Structural regulation-induced Li-electron disentanglement for stabilized oxygen redox of Li-excess disordered rock-salt cathode materials

Jiao, Sichen; Sun, Yujian; Shi, Dekai; Zhang, Yuanpeng; Wang, Xuelong; Liu, Jue; Kang, Le; Wang, Fangwei; Yu, Xiqian; Li, Hong; Chen, Liquan; Huang, Xuejie

doi:10.1039/d4ee00638k

Structural regulation-induced Li-electron disentanglement for stabilized oxygen redox of Li-excess disordered rock-salt cathode materials

Journal Article · Tue Jun 18 00:00:00 EDT 2024 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d4ee00638k· OSTI ID:2476598

Jiao, Sichen ^[1]; Sun, Yujian ^[1]; Shi, Dekai ^[1]; Zhang, Yuanpeng ^[2]; Wang, Xuelong ^[3]; ^[4]; Kang, Le ^[5]; Wang, Fangwei ^[6]; ^[1]; ^[1]; Chen, Liquan ^[3]; ^[3]

Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)
Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
Chinese Academy of Sciences (CAS), Beijing (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP); Spallation Neutron Source Science Center, Dongguan (China)
University of Chinese Academy of Sciences, Beijing (China)

Since the discovery of its electrochemical activity, Li-excess disordered rock-salt (DRX) cathode material has received worldwide attention as it sets up a new way to exploit oxygen redox beyond the conventional layered structure with late-3d transition metals. However, the intricate structure-function relationship in the disordered lattice of the DRX material fogs the researcher's lens on the underlying redox mechanisms. Here, in this study, we employ a synergistic approach combining neutron total scattering with reverse Monte Carlo modeling and density functional theory calculations to unravel the landscape of oxygen redox reactions in DRX. Redox activities are evaluated in diverse oxygen clusters (OLi_xTM_6-x) and the spatial distribution of these clusters in the model DRX structure (Li_1.16Ti_0.37Ni_0.37Nb_0.1O₂ and Li_1.2Ti_0.35Ni_0.35Nb_0.1O_1.8F_0.2) is explicitly determined. The results unveil that by regulating the short-range ordering between cations, fluorine atoms can effectively decouple the location of Li extraction and electron depletion. Such disentanglement between the Li reservoir and electron reservoir in the DRX lattice could play a pivotal role in protecting the oxidized oxygen and preserving the lattice framework during cycling. Through a tentatively designed non-fluorinated DRX oxide realizing similar Li-electron decoupling, an obvious enhancement of the cycling capability can be achieved without compromising the capacity release.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Key Research and Development Program of China; National Natural Science Foundation of China; National Natural Science Foundation of China (NSFC); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2476598

Alternate ID(s):: OSTI ID: 2377844
OSTI ID: 2574875

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 14 Vol. 17; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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