Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides

Shaofeng Li; Zhisen Jiang; Jiaxiu Han; Zhengrui Xu; Chenxu Wang; Hai Huang; Chang Yu; Sang-Jun Lee; Piero Pianetta; Hendrik Ohldag; Jieshan Qiu; Jun-Sik Lee; Feng Lin; Kejie Zhao; Yijin Liu

doi:10.1038/s41467-020-18278-y

Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides

Nat Commun. 2020 Sep 7;11(1):4433. doi: 10.1038/s41467-020-18278-y.

Authors

Shaofeng Li^#^{1

2}, Zhisen Jiang^#¹, Jiaxiu Han^#³, Zhengrui Xu⁴, Chenxu Wang⁵, Hai Huang¹, Chang Yu², Sang-Jun Lee¹, Piero Pianetta¹, Hendrik Ohldag^{6

7

8}, Jieshan Qiu⁹, Jun-Sik Lee¹⁰, Feng Lin⁴, Kejie Zhao¹¹, Yijin Liu¹²

Affiliations

¹ Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA.
² State Key Lab of Fine Chemicals, School of Chemical Engineering, Liaoning Key Lab for Energy Materials and Chemical Engineering, Dalian University of Technology, 116024, Dalian, China.
³ School of Mechanical Engineering, Purdue University, West Lafayette, IN, 47907, USA.
⁴ Department of Chemistry, Virginia Tech, Blacksburg, VA, 24061, USA.
⁵ Department of Geological Sciences, Stanford University, Stanford, CA, 94305, USA.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁷ Department of Material Sciences and Engineering, Stanford University, Stanford, CA, 94305, USA.
⁸ Department of Physics, University of California-Santa Cruz, Santa Cruz, CA, 95064, USA.
⁹ State Key Lab of Fine Chemicals, School of Chemical Engineering, Liaoning Key Lab for Energy Materials and Chemical Engineering, Dalian University of Technology, 116024, Dalian, China. jqiu@dlut.edu.cn.
¹⁰ Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA. jslee@slac.stanford.edu.
¹¹ School of Mechanical Engineering, Purdue University, West Lafayette, IN, 47907, USA. kjzhao@purdue.edu.
¹² Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA. liuyijin@slac.stanford.edu.

^# Contributed equally.

Abstract

Surface lattice reconstruction is commonly observed in nickel-rich layered oxide battery cathode materials, causing unsatisfactory high-voltage cycling performance. However, the interplay of the surface chemistry and the bulk microstructure remains largely unexplored due to the intrinsic structural complexity and the lack of integrated diagnostic tools for a thorough investigation at complementary length scales. Herein, by combining nano-resolution X-ray probes in both soft and hard X-ray regimes, we demonstrate correlative surface chemical mapping and bulk microstructure imaging over a single charged LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) secondary particle. We reveal that the sub-particle regions with more micro cracks are associated with more severe surface degradation. A mechanism of mutual modulation between the surface chemistry and the bulk microstructure is formulated based on our experimental observations and finite element modeling. Such a surface-to-bulk reaction coupling effect is fundamentally important for the design of the next generation battery cathode materials.

Abstract

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