Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products

Jones, Daniel Raymond; M., Haytham E.; Worsley, Eleri; Kiani, Sajad; Kamlungsua, Kittiwat; Fone, Thomas; Phillips, Christopher; Deganello, Davide

doi:10.1002/celc.202300210

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Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products

Daniel Raymond Jones

, Haytham E. M. Hussein, Eleri Worsley, Sajad Kiani, Kittiwat Kamlungsua, Thomas Fone, Christopher Phillips

, Davide Deganello

ChemElectroChem, Volume: 10, Issue: 14

Swansea University Authors: Daniel Raymond Jones , Eleri Worsley, Sajad Kiani, Thomas Fone, Christopher Phillips , Davide Deganello

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DOI (Published version): 10.1002/celc.202300210

Abstract

Manganese(III/IV) oxide is a promising pseudocapacitive material for supercapacitor electrodes due to favorable attributes such as its chemical resilience, high earth abundance and low specific cost. Herein, the morphological, compositional and electrochemical characteristics of co-precipitated mang...

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Published in:	ChemElectroChem
ISSN:	2196-0216 2196-0216
Published:	Wiley 2023
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Herein, the morphological, compositional and electrochemical characteristics of co-precipitated manganese(III/IV) oxide products, each described by the general formula NaxKyMnOz, are investigated to establish how these properties are influenced by synthesis conditions. NaxKyMnOz growths in low-temperature (<100 °C) basic and acidic environments are shown to promote the formation of turbostratic birnessite and cryptomelane phases, respectively, with the latter polymorph containing a relatively low concentration of interstitial Na+ and K+ cations. It is demonstrated that K+ pre-insertion during synthesis yields lower initial charge-transfer resistances than equivalent Na+ intercalation, and that this parameter correlates strongly with storage performance. Accordingly, Na-mediated storage initially delivers inferior specific capacitances and Coulombic efficiencies than K-based mechanisms, but K+ intercalation/deintercalation causes faster capacitance decay during prolonged galvanostatic cycling. Furthermore, whilst crystallographic phase is shown to have a weaker effect on NaxKyMnOz storage properties than the choice of intercalating guest cations, cryptomelane electrodes are more susceptible to cycling-induced capacitance and efficiency losses than their birnessite counterparts. 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spelling	v2 63467 2023-05-16 Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products 7f3a1d866625502ae897ad1672096818 NULL Daniel Raymond Jones Daniel Raymond Jones true true 8484ab36e02699f52d48bbfe36b7ac74 Eleri Worsley Eleri Worsley true false fe9ec46699e095368faf2a0465b598c5 Sajad Kiani Sajad Kiani true false dc60933e11ebcdd7a7fa2be4b12a3b53 Thomas Fone Thomas Fone true false cc734f776f10b3fb9b43816c9f617bb5 0000-0001-8011-710X Christopher Phillips Christopher Phillips true false ea38a0040bdfd3875506189e3629b32a 0000-0001-8341-4177 Davide Deganello Davide Deganello true false 2023-05-16 Manganese(III/IV) oxide is a promising pseudocapacitive material for supercapacitor electrodes due to favorable attributes such as its chemical resilience, high earth abundance and low specific cost. Herein, the morphological, compositional and electrochemical characteristics of co-precipitated manganese(III/IV) oxide products, each described by the general formula NaxKyMnOz, are investigated to establish how these properties are influenced by synthesis conditions. NaxKyMnOz growths in low-temperature (<100 °C) basic and acidic environments are shown to promote the formation of turbostratic birnessite and cryptomelane phases, respectively, with the latter polymorph containing a relatively low concentration of interstitial Na+ and K+ cations. It is demonstrated that K+ pre-insertion during synthesis yields lower initial charge-transfer resistances than equivalent Na+ intercalation, and that this parameter correlates strongly with storage performance. Accordingly, Na-mediated storage initially delivers inferior specific capacitances and Coulombic efficiencies than K-based mechanisms, but K+ intercalation/deintercalation causes faster capacitance decay during prolonged galvanostatic cycling. Furthermore, whilst crystallographic phase is shown to have a weaker effect on NaxKyMnOz storage properties than the choice of intercalating guest cations, cryptomelane electrodes are more susceptible to cycling-induced capacitance and efficiency losses than their birnessite counterparts. In combination, these insights provide an instructive foundation for the optimization of NaxKyMnOz in high-power storage applications. Journal Article ChemElectroChem 10 14 Wiley 2196-0216 2196-0216 Birnessite, Cryptomelane, Intercalation, MnO2, Pseudocapacitance 17 7 2023 2023-07-17 10.1002/celc.202300210 http://dx.doi.org/10.1002/celc.202300210 COLLEGE NANME Engineering COLLEGE CODE Swansea University SU Library paid the OA fee (TA Institutional Deal) This study is partially funded by Enserv Power Co. Ltd., and the research contributes to the IMPACT operation which has been part-funded by the European Regional Development Fund through the Welsh Government and Swansea University. The authors are grateful for access to XPS and TEM instrumentation provided by the Advanced Imaging of Materials (AIM) facility, which is funded in part by EPSRC (EP/M028267/1), the European Regional Development Fund via the Welsh Government (80708), the Ser Solar project via Welsh Government, and Carl Zeiss Microscopy. Swansea University. 