Constraining Interlayer Slipping in P2-Type Layered Oxides with Oxygen Redox by Constructing Strong Covalent Bonds

Cai, Xinyin [Shanghai Jiao Tong Univ. (China)]; Shadike, Zulipiya [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000191407495); Wang, Nan [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000224500689); Li, Xun-Lu [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000278003565); Wang, Yong [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000204968700); Zheng, Qinfeng [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000266703919); Zhang, Yixiao [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000228073936); Lin, Weixiao [Wuhan Univ. of Technology (China)]; Li, Linsen [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000211059070); Chen, Liwei [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000341609771); Shen, Shuiyun [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000324557914); Hu, Enyuan [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000218814534); Zhou, Yong-Ning [Fudan Univ., Shanghai (China)] (ORCID:0000000297913468); Zhang, Junliang [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000323709699)

doi:10.1021/jacs.4c14587

DOE OSTI · 2527297

Constraining Interlayer Slipping in P2-Type Layered Oxides with Oxygen Redox by Constructing Strong Covalent Bonds

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Abstract

Lattice oxygen redox (LOR) in P2-type layered oxides is an effective strategy to break through the limit of energy density of conventional cathodes due to its high redox potential (>4 V vs. Na + /Na) as well as extra capacity. Nevertheless, LOR induced local structure distortion and irreversible phase transitions cause serious electrochemical performance degradation, hindering the practical applications. In this work, we propose that the generation of the OP4 phase can be replaced with the Z phase by introducing Sb element with higher ionic potential and strong covalent bonds within the TMO 6 octahedron. Z phase transition is realized by constraining interlayer slipping between adjacent TM layers compared to OP4, which reduces the strain in the layered structure, lowers the Na+ diffusion energy barrier and creates more efficient Na+ diffusion channels. Consequently, Sb-substituted oxides demonstrates excellent kinetics, rate capability (79 mAh g -1 at 1 A g -1 ) in half cell and a high energy density of 487 Wh kg -1 (on cathode) in full cell.

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25 ENERGY STORAGE Zn batteries aqueous batteries covalent bond identification of optimal crystallographic plane interlayer slipping oxygen redox phase transition suppressing metal corrosion sustainable energy

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Cai, Xinyin [Shanghai Jiao Tong Univ. (China)], Shadike, Zulipiya [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000191407495), Wang, Nan [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000224500689), Li, Xun-Lu [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000278003565), Wang, Yong [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000204968700), Zheng, Qinfeng [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000266703919), Zhang, Yixiao [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000228073936), Lin, Weixiao [Wuhan Univ. of Technology (China)], Li, Linsen [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000211059070), Chen, Liwei [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000341609771), Shen, Shuiyun [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000324557914), Hu, Enyuan [Brookhaven National Laboratory (BNL), Upton, NY (United States)] (ORCID:0000000218814534), Zhou, Yong-Ning [Fudan Univ., Shanghai (China)] (ORCID:0000000297913468), Zhang, Junliang [Shanghai Jiao Tong Univ. (China)] (ORCID:0000000323709699). 2025-02-05. Constraining Interlayer Slipping in P2-Type Layered Oxides with Oxygen Redox by Constructing Strong Covalent Bonds. https://doi.org/10.1021/jacs.4c14587

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