DOCSLIB.ORG

Polymers Made by Inverse Vulcanization for Use As Mercury Sorbents

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Polymers Made by Inverse Vulcanization for Use As Mercury Sorbents Published online: 2021-05-06 362 Organic Materials J. M. Chalker et al. Short Review Polymers Made by Inverse Vulcanization for Use as Mercury Sorbents Justin M. Chalker*a Maximilian Manna Max J. H. Worthingtona Louisa J. Esdaile*a,b a Flinders University, Institute for Nanoscale Science and Technology, Sturt Road, Bedford Park, South Australia, 5035, Australia b Clean Earth Technologies, 112 Robinson Road, #05-04, Singapore 068902 justin.chalker@flinders.edu.au; [email protected] 3 Received: 22.03.2021 compounds, and mercury metal. These different forms of Accepted after revision: 05.05.2021 mercury influence its mobility in the environment, neces- DOI: 10.1055/a-1502-2611; Art ID: om-21-0028sr sitating sorbents that can remove mercury from solid License terms: mixtures, fluids, and gases.5,6 © 2021. The Author(s). This is an open access article published by Thieme under the Mercury sorbents must be cost-effective for uptake in terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, industry. For this reason, relatively low-cost materials such permitting copying and reproduction so long as the original work is given appropriate 7 credit. Contents may not be used for commercial purposes, or adapted, remixed, as activated carbon have been widely used. Nevertheless, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/) there remains a need to develop complementary or superior mercury sorbents to address the many challenges encoun- Abstract Inverse vulcanization is a process in which highly abundant tered in mercury remediation and emission control. For and low-cost elemental sulfur is copolymerized with an unsaturated organic molecule such as a polyene. This process has provided a variety instance, it is useful if the sorbent is effective against the 5 of useful materials with high sulfur content—typically 50% or greater in different forms of mercury. The rate and capacity of sulfur by mass. These materials have garnered increasing interest in mercury sorption should also be high for general use, fi research as sorbents for mercury, due to the high af nity of sulfur for without any leaching of bound mercury.5 mercury. In this review, the features of mercury sorbents made by Sulfur has long been known to form strong bonds with inverse vulcanization are presented. Additionally, case studies are 6 provided to illustrate the variety of polymer architectures accessible heavy metals such as mercury. Accordingly, extensive with this chemistry, the versatility of these materials in mercury research has been carried out to develop mercury sorbents remediation, and prospects for industrial use. functionalized with sulfur.8 Recently, polymers made from elemental sulfur have garnered much attention as mercury 1 Introduction 9–12 2 Sulfur Polymers by Inverse Vulcanization sorbents. These polymeric mercury sorbents are espe- 3 Sulfur Polymers as Mercury Sorbents cially interesting because they are made directly from low- 4 Increasing Surface Area to Improve Mercury Uptake cost and highly abundant elemental sulfur.13 In this review, 5 Crosslinker Considerations we focus on mercury sorbents made by the process of 6 Sorption of Different Forms of Mercury inverse vulcanization—a bulk copolymerization of elemental 7 Life-Cycle Management 14 fi 8 Conclusions and Outlook sulfur and an unsaturated organic crosslinker. We rst provide a brief overview of this reaction and then highlight Key words inverse vulcanization, mercury, polysulfides, sulfur, sulfur some features that make the materials intriguing and useful polymers candidates as mercury sorbents. Our focus will be placed on polysulfide polymers (macromolecules containing S–S bonds in the polymer backbone), so other mercury-binding polymers made from sulfur that do not contain polysulfides will not be discussed in this review.15,16 Likewise, this 1. Introduction review is not intended to be a comprehensive account of mercury remediation or inverse vulcanization, but rather a Mercury is a toxic heavy metal that is encountered in a focused discussion on the unique ways in which poly- variety of industrial activities such as mining, oil and gas sulfides made by inverse vulcanization can be made and refining, and coal combustion.1–3 To prevent emissions and used in versatile ways to trap mercury. To this end, we exposure to mercury, it