A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides

Tao Yuan; Siqing Li; Yuanyuan Sun; Jeng-Han Wang; An-Jie Chen; Qinfeng Zheng; Yixiao Zhang; Liwei Chen; Gyutae Nam; Haiying Che; Junhe Yang; Shiyou Zheng; Zi-Feng Ma; Meilin Liu

doi:10.1021/acsnano.2c04702

A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides

ACS Nano. 2022 Nov 22;16(11):18058-18070. doi: 10.1021/acsnano.2c04702. Epub 2022 Oct 19.

Authors

Tao Yuan^{1

2}, Siqing Li¹, Yuanyuan Sun¹, Jeng-Han Wang³, An-Jie Chen³, Qinfeng Zheng⁴, Yixiao Zhang⁴, Liwei Chen⁴, Gyutae Nam², Haiying Che^{5

6}, Junhe Yang¹, Shiyou Zheng¹, Zi-Feng Ma^{5

6}, Meilin Liu²

Affiliations

¹ School of Materials and Chemistry, University of Shanghai for Science & Technology, Shanghai 200093, China.
² School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States.
³ Department of Chemistry, National Taiwan Normal University, 88, Sec. 4 Ting-Zhou Road, Taipei 11677, Taiwan R.O.C.
⁴ School of Chemistry and Chemical Engineering, In Situ Center for Physical Sciences, Shanghai Electrochemical Energy Device Research Center (SEED), Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, China.
⁵ Shanghai Electrochemical Energy Devices Research Center, Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
⁶ Zhejiang Natrium Energy Co., Ltd., Shaoxing 312000, China.

PMID: 36259968
DOI: 10.1021/acsnano.2c04702

Abstract

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na⁺ diffusion channels and complicated phase evolution during Na⁺ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi_0.5Mn_0.5-xSb_xO₂ (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na⁺ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na⁺ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g^-1 at 0.2 C and 74.5 mAh g^-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

Keywords: NaNi0.5Mn0.5O2; O3-type; Sb doping; layered oxide cathode; sodium-ion battery.