首页|Manipulating Na occupation and constructing protective film of P2-Na0.67Ni0.33Mn0.67O2 as long-term cycle stability cathode for sodium-ion batteries

Manipulating Na occupation and constructing protective film of P2-Na0.67Ni0.33Mn0.67O2 as long-term cycle stability cathode for sodium-ion batteries

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P2-Na0.67Ni0.33Mn0.67O2(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O2 phase transforma-tion,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabiliza-tion are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and intro-ducing lithium difluorophosp(LiPO2F2)film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Naf at Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na0.67Ni0.28Zn0.05Mn0.62Ti0.05O2(NNZMTO).Meanwhile,the LiPO2F2 additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mech-anism of NNZMTO with LiPO2F2 additive.As a result,the NNZMTO displays outstanding capacity reten-tion of 94.44％after 500 cycles at 1C with 0.3 wt％LiPO2F2,excellent rate performance of 92.5 mA h g-1 at 8C with 0.1 wt％LiPO2F2,and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.

Layered cathodeZn/Ti co-dopingNa occupationElectrolyte additiveSodium-ion batteries

Yiran Sun、Pengfei Zhou、Siyu Liu、Zhongjun Zhao、Yihao Pan、Xiangyan Shen、Xiaozhong Wu、Jinping Zhao、Junying Weng、Jin Zhou

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School of Chemistry and Chemical Engineering,Shandong University of Technology,Zibo 0255000,Shandong,China

School of Materials Science and Engineering,Shandong University of Technology,Zibo 255049,Shandong,China

Natural Science Foundation of Shandong ProvinceNatural Science Foundation of Shandong ProvinceNatural Science Foundation of Shandong ProvinceNatural Science Foundation of Shandong ProvinceNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaTaishan Scholar Foundation

ZR2023MB017ZR2021QB055ZR2020QB014ZR2022JQ102190114622078179252007110tsqn201812063

2024

10.1016/j.jechem.2023.09.042

能源化学
中国科学院大连化学物理研究所 中国科学院成都有机化学研究所

能源化学

CSTPCDEI
影响因子：0.654
ISSN：2095-4956
年,卷(期)：2024.88(1)
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