Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO_2 to 4.6 V

Ning Qin; Qingmeng Gan; Zhaofeng ZhuangYanfang WangYingzhi LiZhiqiang LiIftikhar HussainChun ZengGuiyu LiuYunfei BaiKaili ZhangZhouguang Lu

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Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO_2 to 4.6 V

机译：Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO_2 to 4.6 V

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It is highly desirable to raise the charge cutoff voltage to realize the potentialof LiCoO_2 (LCO) with its ultra-high theoretical capacity of 275 mAh g~(-1). However,rapid fading due to structure collapse caused by the formation of theH1-3 metastable phase and the release of surface lattice oxygen has largelyhindered the operation of LCO under voltages of higher than 4.55 V. Here,stable cycling of LCO at 4.6 V through hierarchical doping engineering withinert P-outside and active Ni-inside dual doping is achieved. This ingeniousoutside-in structure design enables Ni~(2+) occupation in the Li layer in the bulklayered phase and P gradient doping at the superficial lattice. Compared withthe conventional inert element substitution strategy, the doped active Ni~(2+)can not only serve as a “pillar” to restrain the formation of the metastableH1-3 phase, but also regulate the electronic structure of LCO and trigger thesuperexchange interaction of Ni~(2+)-O-Co~(4+), together with strong P–O coordinationto substantially suppress the lattice oxygen escape from the surface.Therefore, it considerably reduces the risk of layer structure collapse andconsequently achieves stable and high-capacity operation over 4.6 V. Thishierarchical outside-in doping strategy may serve as inspiration for stabilizinghigh energy electrode materials working under high voltages.

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来源
《Advanced energy materials》 |2022年第31期|2201549.1-2201549.11|共11页
作者
Ning Qin; Qingmeng Gan; Zhaofeng ZhuangYanfang WangYingzhi LiZhiqiang LiIftikhar HussainChun ZengGuiyu LiuYunfei BaiKaili ZhangZhouguang Lu;
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作者单位

Department of Materials Science and EngineeringShenzhen Key Laboratory of Interfacial Science and Engineering ofMaterialsSouthern University of Science and TechnologyShenzhen 518055, P. R. China Department of Mechanical EngineeringCity University of Hong;

Department of Materials Science and EngineeringShenzhen Key Laboratory of Interfacial Science and Engineering ofMaterialsSouthern University of Science and TechnologyShenzhen 518055, P. R. China;

Department of Mechanical EngineeringCity University of Hong Kong83 Tat Chee Avenue, Hong Kong 999077, P. R. China;

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正文语种英语
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hierarchical doping; high voltage cathodes; lithium cobalt oxide; lithium-ion batteries; metastable structure stabilization;

Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO_2 to 4.6 V

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