DOCSLIB.ORG

Solubility-Mediated Sustained Release Enabling Nitrate Additive in Carbonate Electrolytes for Stable Lithium Metal Anode

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Solubility-Mediated Sustained Release Enabling Nitrate Additive in Carbonate Electrolytes for Stable Lithium Metal Anode ARTICLE DOI: 10.1038/s41467-018-06077-5 OPEN Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode Yayuan Liu 1, Dingchang Lin1, Yuzhang Li1, Guangxu Chen1, Allen Pei 1, Oliver Nix1, Yanbin Li1 & Yi Cui1,2 The physiochemical properties of the solid-electrolyte interphase, primarily governed by electrolyte composition, have a profound impact on the electrochemical cycling of metallic 1234567890():,; lithium. Herein, we discover that the effect of nitrate anions on regulating lithium deposition previously known in ether-based electrolytes can be extended to carbonate-based systems, which dramatically alters the nuclei from dendritic to spherical, albeit extremely limited solubility. This is attributed to the preferential reduction of nitrate during solid-electrolyte interphase formation, and the mechanisms behind which are investigated based on the structure, ion-transport properties, and charge transfer kinetics of the modified interfacial environment. To overcome the solubility barrier, a solubility-mediated sustained-release methodology is introduced, in which nitrate nanoparticles are encapsulated in porous poly- mer gel and can be steadily dissolved during battery operation to maintain a high con- centration at the electroplating front. As such, effective dendrite suppression and remarkably enhanced cycling stability are achieved in corrosive carbonate electrolytes. 1 Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA. 2 Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025, USA. Correspondence and requests for materials should be addressed to Y.C. (email: [email protected]) NATURE COMMUNICATIONS | (2018) 9:3656 | DOI: 10.1038/s41467-018-06077-5 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-018-06077-5 he morphology of electrodeposited metals is dictated to a extremely low solubility. However, we observe that the preferential – Tgreat extent by the physiochemical characteristics at the reduction of NO3 during SEI formation in carbonates, albeit at metal/electrolyte interface, including ion transport, inter- very low concentration, could substantially alter the interfacial facial energy, and mechanics, etc.1. This especially stands for the chemistry, resulting in spherical Li nuclei (instead of dendritic) and electrochemical plating of metallic lithium (Li), the ultimate greatly improved CE exceeding the values in ethers. To further anode for next-generation batteries with highest specific capacity overcome the solubility limitation, a solubility-mediated sustained- –1 (3860 mAh g ) and lowest electrode potential of all possible release concept is proposed, where LiNO3 nanoparticles are dis- alternatives2,3. In particular, the electrodeposition of Li is com- persed in porous polymer backbone on anode surface and can be plicated by the instantaneous formation of a resistive interfacial steadily dissolved during battery operation when soluble LiNO is – 3 passivation (i.e. the solid-electrolyte interphase, SEI), originated consumed. With the maintained concentration of NO3 on Li from the parasitic reduction of electrolyte components by the surface frontier, the anode CE can exceed 98% for over 200 cycles, 4 highly reactive Li . The chemical heterogeneity and mechanical and the cycle life of full-cells paired with LiNi1/3Mn1/3Co1/3O2 instability of the SEI layer is generally believed to induce non- (NMC) is more than quadrupled, which is appreciable in corrosive uniform ion flux, resulting in the formation of Li dendrites that carbonate electrolytes. Note that during the peer-review process of could lead to internal short circuit and compromise battery safety, our manuscript, we noticed another work utilizing a slightly similar while the repeated breakdown and repair of SEI brings about engineering method to overcome the solubility barrier of LiNO3 in continuous loss of active materials, giving rise to limited battery carbonate electrolyte, which also resulted in improved Li anode cycle life5. CE29. Nevertheless, we are confident that our comprehensive work Extensive