis(trifluoromethanesulfonyl)imide [NNBH2][TFSI] was previously shown to enable the enhanced cycling performance of a Li|LiFePO4 cell, compared to 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide [Pyr14][TFSI], when both are doped with LiTFSI [1]. This enhancement could be attributed to the solid electrolyte interphase (SEI) that forms on the Li metal surface that can prevent unwanted consumption of the electrolyte/anode materials during cycling. Our present work provides insights into the interfacial reactions leading to beneficial SEI layer formation. Density functional theory (DFT) calculations and ab initio molecular dynamic (AIMD) simulations were used to model the interaction of boronium cation based ionic liquids on the Li(001) surface [2,3]. These ionic liquids are comprised of + the boronium cation [NNBH2] and its cyclic derivative (N,N,N’,N’- + - tetramethylethylenediamine)dihydroborate [(TMEDA)BH2] , paired with the anions [TFSI] or bis(fluorosulfonyl)imide [FSI]- (Figure 1). Decomposition of both anions occurred on the Li(001) surface at 298 K and at 358 K (abuse conditions) during the AIMD simulations, with + the anions forming surface bound Li2O, LiF and Li2S species [4]. Both the [NNBH2] and + [(TMEDA)BH2] cations remained intact during their interaction with the Li surface, suggesting these cations will remain stable at the anode surface and decomposition products originating from the boronium cations are unlikely to be found in the inner SEI layer. a)
c) [NNBH2][FSI] d) [(TMEDA)BH2][FSI]
Li(001) surface Figure 1. Boronium cation based ionic liquids (a–d) studied on the Li(001) surface (e).
References [1] T. Rüther, T.D. Huynh, J. Huang, A.F. Hollenkamp, E.A. Salter, A. Wierzbicki, K. Mattson, A. Lewis, J.H. Davis, Chem. Mater. 2010, 22, 2172- 2173. [2] M.D. Brennan, M. Breedon, A.S. Best, T. Morishita, M.J.S. Spencer, Electrochim. Acta, 2017, 243, 320-330. [3] J. Clarke-Hannaford, M. Breedon, A.S. Best, M.J.S. Spencer, Phys. Chem. Chem. Phys. 2019, 21, 10028-10037. [4] J. Clarke-Hannaford, M. Breedon, T. Rüther, M.J.S. Spencer, ACS Appl. Energy Mater. 2020, 3, 5497-5509. Presentation Deep Eutectic Solvents for Cryopreservation Saffron J. Bryant, Tamar Greaves, and Gary Bryant Centre for Molecular and Nanoscale Physics, College of Science, Engineering and Health, RMIT University, Melbourne, Victoria 3001, Australia
Email: [email protected]
Cryopreservation offers huge advantages in the medical field through the preservation of blood and stem cells, storage of reproductive cells, as well as the potential to store tissues and organs.1 However, cryopreservation is limited by the available cryoprotectants (CPAs). Dimethyl sulfoxide (DMSO) and glycerol are the primary CPAs, but both can be toxic and require extensive washing of preserved cells before use.2 Furthermore, there are some cell types that cannot be cryopreserved using these two CPAs.1 Thus, there is a need for different, non-toxic CPAs, ideally with tuneable properties.3 Deep eutectic solvents (DESs) are a subclass of ionic liquids, many of which are non- toxic. Due to the extensive number of deep eutectic solvents, they offer a broad range of properties, so some may have the potential to be alternative CPAs. To date, only a very few studies have examined the cryoprotective applications of DESs, but these have shown comparable viability of cells stored using DESs compared to those stored using DMSO.4 We have explored the thermal properties of a number of DESs, including in combination with water to identify glass transition and recrystallisation behaviours. We have also studied the shrink/swell behaviour of cells (THP-1 cells) in the presence of DESs in order to measure the permeability of different DESs which gives information on their potential applications as CPAs. The results of this research could provide new avenues of cryopreservation which could be applied to cell types which can’t currently be preserved with existing CPAs. This in turn would have wide-ranging benefits, especially in the biomedical field.
References 1. A. Sputtek and R. Sputtek in Life in the Frozen State, ed. B.J. Fuller, N. Lane and E. Benson, CRC Press, Boca Raton, 2004, Ch. 17, pp. 483-504. 2. B.J. Fuller, Cryoletters, 2004, 25 (6), 375-388. 3. R. Raju, T. Merl, M. Adam, E. Staykov, R. Ben, G. Bryant, and B. Wilkinson, Australian Journal of Chemistry, 2019, DOI: 10.1071/CH19159 4. V. Castro, R. Craveiro, J. Silva, R. Reis, A. Paiva and A. Duarte, Cryobiology, 2018, DOI: 10.1016/j.cryobiol.2018.06.010 Presentation Fully Periodic Constant Potential Simulations of Electric Double Layers Shern Ren Tee, Debra Bernhardt Australian Institute of Bioengineering and Nanotechnology, UQ Email: [email protected]
The development of better batteries and supercapacitors, for advancing technology and addressing climate change, requires better understanding of the electrode-electrolyte interface. Theoretical models of electrolyte layering near interfaces are still in their infancy, especially for ionic liquids, while many molecular models neglect electrode conductivity in using fixed, uniform atomic charges. In this talk I describe the constant-potential method (CPM), which dynamically updates electrode atomic charges to reflect the polarization of a conductive electrode, and its open-source implementation in the popular molecular dynamics package LAMMPS. CPM molecular dynamics enables the rigorous study of electric double layers near a charged surface, allowing the observation of phenomena such as voltage- dependent ionic-liquid density ordering as well as the calculation of capacitance. Recent advances1,2 also enable the application of CPM to fully periodic representations of the electrochemical unit cell, further reducing the computational cost of CPM-enabled simulations, and I will present benchmarks of the performance improvements obtained in LAMMPS.
References: (1) P. Raiteri, P. Kraus, and J. Gale, J. Chem. Phys., 2020, 153 (16), 164714. (2) T. Dufils, G. Jeanmairet, B. Rotenberg, M. Sprik, and M. Salanne, Phys. Rev. Lett., 2019, 123 (19), 195501. Presentation Investigating the Effects of Mixtures of Ionic Liquids on Reaction Outcome
Matthew D. Taylor,a* Ronald. S. Hainesa and Jason. B. Harpera, a School of Chemistry, University of New South Wales, Sydney, Australia. *[email protected] Ionic liquids have been considered as replacements to molecular solvents1 and there is the potential to use them to control reaction outcomes.2 To this point, however, only individual ionic liquids have been investigated; that is, ionic liquids containing only one type of cation and only one type of anion. There is the potential to expand the application of ionic liquids by using multiple types of cations and/or anions at once, generating a wider range of ionic liquids. Because of this flexibility, there is the potential for a greater degree of control when using mixtures. To be effective, such rational design requires an understanding of how mixtures of ionic liquids compare to their 'simple' ionic liquid counterparts, and any deviations from simple additive effects must be accounted for. This concept has been investigated with a well-studied organic reaction; a nucleophilic 3 aromatic substitution (SNAr) process (Scheme 1). The effects of mixtures of ionic liquids (both cases were ionic liquids had the same cation but different anions, and when they had the same anion but different cations) have been considered. Particularly, the effects of changing the proportion of different ionic liquids has been examined (Figure 1).
Scheme 1. The ethanolysis reaction of fluorodinitrobenzene, that proceeds through an SNAr mechanism. This
reaction has been studied in the presence of the ionic liquids [bmim]Cl and [bmim][NTf2].