is essential to have materials that discuss methods to make these materials higher in surface trap and immobilize this element.4,5 Mercury is challenging area, crosslinker effects in mercury sorption, the effect of in this regard because of the many forms in which it mercury speciation, and life-cycle management of the can be found, including inorganic salts, organomercury sorbents. © 2021. The Author(s). Organic Materials 2021, 3, 362–373 Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany ! ~ 363 Organic Materials J. M. Chalker et al. Short Review Biosketches Dr. Justin Chalker was trained in Justin then started his independent include sustainable materials and organic synthesis at the University of career at The University of Tulsa in green chemistry, with a focus on Pittsburgh before completing his D. 2012 and in 2015 he moved to Flinders translating these interests to commer- Phil. in Organic Chemistry at the University in Adelaide, Australia where cial products and processes. In 2020, University of Oxford in 2011 as a heiscurrentlyanAssociateProfessorin Justin was awarded the Prime Minis- Rhodes Scholar and National Science theInstitutefor Nanoscale Science and ter’s Prize for New Innovators—one of Foundation Graduate Research Fellow. Technology. Justin’s research interests the top science prizes in Australia. Maximilian Mann is a Ph.D. candi- applications of polymers made from waste. Max is also studying various date at Flinders University working sulfur. This research spans precision mechanistic aspects and design under the supervision of Associate fertilizers, mercury sorbents, and principles for controlling the proper- Professor Justin Chalker. Max’sre- novel methods for gold extraction ties of polymers made by inverse search focuses on the synthesis and and recovery from ore and electronic vulcanization. Dr.Max Worthingtoncompleted his on innovative applications of sulfur ders University in collaboration with Ph.D. at Flinders University in 2020, polymers including their use as Clean Earth Technologies on multiple working under the supervision of mercury sorbents and materials for commercial products that involve Associate Professor Justin Chalker. oil spill clean-up. Max is currently a sulfur polymers. Max has publisheda numberof studies Research Associate, working at Flin- Dr.Louisa EsdailecompletedherPh. at NorthwesternUniversity in2009. In Esdaile is a Project Manager with D. at Queensland University of Tech- these roles Louisa investigated por- Clean Earth Technologies, with a joint nology (QUT) in 2007 before moving phyrin chemistry, molecular electron- academic appointment at Flinders to post-doctoral research positions ics, and self-assembly. Louisa then University. Louisa directs commercial with Prof. Harry Anderson at the took an industrial position with Dow projects on mercury remediation, University of Oxford in 2007 and Electronic Materials before returning sustainable materials, and electronic then with Prof. Sir J. Fraser Stoddart to Australia in 2015. Currently, Dr. waste recycling. 2. Sulfur Polymers by Inverse Vulcanization elemental sulfur is used to cross-link organic polymers such as natural rubber, while inverse vulcanization is the process While the polymerization of sulfur has a long history in by which organic molecules are used to cross-link sulfur both industry and the chemical sciences,17–19 renewed polymers.14 In this way, inverse vulcanization provides interest in this area was prompted by the publication of a polysulfide-rich materials that are distinct from other landmark study by Pyun and collaborators in Nature classes of carbon-based polymers in their chemical reactiv- Chemistry in 2013.14 In this report, the authors introduced ity and their physical and optical properties (Figure 1).20–23 “inverse vulcanization” as a process to prepare polymeric The mechanism of the inverse vulcanization reaction has materials with high sulfur content (typically >50% by mass). not been fully elucidated and it may vary depending on the Conceptually, classic vulcanization is the process by which reaction conditions, the organic crosslinker,24–26 or the use © 2021. The Author(s). Organic Materials 2021, 3, 362–373 ! ~ 364 Organic Materials J. M. Chalker et al. Short Review resulting polymer can also change on the specific protocol used in the polymerization.26 For instance, the sulfur can be added at the same time to the reaction vessel as the crosslinker, or the sulfur pre-polymer can be formed before the addition of the organic crosslinker.26 Curing the polymer also may result in different crosslinking density and material properties of the final polymer.26 Materials made by inverse vulcanization can also vary widely in their physical properties, which are determined by the amount of sulfur in the polymer, the average length of the polysulfide chains (the sulfur rank), and the structure of the organic crosslinker.26,32 Low-molecular-weight waxes, soft and hard rubber, and brittle glasses are all accessible with this chemistry.32 Glass transition temperatures for these materials can vary from À20 to 130 °C.32,33 Some degree of control can be exerted by varying these Figure