research has been devoted to regulate the surface brings a significant amount of new knowledge complementary to – reactivity of Li metal. Among all the tactics explored to date the other study. Particularly, the mechanism of NO3 in modifying (protective coatings6,7, nanostructured electrodes8,9, high- the SEI properties is studied deliberately on the basis of cryo- modulus separators10,11, etc.), tailoring the electrolyte composi- electron microscopy (cryo-EM)30,31, ultramicroelectrode, X-ray tion is among the most essential and prominent paradigms, for it photoelectron spectroscopy (XPS), and electrochemical impedance can directly impact the physiochemistries of the SEI layer, spectroscopy (EIS). The characterizations unravel a distinct struc- modifying the interfacial environment to alter Li deposition tural change of the SEI from amorphous to bilayered configuration, behavior12–16. a strong presence of nitrogen-containing species inside the SEI, and It is known that the choice of electrolyte solvents can already a greatly increased exchange current density of the Li+/Li couple – offer pronounced effect on Li deposition uniformity. In general, with the addition of NO3 , and the effects of which are discussed in ether-based electrolytes demonstrate relatively controlled detail. This work not only enables uniform Li deposition with high deposition and thus high Coulombic efficiency (CE), ascribed to reversibility in typical carbonate-based electrolytes without com- the formation of oligomeric SEI with superior flexibility17. The promising the stability, ionic conductivity, viscosity, and cost of the application of ether electrolytes, however, is severely hampered by electrolytes, but also provides fruitful insights on the exact role of its high flammability and low oxidation potential (anodic nitrate additive at a fundamental level. decomposition at <4 V vs Li+/Li)18, mismatched with the safety benchmark and the emerging high-voltage cathodes19. On the other hand, carbonate-based electrolytes exhibit lower flamm- Results ability and higher anodic potential, and, therefore, are used Effects of nitrate on Li morphology in carbonate electrolyte.As exclusively in almost all the commercial Li-ion batteries. Never- frequently mentioned in the literature, the cathodic decomposi- – + 32 theless, they are highly corrosive to metallic Li, rendering tion of NO3 can start as early as ~1.7 V vs Li /Li , which is aggravated dendrite formation and poor cycling efficiency. much higher than other carbonate-based electrolyte components, Fluorinated molecules, such as fluoroethylene carbonate (FEC), making it a promising candidate as “electrolyte-agnostic” additive 33 – are frequently adopted as film-forming additives in carbonates, (Fig. 1a) . Therefore, if the preferential reduction of NO3 can which is believed to promote the formation of LiF on Li surface as yield an SEI conducive to controlled Li deposition, the presence of 20–22 – a favorable SEI passivation component . Even with these NO3 in carbonate electrolytes is highly likely to afford improved additives, the Li anode CE remains deficient for practical appli- Li metal performance. To determine the exact reduction potential – cations, and the adverse effects of FEC decomposition at elevated of NO3 , cyclic voltammogram (CV) of 1.0 M LiNO3 was temperatures bring concerns when being used in full-cells23. High obtained on a stainless-steel electrode at a scanning rate of 0.1 salt concentration has recently arisen as another exemplary mV s–1. Dimethoxyethane (DME) was selected as the solvent for method to stabilize Li metal in carbonate electrolytes, the effect of the CV scan, due to its stability against reduction (–1.68 V vs Li + 34 which is originated from the unique solvation structure that /Li) and high LiNO3 solubility . As can be observed in Fig. 1b, reduces the solvent reactivity24–26. Nevertheless, its economic there is a deep cathodic current peak beginning at ~1.69 V vs Li/ effectiveness, rheological properties, and ion transport need to be Li+ in the first CV cycle, which disappeared upon the second evaluated for practical applications. Thus, it is apparent that the scan. And no similar reduction peak can be observed in the first development of new electrolyte reformulation strategies, which CV cycle when LiNO3 was replaced by lithium bis(tri- could