Tuning the Interface Stability of Nickel-Rich NCM Cathode Against Aggressive Structural Collapse via the Synergistic Effect of Additives

Luozeng Zhou; Yiwei Zheng; Tao Qian; Yupeng Gan; Yong Wang; Jinqiu Zhou; Feipeng Cai; Xi Zhou; Jie Liu; Linsen Li

doi:10.1021/acs.inorgchem.4c00269

Tuning the Interface Stability of Nickel-Rich NCM Cathode Against Aggressive Structural Collapse via the Synergistic Effect of Additives

Inorg Chem. 2024 Mar 25;63(12):5727-5733. doi: 10.1021/acs.inorgchem.4c00269. Epub 2024 Mar 12.

Authors

Luozeng Zhou^{1

2}, Yiwei Zheng³, Tao Qian⁴, Yupeng Gan², Yong Wang¹, Jinqiu Zhou⁴, Feipeng Cai⁵, Xi Zhou⁴, Jie Liu⁴, Linsen Li¹

Affiliations

¹ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
² State Key Laboratory of Space Power-sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China.
³ Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry, College of Energy, Soochow University, Suzhou 215006, China.
⁴ College of Chemistry and Chemical Engineering, Nantong University, Seyuan 9, Nantong 226019, China.
⁵ Shandong Academy of Sciences, Energy Research Institute, Qilu University of Technology, Jinan 250014, China.

PMID: 38470094
DOI: 10.1021/acs.inorgchem.4c00269

Abstract

Nickel-rich layered oxides are envisaged as one of the most promising alternative cathode materials for lithium-ion batteries, considering their capabilities to achieve ultrahigh energy density at an affordable cost. Nonetheless, with increasing Ni content in the cathodes comes a severe extent of Ni⁴⁺ redox side reactions on the interface, leading to fast capacity decay and structural stability fading over extended cycles. Herein, dual additives of bis(vinylsulfonyl)methane (BVM) and lithium difluorophosphate (LiDFP) are adopted to synergistically generate the F-, P-, and S-rich passivation layer on the cathode, and the Ni⁴⁺ activity and dissolution at high voltage are restricted. The sulfur-rich layer formed by the polymerization of BVM, combined with the Li₃PO₄ and LiF phases derived from LiDFP, alleviates the problems of increased impedance, cracks, and an irreversible H2-H3 phase transition. Consequently, the Ni-rich LiNi_xM_1-xO₂ (x > 0.95) button half-cell cycled in LiDFP + BVM electrolyte exhibits a significant discharging capacity of 181.4 mAh g^-1 at 1 C (1 C = 200 mA g^-1) with retention of 83.7% after 100 cycles, surpassing the performance of the commercial electrolyte (160.7 mAh g^-1) with retention of 53.3%. Remarkably, the NCM95||graphite pouch cell exhibits a remarkable capacity retention of 95.5% after 200 cycles. This work inspires the rational design of electrolyte additives for ultrahigh-energy batteries with nickel-rich layered oxide cathodes.