Load more

Recommended publications
  • Lib-Carbon.Pdf
    Carbon 122 (2017) 106e113 Contents lists available at ScienceDirect Carbon journal homepage: www.elsevier.com/locate/carbon Graphene-supported highly crosslinked organosulfur nanoparticles as cathode materials for high-rate, long-life lithium-sulfur battery * Shuaibo Zeng a, Ligui Li a, b, , Lihong Xie a, Dengke Zhao a, Ni Zhou a, Nan Wang a, ** Shaowei Chen a, c, a Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, College of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China b Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, College of Environment and Energy, South China University of Technology, Guangzhou 510006, China c Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064, USA article info abstract Article history: Lithium-sulfur batteries represent one of the next-generation Li-ion batteries; yet rapid performance Received 31 March 2017 degradation is a major challenge. Herein, a highly crosslinked copolymer is synthesized through ther- Received in revised form mally activated polymerization of sulfur and trithiocyanuric acid onto the surface of reduced graphene 4 June 2017 oxide nanosheets. Of the thus-synthesized composites, the sample with a high sulfur content of Accepted 14 June 2017 À À 81.79 wt.% shows a remarkable rate performance of 1341 mAh g 1 at 0.1 C and 861 mAh g 1 at 1 C with Available online 18 June 2017
    [Show full text]
  • Science Journals
    SCIENCE ADVANCES | RESEARCH ARTICLE MATERIALS SCIENCE Copyright © 2020 The Authors, some rights reserved; One-step vapor-phase synthesis of transparent high exclusive licensee American Association refractive index sulfur-containing polymers for the Advancement Do Heung Kim1*, Wontae Jang1*, Keonwoo Choi1, Ji Sung Choi2, Jeffrey Pyun3,4, Jeewoo Lim2†, of Science. No claim to 4† 1† original U.S. Government Kookheon Char , Sung Gap Im Works. Distributed under a Creative High refractive index polymers (HRIPs) have recently emerged as an important class of materials for use in a variety Commons Attribution of optoelectronic devices including image sensors, lithography, and light-emitting diodes. However, achieving NonCommercial polymers having refractive index exceeding 1.8 while maintaining full transparency in the visible range still License 4.0 (CC BY-NC). remains formidably challenging. Here, we present a unique one-step vapor-phase process, termed sulfur chemical vapor deposition, to generate highly stable, ultrahigh refractive index (n > 1.9) polymers directly from elemental sulfur. The deposition process involved vapor-phase radical polymerization between elemental sulfur and vinyl monomers to provide polymer films with controlled thickness and sulfur content, along with the refractive index as high as 1.91. Notably, the HRIP thin film showed unprecedented optical transparency throughout the visible range, attributed to the absence of long polysulfide segments within the polymer, which will serve as a key com- Downloaded from ponent
    [Show full text]
  • Highly Crosslinked Organosulfur Copolymer Nanosheets with Abundant Mesopores As Cathode Materials for Efficient Lithium-Sulfur B
    Electrochimica Acta 263 (2018) 53e59 Contents lists available at ScienceDirect Electrochimica Acta journal homepage: www.elsevier.com/locate/electacta Highly crosslinked organosulfur copolymer nanosheets with abundant mesopores as cathode materials for efficient lithium-sulfur batteries * ** Shuaibo Zeng a, Ligui Li a, b, , Jingping Yu a, Nan Wang a, Shaowei Chen a, c, a Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, College of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China b Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, College of Environment and Energy, South China University of Technology, Guangzhou 510006, China c Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064, USA article info abstract Article history: Low sulfur utilization and poor cycling stability are two major factors that currently impede the wide- Received 11 October 2017 spread commercialization of lithium-sulfur (Li-S) batteries. Herein, sulfur-rich side chains are Received in revised form anchored onto Schiff-base copolymer of thiourea aldehyde resin (cp (S-TAR)) nanosheets via inverse 5 December 2017 vulcanization to form a large number of intermolecular crosslinkers as well as mesopores. Application of Accepted 30 December 2017 the resultant copolymer as a cathode material in Li-S batteries can not only provide abundant porous Available online