Figure 1. The rate constant for the reaction between fluorodinitrobenzene and ethanol (Scheme 1) in mixtures of ethanol and the ionic liquids [bmim]Cl and [bmim][NTf2] with a total mole fraction of 0.3 at 51 °C. Uncertainties are the standard deviation of triplicate results; some error bars are smaller than the markers used. The line represents a simple additive effect of both ionic liquids. References 1. Hallett, J. P.; Welton, T. Chem. Rev. 2011, 111, 3508. 2. Hawker, R. R.; Harper, J. B. Adv. Phys. Org. Chem. 2018, 52, 49. 3. For example, Hawker, R. R; Haines, R. S.; Harper, J. B. Org. Biomol. Chem. 2017, 15, 6433; 2018, 16, 3453. Presentation The Effect of Ionic Liquids on Lysozyme and Green Fluorescent Protein: A Multi-technique Approach
Qi (Hank) Han*, Calum J. Drummond and Tamar L. Greaves
School of Science, College of Science, Engineering and Health, RMIT University, Melbourne, Australia
*E-mail: [email protected]
Ionic liquid (ILs) solutions have been widely studied for biochemical applications in recent decades. The IL ions interact with proteins, and can profoundly regulate their properties and functionalities. However, systematic understanding on the solvent-functionality relationships at the molecular level has been challenging. Here, we show a wide range of protic ILs and choline-based ILs usedwith lysozyme and GFP as model proteins. The protein functionalities such as conformational changes, crystallization, specific interactions, aggregation and compactness are discussed based on a multi-technique approach including spectroscopies, small angle x-ray scattering and crystallography. In particular, we show the interaction between ILs and proteins at an atomic level, and that the interactions and specific ion effects affect the protein functionalities. This study can improve our understanding of how and why this protein misfolds and aggregates and structure-property relationships for future solvent design for proteins. Presentation Stabilization of Fluoride Ions in Ionic Liquids Anjali Gaur, Nikhil V. S. Avula, and Sundaram Balasubramanian Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India Email: [email protected]
Ionic liquids are a new paradigm in organic synthesis due to their very low vapor pressure, wide liquid range, and high density as compared with common organic reagents. ILs have been used as fluorinating reagents and catalysts to synthesize organofluorine molecules. Hagiwara et al. recently designed a poor solvate ionic liquid (SIL) based fluorinating agent, 1-Ethyl-3-methylimidazolium fluoride ([EMIM]F) 1 solvated in ethylene glycol (EG) i.e. [EMIM]F-xEG, at various EG concentrations . The [EMIM]F.EG SIL showed advantages in chemical handling, stability, and reaction conditions over conventional fluorinating agents such as hydrogen fluoride and metal fluorides. As [EMIM]F.xEG is liquid at ambient conditions; experimental tools other than NMR and vibrational spectroscopy are limited in their scope to provide a comprehensive microscopic perspective. Further, 19F liquid and solid-state NMR are not necessarily used to compare fluoride ion solvation strength in different chemical environments. Christe et al. have shown that although the theoretically calculated NMR shifts are comparable with the experimentally reported values, the 2 binding energy values do not correlate with the NMR chemical shifts . That is where molecular dynamic (MD) simulations are powerful, realistic, and have often played critical roles in providing microscopic insights. This talk will focus on how computational modeling can be used to investigate the microscopic nature of the SIL, its compositional range of stability, and the specific molecular interactions that offer this stabilization. We examined the geometries of hydrogen bonds that a fluoride ion makes with the acidic protons on the EG molecule and on the [EMIM] cation.Fluoride ions are seen to form a stronger hydrogen bond(s) with the acidic proton of EG than with that of the [EMIM] cation. Fluoride ions in [EMIM]F.xEG have different local coordination environments. Moreover, the Probability of finding a fluoride ion in one kind of coordination environment varies with the change in ethylene glycol concentration. Consequently, the fraction of EG in the solution can influence the stability and fluorination efficiency 3 of the SIL . References [1] Z. Chen. Y. Tonouchi, K. Matsumoto, M. Saimura, R. Atkin, T. Nagata, M. Katahira, R. Hagiwara, J. Phys. Chem. Lett. 2018, 9, 6662–6667 [2] M. Gerken, J. Boatz, A. Kornath, R. Haiges, S. Schneider, T. Schroer,K. Christe, J. Fluorine Chem. 2002, 116, 49– 58 [3] Anjali Gaur, Nikhil V. S. Avula, and S. Balasubramanian, J. Phys. Chem. B 2020, 124, 40, 8844–8856 Presentation Polarisable Force field for Protic Ionic Liquids and Deep Eutectic Solvents Kateryna Goloviznina, Zheng Gong, Margarida Costa Gomes and Agílio A. H. Pádua
Laboratoire de Chimie, École Normale Supérieure de Lyon & CNRS, 69364 Lyon, France Email: [email protected]
The relevance of molecular dynamics simulations of ionic liquids stands on the quality of the underlying interaction model, or force field, which comprises intra- and intermolecular potential energy terms that determine conformations, energetics, ordering and dynamics of molecular and ionic systems. Traditional fixed-charge force fields reproduce well the structural and thermodynamic properties, but the predicted dynamics is too slow when compared to experiment. One of the remedies is to introduce explicit polarization into existing fixed-charge force fields, for example through Drude induced dipoles [1] placed on the atomic sites. The existing effective van der Waals interaction parameters, typically a Lennard-Jones potential, should be rescaled in order to avoid double counting of the polarization (induction) effects, which are now represented explicitly [2]. Following this approach, the existing fixed-charge CL&P [3] force field was transformed into a polarisable version, CL&Pol, validated on different classes of aprotic ionic liquid [4]. Extension of the CL&Pol to protic ionic liquids and deep eutectic solvents requires correct description of strong hydrogen bonds and also of interactions with small, densely-charged ions, not available in the force field until now. An additional charge-dipole damping function was introduced in order to prevent a so called “polarization catastrophe” caused by excessive attraction between a small, densely-charged atom (like hydrogen) and a Drude dipole, as illustrated in Figure 1. A Tang-Toennies damping function [5] was implemented in LAMMPS and parametrized that allows to obtain stable MD trajectories. [6]
Figure 1. Schematic representation of the “polarization catastrophe” (right) in ethylammonium nitrate and its preventing with charge-dipole damping (left).
The CL&Pol force field was validated with a protic ionic liquid (ethylammonium nitrate) and a DES (choline-chloride–ethylene glycol). It reproduces equilibrium and dynamic properties, liquid and solid structure at consistent levels, much improved from fixed-charge models. References [1] G. Lamoureux and B. Roux, J. Chem. Phys., 2003, 119, 3025–3039. [2] A. A. H. Pádua, J. Chem. Phys., 2017, 146, 204501–204509. [3] J. N. Canongia Lopes, J. Deschamps, and A. A. H. Pádua, J. Phys. Chem. B, 2004, 10, 2038–2047. [4] K. Goloviznina, J. N. Canongia Lopes, M. Costa Gomes, and A. A. H. Pádua, J. Chem. Theory Comput., 2019, 15, 5858– 5871. [5] M. Salanne, B. Rotenberg, S. Jahn, R. Vuilleumier, C. Simon and P. A. Madden, Theor Chem Acc, 2012, 131, 1143. [6] K. Goloviznina, Z. Gong, M. Costa Gomes and A. A. H. Pádua, Chemrxiv, 2020, DOI: 10.26434/chemrxiv.12999524 Presentation Ionic Liquids as Stabilising Agents for Nitroxide Redox Flow Batteries Luke Wyliea, Thomas Bleschb, Kan Hakateyamac, Ekaterina Izgorodinab aENS de Lyon, bMonash University, cWaseda University Email: [email protected]
Through previous studies ionic liquids (ILs) have been shown to effectively stabilise radical molecules through strong intermolecular interactions. This was shown in initially in computational analysis of the interactions of nitroxide radicals and ILs and later confirmed by experimental EPR analysis indicating significant rotational hindrance of nitroxides in IL solvents. ILs have also shown the potential to be applied as an electrolyte in redox flow batteries for large-scale energy storage.1
Nitroxide Radicals have long shown promise as cathode active materials in both traditional batteries as polymers and in redox flow batteries as both monomer and polymer materials. They also have the possibility of being used as anode materials, currently with limited success due to the inherent instability of the reduced aminoxy anion charged product formed. However, as a result of the stabilisation effects of ionic liquids, the aminoxy anion of TEMPO was found to have a proton transfer energy from the cation of the IL to the aminoxy anion Figure 1: Photo of 0.1 M TEMPO in [C4mpyr][OTf] before -1 and after complete charging with a current of 0.1 mA cm−2 on often over 100 kJ mol , with the highest -1 the cathode (left) and the anode (right), energy being 193.7 kJ mol in [C1mpyr][OTf]. As a result, they have shown the potential to have reversible reduction reactions as well as the already stable oxidation reaction. Following this a full redox cell was set up and it showed the ability to charge TEMPO as both an anode and cathode active material and hold charge for an extended period of time in an inert atmosphere with the final charged products as well as the standard uncharged TEMPO material shown in Figure 1.2
In addition to stabilising the reduction of TEMPO to make a symmetrical TEMPO cell possible, ILs have also been shown to increase the redox potential of TEMPO calculated theoretically as well as in experimental CV experiments. In this study the theoretical potential 3 was found to increase to up to 5.5 V in [P1,1,1,1][CH3SO3] from the 2.2 V measured in water. In experiment due to resistance the increase was less pronounced but still present increasing the redox potential from 1.3 V in water to 2.1 V in [C4mpyr][OTf].
References [1] L. Wylie, Z. L. Seeger, A. N. Hancock and E. I. Izgorodina, Phys. Chem. Chem. Phys., 2019, 21, 2882-2888. [2] Wylie Luke, Blesch Thomas, Freeman Rebecca, Hatakeyama-Sato Kan, Oyaizu Kenichi, Yoshizawa-Fujita Masahiro and E. I. Izgorodina, ACS Sustainable Chem. Eng., 2020, Under Review. [3] L. Wylie, K. Oyaizu, A. Karton, M. Yoshizawa-Fujita and E. I. Izgorodina, ACS Sustainable Chem. Eng., 2019, 7, 5367-5375. Poster Abstracts Poster 1 Potential-Dependent Superlubricity of Ionic Liquids on Graphite Surface
Yunxiao Zhang1, Mark W. Rutland2,3, Jiangshui Luo4,5, Hua Li1,6*, Rob Atkin1*
1School of Molecular Sciences, The University of Western Australia, Perth, Western Australia, Australia. 2School of Chemical Science and Engineering, KTH Royal Institute of Technology, SE100 44 Sweden 3Surfaces, Processes and Formulation, RISE Research Institutes of Sweden, SE114 86 Stockholm, Sweden 4College of Materials Science and Engineering, Sichuan University, 610065 Chengdu, China 5Laboratory for Soft Matter and Biophysics, Department of Physics and Astronomy, KU Leuven, Leuven 3001, Belgium 6Centre for Microscopy, Characterisation and Analysis, The University of Western Australia, Perth, Western Australia, Australia
Abstract
The frictions of four quaternary phosphonium ionic liquids (ILs) including i trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate ([P6,6,6,14][( C8)2PO2]), trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate ([P6,6,6,14][BEHP]), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P6,6,6,14][TFSI]) and tributylmethylphosphonium bis(trifluoromenthylsulfonyl)imide ([P4,4,4,1][TFSI]) were measured on highly oriented pyrolytic graphite (HOPG) as a function of external potentials using atomic force microscopy (AFM). The frictions of ILs are potential-dependent as the compositions of the boundary layers switch from cation-enriched to anion-enriched as the potential changes from negative to positive.
