Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Yifei Yuan; Ryan Sharpe; Kun He; Chenghang Li; Mahmoud Tamadoni Saray; Tongchao Liu; Wentao Yao; Meng Cheng; Huile Jin; Shun Wang; Khalil Amine; Reza Shahbazian-Yassar; M. Saiful Islam; Jun Lu

doi:10.1038/s41893-022-00919-3

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Yifei Yuan, Ryan Sharpe, Kun He, Chenghang Li, Mahmoud Tamadoni Saray, Tongchao Liu, Wentao Yao, Meng Cheng, Huile Jin, Shun Wang, Khalil Amine, Reza Shahbazian-Yassar, M. Saiful Islam, Jun Lu

Centre for Sustainable and Circular Technologies (CSCT)

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

139 Citations (SciVal)

Abstract

Rechargeable aqueous Zn–MnO₂ technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. Here we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO₂ more specifically. We show that Zn²⁺ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-H_xMnO₂. We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO₂, which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs.

Original language	English
Pages (from-to)	890-898
Number of pages	9
Journal	Nature Sustainability
Volume	5
Issue number	10
Early online date	8 Aug 2022
DOIs	https://doi.org/10.1038/s41893-022-00919-3
Publication status	Published - 31 Oct 2022

Bibliographical note

Funding Information:
The experimental work is primarily supported by the funds from the US National Science Foundation (NSF) under CBET-1805938 and Argonne National Laboratory. Additional supports were provided to Y.Y. by the Natural Science Foundation of China (grant no. 52002287). R.S.-Y., Y.Y., M.C., M.T.S. and W.Y. are thankful to NSF CBET-1805938. R.S. and M.S.I. thank the EPSRC (LiBatt programme grant EP/M0009521/1) and the Faraday Institution (CATMAT project FIRG016, FIRG035) for financial support, and the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1) and the Balena HPC service (Bath) for supercomputer facilities. R.S. and M.S.I. gratefully acknowledge useful discussions with P. Zarabadi-Poor (Oxford), L. Morgan (Bath), K. McColl (Bath), M. J. Clarke (Bath) and J. Dawson (Newcastle). Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. Use of the Advanced Photon Source (APS) {Beamline 9-BM} at Argonne National Laboratory, Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). We acknowledge Quantitative Bio-element Imaging Center (QBIC) at Northwestern University (US) for assistance of ICP measurement. We acknowledge Thermo Fisher Scientific’s Shanghai Nanoport, particularly S. Liu, for their consultative help in atomic imaging of light atoms using electron microscopy.

Funding Information:
The experimental work is primarily supported by the funds from the US National Science Foundation (NSF) under CBET-1805938 and Argonne National Laboratory. Additional supports were provided to Y.Y. by the Natural Science Foundation of China (grant no. 52002287). R.S.-Y., Y.Y., M.C., M.T.S. and W.Y. are thankful to NSF CBET-1805938. R.S. and M.S.I. thank the EPSRC (LiBatt programme grant EP/M0009521/1) and the Faraday Institution (CATMAT project FIRG016, FIRG035) for financial support, and the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1) and the Balena HPC service (Bath) for supercomputer facilities. R.S. and M.S.I. gratefully acknowledge useful discussions with P. Zarabadi-Poor (Oxford), L. Morgan (Bath), K. McColl (Bath), M. J. Clarke (Bath) and J. Dawson (Newcastle). Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. Use of the Advanced Photon Source (APS) {Beamline 9-BM} at Argonne National Laboratory, Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). We acknowledge Quantitative Bio-element Imaging Center (QBIC) at Northwestern University (US) for assistance of ICP measurement. We acknowledge Thermo Fisher Scientific’s Shanghai Nanoport, particularly S. Liu, for their consultative help in atomic imaging of light atoms using electron microscopy.

ASJC Scopus subject areas

Global and Planetary Change
Food Science
Geography, Planning and Development
Ecology
Renewable Energy, Sustainability and the Environment
Urban Studies
Nature and Landscape Conservation
Management, Monitoring, Policy and Law

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1038/s41893-022-00919-3

Cite this

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title = "Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries",

abstract = "Rechargeable aqueous Zn–MnO2 technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. Here we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO2 more specifically. We show that Zn2+ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-HxMnO2. We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO2, which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs.",

author = "Yifei Yuan and Ryan Sharpe and Kun He and Chenghang Li and Saray, {Mahmoud Tamadoni} and Tongchao Liu and Wentao Yao and Meng Cheng and Huile Jin and Shun Wang and Khalil Amine and Reza Shahbazian-Yassar and Islam, {M. Saiful} and Jun Lu",

note = "Funding Information: The experimental work is primarily supported by the funds from the US National Science Foundation (NSF) under CBET-1805938 and Argonne National Laboratory. Additional supports were provided to Y.Y. by the Natural Science Foundation of China (grant no. 52002287). R.S.-Y., Y.Y., M.C., M.T.S. and W.Y. are thankful to NSF CBET-1805938. R.S. and M.S.I. thank the EPSRC (LiBatt programme grant EP/M0009521/1) and the Faraday Institution (CATMAT project FIRG016, FIRG035) for financial support, and the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1) and the Balena HPC service (Bath) for supercomputer facilities. R.S. and M.S.I. gratefully acknowledge useful discussions with P. Zarabadi-Poor (Oxford), L. Morgan (Bath), K. McColl (Bath), M. J. Clarke (Bath) and J. Dawson (Newcastle). Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. Use of the Advanced Photon Source (APS) {Beamline 9-BM} at Argonne National Laboratory, Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). We acknowledge Quantitative Bio-element Imaging Center (QBIC) at Northwestern University (US) for assistance of ICP measurement. We acknowledge Thermo Fisher Scientific{\textquoteright}s Shanghai Nanoport, particularly S. Liu, for their consultative help in atomic imaging of light atoms using electron microscopy. Funding Information: The experimental work is primarily supported by the funds from the US National Science Foundation (NSF) under CBET-1805938 and Argonne National Laboratory. Additional supports were provided to Y.Y. by the Natural Science Foundation of China (grant no. 52002287). R.S.-Y., Y.Y., M.C., M.T.S. and W.Y. are thankful to NSF CBET-1805938. R.S. and M.S.I. thank the EPSRC (LiBatt programme grant EP/M0009521/1) and the Faraday Institution (CATMAT project FIRG016, FIRG035) for financial support, and the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1) and the Balena HPC service (Bath) for supercomputer facilities. R.S. and M.S.I. gratefully acknowledge useful discussions with P. Zarabadi-Poor (Oxford), L. Morgan (Bath), K. McColl (Bath), M. J. Clarke (Bath) and J. Dawson (Newcastle). Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. Use of the Advanced Photon Source (APS) {Beamline 9-BM} at Argonne National Laboratory, Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). We acknowledge Quantitative Bio-element Imaging Center (QBIC) at Northwestern University (US) for assistance of ICP measurement. We acknowledge Thermo Fisher Scientific{\textquoteright}s Shanghai Nanoport, particularly S. Liu, for their consultative help in atomic imaging of light atoms using electron microscopy. ",

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doi = "10.1038/s41893-022-00919-3",

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T1 - Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

AU - Yuan, Yifei

AU - Sharpe, Ryan

AU - He, Kun

AU - Li, Chenghang

AU - Saray, Mahmoud Tamadoni

AU - Liu, Tongchao

AU - Yao, Wentao

AU - Cheng, Meng

AU - Jin, Huile

AU - Wang, Shun

AU - Amine, Khalil

AU - Shahbazian-Yassar, Reza

AU - Islam, M. Saiful

AU - Lu, Jun

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Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

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