Elucidation of Anionic and Cationic Redox Reactions in a Prototype Sodium-Layered Oxide Cathode

Cheng, Chen; Li, Siyuan; Liu, Tiefeng; Xia, Yujian; Chang, Lo-Yueh; Yan, Yingying; Ding, Manling; Hu, Yue; Wu, Jinpeng; Guo, Jinghua; Zhang, Liang

doi:10.1021/acsami.9b13013

Title: Elucidation of Anionic and Cationic Redox Reactions in a Prototype Sodium-Layered Oxide Cathode

Journal Article · Fri Oct 11 00:00:00 EDT 2019 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b13013· OSTI ID:1780731

Cheng, Chen ^[1]; Li, Siyuan ^[2]; Liu, Tiefeng ^[2]; Xia, Yujian ^[1]; Chang, Lo-Yueh ^[1]; Yan, Yingying ^[1]; Ding, Manling ^[1]; Hu, Yue ^[1]; Wu, Jinpeng ^[3];

^[4];

^[1]

Soochow Univ., Suzhou (China). Inst. of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Lab. for Carbon-Based Functional Materials & Devices, Joint International Research Lab. of Carbon-Based Functional Materials and Devices
Zhejiang Univ. of Technology, Hangzhou (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Santa Cruz, CA (United States)

The ever-increasing demand for large-scale energy storage has driven the prosperous investigation of sodium-ion batteries (NIBs). As a promising cathode candidate for NIBs, P2-type Na_2/3Ni_1/3Mn_2/3O₂ (NaNMO), a prototype sodium-layered oxide, has attracted extensive attention because of its high operating voltage and high capacity density. Although its electrochemical properties have been extensively investigated, the fundamental charge compensation mechanism, that is, the cationic and anionic redox reactions, is still elusive. In this report, we have systematically investigated the transition metal and oxygen redox reactions of NaNMO nanoflakes using bulk-sensitive soft X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering from an atomic-level view. We show that the bulk Mn³⁺/Mn⁴⁺ redox couple emerges from the first discharge process with the increment of inactive Mn³⁺ upon cycling, which may have a negative effect on the cyclability. In contrast, the bulk Ni redox mainly stems from the Ni²⁺/Ni³⁺ redox couple, in contrast to the conventional wisdom of the Ni²⁺/Ni⁴⁺ redox couple. The quantitative analysis provides unambiguous evidence for the continuous reduction of the average valence state of Mn and Ni over extended cycles, leading to the voltage fading. In addition, we reveal that the oxygen anions also participate in the charge compensation process mainly through irreversible oxygen release rather than reversible lattice oxygen redox. Such understanding is vital for the precise design and optimization of NaNMO electrodes for rechargeable NIBs with outstanding performance.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1780731

Journal Information:: ACS Applied Materials and Interfaces, Vol. 11, Issue 44; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Elucidation of Anionic and Cationic Redox Reactions in a Prototype Sodium-Layered Oxide Cathode

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