Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

Biwei Xiao; Xiang Liu; Xi Chen; Gi Hyeok Lee; Miao Song; Xin Yang; Fred Omenya; David M. Reed; Vincent Sprenkle; Yang Ren; Cheng Jun Sun; Wanli Yang; Khalil Amine; Xin Li; Guiliang Xu; Xiaolin Li

doi:10.1002/adma.202107141

Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

Biwei Xiao
, Xiang Liu
, Xi Chen
, Gi Hyeok Lee
, Miao Song
, Xin Yang
, Fred Omenya
, David M. Reed
, Vincent Sprenkle
, Yang Ren
, Cheng Jun Sun
, Wanli Yang
, Khalil Amine
, Xin Li^*
, Guiliang Xu^*
, Xiaolin Li^*

^*Corresponding author for this work

Pacific Northwest National Laboratory
Argonne National Laboratory
Harvard University
United States Department of Energy
Dongguk University
Stanford University

Research output: Contribution to journal › Article › peer-review

79 Scopus citations

Abstract

Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in Na_xMnO₂-based chemistries or enabling high covalency transition metals in P2-Na_0.66Mn_xTM₁₋_xO₂ (TM = Fe, Cu, Ni) materials. Here, the effect of Li doping on regulating the oxygen redox activities P2-structured Na_0.66Ni_0.25Mn_0.75O₂ materials is investigated. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn, and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. The findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.

Original language	English
Article number	2107141
Journal	Advanced Materials
Volume	33
Issue number	52
DOIs	https://doi.org/10.1002/adma.202107141
State	Published - 29 Dec 2021
Externally published	Yes

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@article{6ea163a1a85f4dbca73ce3c15d966ae8,

title = "Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes",

abstract = "Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in NaxMnO2-based chemistries or enabling high covalency transition metals in P2-Na0.66MnxTM1−xO2 (TM = Fe, Cu, Ni) materials. Here, the effect of Li doping on regulating the oxygen redox activities P2-structured Na0.66Ni0.25Mn0.75O2 materials is investigated. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn, and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. The findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.",

author = "Biwei Xiao and Xiang Liu and Xi Chen and Lee, \{Gi Hyeok\} and Miao Song and Xin Yang and Fred Omenya and Reed, \{David M.\} and Vincent Sprenkle and Yang Ren and Sun, \{Cheng Jun\} and Wanli Yang and Khalil Amine and Xin Li and Guiliang Xu and Xiaolin Li",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = dec,

day = "29",

doi = "10.1002/adma.202107141",

language = "英语",

volume = "33",

journal = "Advanced Materials",

issn = "0935-9648",

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number = "52",

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TY - JOUR

T1 - Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

AU - Xiao, Biwei

AU - Liu, Xiang

AU - Chen, Xi

AU - Lee, Gi Hyeok

AU - Song, Miao

AU - Yang, Xin

AU - Omenya, Fred

AU - Reed, David M.

AU - Sprenkle, Vincent

AU - Ren, Yang

AU - Sun, Cheng Jun

AU - Yang, Wanli

AU - Amine, Khalil

AU - Li, Xin

AU - Xu, Guiliang

AU - Li, Xiaolin

PY - 2021/12/29

Y1 - 2021/12/29

N2 - Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in NaxMnO2-based chemistries or enabling high covalency transition metals in P2-Na0.66MnxTM1−xO2 (TM = Fe, Cu, Ni) materials. Here, the effect of Li doping on regulating the oxygen redox activities P2-structured Na0.66Ni0.25Mn0.75O2 materials is investigated. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn, and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. The findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.

AB - Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in NaxMnO2-based chemistries or enabling high covalency transition metals in P2-Na0.66MnxTM1−xO2 (TM = Fe, Cu, Ni) materials. Here, the effect of Li doping on regulating the oxygen redox activities P2-structured Na0.66Ni0.25Mn0.75O2 materials is investigated. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn, and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. The findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.

UR - https://www.scopus.com/pages/publications/85117214818

U2 - 10.1002/adma.202107141

DO - 10.1002/adma.202107141

M3 - 文章

C2 - 34632654

AN - SCOPUS:85117214818

SN - 0935-9648

VL - 33

JO - Advanced Materials

JF - Advanced Materials

IS - 52

M1 - 2107141

ER -

Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

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