i At −1.0 V the [P6,6,6,14] cation achieves superlubricity when it pairs with [( C8)2PO2] or [BEHP] i anions. At +1.0 V, [TFSI] shows better lubricity than [( C8)2PO2] and [BEHP]. The lubricity of ILs is influenced by three factors: the alkyl chain length, chemical composition and ionic sizes of the ILs. Longer alkyl chains of [P6,6,6,14] cations assist the formation of robust boundary layers, thus improving lubricity. Fluorine atoms in [TFSI] anions increase packing order and reduce geometric contact corrugations of the boundary layers, thus improving lubricity. In addition, matching the molecular dimensions of cations and anions leads to smoother, more robust boundary layers, which also results in improved lubricity. Poster 2 Chain Dimensions of Polymeric Ionic Liquids through Small-Angle Neutron Scattering Lucas N. Wong,1 Kathleen Wood,2 Seamus Jones,3 Rachel Segalman,3 Gregory G. Warr,4 Tamin Darwish2 and Rob Atkin,*,1 1School of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Perth, WA 6009, Australia 2Australia’s Nuclear Science and Technology Organisation, New Illawarra Rd, Lucas Heights, NSW 2234, Australia 3College of Engineering, University California Santa Barbara, Lagoon Rd, Santa Barbara, CA93106, United States 4School of Chemistry, University of Sydney, Eastern Ave, Camperdown, NSW 2006, Australia
Keywords: Ionic Liquids; Polymers; Nanostructure; Small Angle Neutron Scattering.
The nanostructure of the popular polymeric ionic liquid (PIL) poly(3MAPIm)TFSI in the pure PIL and in the ionic liquid (IL) BMIm TFSI was probed at the nanoscale as a function of concentration and temperature. Small angled neutron scattering (SANS) and statistical modelling reveal that the radius of gyration (Rg) of the poly-cation in the pure PIL slightly increases with temperature due to thermal expansion, indicating no major structural change. In the IL, the Rg of the poly-cation decreases with concentration due to sterics and increases as a function of temperature due to a combination of thermal expansion and entropic effects. Poster 3 Interfacial Nanostructure of Amphiphilic Deep Eutectic Solvents J. J. Buzolic1, H. Li1, G. G. Warr2, R. Atkin1 1 School of Molecular Sciences, The University of Western Australia, Crawley, WA 2 School of Chemistry, The University of Sydney, Camperdown, NSW Email: [email protected]
This project aims to examine a new class of green and economical designer solvents containing both ionic and molecular components, focussing on understanding interfacial nanostructure using Atomic Force Microscopy (AFM) imaging, friction, and force curve measurements, and X-ray and neutron reflectometry. The novel hybrid solvents will be analysed and manipulated to understand the intermolecular forces that induce amphiphilic nanostructure, particularly at the interface between a solid substrate and the solvent. The new classification of the hybrid solvents is based on previously studied liquids and solutions, and aims to function as a highly sustainable and controllable platform for future research and applications.
Initial studies will involve AFM experiments on choline chloride-carboxylic acid deep eutectic solvents (DESs). DESs are a mixture of a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD) in a specific molar ratio, which forms a homogenous liquid phase with a depressed melting point lower than the individual components. DESs are typically non-amphiphilic, therefore the aim of this project is to induce amphiphilic nanostructure in DESs by using hydrophobic groups (the HBD alkyl chain) and hydrophilic groups (the HBD acid group and the HBA).
Amplitude modified AFM will be used to determine the nanostructure of the DESs, primarily from applying friction, force curve, and imaging techniques. These methods will reveal how the type of components and the composition of the DESs affect their nanostructure, and the relationship between the bulk structure and the interfacial structure. The results from this project will be used for the development of complex fluids containing surfactants and polymers as well as lubricants, which will be used for improving the sustainability of fluids used in industry. Poster 4 Temperature-dependant Solubility Determination of Sodium Salts for Sodium-ion Secondary Batteries 1 1 1 2 Dale Duncan , Mega Kar , Douglas R MacFarlane & Maria Forsyth 1Monash University, Wellington Road, Clayton, Victoria, 3800, Australia 2Deakin University, Burwood Highway, Burwood, Victoria, 3125, Australia Email: [email protected]
The solubility of compounds in ionic liquids is a highly important parameter for a wide range of applications, including electrochemical applications such as secondary batteries. Batteries, particularly low-cost and abundant emerging rechargeable sodium batteries, have begun to play a major role in energy storage for the decarbonisation of polluting electricity grids, further promoting the uptake of renewable energy sources as energy storage capacity increases. Batteries must operate efficiently over a wide temperature range, greater than the expected ambient temperature for the intended application. The ambient temperature of the system can have strong influence on the solubility, necessitating a method which allows the determination of solubility with temperature dependence 1, 2. Unfortunately, methods with sufficient precision and accuracy for the determination of solubility are lacking. Herein, we explore the method of laser monitoring which operates by detecting light scattered from suspended particles in solution 3, 4. Neat solvent or ionic liquid is titrated against the saturated solution to the end-point where no analyte particles remain in solution, determining the end-point of solubility at the given temperature. This method has minimal bias, and allows studies of temperature-dependant solubility. The successful outcome of this method will enable us to precisely determine the solubility of novel electrolytes based on sodium salts in organic solvents and room temperature ionic liquids for sodium-ion secondary batteries.
References
1. W. Zou, Q. Xia, W. Zhao, F.-B. Zhang and G.-L. Zhang, The Journal of Chemical Thermodynamics, 2014, 70, 239-244. 2. Q. Xia, S.-N. Chen, Y.-S. Chen, M.-S. Zhang, F.-B. Zhang and G.-L. Zhang, Fluid Phase Equilibria, 2011, 304, 105-109. 3. Y. Wang, S. Fu, Y. Jia, C. Qian and X. Chen, Journal of Chemical & Engineering Data, 2013, 58, 2483-2486. 4. Y.-X. Jia, C. Qian, X.-Z. Chen and C.-H. He, Journal of Chemical & Engineering Data, 2012, 57, 1581-1585. Poster 5 Understanding the Discharge Products Formation in Ionic Liquids Based Na-O2 batteries and Strategy to Limit Side Reactions
The An Ha1, Asier Fdz De Anastro2, Jian Fang1, Maria Forsyth1, David Mecerreyes2, Patrick C. Howlett1, Cristina Pozo-Gonzalo1 1ARC Centre of Excellence for Electromaterials Science, Institute for Frontier Materials, Deakin University, Melbourne, Australia 2Joxe Mari Korta Center, POLYMAT University of the Basque Country UPV-EHU, Avda. Tolosa 72, 20018 Donostia-San Sebastian, Spain E-mail: [email protected].
Sodium oxygen (Na-O2) batteries have attracted growing interest of the research community due to their -1 -1 high theoretical energy density (1605 Wh kg or 1105 Wh kg in the case of sodium peroxide (Na2O2) or sodium superoxide (NaO2) as discharge products) and low cost. These batteries are in an infant stage; and further efforts are required to understand the key parameters governing the formation of discharge products on the air cathode during the oxygen reduction process. In our study, the generation of discharge products during operation on electrospun carbon nanofiber matts (CNFs) air cathode using a pyrrolidinium-based ionic liquid electrolyte were assessed. By combining imaging, ex situ techniques and electrochemical operation, we found the correlation between the discharge product morphology and the electrochemical performance in the Na-O2 cell based on the nucleation and growth of discharge products at various depths of discharge. For instance, at 30% discharge capacity, small cubic particles (around 2µm) are generated and continue to grow with capacity. Then, at 60% discharge capacity, a thin film start covering the surface of the CNFs and coexisted with larger particles. At full depth of discharge, particles of all sizes continued to enlarge to about 4 µm, but the thin film almost fully covered the air cathode. Also, characterization of the discharge products at various depth of discharge by Raman spectroscopy showed that sodium peroxide and sodium superoxide were the main discharge products; however, an unexpected products (Na2-xO2- Thin film) were found after 60% of discharge. Then, we highlight a core strategy to improve sodium oxygen battery capacity through limiting the growth of the thin film on the air cathode (limiting of the passivation air cathode) by using bilayer iongel/ionic liquids. Around 100% high Coulombic efficiency Na−O2 batteries was enabled by a bilayer ionogel/ionic liquid that reduces the formation of the thin film discharge products.
Schematic 1. The formation of discharge products for ionic liquids based Na-O2 batteries for different stages discharge process.
