Exploiting anion and cation redox chemistry in lithium-rich perovskite oxalate: a novel next-generation Li/Na-ion battery electrode

Atin Pramanik; Alexis G. Manche; Rebecca Clulow; Philip Lightfoot; A. Robert Armstrong

doi:10.1039/D2DT01447E

Exploiting anion and cation redox chemistry in lithium-rich perovskite oxalate: a novel next-generation Li/Na-ion battery electrode

Atin Pramanik, Alexis G. Manche, Rebecca Clulow, Philip Lightfoot^*, A. Robert Armstrong^*

^*Corresponding author for this work

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

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Abstract

The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLi₃Fe(C₂O₄)₃ (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g⁻¹ after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.

Original language	English
Pages (from-to)	12467-12475
Number of pages	9
Journal	Dalton Transactions
Volume	51
Issue number	33
Early online date	25 Jul 2022
DOIs	https://doi.org/10.1039/D2DT01447E
Publication status	Published - 7 Sept 2022

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10.1039/D2DT01447ELicence: CC BY

Pramanik_2022_DT_Exploiting-anion_CC
Copyright © The Author(s) 2022. Open Access. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Final published version, 2.77 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{0a5dad9e73fd41d9b5e7cfe476b68dd8,

title = "Exploiting anion and cation redox chemistry in lithium-rich perovskite oxalate: a novel next-generation Li/Na-ion battery electrode",

abstract = "The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLi3Fe(C2O4)3 (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g−1 after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.",

author = "Atin Pramanik and Manche, {Alexis G.} and Rebecca Clulow and Philip Lightfoot and Armstrong, {A. Robert}",

note = "Authors thank EPSRC EP/R030472/1 for financial support. AGM wishes to thank the Faraday Institution for financial support and training (Grant Number FITG033). The authors are also grateful to EPSRC Light Element Analysis Facility Grant EP/T019298/1 and the EPSRC Strategic Equipment Resource Grant EP/R023751/1.",

year = "2022",

month = sep,

day = "7",

doi = "10.1039/D2DT01447E",

language = "English",

volume = "51",

pages = "12467--12475",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "ROYAL SOC CHEMISTRY",

number = "33",

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TY - JOUR

T1 - Exploiting anion and cation redox chemistry in lithium-rich perovskite oxalate

T2 - a novel next-generation Li/Na-ion battery electrode

AU - Pramanik, Atin

AU - Manche, Alexis G.

AU - Clulow, Rebecca

AU - Lightfoot, Philip

AU - Armstrong, A. Robert

N1 - Authors thank EPSRC EP/R030472/1 for financial support. AGM wishes to thank the Faraday Institution for financial support and training (Grant Number FITG033). The authors are also grateful to EPSRC Light Element Analysis Facility Grant EP/T019298/1 and the EPSRC Strategic Equipment Resource Grant EP/R023751/1.

PY - 2022/9/7

Y1 - 2022/9/7

N2 - The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLi3Fe(C2O4)3 (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g−1 after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.

AB - The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLi3Fe(C2O4)3 (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g−1 after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.

U2 - 10.1039/D2DT01447E

DO - 10.1039/D2DT01447E

M3 - Article

SN - 1477-9226

VL - 51

SP - 12467

EP - 12475

JO - Dalton Transactions

JF - Dalton Transactions

IS - 33

ER -

Exploiting anion and cation redox chemistry in lithium-rich perovskite oxalate: a novel next-generation Li/Na-ion battery electrode

Abstract

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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