circumvent the potential drawbacks of the existing ones, fluoromethanesulfonyl)imide (LiTFSI). Thus, the irreversible remains highly desirable. cathodic current starting at ~1.69 V vs Li/Li+ can be assigned Theoretically, if an additive is much more liable towards reduc- with confidence to the reduction of NO –. The easy reduction of – 3 tion than other electrolyte components to form an interfacial NO3 participates as the frontier reaction during SEI formation environment favorable for Li deposition, good electrochemical and plays a decisive role in the physiochemical properties of the performance can be achieved regardless of the electrolyte systems SEI. For this reason, the addition of LiNO3 in ether electrolytes (“electrolyte-agnostic” additive). Herein, we report the discovery of can drastically change the Li deposition morphology from irre- – the pronounced effect of nitrate anions (NO3 )onthemorphology gular to densely packed spheres, together
Load more

Recommended publications
  • University Microfilms, Inc., Ann Arbor, Michigan PART I: ORGANOSILICON COMPOUNDS
    PART I: ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS Item Type text; Dissertation-Reproduction (electronic) Authors Gollmar, Herbert George, 1938- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 02:40:10 Link to Item http://hdl.handle.net/10150/288205 This dissertation has been microfilmed exactly as received 70-1676 GOLLMAR, Herbert George, 1938- PART I: ORGA-NOSELICON COMPOUNDS. PART H: BLOCK POLYMERIZATIONS. University of Arizona, Ph.D., 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan PART I: ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS by Herbert George Gollmar A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 19 6 9 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Herbert George Gollmar entitled . PART I; ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS be accepted as fulfilling the dissertation requirement of the degree of Doctor of Philosophy lb / % ^ Dissertation Director f D^e ' After inspection of the final copy of the dissertation, the folloi7ing members of the Final Examination Committee concur in its approval and recommend its acceptance:" ^Vv^VC,\W vQju—J-v. This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination.
    [Show full text]
  • Investigation of Electrolyte Additives and Lithium Metal Anodes for Lithium Ion Batteries
    University of Rhode Island DigitalCommons@URI Open Access Dissertations 2020 INVESTIGATION OF ELECTROLYTE ADDITIVES AND LITHIUM METAL ANODES FOR LITHIUM ION BATTERIES Satu Kristiina Heiskanen University of Rhode Island, [email protected] Follow this and additional works at: https://digitalcommons.uri.edu/oa_diss Recommended Citation Heiskanen, Satu Kristiina, "INVESTIGATION OF ELECTROLYTE ADDITIVES AND LITHIUM METAL ANODES FOR LITHIUM ION BATTERIES" (2020). Open Access Dissertations. Paper 1171. https://digitalcommons.uri.edu/oa_diss/1171 This Dissertation is brought to you for free and open access by DigitalCommons@URI. It has been accepted for inclusion in Open Access Dissertations by an authorized administrator of DigitalCommons@URI. For more information, please contact [email protected]. INVESTIGATION OF ELECTROLYTE ADDITIVES AND LITHIUM METAL ANODES FOR LITHIUM ION BATTERIES BY SATU KRISTIINA HEISKANEN A DISSERTATION SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY UNIVERSITY OF RHODE ISLAND 2020 DOCTOR OF PHILOSOPHY DISSERTATION OF SATU KRISTIINA HEISKANEN APPROVED: Dissertation Committee: Major Professor Brett L. Lucht Jason R. Dwyer David R. Heskett Nasser H. Zawia DEAN OF THE GRADUATE SCHOOL UNIVERSITY OF RHODE ISLAND 2020 ABSTRACT The continued development of energy storage technology is of high importance in order to facilitate the widespread adoption of intermittent renewable energy sources as well as the expansion of electromobility (for example, fully electric vehicles). These applications require a rechargeable cell with high energy density with a long cycling life, based on the electrochemical cycling of lithium ion batteries, which can be improved by modifying the cell chemistry and construction. Enabling the reversible plating and stripping of lithium metal on the negative electrode substrate – a lithium metal anode – allows for a higher gravimetric capacity necessary for a lightweight battery.