References 1. I. Landa-Medrano, C. Li, N. Ortiz-Vitoriano, I. Ruiz de Larramendi, J. Carrasco and T. Rojo, The Journal of Physical Chemistry Letters, 2016, 7, 1161-1166. 2. The An Ha, Asier Fdz De Anastro, Nagore Ortiz-Vitoriano, Jian FangDouglas R. Macfarlane, Maria Forsyth, David Mecerreyes, Patrick C. Howlett, Cristina Pozo-Gonzalo, J. Phys. Chem. Lett. 2019, DOI: 10.1021/acs.jpclett.9b02947. 500 ∙102 500 500 20 500 20 500 8 10 18 18 7 400 8 400 400 400 400 15 15 6 8
13 13 5 300 6 300 300 300 300 6 10 10 4
200 4 200 200 200 200 4 8 8 3
5 5 2 2 100 100 2 100 100 100 3 3 1
0 0 0 0 0 0 0 0 0 0 μm 0 200 400 μm 0 200 400 μm 0 200 400 μm 0 200 400 μm 0 200 400 total C32H68P+ K+ Fe+ Cr+ MC: 982; TC: 4.778e+007 MC: 11; TC: 6.738e+004 MC: 20; TC: 1.292e+006 MC: 20; TC: 9.490e+005 MC: 8; TC: 7.164e+004
500 ∙103 500 500 500 500 7 20 20 16 1.0 6 400 400 400 400 400 16 16 5 0.8 12 300 300 300 300 300 12 4 12 0.6 8 3 200 200 200 8 8 2 4 4 100 4 100 100 Poster 6 1 0 0 0 0 0 0 0 400 μm 0 200 400 μm 0 200 400 μm 0 200 400 Chemical ransformations by hermomechanical tresses evealed by K+ Fe+ Cr+ T T S R +005 MC: 21; TC: 1.224e+006 MC: 18; TC: 4.712e+005 MC: 7; TC: 3.559e+004 TOF-SIMS Analysis 500 14 500 7 800 1 2 2 3 20 Jeffrey J. Black, Christopher E. Marjo, Soshan Cheong, Sergei Glavatskih, Mark W. 12 6 4 1 400 400 600 Rutland and Jason B. Harper 16 10 5
1 300 300 8 4 School of Chemistry, University of New South Wales, NSW 2052, Australia 12 2 400 6 3 Solid State & Elemental Analysis Unit, UNSW Mark Wainwright Analytical Centre, NSW 200 200 8 2052, Australia 4 2 200 3 4 4 100 100 Department of Machine Design and Division of Surface Chemistry and Corrosion 2 1
Science, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden 0 0 0 0 0 0 400 μm 0 200 400 μm 0 200 400 μm 0 250 500 750 Email: [email protected] BO2- FeO2- Video Snapshot at Start of Measurement (micro) MC: 14; TC: 2.007e+005 MC: 7; TC: 5.136e+004
Research has been conducted into using ionic 500 20 500 8 500 6 800
18 7 5 liquids for lubricating applications, either using neat 400 400 400 15 6 600 ionic liquids as lubricants or using ionic liquids as 4 13 5 300 300 300
additives to more conventional oil and greased based 10 4 3 400
200 200 200 1 8 3 lubricants. Ionic liquids have many properties that 2
5 2 200 100 100 100 make them appropriate as lubricants, including low 1 3 1
volatility, high thermal stability, and being liquid over 0 0 0 0 0 0 0 2 μm 0 200 400 μm 0 200 400 μm 0 200 400 μm 0 250 500 750 a wide temperature range. Ionic liquids also offer BO2- FeO2- Video Snapshot at Start of Measurement (micro) MC: 8; TC: 6.108e+004 MC: 6; TC: 4.644e+004 advantages not accessible with conventional lubricants, such as the ability to control how lubricating the ionic liquid is, including achieving superlubricity, by applying an electric potential to the surface.3
An important aspect of research into the use of ionic liquids as lubricants is how the ionic liquids are chemically changed through such use. TOF-SIMS4 provides a unique
method of analysis which, not only allows the detection of 2- breakdown but also, allows for identification of the breakdown products. Such identification provides insight into the pathway and mechanism of breakdown of the ionic liquids.
This work uses TOF-SIMS to analyse the breakdown of three phosphonium based ionic liquids by thermal and thermomechanical stress, along with considering the resulting tribofilm, to better understand the thermomechanically induced chemical transformations that occur in ionic liquid based lubricants.
References 1. A. Somers, P. Howlett, D. MacFarlane and M. Forsyth, Lubricants, 2013, 1, 3-21. 2. F. U. Shah, S. Glavatskih and O. N. Antzutkin, Tribology Lett., 2013, 51, 281-301. 3. H. Li, R. J. Wood, M. W. Rutland and R. Atkin, Chem. Commun., 2014, 50, 4368-4370. 4. M. Holzweber, E. Pittenauer and H. Hutter, J. Mass. Spec., 2010, 45, 1104-1110. Poster 7 Investigating the Solubility of Petroleum asphaltene in Deep Eutectic Solvents and their Interaction using COSMO-RS
Nikhil Kumara* and Tamal Banerjee a a Department of Chemical Engineering, Indian Institute of Technology Guwahati Guwahati – 781039, Assam, India * Corresponding author: E-mail i.d- [email protected], Tel: +91-7578906414, Fax: +91-361-2690762 Abstract Dispersion of asphaltene in crude oil using Deep Eutectic Solvents (DESs) is being considered as a viable solution, in extraction and transportation processes. In this work, the interplay between asphaltene and DESs has been studied systematically to understand the effect of structural variation of DESs on asphaltene solubility. The activity coefficient of the total of 1517 DESs with different combinations of cation and anion of DESs for representative asphaltene molecule (asphaltene) was estimated via COSMO-RS (Conductor-like Screening Model for Real Solvents). COSMO_RS predictions were validated using experimental data on asphaltene solubility. Among the studied DESs, asphaltene showed high solubility in imidazolium-based DESs with hydrophobic anions. The present approach paved a way forward to rationally understand the impact of structural variation of DESs on their interaction with asphaltene molecule and to design new DESs for the dispersion and stabilization of asphaltene.
Fig. 1. Model asphaltene compound (asphaltene) (a) 3 D structure of asphaltene; oxygen atom (red color), nitrogen atom (blue color), carbon atom (green color) and hydrogen atoms (white color) Keywords: COSMO-RS; Deep Eutectic solvents; Asphaltene; Dispersion. Poster 8 A Bespoke Force Field for DEME-TFSI Ionic Liquid Nikhil V. S. Avula, Anwesa Karmakar, Rahul Kumar, Sundaram Balasubramanian Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India Email: [email protected]
Molecular simulations, working in tandem with experiments, have advanced our understanding of the microscopic structure and dynamics of ionic liquids (ILs) and related materials. Understanding the dynamical properties of ILs is crucial, especially in their applications such as battery electrolytes, Electric Double Layer Capacitors (EDLCs), transistor devices, etc. In this work, we develop a bespoke force field for N,N-Diethyl-N- methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI) IL with the main goal of quantitatively predicting the transport properties.
As the fidelity of the simulations depend on the force fields, much effort has gone into refining the general force fields to suit ionic liquids.[1] Though most force fields predict the structure well, they tend to underestimate the dynamical properties of ILs.[1] Scaling down the net ion charges results in improved dynamical property prediction and is rationalized as capturing the charge transfer effect between the oppositely charged ions.[1] Later works have shown that the charges derived from condensed phase Density Functional Theory (DFT) calculations lead to a better agreement with experiments.[1,2,3,4] Building on these works, we refine the atomic site charges from condensed phase DFT calculations and the Lennard-Jones (LJ) parameters from ab initio potential energy scans.[5,6,7] We have developed a Quenched Monte Carlo (QMC) based heuristic optimization algorithm to automate refining the LJ parameters. The refined force field achieves quantitative agreement with experiments in both structural properties like the X-ray structure factor and transport properties like diffusivity, conductivity, and viscosity over a wide temperature range. References [1] F. Dommert, K. Wendler, R. Berger, L. Delle Site, C. Holm, ChemPhysChem 2012, 13, 1625-1637. [2] J. Schmidt, C. Krekeler, F. Dommert, Y. Zhao, R. Berger, L. Delle Site, C. Holm, J. Phys. Chem. B 2010, 114, 6150-6155 [3] Y. Zhang, E. J. Maginn, J. Phys. Chem. B 2012, 116, 10036-10048 [4] N. V. S. Avula, A. Mondal, S. Balasubramanian, J. Phys. Chem. Lett. 2018, 9, 3511-3516 [5] A. Mondal, S. Balasubramanian, J. Phys. Chem. B 2014, 118, 3409-3422 [6] A. Mondal, S. Balasubramanian, J. Phys. Chem. B 2015, 119, 11041-11051 [7] S. Mukherji, N. V. S. Avula, S. Balasubramanian, ACS Omega 2020, 5, 28285-28295
Headshot of Presenting Author Poster 9 Investigating the effects of an ionic liquid on the nucleofugality of chloride Maxwell D. Coney* and Jason B. Harper School of Chemistry, University of New South Wales, NSW 2052, Australia Email: [email protected]
Ionic liquids and their mixtures have demonstrated potential as solvents for preparative chemistry.1 A significant amount of work has considered their effects on reaction outcome, as they differ from molecular sovlvents.2-4 Quantifying these solvent effects may hold the key to unlocking a predictive model allowing the application of these solvents. A solvent parameter that has been used to quantify solvent effects of molecular solvents is nucleofugality.5 Nucleofugality is commonly referred to as the leaving group ability of a species in a unimolecular solvolysis reaction and reflects interactions between solvent and leaving group. It can be determined by measuring the solvolysis rate constant for a series of electrophiles.6 This quantitative solvent parameter had not been determined for ionic liquids. This work will present the successful application of the methodology for determining the nucleofugality of chloride in mixtures of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][N(SO2CF3)2]) and ethanol. This was done through the collection of rate constants corresponding to the ethanolysis of a series of chlorides allowing mole fraction dependence to be identified (Figure 1). These rate constants across a series of chlorides provided the necessary data for a nucleofugality correlation to be constructed. This quantification of this parameter allowed for comparison of solvent effects between the ionic liquid [bmim][N(SO2CF3)2] and molecular solvents (Figure 2).