    [Show full text]
  • Lithium-Sulfur Batteries: Advances and Trends
    electrochem Review Lithium-Sulfur Batteries: Advances and Trends Claudia V. Lopez, Charini P. Maladeniya and Rhett C. Smith * Department of Chemistry, Clemson University, Clemson, SC 29634, USA; [email protected] (C.V.L.); [email protected] (C.P.M.) * Correspondence: [email protected] Received: 21 April 2020; Accepted: 5 June 2020; Published: 1 July 2020 Abstract: A review with 132 references. Societal and regulatory pressures are pushing industry towards more sustainable energy sources, such as solar and wind power, while the growing popularity of portable cordless electronic devices continues. These trends necessitate the ability to store large amounts of power efficiently in rechargeable batteries that should also be affordable and long-lasting. Lithium-sulfur (Li-S) batteries have recently gained renewed interest for their potential low cost and 1 high energy density, potentially over 2600 Wh kg− . The current review will detail the most recent advances in early 2020. The focus will be on reports published since the last review on Li-S batteries. This review is meant to be helpful for beginners as well as useful for those doing research in the field, and will delineate some of the cutting-edge adaptations of many avenues that are being pursued to improve the performance and safety of Li-S batteries. Keywords: lithium-sulfur batteries; polysulfide; cathode materials; high sulfur materials Review 1. IntroductionLithium-Sulfur Batteries: Advances and Trends Claudia V. Lopez, Charini P. Maladeniya and Rhett C. Smith * 1.1. General OperationDepartmentof of Chemistry, Lithium-Sulfur Clemson University, (Li-S)Clemson, SC Batteries 29634, USA; [email protected] (C.V.L.); [email protected] (C.P.M.) Lithium-sulfur* Correspondence: (Li-S) [email protected] batteries have emerged as preeminent future battery technologies in large Received: 21 April 2020; Accepted: 5 June 2020; Published: date part due to their impressive theoretical specific energy density of 2600 W h kg 1.
    [Show full text]
  • Nano Energy 57 (2019) 635–643
    Nano Energy 57 (2019) 635–643 Contents lists available at ScienceDirect Nano Energy journal homepage: www.elsevier.com/locate/nanoen Communication A robust 2D organic polysulfane nanosheet with grafted polycyclic sulfur for highly reversible and durable lithium-organosulfur batteries T ⁎ ⁎ Hao Hua,b,1, Bote Zhaoa,1, Haoyan Chengb, Shuge Daia, Nicholas Kanea, Ying Yub, , Meilin Liua, a School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245, USA b Institute of Nano-science and Nano-technology, College of Physical Science and Technology, Central China Normal University, Wuhan, Hubei 430079, PR China ARTICLE INFO ABSTRACT Keywords: Organic polysulfanes are new type of attractive organosulfur electrode materials for next generation lithium- Organic polysulfane sulfur (Li-S) batteries because of their high sulfur content, low cost, and desirable energy density. However, Polymer nanosheet conventional organic polysulfanes usually suffer from poor reversibility due to structure variation and irrever- Surface enhanced Raman scattering sible conversion during cycling. Here we report the synthesis and characterization of a novel two-dimensional Lithium-organosulfur battery (2D) organic polysulfane with a unique molecular structure of polycyclic sulfur directly substituting the car- boxyls of poly(acrylic acid) and grafted on the carbon chain through a coupling reaction with KI as a catalyst and KCl as a template. The obtained organic polysulfane nanosheets with 72 wt% sulfur (OPNS-72) exhibit high initial capacity of 891 mAh/g (based on whole composite), excellent cycling stability (0.014% capacity fading per cycle over 620 cycles at 1 C rate), superior rate capability (562 mAh/g at 10 C) and high mass loading of 9.7 mg/cm2.