    [Show full text]
  • Swern Oxidation of Bicyclo [2.2. 1] Hept-5-Ene-2, 3-Diol and Its
    Molecules 2000, 5, 1062-1067 molecules ISSN 1420-3049 © 2000 by MDPI http://www.mdpi.org Swern Oxidation of Bicyclo[2.2.1]hept-5-ene-2,3-diol and Its Pyrazine-fused Derivatives: An Improved Synthesis of Bicyclo[2.2.1]hept-5-ene-2,3-dione and An Unexpected Ring- Opening Reaction Tomoshige Kobayashi* and Sayuri Kobayashi Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto 390-8621, Japan Tel.: (263) 37-2470, Fax: (263) 37-2470, E-mail: [email protected] Received: 14 August 2000 / Accepted: 6 September 2000 / Published: 9 September 2000 Abstract: An improved synthesis of bicyclo[2.2.1]hept-5-ene-2,3-dione by Swern oxidation of bicyclo[2.2.1]hept-5-ene-2,3-diol, and an unexpected ring-opening reaction by the Swern oxida- tion of pyrazine-fused congeners are described. Keywords: Swern oxidation, vicinal cis-diol, a-diketone, ring-opening, norbornene, pyrazine. Introduction Bicyclo[2.2.1]heptane skeletons have been a useful building block for the construction of molecular archi- tectures with a concavity [1]. In the course of our studies to synthesize a host molecule utilizing a negative electrostatic potential filed of pyrazine rings, a general method to prepare norobornene-2,3-dione and its py- razine-fused derivatives was required. We describe here an improved synthesis of bicyclo[2.2.1]hept-5-ene- 2,3-dione (3) by Swern oxidation of bicyclo[2.2.1]hept-5-ene-2,3-diol (6). We also report that a similar Swern oxidation reaction of pyrazine-fused congeners 10 and 11 was found to undergo an unexpected rring- opening reaction.
    [Show full text]
  • CCXL1.- the Electrochemistry of Solutions in Acetone. Part I
    View Article Online / Journal Homepage / Table of Contents for this issue 2 I38 ROSHDESTWENSKY AND LEWlS THE CCXL1.- The Electrochemistry of Solutions in Acetone. Part I. By ALEXANDERROSHDESTWENSEY and WILLIAM CUDMORE MCCULLAGHLEWIS. WHILSTa considerable amount of attention has been directed to the electrochemical behaviour of methyl and ethyl alcohols, rela- tively few measurements are recorded in the caw of solutions in acetone. The present paper contains the resulk of an investigation undertaken to supply to a certain extent this deficiency. The solutes employed were lithium nitrate and silver nitrate, the latter being examined in greater detail. Before giving our own meamrements, it is necessary to indicate briefly some of the results obtained by other observers which bear directly on the results obtained by us.* As regards the electrolysis of saturated silver nitrate solutions in acetone, Kahlenberg (J. physicd C‘Aem., 1900,4, 349) found that the metal was precipitated in a coherent form, but “the solution conducts so poorly ” that it was impossible to verify Faxaday’s law. In the same paper Kahlenberg gives some results of electromotive force measurements of Ag i AgNO, concentration cells in pyridine and acetonitrile respectively, with regard to which he concludes that the Nernst expressions are inapplicable. Kahlenberg asumes that the liquid/liquid potential difference is negligible, which, in the case of acetone at least, we shall show later is not the case. The specific conductivity of acetone itself has been meamred by Dutoit and Levier (J. Chim. phys., 1905, 3,435), the value obtained Published on 01 January 1911. Downloaded by Freie Universitaet Berlin 09/04/2018 17:53:03.
