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

Journal Article · Tue Jan 21 00:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b21738· OSTI ID:1601225

Wu, Jue ^[1]; Zhang, Xiaofeng ^[2]; Zheng, Shiyao ^[3]; Liu, Haodong ^[4]; Wu, Jinpeng ^[5]; Fu, Riqiang ^[6]; Li, Yixiao ^[3]; Xiang, Yuxuan ^[3]; Liu, Rui ^[3]; Zuo, Wenhua ^[3]; Cui, Zehao ^[3]; Wu, Qihui ^[7]; Wu, Shunqing ^[2]; Chen, Zonghai ^[8]; Liu, Ping ^[4]; Yang, Wanli ^[5]; Yang, Yong ^[3]

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1. Xiamen Univ., Xiamen (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
2. Xiamen Univ., Xiamen (China). Jiujiang Research Inst.
3. Xiamen Univ., Xiamen (China)
4. Univ. of California, San Diego, CA (United States)
5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
6. Florida State Univ., Tallahassee, FL (United States
7. Quanzhou Normal Univ., Quanzhou (China)
8. Argonne National Lab. (ANL), Lemont, IL (United States)

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.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
• Sponsoring Organization: National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); State of Florida; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; Xiamen University
• Grant/Contract Number: AC02-05CH11231; AC02-06CH11357
• OSTI ID: 1601225
• Alternate ID(s): OSTI ID: 1606552
• Journal Information: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 6 Vol. 12; ISSN 1944-8244
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrodes
Lattices
Li-rich oxides cathode
Oxygen
Reaction mechanisms
Redox reactions
high capacity battery
oxygen redox reaction
proton insertion
resonant inelastic X-ray scattering (RIXS)