Homeostatic Solid Solution in Layered Transition-Metal Oxide Cathodes of Sodium-Ion Batteries

Meng Ren; Shuo Zhao; Suning Gao; Tong Zhang; Machuan Hou; Wei Zhang; Kun Feng; Jun Zhong; Weibo Hua; Sylvio Indris; Kai Zhang; Jun Chen; Fujun Li

doi:10.1021/jacs.2c09725

Homeostatic Solid Solution in Layered Transition-Metal Oxide Cathodes of Sodium-Ion Batteries

J Am Chem Soc. 2023 Jan 11;145(1):224-233. doi: 10.1021/jacs.2c09725. Epub 2022 Dec 23.

Authors

Meng Ren¹, Shuo Zhao¹, Suning Gao¹, Tong Zhang¹, Machuan Hou¹, Wei Zhang¹, Kun Feng², Jun Zhong², Weibo Hua³, Sylvio Indris³, Kai Zhang^{1

4}, Jun Chen^{1

4}, Fujun Li^{1

4}

Affiliations

¹ Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071, China.
² Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China.
³ Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen D-76344, Germany.
⁴ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China.

PMID: 36562472
DOI: 10.1021/jacs.2c09725

Abstract

Two-phase transformation reaction is ubiquitous in solid-state electrochemistry; however, it usually involves inferior structure rearrangement upon extraction and insertion of large-sized Na⁺, thus leading to severe local strain, cracks, and capacity decay in sodium-ion batteries (SIBs). Here, a homeostatic solid solution reaction is reported in the layered cathode material P'2-Na_0.653Ni_0.081Mn_0.799Ti_0.120O₂ during sodiation and desodiation. It is induced by the synergistic incorporation of Ni and Ti for the reinforced O(2p)-Mn(3d-e_g*) hybridization, which leads to mitigated Jahn-Teller distortion of MnO₆ octahedra, contracted transition-metal oxide slabs, and enlarged Na layer spacings. The thermodynamically favorable solid solution pathway rewards the SIBs with excellent cycling stability (87.2% capacity retention after 500 cycles) and rate performance (100.5 mA h g^-1 at 2500 mA g^-1). The demonstrated reaction pathway will open a new avenue for rational designing of cathode materials for SIBs and beyond.