Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

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

doi:10.1038/s41893-022-00919-3

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Journal Article · Mon Aug 08 04:00:00 EDT 2022 · Nature Sustainability

DOI:https://doi.org/10.1038/s41893-022-00919-3· OSTI ID:1900589

^[1]; Sharpe, Ryan ^[2]; He, Kun ^[1]; Li, Chenghang ^[3]; Saray, Mahmoud Tamadoni ^[4]; Liu, Tongchao ^[5]; Yao, Wentao ^[4]; Cheng, Meng ^[4]; Jin, Huile ^[3]; Wang, Shun ^[3]; ^[5]; ^[4]; Islam, M. Saiful ^[6]; ^[5]

Wenzhou University (China); Univ. of Illinois, Chicago, IL (United States)
Univ. of Bath (United Kingdom)
Wenzhou University (China)
Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Bath (United Kingdom); Univ. of Oxford (United Kingdom)

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. In this work, 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. A rechargeable aqueous Zn-MnO₂ battery features a combination of favourable sustainability characteristics from safety to cost. The authors deploy advanced characterizations and theoretical calculations to provide fresh insight into the charge storage mechanism, which not only closes an ongoing debate but suggests ways forward.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); Engineering and Physical Sciences Research Council (EPSRC); The Faraday Institution

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1900589

Alternate ID(s):: OSTI ID: 1901056

Journal Information:: Nature Sustainability, Journal Name: Nature Sustainability Journal Issue: 10 Vol. 5; ISSN 2398-9629

