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Synergistic strategy of surface-induced spinel structure and f doping to improve the electrochemical performance of Li-rich cathodes

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Progress in Natural Science:Materials International 2024年第3期34卷 524-531页

作者： Yuezhen Wang Ningbo Qin Xun Yuan Shiming Qiu fangli Ji Ruirui Tuo Tingfeng Guan Cheng Yang Jiang Zhu Miao Ge Hui Wang Yan Cheng Zhaozhe Yu Guangxi Key Laboratory of Manufacturing Systems and Advanced Manufacturing Technology Guilin University of Electronic Technology Guangxi Institute of Science and Technology Development Co. Ltd. Guangxi CNGR New Energy Science & Technology Co. Ltd. Guangxi Key Laboratory for High-value Utilization of Manganese Resources Guangxi Minzu Normal University

Li-rich Mn-based materials provide higher capacity than commercial NCM layered materials due to the synergistic redox effect of cations and anions. However, lattice straining and structural collapse caused by the irreversible oxygen release at high voltage range during cycling, which results in severe capacity and voltage decay. Herein, a synergistic strategy of surface-induced spinel structure and f doping is provided to improve the structural stability. The surface spinel structure helps to reduce the structural collapse caused by electrolyte corrosion on the cathode and effectively inhibits voltage decay resulted from structural evolution. The stronger Mn-f bonds are formed by f doping to inhibit migration of transition metal(TM) and induce the uniform deposition of Li f to form the thinner and more stable CEI on the cathode. Accordingly, the designed cathode(LMNO-Nf) shows remarkable cycling performance with the capacity retention of 86.68 % and voltage retention of 96.6 % for 200 cycles at 1C,higher than pristine material(68.76 % and 85.75 %). Therefore, this simple dual-modification strategy of one-step synthesis is promising for solving the structural evolution and voltage decay of Li-rich Mn-based cathode materials effectively, achieving further commercialization.

关键词： f doping High cycling stability Li-rich Mn-Based cathode Surface-induced spinel structure Synergistic strategy

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A robust fluorine-containing ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells

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Journal of Energy Chemistry 2023年第2期77卷 300-309,I0008页

作者： Shaowei Zhang Chengyue Yang Yunan Jiang Ping Li Changrong Xia CAS Key Laboratory of Materials for Energy Conversion Department of Materials Science and EngineeringUniversity of Science and Technology of ChinaHefei 2300026AnhuiChina School of Energy and Power Engineering Nanjing University of Aeronautics and AstronauticsNanjing 210016JiangsuChina Energy Materials Center Anhui Estone Materials Technology Co.LtdHefei 230088AnhuiChina

Stro ntium-doped lanthanum ferrite(LSf)is a potential ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells(SOECs),but its application is limited by insufficient catalytic activity and stability in CO_(2)-containing atmospheres.Herein,a novel strategy is proposed to enhance the electrolytic performance as well as chemical stability,achieved by doping f into the O-site of the perovskite LSf.doping f does not change the phase structure but reduces the cell volume and improves the chemical stability in a CO_(2)-rich atmosphere.Importantly,f doping favors oxygen vacancy formation,increases oxygen vacancy concentration,and enhances the CO_(2) adsorption capability.Meanwhile,doping with f greatly improves the kinetics of the CO_(2) reduction reaction.for example,kchem increases by 78%from3.49×10^(-4) cm s^(-1) to 6.24×10^(-4) cm s^(-1),and Dchem doubles from 4.68×10^(-5) cm^(2) s^(-1) to 9.45×10^(-5)cm^(2) s^(-1).Consequently,doping f significantly increases the electrochemical performance,such as reducing R_(p) by 52.2%from 0.226Ωcm^(2) to 0.108Ωcm^(2) at 800℃.As a result,the single cell with the fcontaining cathode exhibits an extremely high current density of 2.58 A cm^(-2) at 800℃and 1.5 V,as well as excellent durability over 200 h for direct CO_(2) electrolysis in SOECs.

关键词： Solid oxide electrolysis cell CO_(2)electrolysis Ceramic cathode f doping Strontium-doped lanthanum ferrite

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fluorine-induced dual defects in NiP_(2) anode with robust sodium storage performance

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Nano Research 2022年第3期15卷 2147-2156页

作者： Liang Wu Lifeng Wang Xiaolong Cheng Mingze Ma Ying Wu Xiaojun Wu Hengpan Yang Yan Yu Chuanxin He College of Chemistry and Environmental Engineering Shenzhen UniversityShenzhen 518060China College of Physics and Optoelectronic Engineering Shenzhen UniversityShenzhen 518060China Hefei National Laboratory for Physical Sciences at the Microscale Department of Materials Science and EngineeringCAS Key Laboratory of Materials for Energy ConversionUniversity of Science and Technology of ChinaHefei 230026China

Metal phosphides have shown great application potential as anode for sodium-ion batteries(NIBs)owing to high theoretical capacity,suitable operation voltage and abundant resource.Unfortunately,the application of NiP_(2) anode is severely impeded by low practical capacity and fast capacity decay due to the huge volume variation and low reactivity of internal phosphorus(P)component towards Na^(+).Herein,electronic structure modulation of NiP_(2) via heteroatoms doping and introducing vacancies defects to enhance Na+adsorption sites and diffusion kinetics is successfully attempted.The as-synthesized three-dimensional(3D)bicontinuous carbon matrix decorated with well-dispersed fluorine(f)-doped NiP_(2) nanoparticles(f-NiP_(2)@carbon nanosheets)delivers a high reversible capacity(585 mAh·g^(−1) at 0.1 A·g^(−1))and excellent long cycling stability(244 mAh·g^(−1) over 1,000 cycles at 2 A·g^(−1))when tested as anode in NIBs.Density functional theory(DfT)calculations reveal that f doping in NiP_(2) induces the formation of P vacancies with increased Na+adsorption energy and accelerates the alloying of internal P component.The f-NiP_(2)@carbon nanosheets//Na_(3)V_(2)(PO_(4))_(3) full cell is evaluated showing stable long cycling life.The heteroatoms doping-induced dual defects strategy opens up a new way of metal phosphides for sodium storage.

关键词： NiP_(2) electronic structure modulation f doping P vacancies dual defects sodium-ion batteries

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