    [Show full text]
  • High Sulfur-Containing Carbon Polysulfide Polymer As a Novel
    www.nature.com/scientificreports OPEN High sulfur-containing carbon polysulfde polymer as a novel cathode material for lithium-sulfur Received: 29 June 2017 Accepted: 25 August 2017 battery Published: xx xx xxxx Yiyong Zhang1, Yueying Peng1, Yunhui Wang1, Jiyang Li1, He Li1, Jing Zeng1, Jing Wang1, Bing Joe Hwang 2 & Jinbao Zhao1 The lithium-sulfur battery, which ofers a high energy density and is environmental friendly, is a promising next generation of rechargeable energy storage system. However, despite these attractive attributes, the commercialization of lithium-sulfur battery is primarily hindered by the parasitic reactions between the Li metal anode and dissolved polysulfde species from the cathode during the cycling process. Herein, we synthesize the sulfur-rich carbon polysulfde polymer and demonstrate that it is a promising cathode material for high performance lithium-sulfur battery. The electrochemical studies reveal that the carbon polysulfde polymer exhibits superb reversibility and cycle stability. This is due to that the well-designed structure of the carbon polysulfde polymer has several advantages, especially, the strong chemical interaction between sulfur and the carbon framework (C-S bonds) inhibits the shuttle efect and the π electrons of the carbon polysulfde compound enhance the transfer of electrons and Li+. Furthermore, as-prepared carbon polysulfde polymer-graphene hybrid cathode achieves outstanding cycle stability and relatively high capacity. This work highlights the potential promise of the carbon polysulfde polymer as the cathode material for high performance lithium-sulfur battery. With the rapid development of mobile electronic devices and electric vehicles on the market, the batteries to be used as power supplies are more urgently required to have higher performances.
    [Show full text]
  • Removal by Electrospun Sulfur Copolymers
    polymers Communication Rapid Mercury(II) Removal by Electrospun Sulfur Copolymers Michael W. Thielke 1, Lindsey A. Bultema 1, Daniel D. Brauer 1, Bernadette Richter 2, Markus Fischer 2 and Patrick Theato 1,* 1 Institute of Technical and Macromolecular Chemistry, University of Hamburg, Bundesstr. 45, 20146 Hamburg, Germany; [email protected] (M.W.T.); [email protected] (L.A.B.); [email protected] (D.D.B.) 2 Hamburg School of Food Science, University of Hamburg, Grindelallee 117, 20146 Hamburg, Germany; [email protected] (B.R.); [email protected] (M.F.) * Correspondence: [email protected]; Tel.: +49-40-42838-6009 Academic Editor: André Laschewsky Received: 16 June 2016; Accepted: 14 July 2016; Published: 20 July 2016 Abstract: Electrospinning was performed with a blend of commercially available poly(methyl methacrylate) (PMMA) and a sulfur-rich copolymer based on poly(sulfur-statistical-diisopropenylbenzene), which was synthesized via inverse vulcanization. The polysulfide backbone of sulfur-containing polymers is known to bind mercury from aqueous solutions and can be utilized for recycling water. Increasing the surface area by electrospinning can maximize the effect of binding mercury regarding the rate and maximum uptake. These fibers showed a mercury decrease of more than 98% after a few seconds and a maximum uptake of 440 mg of mercury per gram of electrospun fibers. These polymeric fibers represent a new class of efficient water filtering systems that show one of the highest and fastest mercury uptakes for electrospun fibers reported. Keywords: electrospinning; inverse vulcanization; sulfur; mercury removal; polysulfide 1.
