journal article·2020-02-12Open access

Tuning Oxygen Redox Reaction through the Inductive Effect with Proton Insertion in Li-Rich Oxides

Jue Wu, Xiaofeng Zhang, Shiyao Zheng, Haodong Liu, Jinpeng Wu, Riqiang Fu, Yixiao Li, Yuxuan Xiang, Rui Liu, Wenhua Zuo, Zehao Cui, Qihui Wu, Shunqing Wu, Zonghai Chen, Ping Liu, Wanli Yang, Yong Yang

Abstract

As a parent compound of Li-rich electrodes, Li2MnO3 exhibits high capacity during the initial charge; however, it suffers notoriously low Coulombic efficiency due to oxygen and surface activities. Here, we successfully optimize the oxygen activities toward reversible oxygen redox reactions by intentionally introducing protons into lithium octahedral vacancies in the Li2MnO3 system with its original structural integrity maintained. Combining structural probes, theoretical calculations, and resonant inelastic X-ray scattering results, a moderate coupling between the introduced protons and lattice oxygen at the oxidized state is revealed, which stabilizes the oxygen activities during charging. Such a coupling leads to an unprecedented initial Coulombic efficiency (99.2%) with a greatly improved discharge capacity of 302 mAh g–1 in the protonated Li2MnO3 electrodes. These findings directly demonstrate an effective concept for controlling oxygen activities in Li-rich systems, which is critical for developing high-energy cathodes in batteries.
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Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Advanced Memory and Neural Computing

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

Affiliations

State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, and College of Energy, Xiamen University, Xiamen 361005, China

Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, United States

Department of Physics, Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Key Laboratory of Low Dimensional Condensed Matter Physics (Department of Education of Fujian Province), and Jiujiang Research Institute, Xiamen University, Xiamen 361005, China

Department of NanoEngineering, University of California, San Diego, La Jolla, California 92093, United States

National High Magnetic Field Laboratory, Florida State University, 1800 E. Paul Dirac Drive, Tallahassee, Florida 32310, United States

Department of Materials Chemistry, School of Chemical Engineering of Materials Science, Quanzhou Normal University, Quanzhou 362000, China

Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States

Funding

Ministry of Science and Technology of the People's Republic of China · Energy Biosciences Institute · National Natural Science Foundation of China · Xiamen University · College of Chemistry and Chemical Engineering, Xiamen Universit

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