    [Show full text]
  • Investigations on Vinylene Carbonate, 2. Copolymerization with N-Vinyl-2
    Makromol. Chem., Rapid Commun. 11, 501-506 (1990) 501 Investigations on vinylene carbonate, 2 a) Copolymerization with N-vinyl-2-pyrrolidone and ethyl vinyl ether Edze Jan Tijsma, Guohua Chen, Leen van der Does*, Adriaan Bantjes Department of Chemical Technology, Biomaterials Section, Twente University of Technology, P.O. Box 217, 7500 AE, Enschede, The Netherlands (Date of receipt: March 16, 1990) Introduction Functional monomers and polymers have received considerable attention in recent years, especially in the biomedical field. In this respect, poly(viny1ene carbonate) is very interesting, because the reactive carbonate groups offer the possibility of coupling with bioactive compounds containing amino groups, e. g. proteins or enzymes. Copolymeri- zation of vinylene carbonate with other vinyl monomers will affect the amount of carbonate groups as well as other properties of the copolymers. In a previous paper we described the preparation and properties of poly(viny1ene carbonate) I), and this paper reports the copolymerization of vinylene carbonate with N-vinyl-2-pyrrolidone and with ethyl vinyl ether. Radical copolymerization of vinylene carbonate (VCA) was first reported by Price and Padbury’). Several investigations on copolymerization of VCA with vinyl mono- mers were carried out, and in some cases the monomer reactivity ratios were deter- mined3s4).Copolymers of VCA (1) with vinyl compounds (2) in general contain only small amounts of VCA (r, c 1 and r2 > 1) and show more or less characteristics of an ideal copolymerization (rl = l/r2).The radical copolymerization of VCA with isobutyl vinyl ether, on the other hand, leads to predominantly alternating copoly- mers’). However, in all these copolymerizations a relatively low reactivity of VCA was observed, due to the 1,Zdisubstitution of the vinylene group.
    [Show full text]
  • Designing Polymers for Advanced Battery Chemistries
    REVIEWS Designing polymers for advanced battery chemistries Jeffrey Lopez 1, David G. Mackanic 1, Yi Cui 2,3 and Zhenan Bao 1* Abstract | Electrochemical energy storage devices are becoming increasingly important to our global society , and polymer materials are key components of these devices. As the demand for high- energy density devices increases, innovative new materials that build on the fundamental understanding of physical phenomena and structure–property relationships will be required to enable high-capacity next-generation battery chemistries. In this Review , we discuss core polymer science principles that are used to facilitate progress in battery materials development. Specifically , we discuss the design of polymeric materials for desired mechanical properties, increased ionic and electronic conductivity and specific chemical interactions. We also discuss how polymer materials have been designed to create stable artificial interfaces and improve battery safety. The focus is on these design principles applied to advanced silicon, lithium-metal and sulfur battery chemistries. The development of new electrochemical energy storage of existing materials or to enable the application of new technologies has been instrumental to the proliferation battery chemistries. In this Review, we summarize the of portable electronic devices and the increasing adop- fundamental polymer science and engineering con- tion of electric vehicles. Intermittent electricity genera- cepts related to the development of polymers for next- tion (for example, from wind and solar power sources) generation battery applications (Table 1). We specifically has further intensified the demand for high-energy den- discuss how these core concepts drive the design of new sity, high- power and low-cost energy storage devices1,2.