    [Show full text]
  • Journal Name COMMUNICATION
    Please do not adjust margins Journal Name COMMUNICATION Functionalized Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs) via Inverse Vulcanization of Elemental Sulfur and Vinylanilines Received 00th January 20xx, a a a b a b,c Accepted 00th January Yueyan Zhang, Tristan S. Kleine, Kyle J. Carothers, David D. Phan, Richard S. Glass, Michael, E. Mackay, 20xx Kookheon Char d and Jeffrey Pyun a,d DOI: 10.1039/x0xx00000x www.rsc.org/ In this report, a new class of functional chalcogenide hybrid However, utilizing surplus sulfur as an in expensive feed stock inorganic/organic polymers (CHIPs) bearing free aryl amine groups to be smartly exploited toward novel industrial applications is a that are amenable to post-polymerization modifications were convenient way to address the problem.3, 4 synthesized. These functional CHIPs were synthesized via the In 2013, Pyun and co-workers developed a new process, inverse vulcanization of elemental sulfur with 4-vinylaniline termed, inverse vulcanization, which enabled the direct without the need for functional group protection of amines. This copolymerization of molten elemental sulfur with vinylic polymer is the first example of a polysulfide or CHIPs material to comonomers. The inverse vulcanization process has more carry a useful primary amine functional group which can be recently been extended into a wider class of organic successfully post functionalized with acid chlorides and isocyanates to improve the mechanical properties. Sustainable chemical processes from naturally occurring and industrial
    [Show full text]
  • On the Reactivity of Nanoparticulate Elemental Sulfur
    ON THE REACTIVITY OF NANOPARTICULATE ELEMENTAL SULFUR: EXPERIMENTATION AND FIELD OBSERVATIONS Fotios Christos Kafantaris Submitted to the faculty of the University Graduate School in partial fulfillment of the requirements for the degree Doctor of Philosophy in the Department of Earth Sciences, Indiana University December 2017 ii Accepted by the Graduate Faculty of Indiana University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Doctoral Committee ___________________________ Gregory K. Druschel, PhD, Chair ___________________________ Kevin Mandernack, PhD ___________________________ William P. Gilhooly III, PhD ___________________________ Gabriel Filippelli, PhD ___________________________ Steven E. Lacey, PhD October 2, 2017 ___________________________ Brandy M. Toner, PhD iii © 2017 Fotios Christos Kafantaris iv DEDICATION I would like to dedicate this work to three women. The first one is the Most Holy Theotokos and Ever-Virgin Mary, the most precious individual the human race has and will ever have, the Bridge from earth to Heaven and the Gate to Paradise. Through Her intercessions to the Holy Trinity I am still alive and safe. The second woman is my mother, Eleni, who is the angel-on-earth that protects, nourishes, teaches, provides, inspires and guides me in life. Words would be poor to attempt to describe her and her virtues in an accurate manner. My mother is the main contributor of what I have become so far in life. The third woman is my σύζυγος (spouse) Diana, who has given me life, as well as meaning for life. Diana is the main contributor of what I will hopefully do in life from this point onward, and through her help I will hopefully manage to be with the other two forever.
    [Show full text]
  • Removal by Electrospun Sulfur Copolymers
    Thielke, M., Bultema, L., Brauer, D., Richter, B., Fischer, M., & Theato, P. (2016). Rapid Mercury(II) Removal by Electrospun Sulfur Copolymers. Polymers, 8(7), [266]. https://doi.org/10.3390/polym8070266 Publisher's PDF, also known as Version of record License (if available): CC BY Link to published version (if available): 10.3390/polym8070266 Link to publication record in Explore Bristol Research PDF-document This is the final published version of the article (version of record). It first appeared online via MDPI at https://doi.org/10.3390/polym8070266 . Please refer to any applicable terms of use of the publisher. University of Bristol - Explore Bristol Research General rights This document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/red/research-policy/pure/user-guides/ebr-terms/ polymers Communication Rapid Mercury(II) Removal by Electrospun Sulfur Copolymers Michael W. Thielke 1, Lindsey A. Bultema 1, Daniel D. Brauer 1, Bernadette Richter 2, Markus Fischer 2 and Patrick Theato 1,* 1 Institute of Technical and Macromolecular Chemistry, University of Hamburg, Bundesstr. 45, 20146 Hamburg, Germany; [email protected] (M.W.T.); [email protected] (L.A.B.); [email protected] (D.D.B.) 2 Hamburg School of Food Science, University of Hamburg, Grindelallee 117, 20146 Hamburg, Germany; [email protected] (B.R.); [email protected] (M.F.) * Correspondence: [email protected]; Tel.: +49-40-42838-6009 Academic Editor: André Laschewsky Received: 16 June 2016; Accepted: 14 July 2016; Published: 20 July 2016 Abstract: Electrospinning was performed with a blend of commercially available poly(methyl methacrylate) (PMMA) and a sulfur-rich copolymer based on poly(sulfur-statistical-diisopropenylbenzene), which was synthesized via inverse vulcanization.