Figure 1. The dependence of the solvolysis rate constant of chlorodiphenylmethane in mixtures of ethanol and the ionic liquid [bmim][N(SO2CF3)2].
Figure 2. The nucleofugality (Nf) of chloride in [bmim][N(SO2CF3)2] (ca. Nf = -0.5, ¦), a mixture of [bmim][N(SO2CF3)2] and ethanol (χ10 = 0.80, |), and the each of the molecular solvents 2-propanol (|), ethanol (|) and methanol (|). References 1. R. R. Hawker and J. B. Harper, Adv. Phys. Org. Chem., 2018, 52, 49-85. 2. A. Gilbert, R. S. Haines and J. B. Harper, Org. Biomol. Chem., 2020, 18, 5442-5452. 3. A. Gilbert, R. S. Haines and J. B. Harper, Org. Biomol. Chem., 2019, 17, 675-682. 4. A. Gilbert, G. Bucher, R. S. Haines and J. B. Harper, Org. Biomol. Chem., 2019, 17, 9336-9342. 5. N. Streidl, B. Denegri, O. Kronja and H. Mayr, Acc. Chem. Res., 2010, 43, 1537-1549. 6. B. Denegri, S. Minegishi, O. Kronja and H. Mayr, Angew. Chem. Int. Ed., 2004, 43, 2302-2305. Poster 10 Effect of surfactant ionicity on critical micelle concentration in aqueous ionic liquid mixtures Sachini P Kadaoluwa Pathirannahalagea,b, Michael Hassetta, Andrew Christoffersona, Tu Lea, Margarida Costa Gomesc, Calum J Drummonda, Tamar L Greavesa*
a College of Science, Engineering and Health, RMIT University, Australia b Laboratoire de Chimie, Ecole Normale Supérieure de Lyon and CNRS, Lyon, France
Protic ionic liquids are the largest known solvent class capable of promoting surfactant self-assembly. However, ILs are increasingly used as mixtures with molecular solvents, such as water, to reduce their cost, viscosity and melting point, and the self-assembly promoting properties of these mixtures are largely unknown. Here we investigated the critical micelle concentration (CMC) of ionic and non-ionic amphiphiles in ethylammonium nitrate (EAN)-water mixtures to gain insight into the role of solvent species, and effect of solvent ionicity on the self-assembly process. The amphiphiles used were the cationic cetyltrimethylammonium bromide (CTAB), anionic sodium octanoate sulfate (SOS), and the non-ionic surfactant tetraethylene glycol monododecyl ether (C12E4). Surface tensiometry was used to obtain the CMCs and free energy parameters of micelle formation, and Small angle x-ray scattering (SAXS) was used to characterise the micelle shape and size. The EAN-water solvents displayed self-assembly results consistent with a salt in water for EAN proportions below 5 mol% across all three surfactants, leading to CMC values lower than the CMC observed in water. A steep incline in the CMC was observed for concentrations between 5 mol% to 50 mol% of EAN for SOS and C12E4. However, CTAB displayed more complex behaviour where the CMC remained below the CMC of water until 33 mol% EAN. Across all surfactants, a plateau in CMC values were observed at very high EAN concentrations, which could indicate that there is a shift in the dominant solvent beyond EAN concentrations of 50 mol%. This study furthers our understanding of PIL solvent behaviour in ternary mixtures with amphiphiles.
References 1. Greaves, T. L.; Drummond, C. J., Ionic liquids as amphiphile self-assembly media. Chemical Society Reviews 2008, 37 (8), 1709-1726. 2. Wakeham, D.; Warr, G. G.; Atkin, R., Surfactant Adsorption at the Surface of Mixed Ionic Liquids and Ionic Liquid Water Mixtures. Langmuir 2012, 28 (37), 13224-13231. 3. J. Bryant, S.; Jafta, C.; Atkin, R.; Gradzielski, M.; Warr, G., Catanionic and Chain-packing Effects on Surfactant Self-Assembly in the Ionic Liquid Ethylammonium Nitrate. Journal of Colloid and Interface Science 2019, 540. Poster 11 Graphite Infused Ionic Liquid Greases
Wade J. Millar,1 Hua Li,1 Rob Atkin,*,1 1School of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Perth, WA 6009, Australia
Keywords: Ionic liquids, Grease, Electric contacts, Graphite, Lubrication
Inverter induced bearing currents cause non-conductive greases accumulate charge which arc discharges and damages the bearing. Mitigating charge build-up is possible with the development of electrically conductive grease. Ionic liquid (IL) lubricating greases were prepared using 1-ethyl-3-methylimidazolium trifluoromethansulfonate (EMIm TFMS) or 1- ethyl-3-methylimidazolium acetate (EMIm Ac) as the base oils and polytetrafluoroethylene (PTFE) or graphite as the thickener. IL + PTFE greases were modified with a graphite additive in order to determine changes in their physical properties. Mineral oil base lubricant was used in the same compositions to compare lubricating ability. Multiple lubricating greases with electrical conductivity between 3 mS·cm-¹ and 13 mS·cm-¹ were produced. A rheometer with a 3-ball on plate tribology geometry was used to investigate the friction of these greases and optical profilometry was used to investigate the subsequent wear scars. Results of tribology and wear investigation showed that the IL based greases had similar friction and wear reduction to the mineral oil grease. Especially, EMIm TFMs based greases exhibited very low wear and high conductivities, the greatest results were achieved with the graphite thickened EMIm TFMS grease. Poster 12 Ionic Liquid Based Deep Eutectic Solvents Aided Thermal Dehydrogenation of Chemical Hydrides
Dhirendra Kumar Mishra1*, Gopal Pugazhenthi1, Tamal Banerjee1 1Department of Chemical Engineering, Indian Institute of Technology, Guwahati, Assam 1* [email protected], 2 [email protected], 3 [email protected] Hydrogen Fuel is considered globally as the new face of the energy sector because of its environment-friendly nature. The storage of hydrogen is a primary concern, and that is when chemical hydrides come into the picture. Owing to its high hydrogen content, amine borane complexes are the most promising candidate in chemical hydride family. These complexes are known to release a high amount of hydrogen with less residual products. Ammonia Borane (AB) and Ethylene diamine Bisborane (EDAB) are the most promising candidates in the chemical hydride family and are considered best for the dehydrogenation process. AB and EDAB are known to release 14 wt% and 10 wt% of hydrogen respectively. However, the disadvantages of 1 AB are in the formation of borazine and ammonia during thermolysis . EDAB, on the other hand, produces less wt% of H2 but is less pollutant and shows the absence of an induction period, as well as the rate of dehydrogenation, which is faster than AB. The current work explores the comparison of Ionic Liquid and Deep Eutectic Solvent as reaction media for dehydrogenation. Initially, the quantum chemical-based COSMO-SAC (COnductor like Screening MOdel Segment Activity Coefficient) model was used for the selection of ILs. The following systems were considered namely : System 1: 1-allyl-3-methylimidazolium bromine, System 2: 1-butyl-3-methylimidazolium methylsulfate, System 3: tributylmethylphosphonium dibutyl phosphate, System 4: 1-butyl-1-methylpyrrolidinium methyl carbonate, System 5: 1-Butyl-3-methylimidazolium methanesulfonate. Methanesulfonate based ILs and System 6: 1-butyl-3-methylimidazolium methanesulfonate: Imidazole (figure 1). The latter is considered as a DES owing to the addition of Hydrogen Bond Donor namely Imidazole. The thermal dehydrogenation with measurement of equivalents from toepler pump (figure 2) were done with both EDAB and AB at 105°C for 7 hours at a vacuum of 4×10-2 mbar (gauge pressure). The residue was further used for 1H NMR and FTIR analysis. The role of IL and DES as a catalyst cum solvent is confirmed by the 1H NMR studies on the residual products.
