Syntheses of a wide family of new aryl based perfluorosulfonimide lithium salts. Electrochemical performances of the related polymer electrolytes

This paper reports both on a general multistep synthesis of a wide family of aryl substituted perfluorosulfonimides and on a preliminary electrochemical investigation of two lithium salts hosted by a poly(oxyethylene) homopolymer. Both salts have a cationic transference number more than twice that of LiTFSI. Additionally, one of these salts exhibits markedly higher cationic conductivities than POE/LiTFSI electrolytes. These preliminary data are very encouraging as, thanks to the aryl moiety, a wide variety of salts can be considered in order to still improve the performances of polymer electrolytes.     

含烷氧磺酸锂盐及对称星形醚的聚环氧乙烷基聚合物电解质的制备及电化学性能

合成了低聚度烷氧磺酸锂盐（LiSA(EO)n)和对称星形醚（STEO）增塑剂,并制备了聚环氧乙烷（PEO）基聚合物电解质。 研究了PEO16+LiSA(EO)n体系的锂离子迁移数和电导率与锂盐结构的关系,实验结果表明,LiSA(EO)n代替LiClO4作为锂盐时,其电导率得到提高,而且聚合物电解质的锂离子迁移数随着烷氧磺酸锂盐阴离子体积的增大而增加,并且其中PEO16+LiSA(EO)2体系的锂离子迁移数达到0.35。 STEO可明显地提高PEO16-LiSAEO-STEO体系的电导率,PEO16-LiSAEO-20%STEO室温电导率可达到0.5×10-4 S/cm。 通过DSC实验结果表明,STEO的加入,可有效降低聚合物电解质体系的熔融温度和结晶度,PEO16-LiSAEO-20%STEO电化学稳定窗口在4.4 V以上,可满足锂电池的应用要求。     

Enhanced Lithium‐Ion Conductivity of Polymer Electrolytes by Selective Introduction of Hydrogen into the Anion

The anion chemistry of lithium salts plays a pivotal role in dictating the physicochemical and electrochemical performance of solid polymer electrolytes (SPEs), thus affecting the cyclability of all‐solid‐state lithium metal batteries (ASSLMBs). The bis(trifluoromethanesulfonyl)imide anion (TFSI^?) has long been studied as the most promising candidate for SPEs; however, the Li‐ion conductivities of the TFSI‐based SPEs still remain low (Li‐ion transference number: ca. 0.2). In this work, we report new hydrogen‐containing anions, conceived based on theoretical considerations, as an electrolyte salt for SPEs. SPEs comprising hydrogen‐containing anions achieve higher Li‐ion conductivities than TFSI‐based ones, and those anions are electrochemically stable for various kinds of ASSLMBs (Li–LiFePO₄, Li–S, and Li–O₂ batteries). This opens up a new avenue for designing safe and high‐performance ASSLMBs in the future.     

Molar conductivity calculation of Li-ion battery electrolyte based on mode coupling theory

A method is proposed to calculate molar conductivity based on mode coupling theory in which the ion transference number is introduced into the theory. The molar conductivities of LiPF6, LiClO4, LiBF4, LiAsF6 in PC (propylene carbonate) are calculated based on this method. The results fit well to the literature data. This presents a potential way to calculate the conductivities of Li-ion battery electrolytes.     

Transference Numbers and Activity Coefficients of Some Alkali Metal Halide Solutions in Ethylene Glycol,Using Concentration Cells

Abstract

The reliability of the concentration cell method for determining cation transference numbers has been tested using solutions of LiCl, NaCl, KCl, NaBr and LiBr in ethylene glycol at 25°C. Concentrations in the range 0.0005 to 0.5 mol dm^?3 were used. Our transference numbers have been compared with those deduced from previous data on moving boundary and conductivity experiments. Good agreement between both sets of values has been found in most of the solutions, but significant discrepancies appear in the cases of NaBr and LiCl. The mean activity coefficients have been calculated from the EMF data and the transference numbers.     

聚合物电解质离子迁移数的测定方法

介绍了用于测定理想聚合物电解质中离子迁移数的三种比较常用的电化学方法,阐述了实际聚合物电解质输运性质和理想聚合物电解质输运性质之间的区别,并说明了实际聚合物电解质的离子迁移数的测定方法。     

Li-SGO掺杂半互穿网络型多孔单离子传导聚合物复合电解质的制备

本文成功制备了磺酸锂功能化石墨烯,通过原位聚合方式成功将其添加到单离子传导聚合物电解质中制备出磺酸锂功能化石墨烯改性半互穿网络型多孔单离子传导聚合物复合电解质.与未掺杂磺酸锂功能化石墨烯半互穿网络型多孔单离子传导聚合物电解质相比,该电解质具有更高的孔隙率、吸液率、机械拉伸强度和离子电导率.电化学测试结果表明,掺杂磺酸锂...     