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Accessing the Two‐Electron Charge Storage Capacity of MnO ₂ in Mild Aqueous Electrolytes Mateos, Mickaël; Makivic, Nikolina; Kim, Yee‐Seul Advanced Energy Materials, Vol. 10, Issue 23 https://doi.org/10.1002/aenm.202000332	journal	May 2020
An Electrolytic Zn–MnO ₂ Battery for High‐Voltage and Scalable Energy Storage Chao, Dongliang; Zhou, Wanhai; Ye, Chao Angewandte Chemie International Edition, Vol. 58, Issue 23 https://doi.org/10.1002/anie.201904174	journal	June 2019
Unravelling the Mechanism of Rechargeable Aqueous Zn–MnO ₂ Batteries: Implementation of Charging Process by Electrodeposition of MnO ₂ Yang, Jie; Cao, Jianyun; Peng, Yudong ChemSusChem, Vol. 13, Issue 16 https://doi.org/10.1002/cssc.202001216	journal	June 2020
Graphene Scroll-Coated α-MnO ₂ Nanowires as High-Performance Cathode Materials for Aqueous Zn-Ion Battery Wu, Buke; Zhang, Guobin; Yan, Mengyu Small, Vol. 14, Issue 13 https://doi.org/10.1002/smll.201703850	journal	February 2018
H ⁺ ‐Insertion Boosted α‐MnO ₂ for an Aqueous Zn‐Ion Battery Gao, Xu; Wu, Hanwen; Li, Wenjie Small, Vol. 16, Issue 5 https://doi.org/10.1002/smll.201905842	journal	January 2020
Revealing the Atomic Structures of Exposed Lateral Surfaces for Polymorphic Manganese Dioxide Nanowires Yuan, Yifei; Yao, Wentao; Byles, Bryan W. Small Structures, Vol. 2, Issue 3 https://doi.org/10.1002/sstr.202000091	journal	December 2020
First Principles Study of H-insertion in MnO2 Balachandran, D.; Morgan, D.; Ceder, G. Journal of Solid State Chemistry, Vol. 166, Issue 1 https://doi.org/10.1006/jssc.2002.9564	journal	June 2002
Deciphering the Atomic Patterns Leading to MnO2 Polymorphism Yuan, Yifei; He, Kun; Byles, Bryan W. Chem, Vol. 5, Issue 7 https://doi.org/10.1016/j.chempr.2019.03.021	journal	July 2019
A high surface area tunnel-type α-MnO2 nanorod cathode by a simple solvent-free synthesis for rechargeable aqueous zinc-ion batteries Alfaruqi, Muhammad Hilmy; Islam, Saiful; Gim, Jihyeon Chemical Physics Letters, Vol. 650 https://doi.org/10.1016/j.cplett.2016.02.067	journal	April 2016
Preparation and Characterization of MnO2/acid-treated CNT Nanocomposites for Energy Storage with Zinc Ions Xu, Dongwei; Li, Baohua; Wei, Chunguang Electrochimica Acta, Vol. 133 https://doi.org/10.1016/j.electacta.2014.04.001	journal	July 2014
Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage Yuan, Yifei; Liu, Cong; Byles, Bryan W. Joule, Vol. 3, Issue 2 https://doi.org/10.1016/j.joule.2018.10.026	journal	February 2019
Scientific Challenges for the Implementation of Zn-Ion Batteries Blanc, Lauren E.; Kundu, Dipan; Nazar, Linda F. Joule, Vol. 4, Issue 4 https://doi.org/10.1016/j.joule.2020.03.002	journal	April 2020
Enhanced reversible divalent zinc storage in a structurally stable α-MnO 2 nanorod electrode Alfaruqi, Muhammad Hilmy; Gim, Jihyeon; Kim, Sungjin Journal of Power Sources, Vol. 288 https://doi.org/10.1016/j.jpowsour.2015.04.140	journal	August 2015
Charge storage mechanism of α-MnO2 in protic and aprotic ionic liquid electrolytes Lindberg, S.; Jeschke, S.; Jankowski, P. Journal of Power Sources, Vol. 460 https://doi.org/10.1016/j.jpowsour.2020.228111	journal	June 2020
Dynamic study of (De)sodiation in alpha-MnO2 nanowires Yuan, Yifei; Ma, Lu; He, Kun Nano Energy, Vol. 19 https://doi.org/10.1016/j.nanoen.2015.11.028	journal	January 2016
Oxidation state and chemical shift investigation in transition metal oxides by EELS Tan, Haiyan; Verbeeck, Jo; Abakumov, Artem Ultramicroscopy, Vol. 116 https://doi.org/10.1016/j.ultramic.2012.03.002	journal	May 2012
Reaction Mechanisms for Long-Life Rechargeable Zn/MnO ₂ Batteries Li, Yun; Wang, Shanyu; Salvador, James R. Chemistry of Materials, Vol. 31, Issue 6 https://doi.org/10.1021/acs.chemmater.8b05093	journal	June 2018
Proton Insertion Promoted a Polyfurfural/MnO₂ Nanocomposite Cathode for a Rechargeable Aqueous Zn–MnO₂ Battery Zhao, Qin; Huang, Xinjun; Zhou, Mengmeng ACS Applied Materials & Interfaces, Vol. 12, Issue 32 https://doi.org/10.1021/acsami.0c08579	journal	July 2020
Superfine MnO ₂ Nanowires with Rich Defects Toward Boosted Zinc Ion Storage Performance Wang, Jinjin; Wang, Jian-Gan; Qin, Xueping ACS Applied Materials & Interfaces, Vol. 12, Issue 31 https://doi.org/10.1021/acsami.0c08812	journal	July 2020
Manganese and Vanadium Oxide Cathodes for Aqueous Rechargeable Zinc-Ion Batteries: A Focused View on Performance, Mechanism, and Developments Mathew, Vinod; Sambandam, Balaji; Kim, Seokhun ACS Energy Letters, Vol. 5, Issue 7 https://doi.org/10.1021/acsenergylett.0c00740	journal	June 2020
Superior-Performance Aqueous Zinc-Ion Batteries Based on the In Situ Growth of MnO ₂ Nanosheets on V ₂ CT _X MXene Zhu, Xiaodong; Cao, Ziyi; Wang, Wenjie ACS Nano, Vol. 15, Issue 2 https://doi.org/10.1021/acsnano.0c09205	journal	January 2021
Advances and Perspectives of Cathode Storage Chemistry in Aqueous Zinc-Ion Batteries Wang, Xiao; Zhang, Zhengchunyu; Xi, Baojuan ACS Nano, Vol. 15, Issue 6 https://doi.org/10.1021/acsnano.1c01389	journal	June 2021
Nanostructuring of β-MnO ₂ : The Important Role of Surface to Bulk Ion Migration Tompsett, David A.; Parker, Steve C.; Bruce, Peter G. Chemistry of Materials, Vol. 25, Issue 4 https://doi.org/10.1021/cm303295f	journal	February 2013