    [Show full text]
  • Investigations on Vinylene Carbonate. IV. Radiation Induced Graft Copolymerization of Vinylene Carbonate and N-Vinyl-N-Methylacetamide Onto Polyethylene Films
    Investigations on Vinylene Carbonate. IV. Radiation Induced Graft Copolymerization of Vinylene Carbonate and N-Vinyl-N-Methylacetamide onto Polyethylene Films CUOHUA CHEN, LEEN VAN DER DOES, and ADRIAAN BANTJES Department of Chemical Technology, Biomaterials Section, Twente University, P.O. Box 21 7, 7500 AE Enschede, The Netherlands SYNOPSIS Graft copolymerization of binary mixtures of vinylene carbonate (VCA) and N-vinyl-N- methylacetamide (VIMA) onto low density polyethylene (LDPE) films was studied by the mutual y-irradiation technique. Sufficient amounts of functionally active VCA groups could be grafted onto the surface and the hydrophilicity of the surface was also improved. The grafting of VCA onto polyethylene films in the binary solutions was found to be promoted by the presence of VIMA, thus showing a positive synergism. The VCA content in the graft copolymers was always higher than in the copolymers obtained by homogeneous copoly- merization using the same monomer feed composition. The monomer reactivity ratios, as well as a preferential partitioning of the monomers surrounding the polymeric substrate, were considered to explain the grafting reactions in the binary systems. INTRODUCTION It has been proved that the biological endothelium owes its nonthrombogenic character to its negative Surface modification of polymers has received a charge so that it is obvious that the chemical group great deal of attention during the last decades since distribution involving polar and nonpolar compo- it could bring about specific surface properties in- nents plays a significant role in blood ~ompatibility.~ cluding adhesion, printability, nonthrombogenicity, In addition, a particular ratio of hydrophilic to hy- and antistatic properties, among others.
    [Show full text]
  • United States Patent Office Patented Dec
    3,069,391 United States Patent Office Patented Dec. 18, 1962 2 polymeric structure comprising no more than about 25% 3,069,391 POLYHYEOROXYMETHYLENE POLYMERS of a repeating unit of the formula John Raymond Schaefgeia, Wilmington, Del, assignor to E. E. du Peret de Nenagers and Company, Wilmington, O O Del, a corporation of Delaware 5 N / No Drawing. Fied Feb. 5, 1960, Ser. No. 6,838 4 Claims. (C. 260-77.5) O This invention relates to shaped structures of polymeric and at least about 75% of a repeating structural unit of materials derived from polyvinylene carbonate. More the formula particularly, it relates to a process for producing shaped -C-CH articles of predominantly polyhydroxymethylene or deriva or R tives thereof. wherein -R represents the same or different members of OBJECTS the class consisting of a hydrogen atom and a monovalent It is an object of this invention to produce shaped arti radical, is formed by a process which comprises immers cles comprising high molecular weight polymeric mate ing a useful shaped structure of polyvinylene carbonate rials derived from polyvinylene carbonate. in a hydrolyzing reagent. In a preferred method a shaped Another object is to produce shaped articles compris structure of polyvinylene carbonate is immersed in a ing polyhydroxymethylene. dilute alkaline methanol solution for periods ranging up A still further object is to produce shaped articles from 20 to several days. It is found that the hydrolysis may be derivatives of polyhydroxymethylene. effected quantitatively in about 1 or 2 days if the immersed These and other objects will become apparent in the structure is maintained at a temperature of between about course of the following specification and claims.
