DataVXAdvanced Energy MaterialsPaper
journal article·2023-01Open access

Optimizing Li‐Excess Cation‐Disordered Rocksalt Cathode Design Through Partial Li Deficiency

Liliang Huang, Peichen Zhong, Yang Ha, Zijian Cai, Young‐Woon Byeon, Tzu‐Yang Huang, Yingzhi Sun, Fengyu Xie, Han‐Ming Hau, Haegyeom Kim, Mahalingam Balasubramanian, Bryan D. McCloskey, Wanli Yang, Gerbrand Ceder

Advanced Energy Materials· Volume 13· Issue 4
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Source abstract

Abstract

Abstract Li‐excess disordered rocksalts (DRXs) are emerging as promising cathode materials for Li‐ion batteries due to their ability to use earth‐abundant transition metals. In this work, a new strategy based on partial Li deficiency engineering is introduced to optimize the overall electrochemical performance of DRX cathodes. Specifically, by using Mn‐based DRX as a proof‐of‐concept, it is demonstrated that the introduction of cation vacancies during synthesis (e.g., Li1.3‐xMn2+0.4‐xMn3+xNb0.3O1.6F0.4, x = 0, 0.2, and 0.4) improves both the discharge capacity and rate performance due to the more favored short‐range order in the presence of Mn3+. Density functional theory calculations and Monte Carlo simulations, in combination with spectroscopic tools, reveal that introducing 10% vacancies (Li1.1Mn2+0.2Mn3+0.2Nb0.3O1.6F0.4) enables both Mn2+/Mn3+ redox and excellent Li percolation. However, a more aggressive vacancy doping (e.g., 20% vacancies in Li0.9Mn3+0.4Nb0.3O1.6F0.4) impairs performance because it induces phase separation between an Mn‐rich and a Li‐rich phase.
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Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Extraction and Separation Processes

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

Affiliations

Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Department of Materials Science and Engineering University of California Berkeley Berkeley CA 94720 USA

Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Department of Chemical and Biomolecular Engineering University of California Berkeley Berkeley CA 94720 USA

Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Advanced Photon Source–X‐ray Science Division Argonne National Laboratory Argonne IL 60439 USA

Funding

Office of Energy Efficiency and Renewable Energy · Vehicle Technologies Office · U.S. Department of Energy · Office of Science · Basic Energy Sciences · UC Berkeley College of Chemistry · National Science Foundation · National Energy Research Scientific Computing Center · Lawrence Berkeley National Laboratory

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