Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was perf...Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate (EC)/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface (SEI) film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.展开更多
随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完...随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完善有十分重要的意义。基于此,该文通过容量增量曲线对电池容量衰减的内因展开分析;在不同影响因素下自放电过程中电池阻抗谱变化规律的基础上,利用弛豫时间分布法进行理论原理分析;最后,在电池自放电老化过程的原理推导的基础上总结电池容量衰减量随时间的变化规律,并结合实验数据建立不同影响因素下电池容量衰减模型。结果表明,在存储过程中,电池的固体电解质界面(solid electrolyte interface,SEI)膜内阻增大,且存储温度越高、初始充电状态(state of charge,SOC)越大,相应的阻抗增加幅度越大。自放电过程电池老化主要原因是可循环活性锂离子的消耗和SEI膜的生长。同时该文推导出电池容量损失与时间近似呈0.5次方关系,并利用实验数据拟合得到电池在不同初始SOC和不同存储温度影响下的容量变化模型,为锂电池寿命模型预测提供更进一步的参考。展开更多
研究四氟硼酸锂(LiBF_4)和二氟草酸硼酸锂(LiODFB)混合锂盐电解液用于磷酸铁锂(LiFePO4)锂离子电池时的低温-20℃性能。探讨电导率与电解液组成、温度的关系;通过循环伏安、充放电、倍率性能及电化学阻抗谱(EIS)测试,比较不同电解液体系...研究四氟硼酸锂(LiBF_4)和二氟草酸硼酸锂(LiODFB)混合锂盐电解液用于磷酸铁锂(LiFePO4)锂离子电池时的低温-20℃性能。探讨电导率与电解液组成、温度的关系;通过循环伏安、充放电、倍率性能及电化学阻抗谱(EIS)测试,比较不同电解液体系中LiFePO_4正极在25℃和-20℃的放电比容量、循环稳定性等。在25℃和-20℃下于2.5~4.2 V充放电,LiFePO_4电极在LiBF_4/Li ODFB基电解液体系中的电化学性能较好:在25℃时以1.0 C倍率充放电,混合盐基电解液电池的首次放电比容量为140 m Ah/g,优于六氟磷酸锂(Li PF6)基电解液的130.5 m Ah/g;-20℃时0.1 C倍率下,首次放电比容量为101.7 m Ah/g,100次循环的容量保持率为86.62%,优于Li PF6基电解液的97.4 m Ah/g和60.57%。展开更多
基金Project(2007BAE12B01) supported by the National Key Technology Research and Development Program of ChinaProject(20803095) supported by the National Natural Science Foundation of China
文摘Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate (EC)/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface (SEI) film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.
文摘随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完善有十分重要的意义。基于此,该文通过容量增量曲线对电池容量衰减的内因展开分析;在不同影响因素下自放电过程中电池阻抗谱变化规律的基础上,利用弛豫时间分布法进行理论原理分析;最后,在电池自放电老化过程的原理推导的基础上总结电池容量衰减量随时间的变化规律,并结合实验数据建立不同影响因素下电池容量衰减模型。结果表明,在存储过程中,电池的固体电解质界面(solid electrolyte interface,SEI)膜内阻增大,且存储温度越高、初始充电状态(state of charge,SOC)越大,相应的阻抗增加幅度越大。自放电过程电池老化主要原因是可循环活性锂离子的消耗和SEI膜的生长。同时该文推导出电池容量损失与时间近似呈0.5次方关系,并利用实验数据拟合得到电池在不同初始SOC和不同存储温度影响下的容量变化模型,为锂电池寿命模型预测提供更进一步的参考。
文摘研究四氟硼酸锂(LiBF_4)和二氟草酸硼酸锂(LiODFB)混合锂盐电解液用于磷酸铁锂(LiFePO4)锂离子电池时的低温-20℃性能。探讨电导率与电解液组成、温度的关系;通过循环伏安、充放电、倍率性能及电化学阻抗谱(EIS)测试,比较不同电解液体系中LiFePO_4正极在25℃和-20℃的放电比容量、循环稳定性等。在25℃和-20℃下于2.5~4.2 V充放电,LiFePO_4电极在LiBF_4/Li ODFB基电解液体系中的电化学性能较好:在25℃时以1.0 C倍率充放电,混合盐基电解液电池的首次放电比容量为140 m Ah/g,优于六氟磷酸锂(Li PF6)基电解液的130.5 m Ah/g;-20℃时0.1 C倍率下,首次放电比容量为101.7 m Ah/g,100次循环的容量保持率为86.62%,优于Li PF6基电解液的97.4 m Ah/g和60.57%。