    [Show full text]
  • LISTA PUBLIKACJI 2009 LIST of PUBLICATIONS
    Instytut Niskich Temperatur i Badań Strukturalnych PAN Wrocław, 2011.12 31 LISTA PUBLIKACJI 2009 LIST of PUBLICATIONS KSIĄŻKI, MONOGRAFIE i ARTYKUŁY PRZEGLĄDOWE Books, Monographs & Reviews 1. R. Troć, 6.β Actinide monochalcogenides. In: Landolt–Börnstein Numerical Data and Functional Relationship in Science and Technology, New Series, ed. by W.Martienssen, Group III: Condensed Matter, Vol. 27: Magnetic Properties of Non-Metallic Inorganic Compounds Based on Transition Elements, ed. by H.P.J. Wijn, Subvol. B Pnictides and Chalcogenides III (Berlin: Springer-Vg 2009) Pt 6β, X + 574 pp. ARTYKUŁY W CZASOPISMACH NAUKOWYCH Articles in Scientific Journals 2. L.C.Alves, M.M.M.Rubinger, R.H.Lindemann, G.J.Perpétuo, J. Janczak, L.D.L.Miranda, L.Zambolim, M.R.L.Oliveira, Syntheses, Crystal Structure, Spectroscopic Characterization and Antifungal Activity of New N -R-Sulfonyldithiocarbimate Metal Complexes. J. Inorg. Biochem. 103 7 (2009) 1045–53. [DOI] 3. R.Acevedo, A.Soto-Bubert, M.E.G.Valerio, W. Stręk, On the Theory of Interaction Potentials in Ionic Crystals: An Application to the Thermodynamics of Lanthanide Type Crystals. Asian J. Spectrosc. 13 1 (2009) 43–65. 4. L.G.Akselrud, I.A.Ivashchenko, O.F.Zmiy, I.D.Olekseyuk, J. Stępień-Damm, Description of Concentration Polytypism in Cd1−xCuxIn2Se4 by Commensurately Modulated Structures. Chem. Met. Alloys 2 1/2 (2009) 108–14. 5. Tran Kim Anh, Dinh Xuan Loc, Lam thi Kieu Giang, W. Stręk, Le Quoc Minh, Preparation, Optical Properties of ZnO, ZnO : Al Nanorods and Y(OH)3 : Eu Nanotube. J. Phys. Conf. Ser. 146 (2009) 012001 (5). [DOI] II Kraj.Konf.
    [Show full text]
  • Hexaalkylguanidinium Salts As Ionic Liquids – New Applications In
    Institut für Organische Chemie I Hexaalkylguanidinium Salts as Ionic Liquids – New Applications in Titanium and Aluminium Alcoholates Assisted Synthesis and as Electrolytes for Electrodeposition of Metals Dissertation zur Erlangung des Grades des Doktors Dr. rer. nat. der Fakultät für Naturwissenschaften der Universität Ulm vorgelegt von Dipl.-Ing. Maria Arkhipova aus Leningrad (St. Petersburg) Ulm 2014 Die vorliegende Arbeit entstand in der Zeit von Januar 2010 bis Januar 2014 in dem Institut für Organische Chemie I der Universität Ulm. Amtierender Dekan: Prof. Dr. Joachim Ankerhold 1. Gutachter: Prof. Dr. Gerhard Maas 2. Gutachter: Prof. Dr. Willi Kantlehner Tag der Promotion: 17.03.2014 Моим родителям List of abbreviations APIs Active Pharmaceutical Ingredients AES Auger Electron Spectroscopy BASIL Biphasic Acid Scavenging Utilising Ionic Liquids BINOL 1,1'-Bi-2-naphthol BMIm 1-Butyl-3-methylimidazolium BMPyr N-Butyl-N-methylpyrrolidinium Bn Benzyl Bu Butyl tBu tert-Butyl CHN Elemental analysis CI Chemical Ionisation CV Cyclic Voltammetry d day(s) DLS Dynamic Light Scattering DMC Dimethyl carbonate DMF Dimethylformamide DSC Differential Scanning Calorimetry DSSC Dye-Sensitised Solar Cell EC Ethylene carbonate EDX Energy-Dispersive X-ray analysis EIS Electrochemical Impedance Spectroscopy EMIm 1-Ethyl-3-methylimidazolium Et Ethyl FAP Tris(perfluoroalkyl)trifluorophosphate FSI Bis(fluorosulfonyl)imide GC Glassy Carbon Gu Guanidinium h hour(s) Hex Hexyl cHex Cyclohexyl HMBC Heteronuclear Multiple Bond Correlation HMMIm 1-Hexyl-2,3-dimethylimidazolium
    [Show full text]
  • Techno-Economic Forecasts of Lithium Nitrates for Thermal Storage Systems