Electrochemistry of Hollandite α-MnO ₂ : Li-Ion and Na-Ion Insertion and Li ₂ O Incorporation Tompsett, David A.; Islam, M. Saiful Chemistry of Materials, Vol. 25, Issue 12 https://doi.org/10.1021/cm400864n	journal	June 2013
Rutile (β-)MnO ₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance Tompsett, David A.; Parker, Stephen C.; Islam, M. Saiful Journal of the American Chemical Society, Vol. 136, Issue 4 https://doi.org/10.1021/ja4092962	journal	January 2014
Redox Chemistry and the Role of Trapped Molecular O₂ in Li-Rich Disordered Rocksalt Oxyfluoride Cathodes Sharpe, Ryan; House, Robert A.; Clarke, Matt J. Journal of the American Chemical Society, Vol. 142, Issue 52 https://doi.org/10.1021/jacs.0c10270	journal	December 2020
Zn/MnO ₂ Battery Chemistry With H ⁺ and Zn ²⁺ Coinsertion Sun, Wei; Wang, Fei; Hou, Singyuk Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b04471	journal	July 2017
Asynchronous Crystal Cell Expansion during Lithiation of K ⁺ -Stabilized α-MnO ₂ Yuan, Yifei; Nie, Anmin; Odegard, Gregory M. Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/nl5048913	journal	April 2015
The influence of large cations on the electrochemical properties of tunnel-structured metal oxides Yuan, Yifei; Zhan, Chun; He, Kun Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13374	journal	November 2016
Reversible aqueous zinc/manganese oxide energy storage from conversion reactions Pan, Huilin; Shao, Yuyan; Yan, Pengfei Nature Energy, Vol. 1, Issue 5 https://doi.org/10.1038/nenergy.2016.39	journal	April 2016
Direct imaging of hydrogen-atom columns in a crystal by annular bright-field electron microscopy Ishikawa, Ryo; Okunishi, Eiji; Sawada, Hidetaka Nature Materials, Vol. 10, Issue 4 https://doi.org/10.1038/nmat2957	journal	February 2011
Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities Zhang, Ning; Cheng, Fangyi; Liu, Junxiang Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00467-x	journal	September 2017
Fluid-enhanced surface diffusion controls intraparticle phase transformations Li, Yiyang; Chen, Hungru; Lim, Kipil Nature Materials, Vol. 17, Issue 10 https://doi.org/10.1038/s41563-018-0168-4	journal	September 2018
Charging sustainable batteries Bauer, Christian; Burkhardt, Simon; Dasgupta, Neil P. Nature Sustainability, Vol. 5, Issue 3 https://doi.org/10.1038/s41893-022-00864-1	journal	March 2022
Electrochemically-induced reversible transition from the tunneled to layered polymorphs of manganese dioxide Lee, Boeun; Yoon, Chong Seung; Lee, Hae Ri Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06066	journal	August 2014
Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties Islam, M. Saiful; Fisher, Craig A. J. Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60199D	journal	January 2014
Elucidating the intercalation mechanism of zinc ions into α-MnO ₂ for rechargeable zinc batteries Lee, Boeun; Lee, Hae Ri; Kim, Haesik Chemical Communications, Vol. 51, Issue 45 https://doi.org/10.1039/C5CC02585K	journal	January 2015
High voltage structural evolution and enhanced Na-ion diffusion in P2-Na _2/3 Ni _1/3−x Mg _x Mn _2/3 O ₂ (0 ≤ x ≤ 0.2) cathodes from diffraction, electrochemical and ab initio studies Tapia-Ruiz, Nuria; Dose, Wesley M.; Sharma, Neeraj Energy & Environmental Science, Vol. 11, Issue 6 https://doi.org/10.1039/C7EE02995K	journal	January 2018
Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes Naylor, Andrew J.; Makkos, Eszter; Maibach, Julia Journal of Materials Chemistry A, Vol. 7, Issue 44 https://doi.org/10.1039/C9TA09019C	journal	January 2019
Quantitative temporally and spatially resolved X-ray fluorescence microprobe characterization of the manganese dissolution-deposition mechanism in aqueous Zn/α-MnO ₂ batteries Wu, Daren; Housel, Lisa M.; Kim, Sung Joo Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE02168G	journal	January 2020
Enabling stable MnO₂ matrix for aqueous zinc-ion battery cathodes Jiao, Yiding; Kang, Liqun; Berry-Gair, Jasper Journal of Materials Chemistry A, Vol. 8, Issue 42 https://doi.org/10.1039/D0TA08638J	journal	January 2020
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Resolving hydrogen atoms at metal-metal hydride interfaces de Graaf, Sytze; Momand, Jamo; Mitterbauer, Christoph Science Advances, Vol. 6, Issue 5 https://doi.org/10.1126/sciadv.aay4312	journal	January 2020
Ab Initio Studies of Hydrogen Ion Insertion into β-, R-, and γ-MnO ₂ Polymorphs and the Implications for Shallow-Cycled Rechargeable Zn/MnO ₂ Batteries Vasiliev, Igor; Magar, Birendra Ale; Duay, Jonathon Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.1161814jes	journal	January 2018

Similar Records

Opportunities of Aqueous Manganese-Based Batteries with Deposition and Stripping Chemistry

Journal Article · Sun Dec 20 23:00:00 EST 2020 · Advanced Energy Materials · OSTI ID:1768031

Joint Charge Storage for High‐Rate Aqueous Zinc–Manganese Dioxide Batteries

Journal Article · Mon Jun 03 00:00:00 EDT 2019 · Advanced Materials · OSTI ID:1545406

Related Subjects

25 ENERGY STORAGE

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Citation Formats

References (50)

Similar Records

Related Subjects