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采用液相色谱/电喷雾电离质谱和常压固体分析探头质谱研究锂离子电池中单个降解产物的鉴定及形成机制。

Identification and formation mechanism of individual degradation products in lithium-ion batteries studied by liquid chromatography/electrospray ionization mass spectrometry and atmospheric solid analysis probe mass spectrometry.

作者信息

Takeda Sahori, Morimura Wataru, Liu Yi-Hung, Sakai Tetsuo, Saito Yuria

机构信息

Research Institute of Electrochemical Energy, Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda, Osaka, 563-8577, Japan.

Department of Greenergy, National University of Tainan (NUTN), Tainan, 70005, Taiwan.

出版信息

Rapid Commun Mass Spectrom. 2016 Aug 15;30(15):1754-62. doi: 10.1002/rcm.7652.

Abstract

RATIONALE

Improvement of lithium ion batteries (LIBs) in terms of performance and robustness requires good understanding of the reaction processes. The analysis of the individual degradation products in LIB electrolytes and on the surface of the electrodes provides vital information in this regard. In this study, mass spectrometric analytical methods were utilized for the identification of the individual degradation products.

METHODS

The degradation products in the electrolytes recovered from cycle-tested cells were separated by liquid chromatography (LC) and their mass spectrometric analysis was conducted by electrospray ionization mass spectrometry (ESI-MS). For identification of degradation products on the surface of electrodes, atmospheric solid analysis probe (ASAP)-MS analysis was conducted by time-of-flight mass spectrometry with an ASAP probe and an atmospheric pressure chemical ionization source.

RESULTS

The degradation products in the electrolytes, namely carbonate oligomers and organophosphates, were identified simultaneously by LC/ESI-MS. Their formation mechanisms were estimated, which explain their different compositions at different temperatures. One degradation product was found on the anode surface by ASAP-MS, and its formation mechanism was explained similarly to those in the electrolyte.

CONCLUSIONS

The results suggest that the electrolyte degradation is correlated with the formation of a solid electrolyte interphase, which is an important factor in the performance of LIBs. We expect that further investigation of the degradation products by LC/ESI-MS and ASAP-MS will be helpful for studying their degradation processes in LIBs. Copyright © 2016 John Wiley & Sons, Ltd.

摘要

原理

要提高锂离子电池(LIBs)的性能和耐用性,需要深入了解其反应过程。分析LIB电解质和电极表面的单个降解产物能在这方面提供重要信息。在本研究中,采用质谱分析方法来识别单个降解产物。

方法

从经过循环测试的电池中回收的电解质中的降解产物通过液相色谱(LC)进行分离,并用电喷雾电离质谱(ESI-MS)进行质谱分析。为了识别电极表面的降解产物,使用带有常压固体分析探头(ASAP)和大气压化学电离源的飞行时间质谱仪进行常压固体分析探头(ASAP)-MS分析。

结果

通过LC/ESI-MS同时识别出电解质中的降解产物,即碳酸酯低聚物和有机磷酸盐。估计了它们的形成机制,这解释了它们在不同温度下的不同组成。通过ASAP-MS在阳极表面发现了一种降解产物,其形成机制与电解质中的类似。

结论

结果表明电解质降解与固体电解质界面的形成相关,这是影响LIBs性能的一个重要因素。我们预计,通过LC/ESI-MS和ASAP-MS对降解产物进行进一步研究将有助于了解它们在LIBs中的降解过程。版权所有©2016约翰威立父子有限公司。

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