Lithium-ion batteries with conventional LiPF6 carbonate electrolytes are prone to failure at high temperature. In this work, the thermal stability of a dual-salt electrolyte of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluoro(oxalato)borate (LiODFB) in carbonate solvents was analyzed by accelerated rate calorimetry (ARC) and differential scanning calorimetry (DSC). LiTFSI-LiODFB dual-salt carbonate electrolyte decomposed when the temperature exceeded 138.5 °C in the DSC test and decomposed at 271.0 °C in the ARC test. The former is the onset decomposition temperature of the solvents in the electrolyte, and the latter is the LiTFSI-LiODFB dual salts. Flynn-Wall-Ozawa, Starink, and autocatalytic models were applied to determine pyrolysis kinetic parameters. The average apparent activation energy of the dual-salt electrolyte was 53.25 kJ/mol. According to the various model fitting, the thermal decomposition process of the dual-salt electrolyte followed the autocatalytic model. The results showed that the LiTFSI-LiODFB dual-salt electrolyte is significantly better than the LiPF6 electrolyte in terms of thermal stability.
23 March 2021 in Journal of Thermal Analysis and Calorimetry
In recent years, the prosperous electric vehicle industry has contributed to the rapid development of lithium-ion batteries. However, the increase in the energy density of lithium-ion batteries has also created more pressing safety concerns. The emergence of a new flame-retardant material with the additive ethoxy (pentafluoro) cyclotriphosphazene can ameliorate the performance of lithium-ion batteries while ensuring their safety. The present study proposes a new polymer composite flame-retardant electrolyte and adopts differential scanning calorimetry (DSC) and accelerating rate calorimetry to investigate its thermal effect. The study found that the heating rate is positively correlated with the onset temperature, peak temperature, and endset temperature of the endothermic peak. The flame-retardant modified polymer electrolyte for new lithium-ion batteries has better thermal stability than traditional lithium-ion battery electrolytes. Three non-isothermal methods (Kissinger; Kissinger–Akahira–Sunose; and Flynn–Wall–Ozawa) were also used to calculate the kinetic parameters based on the DSC experimental data. The apparent activation energy results of the three non-isothermal methods were averaged as 54.16 kJ/mol. The research results can provide valuable references for the selection and preparation of flame-retardant additives in lithium-ion batteries.
The capacity fading and thermal safety issues caused by the volume effect of Si-based anodes and unstable solid electrolyte interphase (SEI) films during long-term cycling limit its large-scale application. In this study, silane polymer compound (2-cyanoethyl) triethoxysilane (TCN) was selected as an electrolyte additive to improve the reversibility and thermal safety of Si-based anode lithium-ion batteries (LIBs). TCN prevented the thermal interaction between the vitiated anode and electrolyte, and the onset temperature of the thermal reaction increased from 122.22 to 127.07 °C, as demonstrated by the results of thermogravimetric analysis and differential scanning calorimetry. The thermal stability of lithiated anodes containing various electrolytes was then assessed using a range of thermo-kinetic models. The results revealed that the activation energy of Si-based lithiated anodes increased from 68.46 to 91.32 kJ/mol, while the thermal hazard greatly decreased. Additionally, the electrochemical test and characterization results showed that TCN helped generate a stable SEI coating with more Li2CO3 components, which improved the cells’ cycle stability. This study provides a new reference for the growth of LIBs with high security and energy density.
Nitrocellulose (NC) is widely used in both military and civilian fields. Because of its high chemical sensitivity and low decomposition temperature, NC is prone to spontaneous combustion. Due to the dangerous properties of NC, it is often dissolved in other organic solvents, then stored and transported in the form of a solution. Therefore, this paper took NC solutions (NC-S) with different concentrations as research objects. Under different atmospheric conditions, a series of thermal analysis experiments and different reaction kinetic methods investigated the influence of solution concentration and oxygen concentration on NC-S’s thermal stability. The variation rules of NC-S’s thermodynamic parameters with solution and oxygen concentrations were explored. On this basis, the spontaneous combustion characteristics of NC-S under actual industrial conditions were summarized to put forward the theoretical guidance for the spontaneous combustion treatment together with the safety in production, transportation, and storage.
27 May 2022 in Journal of Thermal Analysis and Calorimetry