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基于氧化锂的阴极中的界面反应,取决于电极中的粘结剂和电解质中的盐。

Interfacial reactions in lithia-based cathodes depending on the binder in the electrode and salt in the electrolyte.

作者信息

Im Hee Jeong, Park Yong Joon

机构信息

Department of Advanced Materials Engineering, Kyonggi University, 154-42, Gwanggyosan-Ro, Yeongtong-Gu, Suwon-Si, Gyeonggi-Do, 16227, Republic of Korea.

出版信息

Sci Rep. 2022 Jan 11;12(1):527. doi: 10.1038/s41598-021-04439-6.

Abstract

Lithia (LiO)-based cathodes, utilizing oxygen redox reactions for obtaining capacity, exhibit higher capacity than commercial cathodes. However, they are highly reactive owing to superoxides formed during charging, and they enable more active parasitic (side) reactions at the cathode/electrolyte and cathode/binder interfaces than conventional cathodes. This causes deterioration of the electrochemical performance limiting commercialization. To address these issues, the binder and salt for electrolyte were replaced in this study to reduce the side reaction of the cells containing lithia-based cathodes. The commercially used polyvinylidene fluoride (PVDF) binder and LiPF salt in the electrolyte easily generate such reactions, and the subsequent reaction between PVDF and LiOH (from decomposition of lithia) causes slurry gelation and agglomeration of particles in the electrode. Moreover, the fluoride ions from PVDF promote side reactions, and LiPF salt forms POF and HF, which cause side reactions owing to hydrolysis in organic solvents containing water. However, the polyacrylonitrile (PAN) binder and LiTFSI salt decrease these side reactions owing to their high stability with lithia-based cathode. Further, thickness of the interfacial layer was reduced, resulting in decreased impedance value of cells containing lithia-based cathodes. Consequently, for the same lithia-based cathodes, available capacity and cyclic performance were increased owing to the effects of PAN binder and LiTFSI salt in the electrolyte.

摘要

基于氧化锂(LiO)的阴极利用氧氧化还原反应来获得容量,其表现出比商业阴极更高的容量。然而,由于充电过程中形成的超氧化物,它们具有高反应活性,并且与传统阴极相比,它们在阴极/电解质和阴极/粘结剂界面处会引发更活跃的寄生(副)反应。这导致电化学性能恶化,限制了商业化。为了解决这些问题,本研究中更换了电解质的粘结剂和盐,以减少含氧化锂基阴极的电池的副反应。商业上使用的聚偏二氟乙烯(PVDF)粘结剂和电解质中的LiPF盐很容易产生此类反应,并且PVDF与LiOH(来自氧化锂的分解)之间的后续反应会导致浆料凝胶化和电极中颗粒的团聚。此外,PVDF中的氟离子会促进副反应,LiPF盐会形成POF和HF,它们在含有水的有机溶剂中由于水解而导致副反应。然而,聚丙烯腈(PAN)粘结剂和LiTFSI盐由于与氧化锂基阴极具有高稳定性而减少了这些副反应。此外,界面层的厚度减小,导致含氧化锂基阴极的电池的阻抗值降低。因此,对于相同的氧化锂基阴极,由于电解质中PAN粘结剂和LiTFSI盐的作用,可用容量和循环性能得到了提高。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d363/8752660/f48e3e73f736/41598_2021_4439_Fig1_HTML.jpg

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