-30 3.5
AB 3.0 -25 EDAB 2.5 -20 2.0 -15 1.5
ln (IDAC) ln -10 1.0
-5 0.5 AB/BMIM[MeSO3]+Imidazole EDAB/BMIM[MeSO ]+Imidazole 0 Equivalents of Hydrogen Released 3 1 2 3 4 5 6 0.0 Ionic Liquid/ DES Systems 0 50 100 150 200 250 300 350 400 Time(mins)
Fig. 1 Logarithmic value of infinite Dilution activity Fig. 2 Time-resolved equivalent hydrogen released coefficient [ln (IDAC)] of AB (black) and EDAB (red) from AB and EDAB dissolved in Methanesulfonate anion dissolved in ILs and DESs. based DES
References 1. Himmelberger, D. W.; Alden, L. R.; Bluhm, M. E.; Sneddon, L. R Inorg. Chem.2009, 48, 9883−9889. 2. Basudhrity Banerjee, G.Pugazhenthi, and Tamal Banerjee. Energy Fuels 2017, 31, 5428−5440. 3. Mal S. S., Stephens F. H. and Baker R. T., 2011. Chem. Commun., 1, 47, 2922. 4. Satyapal S., Petrovic J., Read C, Thomas G., and Ordaza G., 2007. Catal Today.120, 246. 5. Banerjee B., Kundu D., Pugazhenthi G., and Banerjee T., 2015. RSC Adv. Poster 13 Ordered Solvents and Ionic Liquids Can be Harnessed for Electrostatic Catalysis Longkun Xu,1 Ekaterina I. Izgorodina,2* Michelle L. Coote1* 1 ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory, 2601, Australia 2 Monash Computational Chemistry Group, School of Chemistry, Monash University, 17 Rainforest Walk, Clayton, Victoria 3800, Australia Abstract: Herein, we employ classical molecular dynamics simulations using the Drude oscillator- based polarizable force field, quantum chemical calculations, and ONIOM multiscale calculations to study (a) how an external field orders the solvent environment in a chemical reaction and then (b) whether in the absence of this same applied field the ordered solvent environment alone can electrostatically catalyze a chemical reaction when compared with the corresponding disordered solvent. Our results show that a 0.2 V/Å external electric field, which is below the threshold for bond breaking of solvent molecules, leads to significant ordering of bulk methanol solvent and the ionic liquid [EMIM][BF4]. Importantly, in the absence of this same field, the ordered solvent lowers the activation energy of the hydrogen-transfer reaction of o-alkylphenyl ketones in excess of 20 kcal/mol when the solvent is methanol and by over 30 kcal/mol for [EMIM][BF4]. Even a 0.1 V/Å external field has effects of ca. 10 and 20 kcal/mol, respectively. This work suggests a possible strategy for scaling electrostatic catalysis by applying a pulsed external field to the reaction medium to maintain solvent ordering while allowing the reaction to proceed largely in the absence of an external field. Poster 14 Combined Experimental and Simulation Understanding of Structure, Dynamics and Temperature Dependent Phase Transitions in Novel Ammonium based Organic Ionic Plastic Crystals
Nanditha Sirigiri, Maria Forsyth, Fangfang Chen ARC Centre of Excellence for Electromaterials Science. Institute for Frontier Materials, Deakin University, Burwood Campus, Burwood, VIC 3125, Australia. Email: [email protected]
Sustainable, affordable green energy technologies and innovation of environmental friendly energy materials are necessary for resolving current global environmental and energy consumption issues.1Organic Ionic Plastic Crystals (OIPCs) as a new class of solid-state ion conductive materials are particularly appealing due to their non-flammability and negligible vapor pressure. OIPCs have shown short range orientational and/or rotational motions related to ion molecules, while preserving their long range-orderly crystallinity, and normally present more than one solid-solid phase transitions. These materials have attracted wide attention due to their attractive intrinsic characteristics including phase-dependent ionic conductivity, and also support the small metal ion conduction (such as lithium). Hence, they can be applied as solid electrolytes for lithium-ion or lithium metal batteries. The different combinations of cations and anions in these materials can lead to a wide variety of intermolecular and intramolecular motions that trigger different levels of phase transitions and different physical and chemical properties, which have not been well understood. Here we combined both experimental characterisations (X-ray and NMR) and molecular dynamics simulations to investigate a newly developed ammonium based OIPC, Tetramethylammonium bisfluorosulfunyl(Imide). This study will provide an in-depth elucidation of the structure and dynamics of this novel OIPC in order to advance the knowledge of OIPCs served as the better solid state electrolyte materials in the new generation of battery technology.
Figure: Molecular Packing of the crystal structure of tetramethylammonium bis(fluorosulfonyl)Imide
References [1] M. Hu, X. Pang, and Z. Zhou, J. Power Sources, vol. 237, pp. 229–242, 2013.
[2] G. E. Blomgren, J. Electrochem. Soc., vol. 164, no. 1, pp. A5019–A5025, 2017.
[3] J. B. Goodenough and Y. Kim, Chem. Mater., vol. 22, no. 3, pp. 587–603, 2010.
[4] D. R. MacFarlane and M. Forsyth, Adv. Mater., vol. 13, no. 12–13, pp. 957–966, 2001.
[5] D. R. Macfarlane, J. Huang, and M. Forsyth, Nature, vol. 402, no. 6763, pp. 792– 794, 1999.
[6] J. M. Pringle, P. C. Howlett, D. R. MacFarlane, and M. Forsyth, J. Mater. Chem., vol. 20, no. 11, pp. 2056–2062, 2010. Nanditha Sirigiri Poster 15 Improved high temperature cycling sodium vanadium phosphate cathodes using NaFSI rich organic ionic plastic crystal electrolyte
Faezeh makhlooghiazad,1 Patrick C. Howlett,1 Maria Forsyth,1 Linda Nazar2 1Institute for Frontier Materials, Deakin University 2Department of Chemistry University of Waterloo 1Building HI, 221 Burwood Highway, Burwood, 3125, VIC Australia 2Department of Chemistry University of Waterloo 200 University Avenue West Waterloo, Ontario, N2L 3G1 Canada [email protected]
Sodium batteries have emerged as promising alternative for large‐scale energy storage applications due to the low cost and high abundance of sodium.1,2 However, sodium batteries are not commercially available because they are still suffer from safety concerns and poor performance associated with the organic solvent electrolytes and electrode-active materials currently used in these batteries.3 Sodium batteries need safe, high voltage and cost effective electrolyte and cathode materials for practical applications. In the present study, Na cells based on sodium vanadium phosphate–carbon composite (NVP/C) cathode material and high concentration of Na salt (NaFSI) in an organic ionic plastic crystal (OIPC) namely (triisobutylmethylphosphonium bis(fluorosulfonyl)imide) (90 and 45 mol% NaFSI in P1i444FSI) are investigated. The Na/NVP/C cells are studied using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic cycling tests at 60 °C and room temperature. Higher current density, lower polarization potential, higher capacity and rate capability was observed for cells operating at 60 °C compared with room temperature due to higher ionic conductivity of bulk electrolyte and electron transfer at the electrode surface. These cells were cycled at high temperatures at which conventional organic solvent electrolytes have a tendency to fail and show fast capacity decay. It was observed initial discharge capacity for cells with solid and commercial organic solvent electrolyte was the same at C/5 (96 and 96.2 mA h/g respectively) but the capacity retention for solid electrolyte after 140 cycles was 93.2 %. While this value for organic solvent is 86.6 % after 65 cycles. 45 mol% NaFSI in P1i444FSI that is liquid showed highest reversible initial discharge capacity 98.9 mA h/g and capacity retention (96%) after 93 cycles at the same current rate. We therefore exhibited that combining the economically viable positive electrode NVP@C with the non-volatile and non-flammable mixture of NaFSI/P1i444FSI electrolyte could be a promising for high temperature applications of Na batteries.
References
1-Brain L.Ellis, Linda F.Nazar, Current Opinion in Solid State and Materials Science 2012, 16 (4), 168-177. 2-Michael D. Slater, Donghan Kim, Eungje Lee, Christopher S. Johnson. Advanced Functional Materials 2013, 23 (8), 947-958. 3-Zhizhen Zhang, Yuanjun Shao, Bettina Lotsch, Yong-Sheng Hu, Hong Li, Ju¨rgen Janek, Linda F. Nazar, Ce-Wen Nan, Joachim Maier, Michel Armand and Liquan Chen, Energy Environ. Sci., 2018, 11, 1945--1976 Poster 16
Study of Ion Gel Electrolytes for Na-battery Application Comprising of OIPC/Na-salt/ Electrospun PVDF Nanofiber
Sneha Malunavara, Xiaoen Wanga,*, Faezeh Makhlooghiazada, Michel Armandb, Patrick Howletta, Maria Forsytha,*. [email protected] [email protected] aInstitute for Frontier Materials (IFM) Deakin University, Burwood, Victoria 3125, Australia. b CIC Energigune, Parque Tecnológico de Álava, Albert Einstein, 48. Edificio CIC, 01510 Miñano, Araba, Spain
Abstract
The development of highly conductive and safe electrolytes for sodium-ion batteries is an emerging field beyond lithium battery technologies. In this work we have developed new iongel electrolytes consisting of binary salt mixture of organic ionic plastic crystal, OIPC N-ethyl-N- methylpyrrolidiniumbis(fluorosulfonyl)imide (C2mpyrFSI), NaFSI salts supported by electrospun PVDF nanofibers. The binary mixture near to eutectic point was selected after detailed phase diagram analysis and then to prepare iongel electrolytes. The ionic conductivity of prepared iongel composite reaches to 2.6 × 10-3 S cm-1 at ambient temperature. This iongel membrane possessed a relatively high Na-ion transference number of 0.44 at 50 oC. We also demonstrate the performance of Na-ion batteries using NaFePO4 cathode (1.75 -4.0 V). The assembled cells show a good capacity retention with close to 100 % columbic efficiency at various C rates between C/20, C/10 and C/5, achieving 120 mAhg-1 at C/20. The long-term charge/discharge performance is also demonstrated. Our study provides a feasible method to prepare highly conductive iongel electrolytes for future Na- battery applications.
