Small dissymmetry, yet large effects on the transport propertiesof electrolytes based on imide salts: Consequences on performancein Li-ion batteries

作     者：Joseph Chidiac Laure Timperman Mérièm Anouti Joseph Chidiac;Laure Timperman;Mérièm Anouti

作者机构：Laboratoire PCM2EUniversitéde ToursParc de Grandmont37200 ToursFrance 

出 版 物：《Journal of Energy Chemistry》 (能源化学（英文版）)

年 卷 期：2022年第31卷第2期

页      面：352-366页

核心收录：

学科分类：0820[工学-石油与天然气工程] 081702[工学-化学工艺] 0808[工学-电气工程] 08[工学] 0817[工学-化学工程与技术] 0807[工学-动力工程及工程热物理] 0827[工学-核科学与技术] 0703[理学-化学] 

基　　金：“La Région Centre Val de Loire” for financial support。 

主　　题：LiFTFSI Electrolyte Viscosity Interface Li-ion battery 

摘      要：To gain better insight into the influence of the anion size and symmetry on the transport properties and thermal stability of an electrolyte based on lithium(fluorosulfonyl)(trifluoromethanesulfonyl)-imide(FTFSI)salt,we performed the physical and electrochemical characterization of an electrolyte based on FTFSI incorporated in standard binary(3 EC/7 EMC)and ternary(EC/PC/3 DMC)alkylcarbonate mixtures.By applying the Jones-Dole-Kaminsky(JDK),Eyring and Arrhenius empirical models to the electrolyte viscosity we show that the activation enthalpy and entropy energy barriers(ΔH≠,ΔS≠)for viscous flow are between 12 and 15 kJ·mol^(-1).They are strongly dependent on the solvent nature and are significantly lower than their symmetric anions LiFSI and LiTFSI(19-20 kJ·mol^(-1))in the binary mixture.Furthermore,the hydrodynamic radius,rs,calculated by JDK,and the ionicity behavior illustrated by the Walden role,showed that the FTFSI anion is outside the solvation sphere(rs0.6 nm)which is smaller in the case of an EC/EMC solvent base.In the 3 EC/7 EMC solvent mixture,LiFTFSI is less conductive than in the ternary mixture i.e.,σ_(max)=8.9 mS cm^(-1) at C_(max)=1.1 mol L^(-1) for 3 EC/7 EMC and,σ_(max)=10.5 mS cm^(-1) at max=0.7 mol L^(-1) for EC/PC/3 DMC,due to a strong solvation and a greater association of FTFSI ions in the binary solvent mixture.The thermal stability of FTFSI based electrolytes was determined by the shift of the evaporation temperature of the volatile solvents(DMC,EMC)in the presence of salt,towards the higher temperatures.This feature is visible on the thermograms obtained by DSC both with the liquid electrolyte and with charged LMO cathodes in presence of electrolytes.The consequences of these properties on the electrochemical behavior of a graphite(Gr)half-cell,a lithium metal(Li)anode and a manganese lithium oxide(LMO)cathode demonstrated on the one hand the formation of a thick solid electrolyte interphase(SEI)on graphite that consumed a significant amount of lithium i.e.,18%of total capacity of the first charge.Furthermore,LiFTFSI delivered 95%of the initial capacity C=360 mAh g^(-1) at C/10 with EC/PC/3 DMC versus 91%when it was combined with 3 EC/7 EMC C=348 mAh g^(-1),while the capacities obtained for LiTFSI in EC/PC/3 DMC were the lowest(C=275 mAh g^(-1))compared to those of the other salts.After 10 cycles,the capacity loss at C/20 is2%for LiFSI and LiFTFSI with the two solvent mixtures.On the other hand,manganese dissolution from LMO as well as current collector corrosion were confirmed by post-mortem examination of opened coin cells.The incompatibility of the LMO cathode with an electrolyte based on FTFSI was confirmed by the position of the decomposition peak of charged LMO in contact with this electrolyte observed by DSC These results demonstrate that the nature of the anion as well as the composition of the solvent considerably influence the performance of imide-based lithium salts both on the anode,but especially on the high voltage cathode.