2023-07-26T17:12:38.4399383 2023-05-16T11:46:30.5739845 Faculty of Science and Engineering School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering Daniel Raymond Jones NULL 1 Haytham E. M. Hussein 2 Eleri Worsley 3 Sajad Kiani 4 Kittiwat Kamlungsua 5 Thomas Fone 6 Christopher Phillips 0000-0001-8011-710X 7 Davide Deganello 0000-0001-8341-4177 8 63467__28192__e1dc78d0ebc348469a7a05672fbda77e.pdf 63467.VOR.pdf 2023-07-26T17:11:03.4699076 Output 2976285 application/pdf Version of Record true © 2023 The Authors. ChemElectroChem published by Wiley-VCH GmbH. Distributed under the terms of a Creative Commons Attribution 4.0 License (CC BY 4.0). true eng https://creativecommons.org/licenses/by/4.0/
title	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
spellingShingle	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products Daniel Raymond Jones Eleri Worsley Sajad Kiani Thomas Fone Christopher Phillips Davide Deganello
title_short	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
title_full	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
title_fullStr	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
title_full_unstemmed	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
title_sort	Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products
author_id_str_mv	7f3a1d866625502ae897ad1672096818 8484ab36e02699f52d48bbfe36b7ac74 fe9ec46699e095368faf2a0465b598c5 dc60933e11ebcdd7a7fa2be4b12a3b53 cc734f776f10b3fb9b43816c9f617bb5 ea38a0040bdfd3875506189e3629b32a
author_id_fullname_str_mv	7f3a1d866625502ae897ad1672096818_*_Daniel Raymond Jones 8484ab36e02699f52d48bbfe36b7ac74__Eleri Worsley fe9ec46699e095368faf2a0465b598c5__Sajad Kiani dc60933e11ebcdd7a7fa2be4b12a3b53__Thomas Fone cc734f776f10b3fb9b43816c9f617bb5__Christopher Phillips ea38a0040bdfd3875506189e3629b32a_*_Davide Deganello
author	Daniel Raymond Jones Eleri Worsley Sajad Kiani Thomas Fone Christopher Phillips Davide Deganello
author2	Daniel Raymond Jones Haytham E. M. Hussein Eleri Worsley Sajad Kiani Kittiwat Kamlungsua Thomas Fone Christopher Phillips Davide Deganello
format	Journal article
container_title	ChemElectroChem
container_volume	10
container_issue	14
publishDate	2023
institution	Swansea University
issn	2196-0216 2196-0216
doi_str_mv	10.1002/celc.202300210
publisher	Wiley
college_str	Faculty of Science and Engineering
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hierarchy_top_id	facultyofscienceandengineering
hierarchy_top_title	Faculty of Science and Engineering
hierarchy_parent_id	facultyofscienceandengineering
hierarchy_parent_title	Faculty of Science and Engineering
department_str	School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Aerospace, Civil, Electrical, General and Mechanical Engineering - Mechanical Engineering
url	http://dx.doi.org/10.1002/celc.202300210
document_store_str	1
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description	Manganese(III/IV) oxide is a promising pseudocapacitive material for supercapacitor electrodes due to favorable attributes such as its chemical resilience, high earth abundance and low specific cost. Herein, the morphological, compositional and electrochemical characteristics of co-precipitated manganese(III/IV) oxide products, each described by the general formula NaxKyMnOz, are investigated to establish how these properties are influenced by synthesis conditions. NaxKyMnOz growths in low-temperature (<100 °C) basic and acidic environments are shown to promote the formation of turbostratic birnessite and cryptomelane phases, respectively, with the latter polymorph containing a relatively low concentration of interstitial Na+ and K+ cations. It is demonstrated that K+ pre-insertion during synthesis yields lower initial charge-transfer resistances than equivalent Na+ intercalation, and that this parameter correlates strongly with storage performance. Accordingly, Na-mediated storage initially delivers inferior specific capacitances and Coulombic efficiencies than K-based mechanisms, but K+ intercalation/deintercalation causes faster capacitance decay during prolonged galvanostatic cycling. Furthermore, whilst crystallographic phase is shown to have a weaker effect on NaxKyMnOz storage properties than the choice of intercalating guest cations, cryptomelane electrodes are more susceptible to cycling-induced capacitance and efficiency losses than their birnessite counterparts. In combination, these insights provide an instructive foundation for the optimization of NaxKyMnOz in high-power storage applications.
published_date	2023-07-17T17:11:52Z
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score	11.016258

Scalable Synthesis of Pre‐Intercalated Manganese(III/IV) Oxide Nanostructures for Supercapacitor Electrodes: Electrochemical Comparison of Birnessite and Cryptomelane Products

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