References
[1] F. Castiglione, E. Ragg, A. Mele, G. B. Appetecchi, M. Montanino, S. Passerini, J. Phys. Chem. Lett. 2011, 2, 153–157. [2] D. Ostrovskii, L. M. Torell, G. B. Appetecchi, B. Scrosati, Solid State Ionics 1998, 106, 19–24. [3] M. Forsyth, M. E. Smith, n.d., 2077–2084. [4] H. Zhu, F. Chen, L. Jin, L. A. O’Dell, M. Forsyth, ChemPhysChem 2014, 15, 3720–3724. [5] Y. Zhou, X. Wang, H. Zhu, M. Yoshizawa-Fujita, Y. Miyachi, M. Armand, M. Forsyth, G. W. Greene, J. M. Pringle, P. C. Howlett, ChemSusChem 2017, 10, 3135–3145. [6] X. Wang, G. M. A. Girard, H. Zhu, R. Yunis, D. R. Macfarlane, D. Mecerreyes, A. J. Bhattacharyya, P. C. Howlett, M. Forsyth, ACS Appl. Energy Mater. 2019, 2, 6237–6245. [7] A. M. Stephan, Eur. Polym. J. 2006, 42, 21–42. [8] J. A. Dawson, P. Canepa, M. J. Clarke, T. Famprikis, D. Ghosh, M. S. Islam, Chem. Mater. 2019, 31, 5296–5304. [9] F. Nti, L. Porcarelli, G. W. Greene, H. Zhu, F. Makhlooghiazad, D. Mecerreyes, P. C. Howlett, M. Forsyth, X. Wang, J. Mater. Chem. A 2020, 8, 5350–5362. Poster 17 Towards Sustainable Nd Recovery: An Electrochemical Approach Using Fluorine-Free Ionic Liquid Electrolytes Kalani Periyapperuma,* Maria Forsyth, Jennifer M. Pringle and Cristina Pozo-Gonzalo Institute for Frontier Materials, Deakin University, Melbourne, Victoria 3125, Australia. *Email: [email protected]
Rare earth metals (REMs) are considered critical materials due to their wide usage in many current technologies ranging from electronic devices to renewable energy storage, which are essential to establish a greener economy.1,2 Neodymium metal in particular is in high demand for the production of Nd-Fe-B permanent magnets (e.g.: for use in electric motors, computers and wind turbines) and Ni-MH batteries that fuel hybrid vehicles. However, the primary sourcing method of Nd and REMs in general, i.e. mining leads to critical environmental and health issues such as co-extraction of radioactive species. 2 The traditional Nd recovery methods based on hydrometallurgy and pyrometallurgy are often energy intensive and/or use significant amounts of water and chemicals resulting secondary waste.2,3 Therefore, it is essential to develop metal recovery approaches that are sustainable and environmentally friendly. Here we have investigated a cleaner approach to recover Nd via electrochemical deposition. In contrast to most typically studied bis(trifluoromethanesulfonyl)imide [TFSI]- anion based ILs,4 successful Nd electrodeposition was achieved using fluorine-free N-butyl-N- methylpyrrolidinium dicyanamide ([C4mpyr][DCA]) IL at relatively low temperature (50 °C) 3+ and less controlled environment (up to 4.6 wt% H2O). Among the Nd salts analysed, [trifluoromethanesulfonate [OTf]-] and nitrate based, the latter showed the highest solubility (0.5 vs 0.2 mol kg-1) along with higher recovery efficiency and superior electrochemical behaviour in terms of onset reduction potential and peak current density. Their in-depth electrochemical behaviour, deposition morphology and quantitative composition analysis will be further discussed.
References 1 M. K. Jha, A. Kumari, R. Panda, J. Rajesh Kumar, K. Yoo and J. Y. Lee, Hydrometallurgy, 2016, 165, 2–26. 2 K. Binnemans, P. T. Jones, B. Blanpain, T. Van Gerven, Y. Yang, A. Walton and M. Buchert, J. Clean. Prod., 2013, 51, 1–22. 3 M. Firdaus, M. A. Rhamdhani, Y. Durandet, W. J. Rankin and K. McGregor, J. Sustain. Metall., 2016, 2, 276–295. 4 L. Sanchez-Cupido, J. M. Pringle, A. L. Siriwardana, A. Unzurrunzaga, M. Hilder, M. Forsyth and C. Pozo-Gonzalo, J. Phys. Chem. Lett., 2019, 10, 289–294. Poster 18 Solid Ionic Composite Membranes for CO2 Separation Fernando Ramos Saza,b, Jennifer M. Pringleb, Maria Forsythb a) [email protected] b) Institute for Frontier Materials, Deakin University, Burwood, VIC 3125, Australia
Supported ionic liquid membranes (SILMs) occupy a promising place in the ranking of materials for light gas separation, showing high transmembrane flux rates and quite competitive selectivities. Although they present advantages inherent to their liquid state, they also face some limitations, which is why there is interest in studying solid alternatives.[1] Novel organic ionic plastic crystal (OIPC)-based composite membranes have been demonstrated to have [2] promising light gas separation performance (CO2/N2 > 40). A series of OIPCs based on bis(fluorosulfonyl)imide anion combined with different cations (N-methyl-N- ethylpyrrolidinium, methyl(triethyl)phosphonium, hexamethylguanidinium, tetramethylammonium and (cyanomethyl)trimethylammonium) have been co-cast with poly(vinylidene fluoride) (PVDF) or poly(ethylene oxide) (PEO). The aim of this work is to study the OIPC/polymer interactions in order to understand how the addition of polymer affects the thermophysical and gas transport properties of these different OIPCs. The thermophysical properties of the composites indicate that the co-casting method is a good way to fabricate solid, homogeneous, mechanically stable, and durable membranes. Additionally, the enhanced molecular interactions indicated in some of the OIPC/polymer mixtures point to a new approach for synthesis of other highly selective OIPC-based membranes and also as a possible route to more ionically conductive solid-state electrolytes.
References [1] B. Sasikumar, G. Arthanareeswaran, A. F. Ismail, J. Mol. Liq. 2018, 266, 330-341. [2] F. Ramos, M. Forsyth, J. M. Pringle, ChemSusChem, 2022, doi.org/10.1002/cssc.202001921 Poster 19 Investigating the Effects of Ionic Liquids on Cyclisation Reactions Andrew Hsieh1, * and Jason B. Harper1 1School of Chemistry, the University of New South Wales, NSW 2052, Australia *Email: [email protected]
Ionic liquids represent a promising alternative to molecular solvents for preparative chemistry, and have been demonstrated to affect reaction outcomes.1, 2 Previous studies have explored the effects of ionic liquids on reaction outcome, primarily focusing on maximising solute-solvent interaction to promote reaction.2 However, a recent example has shown a case in which the opposite is true; minimising the solute-solvent interaction to promote reaction.3 This outcome was argued to be based on a ‘solvophobic effect’,4 and there is the potential to use this effect to promote cyclisation reactions. To measure this potential, competition reactions between a cyclisation reaction (an intramolecular process) and an equivalent intermolecular reaction can be used.
The work described here investigates the effects of varying proportions of the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide 1 (Figure 1) on the competition reaction of methyl 8-bromooctanoate 2 with 1-bromobutane 3 to form the cyclised ether 4 and the competing intermolecular product 5 (Scheme 1).
Figure 1. The ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide 1
Scheme 1. The competition reaction of methyl 8-bromooctanoate 2 with 1-bromobutane 3 to form the cyclised ether 4 and the competing intermolecular product 5. i) LDA, salt 1, -84 ˚C, 1 h.