    Article Techno-Economic Forecasts of Lithium Nitrates for Thermal Storage Systems Macarena Montané 1,*, Gustavo Cáceres 1, Mauricio Villena 2 and Raúl O’Ryan 1 1 Facultad de Ingeniería y Ciencias, Universidad Adolfo Ibáñez, Avenida Diagonal Las Torres 2640, Peñalolén, Santiago 7941169, Chile; [email protected] (G.C.); [email protected] (R.O.) 2 Escuela de Negocios, Universidad Adolfo Ibáñez, Avenida Diagonal Las Torres 2640, Peñalolén, Santiago 7941169, Chile; [email protected] * Corresponding author: [email protected]; Tel.: +56-2-2331-1416 Academic Editor: Manfred Max Bergman Received: 24 March 2017; Accepted: 8 May 2017; Published: 12 May 2017 Abstract: Thermal energy storage systems (TES) are a key component of concentrated solar power (CSP) plants that generally use a NaNO3/KNO3 mixture also known as solar salt as a thermal storage material. Improvements in TES materials are important to lower CSP costs, increase energy efficiency and competitiveness with other technologies. A novel alternative examined in this paper is the use of salt mixtures with lithium nitrate that help to reduce the salt’s melting point and improve thermal capacity. This in turn allows the volume of materials required to be reduced. Based on data for commercial plants and the expected evolution of the lithium market, the technical and economic prospects for this alternative are evaluated considering recent developments of Lithium Nitrates and the uncertain future prices of lithium. Through a levelized cost of energy (LCOE) analysis it is concluded that some of the mixtures could allow a reduction in the costs of CSP plants, improving their competitiveness.
    [Show full text]
  • Effects of Lithium Nitrate Admixture on Early Age
    EFFECTS OF LITHIUM NITRATE ADMIXTURE ON EARLY AGE CONCRETE BEHAVIOR A Thesis Presented to the Academic Faculty By Marcus J. Millard In Partial Fulfillment of the Requirements for the Degree Master of Science in Civil and Environmental Engineering Georgia Institute of Technology August 2006 EFFECTS OF LITHIUM NITRATE ADMIXTURE ON EARLY AGE CONCRETE BEHAVIOR Approved by: Dr. Kimberly E. Kurtis, Advisor School of Civil and Environmental Engineering Georgia Institute of Technology Dr. Lawrence F. Kahn, Professor School of Civil and Environmental Engineering Georgia Institute of Technology Dr. James S. Lai, Professor Emeritus School of Civil and Environmental Engineering Georgia Institute of Technology Date Approved: July 10, 2006 TABLE OF CONTENTS LIST OF TABLES v LIST OF TABLES vi SUMMARY x I. INTRODUCTION 1 II. LITERATURE REVIEW 6 2.1 ASR Reactions and Mechanisms of Damage 6 2.2 Prevention of ASR Damage in New Concrete Construction 8 2.2.1 Materials Selection for ASR mitigation 8 2.2.2 Lithium-containing admixtures for ASR mitigation 9 2.3 Effects of Lithium Admixtures on Early Age Behavior 11 2.3.1 Concrete Pore Solution and Hydration Product Chemistry 12 2.3.2 Workability 13 2.3.3 Setting Time 14 2.3.4 Shrinkage 16 2.3.5 Air Content and Unit Weight 16 2.3.6 Strength 18 III. MATERIALS AND EXPERIMENTAL METHODS 23 3.1 Materials 23 3.1.1 Concrete Materials 24 3.1.2 Lithium 27 3.2 Experimental Methods 29 3.2.1 Isothermal Calorimetry 32 3.2.2 Rheology and Slump 33 3.2.3 Bleeding 36 3.2.4 Vicat Time of Setting 37 3.2.5 Chemical Shrinkage 40 3.2.6 Autogenous Shrinkage 43 3.2.7 Free Shrinkage 45 3.2.8 Restrained Shrinkage 47 3.2.9 Strength 49 IV.
    [Show full text]