    [Show full text]
  • Polyisoprene Captured Sulfur Nanocomposite Materials for High Areal Capacity Lithium Sulfur Battery
    Polyisoprene Captured Sulfur Nanocomposite Materials for High Areal Capacity Lithium Sulfur Battery Zeheng Li,§ Chen Fang†, Chao Qian,§ Shudong Zhou§, Xiangyun Song†, Min. Ling§* Chengdu Liang§, Gao Liu†* § Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China. † Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States. KEYWORDS: polyisoprene, inverse vulcanization, binder, shuttle effects, lithium sulfur battery ABSTRACT: A polyisoprene-sulfur (PIPS) copolymer and nano sulfur composite materials (90 wt% sulfur) is synthesized through inverse vulcanization of PIP polymer with sulfur micron size particles for high areal capacity lithium sulfur batteries. The polycrystalline structure and nanodomain nature of the copolymer are revealed through high-resolution transmission electron microscopy (HRTEM). PIP polymer is also used as binders for the electrode to further capture the dissovlved polysulfides. A high areal capacity of ca. 7.0 mAh/cm2 and stable cycling are achieved 1 based on the PIPS nanosulfur composite with a PIP binder, crucial to commercialization of lithium sulfur batteries. The chemical confinement both at material and electrode level alleviates the diffusion of polysulfides and the shuttle effect. The sulfur electrodes, both fresh and cycled, are analyzed through the scanning electron microscopy (SEM). This approach enables scalable materials production and high sulfur utilization in the cell level. 1. INTRODUCTION Due to sulfur’s high theoretical capacity, nature abundance and low material cost, lithium sulfur (Li-S) cells are the ideal choice for the next-generation energy storage devices for emerging technologies, e.g., unmanned aerial vehicles (UAV) and air-taxi, and short-duration electric airplane.
    [Show full text]
  • Inverse Vulcanisation of Elemental Sulfur for Functional Materials
    INVERSE VULCANISATION OF ELEMENTAL SULFUR FOR FUNCTIONAL MATERIALS JESSICA A. SMITH DATE: JULY 2020 Thesis submitted in accordance with the requirements of the University of Liverpool for the degree of Doctor of Philosophy ii ABSTRACT Synthetic polymers are the most extensively manufactured material on earth. The exponential increase in the production and application of synthetic polymers has led to growing concerns such as, depletion of fossil fuels. Due to this, there is a growing research interest in the development of sustainable, safe, biodegradable, and environmentally friendly plastics from renewable resources. Until recently, inorganic waste for functional renewable materials had been overlooked. Sulfur is a highly abundant element and is also produced as a by-product of the petrochemicals industry. Over 70 million tonnes of sulfur is produced annually, with only a small fraction of this being used to produce commodity chemicals, such as sulfuric acid and fertilisers. This leaves huge unused stockpiles around the world, meaning sulfur is a cheap waste by-product. However, until recently, it has not been conventionally used to produce functional materials because polymeric sulfur is unstable and decomposes back to crystalline sulfur (S8). In 2013 Pyun and co-workers discovered inverse vulcanisation which allows polymeric sulfur to be stabilised by a small alkene crosslinker. This work explores different inverse vulcanised sulfur polymers for functional materials and focuses on both discovering and improving the physical properties for different functions. The effect of crosslinker structure on the resultant polymer is assessed; the materials’ mechanical properties are explored; the antibacterial activity of the materials is investigated, and catalyst/accelerators are explored to improve reaction conditions.
    [Show full text]