DataVXAdvanced SciencePaper
journal article·2023-03Open access

Oxygen Anion Redox Chemistry Correlated with Spin State in Ni‐Rich Layered Cathodes

Zhihua Lu, Jicheng Zhang, Qinghua Zhang, Deniz Wong, Wen Yin, Nian Zhang, Zhongjun Chen, Lin Gu, Zhongbo Hu, Xiangfeng Liu

Advanced Science· Volume 10· Issue 9
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Source abstract

Abstract

Abstract Despite the low cost and high capacity of Ni‐rich layered oxides (NRLOs), their widespread implementation in electric vehicles is hindered by capacity decay and O release. These issues originate from chemo‐mechanical heterogeneity, which is mainly related to oxygen anion redox (OAR). However, what to tune regarding OAR in NRLOs and how to tune it remains unknown. In this study, a close correlation between the OAR chemistry and Li/Ni antisite defects is revealed. Experiments and calculations show the opposite effects of aggregative and dispersive Li/Ni antisite defects on the NiO6 configuration and Ni spin state in NRLOs. The resulting broad or narrow spans for the energy bands caused by spin states lead to different OAR chemistries. By tuning the Li/Ni antisite defects to be dispersive rather than aggregative, the threshold voltage for triggering OAR is obviously elevated, and the generation of bulk‐O2‐like species and O2 release at phase transition nodes is fundamentally restrained. The OAR is regulated from irreversible to reversible, fundamentally addressing structural degradation and heterogeneity. This study reveals the interaction of the Li/Ni antisite defect/OAR chemistry/chemo‐mechanical heterogeneity and presents some insights into the design of high‐performance NRLO cathodes.
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Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Supercapacitor Materials and Fabrication

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Center of Materials Science and Optoelectronics Engineering College of Materials Science and Optoelectronic Technology University of Chinese Academy of Sciences Beijing 100049 P. R. China

Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of Science Beijing 100190 P. R. China

Dynamics and Transport in Quantum Materials Helmholtz‐Zentrum Berlin für Materialen und Energie Albert‐Einstein‐Strasse 15 12489 Berlin Germany

Spallation Neutron Source Science Center Dongguan 523803 P. R. China

Shanghai Institute of Microsystem and Information Technology Chinese Academy of Sciences Shanghai 200050 P. R. China

Lirong Zheng Beijing Synchrotron Radiation Facility Institute of High Energy Physics Chinese Academy of Sciences Beijing 100049 China

CAS Center for Excellence in Topological Quantum Computation University of Chinese Academy of Sciences Beijing 100190 China

Funding

National Natural Science Foundation of China · Natural Science Foundation of Beijing Municipality · China Postdoctoral Science Foundation · Fundamental Research Funds for the Central Universities

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