Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization

Cao, Xia; Ren, Xiaodi; Zou, Lianfeng; Engelhard, Mark H.; Huang, William; Wang, Hansen; Matthews, Bethany E.; Lee, Hongkyung; Niu, Chaojiang; Arey, Bruce W.; Cui, Yi; Wang, Chongmin; Xiao, Jie; Liu, Jun; Xu, Wu; Zhang, Ji-Guang

doi:10.1038/s41560-019-0464-5

Title: Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization

Journal Article · 13 September 2019 · Nature Energy

DOI: https://doi.org/10.1038/s41560-019-0464-5 · OSTI ID:1573017

Cao, Xia ^[1];

^[1]; Zou, Lianfeng ^[1];

^[1];

^[2];

^[2]; Matthews, Bethany E. ^[1];

^[1];

^[1]; Arey, Bruce W. ^[1];

^[2];

^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Stanford Univ., Stanford, CA (United States)

Lithium (Li) pulverization and associated large volume expansion during cycling is one of the most critical barriers for the safe operation of Li-metal batteries. Here, we report an approach to minimize the Li pulverization using an electrolyte based on a fluorinated orthoformate solvent. The solid–electrolyte interphase (SEI) formed in this electrolyte clearly exhibits a monolithic feature, which is in sharp contrast with the widely reported mosaic- or multilayer-type SEIs that are not homogeneous and could lead to uneven Li stripping/plating and fast Li and electrolyte depletion over cycling. The highly homogeneous and amorphous SEI not only prevents dendritic Li formation, but also minimizes Li loss and volumetric expansion. Furthermore, this new electrolyte strongly suppresses the phase transformation of the LiNi_0.8Co_0.1Mn_0.1O₂ cathode (from layered structure to rock salt) and stabilizes its structure. In conclusion, tests of high-voltage Li||NMC811 cells show long-term cycling stability and high rate capability, as well as reduced safety concerns.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1573017

Report Number(s):: PNNL-SA-141828

Journal Information:: Nature Energy, Vol. 4, Issue 9; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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