References 1. Welton, T., Chem. Rev., 1999, 99, 2071-84. 2. Hawker, R. R.; Harper, J. B., Adv. Phys. Org. Chem., 2018, 52, 49-85. 3. Keaveney, S. T.; Haines, R. S.; Harper, J. B., ChemPlusChem, 2017, 82, 449-57. 4. Greaves, T. L.; Drummond, C. J., Chem. Soc. Rev., 2013, 42, 1096-120. Poster 20 Thermal Energy Storage in Ionic Liquids/organic Salts Samantha Piper,a,* Karolina Matuszek,a Mega Kar,a Jennifer Pringle,b and Douglas MacFarlanea a School of Chemistry, Monash University, Clayton, VIC 3800, Australia b Institute for Frontier Materials, Deakin University, Melbourne, VIC 3125, Australia Email: [email protected]
Depleting reserves of fossil fuels and concern over the environmental cost at which they come have brought the challenge of decarbonising the energy sector to the forefront of modern- day science. Renewable energy sources have the potential to resolve these challenges by providing a clean and inexhaustible alternative to fossil fuels, but are limited in this capacity by their intermittent nature. To overcome discrepancies between peak demand and availability of supply, inexpensive and efficient energy storage technologies need to be incorporated into the design of renewable energy systems. Thermal energy storage (TES) systems are a desirable option as they are able to directly provide thermal energy to industrial and domestic settings, the heating of which constitutes a large portion of the global energy demand.1 Phase change materials (PCMs) are ideal for such applications as they are able to store latent heat as well as sensible heat, providing a greater density of energy storage and requiring smaller temperature differences between storing and releasing heat than sensible heat storage methods.2 Latent energy is stored when the PCM melts upon heating, and is released upon refreezing as
either heat of fusion (Hf) or energy of crystallisation. Key parameters dictating the application
and efficiency of PCMs are thus the melting point and Hf. Ionic liquids/organic salts are a promising alternative to conventional PCM materials (i.e. salt hydrates, paraffins, eutectics, metal alloys, and polymers) in that they evade many of the typical drawbacks including flammability, volatility, corrosivity and phase separation tendencies. Our group has recently investigated the use of protic ionic liquids/organic salts as PCMs, and proposed that hydrogen bonding plays a key role in obtaining materials with high latent heat of fusion.3 Here, we use X-ray crystallography to explore the molecular origins of
the latent heat of fusion and elucidate the often unexpected differences in Hf observed for materials with similar structures and functionalities. By deepening our understanding of the interactions dictating thermal properties of PCMs, we are able to address the synthetic challenge of optimising these properties with a more focused approach.
References [1] I. Sarbu and C. Sebarchievici, Sustainability, 2018, 10, 191. [2] K. Pielichowska and K. Pielichowski, Prog. Mater. Sci., 2014, 65, 67– 123. [3] K. Matuszek, R. Vijayaraghavan, M. Kar and D. R. MacFarlane, Cryst. Growth Des., 2019, 20, 1285–1291. Poster 21 Development of New Ionic Electrolytes with Ethoxy Side Chains Anna Warrington, Dr. Colin Kang, Professor Jenny Pringle and Dr. Oliver Hutt Institute for Frontier Materials, Deakin University and Boron Molecular Email: [email protected] Twitter: @ak_warrington
Energy storage devices are essential to our utilisation of renewable energy and reduction in greenhouse gas emissions. Li-ion batteries face critical safety challenges as flammable electrolytes are employed, and they have low energy density than lithium metal batteries, meaning the technology is not viable for widespread use of electric vehicles (EVs) or for large- scale energy storage. Ionic liquids (ILs) have received substantial attention as electrolytes for lithium batteries and organic ionic plastic crystals (OIPCs), considered the solid state cousins of ILs, are also gaining popularity for use as solid-state electrolytes that have excellent thermal properties and reduced risk of leakage from batteries. OIPCs are more likely to be formed with small cations. For both OIPCs and ILs, the nature of the cation and anion is important in determining their chemical and physical properties and thus varying these structures is a powerful tool for improving their electrochemical performance. One such variation is by the incorporation of oxygen into the organic cation structure. It is understood that the presence of oxygen in organic cations can have benefits on the performance of ionic electrolytes in batteries, such as lowered viscosity, increased conductivity, and lowered charge transfer resistance. In this work, towards developing safer batteries with higher energy density, a series of small ether-functionalised cations have been developed and paired with FSI and TFSI anions. As shorter chains on the organic cation are more likely to form OIPCs, the methoxymethyl group
(C1O1 chain) is the primary focus of the cations synthesised. A conventional synthetic route to the ether-functionalised cations has been employed involving quaternisation of a tertiary amine with an alkoxy halide. Progress towards the synthesis of ethoxy-containing ILs and OIPCs is discussed, with conclusions about the relative pros and cons in terms of yield and purity. Poster 22 Development of Mixed Organic Ionic Plastic Crystal Electrolytes for Energy Storage Shanika Abeysooriya,1 Jenny Pringle,1 Luke O’Dell,1 1Institute for Frontier Materials, Deakin University 221 Burwood Highway, Burwood, 3125, VIC Australia [email protected] Organic ionic plastic crystals (OIPCs) are promising candidates for solid-state electrolyte materials for Li battery applications.1 OIPCs consist entirely of ions and possess a long-range ordered crystalline lattice but short-range disorder, such as rotational motions that increase when the temperature is increased.2 OIPCs possess other advantageous properties such as non-volatility, non-flammability, high ionic conductivity, and wide electrochemical window. Therefore, this has prompted many researchers to investigate different combinations of cations and anions to produce new OIPCs especially for Li battery applications.2 Many cation and anion combinations have been investigated to develop new OIPC systems, and these have been mixed with lithium salts to allow their use as electrolyte materials in Li batteries.1 But mixing of two OIPCs to produce new solid-state electrolyte materials has been scarcely investigated, and this is proposed to be a route to increasing the disorder and conductivity of the materials. Therefore, this research study focuses on developing new binary OIPC systems by mixing two OIPCs and studying their physicochemical behaviour to understand the fundamentals of their structure and dynamics, ultimately to allow increased performance in devices such as Li batteries. Among the various types of OIPCs known, pyrrolidinium FSI (bis(fluorosulfonyl)imide)-based OIPCs have been selected for initial study because they typically show wide electrochemical stabilities and higher ionic conductivity.3,4
5 In this work, isomeric OIPCs diethylpyrrolidinium bis(fluorosulfonyl)imide ([C2epyr][FSI]) and N- 6 isopropyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C(i3)mpyr][FSI]) and their binary mixtures were synthesized. For the first time binary OIPC mixtures were prepared by mixing [C2epyr][FSI] with 1–90 mol % of [C(i3)mpyr][FSI]. Thermal properties of the novel binary OIPC mixtures were determined using Differential Scanning Calorimetry (DSC) and show that the incorporation of the isomeric cation can have a significant influence on the thermal phase behaviour.
References
1. Armel, V., Forsyth, M., MacFarlane, D. R. & Pringle, J. M. Organic ionic plastic crystal electrolytes; A new class of electrolyte for high efficiency solid state dye-sensitized solar cells. Energy Environ. Sci. 4, 2234–2239 (2011).
2. Jin, L. et al. Structure and transport properties of a plastic crystal ion conductor: Diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate. J. Am. Chem. Soc. 134, 9688–9697 (2012).
3. Best, A. S., Bhatt, A. I. & Hollenkamp, A. F. Ionic Liquids with the Bis(fluorosulfonyl)imide Anion: Electrochemical Properties and Applications in Battery Technology. J. Electrochem. Soc. 157, A903 (2010).
4. Zhou, Q., Henderson, W. A., Appetecchi, G. B., Montanino, M. & Passerini, S. Physical and electrochemical properties of N-alkyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ionic liquids: PY13FSI and PY 14FSI. J. Phys. Chem. B 112, 13577–13580 (2008).
5. Yunis, R., Newbegin, T. W., Hollenkamp, A. F. & Pringle, J. M. Ionic liquids and plastic crystals with a symmetrical pyrrolidinium cation. Mater. Chem. Front. 2, 1207–1214 (2018).
6. Al-Masri, D., Yunis, R., Hollenkamp, A. F., Doherty, C. M. & Pringle, J. M. The influence of alkyl chain branching on the properties of pyrrolidinium-based ionic electrolytes. Phys. Chem. Chem. Phys. 22, 18102–18113 (2020). Poster 23 Insights into the Anion Originated Interactions in OIPC/PVDF Composites
Frederick Nti,a George W. Greene,a Haijin Zhu,a Patrick Howlett,a Maria Forsyth,a,b Xiaoen Wang*a aInstitute for Frontier Materials, Deakin University, Geelong, VIC 3217, Australia bAustralian Centre of Excellence for Electromaterials Science, Monash University, Clayton, Victoria 3800, Australia Email: [email protected]
Organic ionic plastic crystals (OIPCs) are promising solid electrolytes because of their inherent advantages such as non-volatility, non-flammability, good thermal stability, favourable plasticity, and improved electrolyte/electrode interfacial contact. Incorporating nanoparticles into some OIPC matrixes has been proved as an effective strategy for further increasing conductivity and mechanical integrity.1,2 However, the nature of the interaction between cations and anions of OIPCs with polymers is not yet studied. In this work, various OIPCs + consisting of N-ethyl N-methyl pyrrolidinium cations ([C2mpyr] ) and three different anions bis(trifluoromethanesulfonyl)imide ([TFSI]-), (bis(fluorosulfonyl)imide ([FSI]-) and - tetrafluoroborate, [BF4] ) are selected. The interaction between the OIPCs and poly(vinylidene fluoride) (PVDF) are studied by incorporating different volume fractions of PVDF nanoparticles into the OIPC matrix.
Differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance (NMR). This interaction induces the formation disordered OIPC interphases which account for the ionic conductivity enhancement. The degree of the interaction and ionic conductivity enhancement depends on the fluorophilicity of the anions of the OIPC.
References 1. Pringle, J. M., Howlett, P. C., MacFarlane, D. R. & Forsyth, M. Organic ionic plastic crystals: Recent advances. J. Mater. Chem. 20, 2056–2062 (2010). 2. Sun, J., MacFarlane, D. R. & Forsyth, M. Conductive plastic crystal phases of the 1-alkyl-2-methyl pyrrolinium TFSA salts. Solid State Ionics 148, 145–151 (2002).