Modulation of Redox Chemistry of Na2Mn3O7by Selective Boron Doping Prompted by Na Vacancies

Wan，Jing1; Qiu，Yuegang1; Sun，Xueping2; Ou，Mingyang1; Xu，Jia1; Zhang，Xiaoyu1; Liu，Yi1; Sun，Shixiong1; Xu，Yue1,4; Fang，Chun1; Huang，Li3; Chu，Paul K.4; Han，Jiantao1

2022

10.1021/acsami.2c09719

ACS Applied Materials & Interfaces   Impact Factor & Quartile

1944-8244

1944-8252

The small energy density and chemomechanical degradation of layered manganese oxide limit practical application to sodium-ion batteries (SIBs). Typically, Na2Mn3O7 shows a low redox plateau at 2.1 V versus Na/Na+, and the oxygen redox reaction at a high voltage causes structural collapse. Herein, a Na vacancy-induced boron doping strategy is demonstrated to improve the properties. Boron is incorporated into selective sites in the lattice in the center of the MnO6 octahedral ring at the O-layer. Bonding of boron in the TM layer enhances the electrochemical activity of low-valence Mn, giving rise to two reversible redox peaks at 2.45 and 2.55 V to enhance the average redox voltage. At the same time, the O 2p chemical state becomes weaker around the Fermi level, thus suppressing oxygen overoxidation for the high charge state and strengthening the layered structure during the redox reactions. The reduced Mn-O covalency and small diffusion barrier energy stemming from bonding of boron in the oxygen layer produce excellent rate characteristics. Modulation of the Mn 3d and O 2p orbital in Na2Mn3O7 by Na vacancies leads to selective doping of boron at different sites, and our results reveal that it is an important strategy for studying transition-metal-oxide-layered electrode materials.

boron doping layered materials Na2Mn3O7 sodium-ion batteries vacancies

SCI ; EI

English

Others

WOS:000844334400001

20223512648144

Boron ; Chemical bonds ; Manganese oxide ; Metal ions ; Modulation ; Oxygen ; Redox reactions ; Sodium-ion batteries ; Transition metal oxides ; Transition metals

Metallurgy and Metallography:531 ; Metallurgy:531.1 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Secondary Batteries:702.1.2 ; Electronic Components and Tubes:714 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804

2-s2.0-85136683627

Scopus

1.State Key Laboratory of Material Processing and Die and Mould Technology,School of Materials Science and Engineering,Huazhong University of Science and Technology,Wuhan,Hubei,430074,China
2.The Institute for Advanced Studies,Wuhan University,Wuhan,Hubei,430072,China
3.Guangdong Provincial Key Laboratory of Energy Materials for Electric Power,Southern University of Science and Technology,Shenzhen,518055,China
4.Department of Physics,Department of Materials Science and Engineering,Department of Biomedical Engineering,City University of Hong Kong,Kowloon,Tat Chee Avenue,999077,Hong Kong

Wan，Jing,Qiu，Yuegang,Sun，Xueping,et al. Modulation of Redox Chemistry of Na2Mn3O7by Selective Boron Doping Prompted by Na Vacancies[J]. ACS Applied Materials & Interfaces,2022,14:38769-38777.

Wan，Jing.,Qiu，Yuegang.,Sun，Xueping.,Ou，Mingyang.,Xu，Jia.,...&Han，Jiantao.(2022).Modulation of Redox Chemistry of Na2Mn3O7by Selective Boron Doping Prompted by Na Vacancies.ACS Applied Materials & Interfaces,14,38769-38777.

Wan，Jing,et al."Modulation of Redox Chemistry of Na2Mn3O7by Selective Boron Doping Prompted by Na Vacancies".ACS Applied Materials & Interfaces 14(2022):38769-38777.