New electrolytes using Li2O or Li2O2 oxides and tris(pentafluorophenyl) borane as boron based anion receptor for lithium batteries

A new system of electrolytes has been developed and studied for lithium-ion batteries. This new system is based on the interactions between Li₂O or Li₂O₂ and tris(pentafluorophenyl) borane (TPFPB) in carbonate based organic solvents. This opens up a completely new approach in developing non-aqueous electrolytes. In general, the solubility of Li₂O or Li₂O₂ is very low in organic solvents and the ionic conductivities of these solutions are almost undetectable. By adding certain amount of tris(pentafluorophenyl) borane (TPFPB), one type of boron based anion receptors (BBARs), the solubility of Li₂O or Li₂O₂ in carbonate based solvents was significantly enhanced. In addition, the Li⁺ transference numbers of these new electrolytes measured were as high as 0.7, which are more than 100% higher than the values for the conventional electrolytes for lithium-ion batteries. The room-temperature conductivities are around 1 × 10⁻³ S/cm. These new electrolytes are compatible with LiMn₂O₄ cathode for lithium-ion batteries.     

Determination of transference numbers with ion-selective electrodes. Transference numbers and activity coefficients of concentrated aqueous solutions of potassium fluoride

An experimental method has been developed to determine transference numbers by simultaneous emf measurements of cells with liquid junction using cation- and anion-responsive electrodes. As a corrolary of the transference measurements, activity coefficient data have been obtained. The method is illustrated by reporting transference and activity coefficient data of aueous KF solutions at 25°C from about 0.05 to 3 m obtained with potassium selective glass electrodes and fluoride selective solid state electrodes. The activity coefficients are in good agreement with literature data, which reflects the excellent Nernstian response of these electrodes in solutions up to 3m. The transference numbers show the typical behavior expected for a non-associated 1:1 electrolyte.     

Preliminary communication Electron beam cured liquid crystal-polymer composite materials: electro-optical enhancement effect

Polymerization induced phase separation initiated by electron beam radiation has been used as a powerful method to obtain well defined PDLC films. Mixtures of different amounts of an aromatic polyester acrylate, an oligoether triacrylate and nematic liquid crystal material E7 were exposed to the electron beam radiation. The electro-optical properties strongly depend on the liquid crystal concentration and on the amount of the oligoether triacrylate in the prepolymer mixture, and are highly reproducible. An unusual enhancement effect of the electro-optical sensitivity was found for samples containing 28 weight per cent and 34 weight per cent of the oligoether triacrylate.     

Transport properties of solid polymer electrolytes prepared from oligomeric fluorosulfonimide lithium salts dissolved in high molecular weight poly(ethylene oxide)

Transport properties such as ionic conductivity, lithium transference number, and apparent salt diffusion coefficient are reported for solid polymer electrolytes (SPEs) prepared using several oligomeric bis[(perfluoroalkyl)sulfonyl]imide (fluorosulfonimide) lithium salts dissolved in high molecular weight poly(ethylene oxide) (PEO). The salt series consists of polyanions in which two discrete fluorosulfonimide anions are linked together by [(perfluorobutylene)disulfonyl]imide linker chains. The restricted diffusion technique was used to measure the apparent salt diffusion coefficients in SPEs, and cationic transference numbers were determined using both potentiostatic polarization and electrochemical impedance spectroscopy methods. A general trend of diminished salt diffusion coefficient with increasing anion size was observed and is opposite to the trend observed in ionic conductivity. This unexpected finding is rationalized in terms of the cumulative effects of charge carrier concentration, anion mobility, ion pairing, host plasticization by the anions, and salt phase segregation on the conductivity.     

Moving and stationary boundaries in immobilized pH gradients

The relations describing the concentration changes at moving boundaries in a medium containing bound, buffering group are derived for a system which, except for hydrogen and hydroxyl ions, contains one anionic and one cationic mobile constituent. The relations found have been used to calculate concentrations and conductivities in zones developing in immobilized pH gradients. Assumptions used in the calculations as well as conductivity ratios between zones have been experimentally controlled and were found to reasonably agree with expectations. It is also shown how difference in transference numbers between sample droplet and gel will cause concentration and pH changes at the gel-sample droplet interfaces and it is explained how these changes are related to ionic concentrations in the gel. The high concentration zone generated at one of the interfaces will be transported into the gel. This transport has been numerically simulated and experimentally verified. The low concentration generated at the opposite interface will cause titration impeding sample entrance in the gel through this interface even when the gel contains ions other than H+ or OH- transported towards the interface. The described phenomena explain the dependence of lateral spreading, precipitation at the application site as well as streaking and smearing along sample lanes, on the type and concentration of low molecular weight ions originally present in the gel.     

LiBPON薄膜电解质的制备及电化学性能研究

应用磁控溅射法在N2气氛中制备LiBPON薄膜电解质,研究薄膜性能与沉积条件的关系,优化其制备条件.扫描电镜图显示其表面平整均匀致密,X射线衍射及交流阻抗测试分别表明该薄膜呈非晶态,室温离子电导率随溅射功率增大而减小,随N2压力增大而增大,最高达3.5×10-6S/cm;薄膜的沉积速率随溅射功率增大而增大,随N2压力增大而减小.N的结合对电解质的电化学性能有明显改善,作为薄膜锂电池电解质有良好的应用前景.     

