Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide

Stephanie F. Linnell; Moritz Hirsbrunner; Saki Imada; Giannoantonio Cibin; Aaron B. Naden; Alan V. Chadwick; John T. S. Irvine; Laurent C. Duda; A. Robert Armstrong

doi:10.1002/celc.202200240

Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide

Stephanie F. Linnell, Moritz Hirsbrunner, Saki Imada, Giannoantonio Cibin, Aaron B. Naden, Alan V. Chadwick, John T. S. Irvine, Laurent C. Duda, A. Robert Armstrong^*

^*Corresponding author for this work

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

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Abstract

Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‑ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‑doping on the electrochemical properties of P3-type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‑Na 0.67 Mn 0.9 Zn 0.1 O 2 and Oxy‑Na 0.67 Mn 0.9 Zn 0.1 O 2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96% of their initial capacity after 30 cycles, where Mn 3+ /Mn 4+ redox dominates. Increasing the voltage range to 1.8‑4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‑capacity and structurally stable oxygen redox‑based materials for SIBs.

Original language	English
Article number	e202200240
Journal	ChemElectroChem
Volume	9
Issue number	11
DOIs	https://doi.org/10.1002/celc.202200240
Publication status	Published - 7 Jun 2022

Keywords

Anion redox chemistry
Layered compounds
Positive electrode material
Sodium
Transition metal vacancies

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10.1002/celc.202200240Licence: CC BY

Linnell_2022ChemElectroChem_Enhancedcycling_CC
Copyright © 2022 The Authors. ChemElectroChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 2.26 MBLicence: CC BY

Light Element Analysis Facility (LEAF): Light Element Analysis Facility (LEAF)
Irvine, J. T. S. (PI), Baker, R. (CoI) & Miller, D. N. (CoI)
EPSRC
5/04/20 → 4/04/23
Project: Standard
Electon Microscopy: Electon Microscopy for the characterisation and manipulation of advanced function materials and their interfaces at the nanoscale
Irvine, J. T. S. (PI), Baker, R. (CoI) & Zhou, W. (CoI)
EPSRC
1/04/18 → 2/09/20
Project: Standard

Cite this

@article{337a5ce172ea48569a48397068081b46,

title = "Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide",

abstract = "Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‑ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‑doping on the electrochemical properties of P3-type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‑Na 0.67 Mn 0.9 Zn 0.1 O 2 and Oxy‑Na 0.67 Mn 0.9 Zn 0.1 O 2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96% of their initial capacity after 30 cycles, where Mn 3+ /Mn 4+ redox dominates. Increasing the voltage range to 1.8‑4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‑capacity and structurally stable oxygen redox‑based materials for SIBs.",

keywords = "Anion redox chemistry, Layered compounds, Positive electrode material, Sodium, Transition metal vacancies",

author = "Linnell, {Stephanie F.} and Moritz Hirsbrunner and Saki Imada and Giannoantonio Cibin and Naden, {Aaron B.} and Chadwick, {Alan V.} and Irvine, {John T. S.} and Duda, {Laurent C.} and Armstrong, {A. Robert}",

note = "Funding: Faraday Institution (Grant Number(s): FIRG018), Diamond Light Source (Grant Number(s): SP14239), Engineering and Physical Sciences Research Council (Grant Number(s): EP/L017008/1, EP/R023751/1, EP/T019298/1), SPRing8 (Grant Number(s): 2021A1425).",

year = "2022",

month = jun,

day = "7",

doi = "10.1002/celc.202200240",

language = "English",

volume = "9",

journal = "ChemElectroChem",

issn = "2196-0216",

publisher = "John Wiley & Sons, Ltd",

number = "11",

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TY - JOUR

T1 - Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide

AU - Linnell, Stephanie F.

AU - Hirsbrunner, Moritz

AU - Imada, Saki

AU - Cibin, Giannoantonio

AU - Naden, Aaron B.

AU - Chadwick, Alan V.

AU - Irvine, John T. S.

AU - Duda, Laurent C.

AU - Armstrong, A. Robert

N1 - Funding: Faraday Institution (Grant Number(s): FIRG018), Diamond Light Source (Grant Number(s): SP14239), Engineering and Physical Sciences Research Council (Grant Number(s): EP/L017008/1, EP/R023751/1, EP/T019298/1), SPRing8 (Grant Number(s): 2021A1425).

PY - 2022/6/7

Y1 - 2022/6/7

N2 - Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‑ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‑doping on the electrochemical properties of P3-type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‑Na 0.67 Mn 0.9 Zn 0.1 O 2 and Oxy‑Na 0.67 Mn 0.9 Zn 0.1 O 2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96% of their initial capacity after 30 cycles, where Mn 3+ /Mn 4+ redox dominates. Increasing the voltage range to 1.8‑4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‑capacity and structurally stable oxygen redox‑based materials for SIBs.

AB - Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‑ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‑doping on the electrochemical properties of P3-type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‑Na 0.67 Mn 0.9 Zn 0.1 O 2 and Oxy‑Na 0.67 Mn 0.9 Zn 0.1 O 2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96% of their initial capacity after 30 cycles, where Mn 3+ /Mn 4+ redox dominates. Increasing the voltage range to 1.8‑4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‑capacity and structurally stable oxygen redox‑based materials for SIBs.

KW - Anion redox chemistry

KW - Layered compounds

KW - Positive electrode material

KW - Sodium

KW - Transition metal vacancies

U2 - 10.1002/celc.202200240

DO - 10.1002/celc.202200240

M3 - Article

SN - 2196-0216

VL - 9

JO - ChemElectroChem

JF - ChemElectroChem

IS - 11

M1 - e202200240

ER -

Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide

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Keywords

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Projects

Light Element Analysis Facility (LEAF): Light Element Analysis Facility (LEAF)

Electon Microscopy: Electon Microscopy for the characterisation and manipulation of advanced function materials and their interfaces at the nanoscale

Cite this