Role of Fluorine in Chemomechanics of Cation-Disordered Rocksalt Cathodes

Chen, Dongchang; Zhang, Jin; Jiang, Zhisen; Wei, Chenxi; Burns, Jordan; Li, Linze; Wang, Chongmin; Persson, Kristin; Liu, Yijin; Chen, Guoying

doi:10.1021/acs.chemmater.1c02118

Role of Fluorine in Chemomechanics of Cation-Disordered Rocksalt Cathodes

Journal Article · Thu Aug 26 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c02118· OSTI ID:1839262

^[1]; Zhang, Jin ^[2]; Jiang, Zhisen ^[2]; Wei, Chenxi ^[2]; Burns, Jordan ^[3]; ^[4]; ^[4]; ^[5]; Liu, Yijin ^[2]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States)

The role of nanoscale chemomechanical behavior in the macroscopic performance of functional materials is well recognized. For lithium-ion battery cathodes, tremendous effort has been devoted to the development of new chemistry and structure, yet fundamental understanding of the correlation between redox processes and mechanical properties of the novel materials lags behind. In the present study, we prepare large discrete single grains of Li-excess cation-disordered rocksalts (DRX) and investigate their chemomechanical behavior at the particle level, using nanoresolution X-ray and electron-based spectro-imaging and chemical mapping techniques. While irregular cracking upon lithium extraction leads to the eventual breakdown of the baseline DRX oxide (Li_1.2Ti_0.4Mn_0.4O₂) particles at a high delithiation state, the fluorinated-DRX (Li_1.3Ti_0.3Mn_0.4O_1.7F_0.3) clearly displays aligned cracking along the <001> direction. The resulting periodicity in the cracking pattern enables the particles to retain their integrity and, consequently, improved electrochemical stability. Density functional theory (DFT) calculations showed that fluorination leads to increased concentration of Li+ on the (001) planes and preferential Li movements along the <001>-family directions, revealing the underlying mechanism for directional cracking. Overall, our study demonstrates the unique role of fluorine in modulating nanoscale chemomechanics, which in turn influences the evolution of charge and strain heterogeneity at the particle level. These insights provide important design guidelines in further improving DRX cathode materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC05-76RL01830

OSTI ID:: 1839262

Alternate ID(s):: OSTI ID: 1894490

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 17 Vol. 33; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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