THERMAL BEHAVIOR AND IONIC CONDUCTIVITY OF POLY[LITHIUM-N(4-SULFO-PHENYL) MALEIMIDE -CO-METHOXY OLIGO(OXYETHYLENE) METHACRYLATE]

Poly[lithium-N(4-sulfophenyl) maleimide -co- methoxy oligo-(oxyethylene) methacrylates] [P(LiSMOE_n)s] with three different oligoether side chains and different salt concentrations were synthesized. The copolyelectrolytes are essentially random in structure, with blocks of methoxy oligo(oxyethylene) meth-acrylate (MOE_nM) recurring sporadically in between the salt units of N(4-sulfophenyl) maleimide. They all show two glass transitions in the temperature range of ?100 to 100°C. The first one below ?30°C is assigned to the oligo(oxyethylene) side chain (T _g1), while the second one located between 20 and 50°C is attributed to the main chain of the polymer host (T _g2). The maximum ionic conductivity of the copolymer electrolytes, 1.6 × 10^?7 S cm^?1 at 25°C, occurs at lithium salt concentration [Li⁺]/[EO] = 2.2 mol%. The ionic conductive behavior of the copolyelectrolytes follows the Vogel-Tammann-Fulcher (VTF) equation. Moreover, a special VTF behavior exists in the copolymers with shorter oligoether side chain and higher salt concentration. Sweep voltammetric results indicate that these copolyelectrolytes have a good electrochemical stability window.     

Kinetics of Formation and Curing of Oligoether Urethane Allyl Ester

Kinetic parameters of formation of P-9AD oligoether urethane allyl ester with terminal double bonds and of its curing with dinitrile oxide were determined. The dependence of the rate constant on the allyl alcohol concentration and temperature was studied. The mechanism of reaction of P-9A prepolymer with allyl alcohol was proposed. The kinetic and thermodynamic parameters of curing of oligoether urethane allyl ester with dinitrile oxide were determined. The mechanism of reaction of P-9AD oligoether urethane allyl ester with dinitrile oxide was proposed.     

Density,viscosity, conductance,and transference number of concentrated aqueous magnesium chloride at 25°C

The density, viscosity, conductance, and transference number of aqueous magnesium chloride at 298.15°K are reported for the concentration range 0 to 5.7m. The transference numbers were determined using the emf method. It was found that the viscosity, conductance, and transference number of aqueous magnesium chloride are similar to those for aqueous nickel chloride. It was therefore tentatively concluded that incomplete dissociation and complex formation was unlikely to be of importance in nickel chloride solutions.     

Ionic limiting molar conductivity calculation of Li-ion battery electrolyte based on mode coupling theory

A method is proposed based on mode coupling theory in which the ion transference number is introduced into the theory. The ionic limiting molar conductivities of LiPF6, LiClO4, LiBF4, LiCF3SO3, Li(CF3SO3)2N, LiC4F9SO3, and LiAsF6 in PC(propylene carbonate), GBL(gamma-butyrolactone), PC(propylene carbonate)/EMC(ethylmethyl carbonate), and PC(propylene carbonate)/DME(dimethoxyethane) are calculated based on this method, which does not involve any adjustable parameter. The results fit well to the literature data which are calculated by an empirically adjusted formula. This presents a potential way to calculate the conductivities of Li-ion battery electrolytes.     

Ionic interactions in solutions. V. transference number variation with concentration—contribution to a theoretical interpretation for binary symmetrical electrolytes

The introduction of the echo effect in the conductance functions shows that the variation of transference numbers with concentration is independent of the relaxation field and can be exclusively attributed to electrophoresis. The theoretical expression of transference number variation with concentration is checked by reprocessing literature data. The dependence of the electrophoretic contribution on the distance of approach of two ions of opposite charge is discussed and is found to be independent of the parameters controlling short-range configurations. By combining transference numbers and conductance data, it is possible to get an experimental evaluation of the electrophoretic and relaxation effects which are compared to the corresponding theoretical derivations.     

Studies on silver(I) solvation in binary solvent mixtures containing dimethylsulfoxide. IV determination of solvent transference numbers for AgSCN and ionic coordination numbers of Ag+ in methanol-dimethylsulfoxide mixtures at 25°C

Solvent transport by AgSCN in the methanol (M)+dimethylsulfoxide (DMSO) system has been studied at 25°C by e.m.f. measurements. The solvent transference number of DMSO is positive as its concentration increases in the cathode compartment during electrolysis. The solubility of AgSCN has been determined in methanol, in DMSO and in methanol-DMSO mixtures. Using the known Gibbs free energy of solvation for the Ag⁺ ion, the corresponding energy for SCN, was found to be independent of the mole fraction. The experimental solvent transference numbers therefore only represent the contribution of Ag⁺, this is because it is preferentially solvated by DMSO. A coordination model has been applied to the Gibbs free energy of transfer of Ag⁺ in order to obtain coordination numbers thereby allowing calculation of solvent transference numbers. The experimental and the calculated solvent transference numbers are in good agreement at mole fractions of DMSO greater than 0.5. In highly methanolic solutions the assumption that the solvation of Ag⁺ in the solvent system studied is adequately represented by a total coordination number of four, proves to be too simple.