Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy

Xing Ou; Tongchao Liu; Wentao Zhong; Xinming Fan; Xueyi Guo; Xiaojing Huang; Liang Cao; Junhua Hu; Bao Zhang; Yong S Chu; Guorong Hu; Zhang Lin; Mouad Dahbi; Jones Alami; Khalil Amine; Chenghao Yang; Jun Lu

doi:10.1038/s41467-022-30020-4

Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy

Nat Commun. 2022 Apr 28;13(1):2319. doi: 10.1038/s41467-022-30020-4.

Authors

Xing Ou^#^{1

2}, Tongchao Liu^#³, Wentao Zhong¹, Xinming Fan⁴, Xueyi Guo², Xiaojing Huang⁵, Liang Cao^{1

2}, Junhua Hu⁶, Bao Zhang², Yong S Chu⁵, Guorong Hu², Zhang Lin², Mouad Dahbi⁷, Jones Alami⁷, Khalil Amine⁸, Chenghao Yang⁹, Jun Lu¹⁰

Affiliations

¹ Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou, 510006, China.
² School of Metallurgy and Environment, Central South University, Changsha, 410083, China.
³ Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States.
⁴ School of Metallurgy and Environment, Central South University, Changsha, 410083, China. fanxinming@csu.edu.cn.
⁵ National Synchrotron Light source II, Brookhaven National Laboratory, Upton, NY, 11973, United States.
⁶ School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450001, China.
⁷ Materials Science and Nano-Engineering Department, Mohammed VI Polytechnic University, Ben Guerir, Morocco.
⁸ Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States. amine@anl.gov.
⁹ Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou, 510006, China. esyangc@scut.edu.cn.
¹⁰ Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States. junlu@anl.gov.

^# Contributed equally.

Abstract

High-capacity Ni-rich layered oxides are promising cathode materials for secondary lithium-based battery systems. However, their structural instability detrimentally affects the battery performance during cell cycling. Here, we report an Al/Zr co-doped single-crystalline LiNi_0.88Co_0.09Mn_0.03O₂ (SNCM) cathode material to circumvent the instability issue. We found that soluble Al ions are adequately incorporated in the SNCM lattice while the less soluble Zr ions are prone to aggregate in the outer SNCM surface layer. The synergistic effect of Al/Zr co-doping in SNCM lattice improve the Li-ion mobility, relief the internal strain, and suppress the Li/Ni cation mixing upon cycling at high cut-off voltage. These features improve the cathode rate capability and structural stabilization during prolonged cell cycling. In particular, the Zr-rich surface enables the formation of stable cathode-electrolyte interphase, which prevent SNCM from unwanted reactions with the non-aqueous fluorinated liquid electrolyte solution and avoid Ni dissolution. To prove the practical application of the Al/Zr co-doped SNCM, we assembled a 10.8 Ah pouch cell (using a 100 μm thick Li metal anode) capable of delivering initial specific energy of 504.5 Wh kg^-1 at 0.1 C and 25 °C.