Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

Carlson, Evan Z.; Chueh, William C.; Mefford, J. Tyler; Bajdich, Michal

doi:10.1021/acsami.2c16589

Title: Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

Journal Article · Thu Dec 22 00:00:00 EST 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c16589· OSTI ID:2006625

Carlson, Evan Z. ^[1];

^[1];

^[2]

Stanford Univ., CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

The ion insertion redox chemistry of manganese dioxide has diverse applications in energy storage, catalysis, and chemical separations. Unique properties derive from the assembly of Mn–O octahedra into polymorphic structures that can host protons and nonprotonic cations in interstitial sites. Despite many reports on individual ion-polymorph couples, much less is known about the selectivity of electrochemical ion insertion in MnO₂. In this work, we use density functional theory to holistically compare the electrochemistry of A_xMnO₂ (where A = H⁺, Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, Al³⁺) in aqueous and nonaqueous electrolytes. We develop an efficient computational scheme demonstrating that Hubbard-U correction has a greater impact on calculating accurate redox energetics than choice of exchange-correlation functional. Using PBE+U, we find that for nonprotonic cations, ion selectivity depends on the oxygen coordination environments inside a polymorph. When H⁺ is present, however, the driving force to form hydroxyl bonds is usually stronger. In aqueous electrolytes, only three ion-polymorph pairs are thermodynamically stable within water’s voltage stability window (Na⁺ and K⁺ in α-MnO₂, and Li⁺ in λ-MnO₂), with all other ion insertion being metastable. We find Al³⁺ may insert into the δ, R, and λ polymorphs across the full 2-electron redox of MnO₂ at high voltage; however, electrolytes for multivalent ions must be designed to impede the formation of insoluble precipitates and facilitate cation desolvation. We also show that small ions coinsert with water in α-MnO₂ to achieve greater coordination by oxygen, while solvation energies and kinetic effects dictate water coinsertion in δ-MnO₂. Finally, taken together, these findings explain reports of mixed ion insertion mechanisms in aqueous electrolytes and highlight promising design strategies for safe, high energy density electrochemical energy storage, desalination batteries, and electrocatalysts.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; DGE-1656518; AC02-05CH11231

OSTI ID:: 2006625

Journal Information:: ACS Applied Materials and Interfaces, Vol. 15, Issue 1; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (65)

Discharging Behavior of Hollandite α-MnO ₂ in a Hydrated Zinc-Ion Battery Le, Thanh; Sadique, Nahian; Housel, Lisa M. ACS Applied Materials & Interfaces, Vol. 13, Issue 50 https://doi.org/10.1021/acsami.1c18849	journal	December 2021
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235438	journal	June 2012
Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries Yuan, Yifei; Sharpe, Ryan; He, Kun Nature Sustainability, Vol. 5, Issue 10 https://doi.org/10.1038/s41893-022-00919-3	journal	August 2022
How General is the Conversion Reaction in Mg Battery Cathode: A Case Study of the Magnesiation of α-MnO ₂ Ling, Chen; Zhang, Ruigang; Arthur, Timothy S. Chemistry of Materials, Vol. 27, Issue 16 https://doi.org/10.1021/acs.chemmater.5b02488	journal	August 2015
A manganese–hydrogen battery with potential for grid-scale energy storage Chen, Wei; Li, Guodong; Pei, Allen Nature Energy, Vol. 3, Issue 5 https://doi.org/10.1038/s41560-018-0147-7	journal	April 2018
A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation Gorlin, Yelena; Jaramillo, Thomas F. Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614 https://doi.org/10.1021/ja104587v	journal	October 2010
Understanding the Behaviors of λ-MnO ₂ in Electrochemical Lithium Recovery: Key Limiting Factors and a Route to the Enhanced Performance Kim, Seoni; Kang, Jin Soo; Joo, Hwajoo Environmental Science & Technology, Vol. 54, Issue 14 https://doi.org/10.1021/acs.est.9b07646	journal	June 2020
Cation-Deficient Spinel ZnMn ₂ O ₄ Cathode in Zn(CF ₃ SO ₃ ) ₂ Electrolyte for Rechargeable Aqueous Zn-Ion Battery Zhang, Ning; Cheng, Fangyi; Liu, Yongchang Journal of the American Chemical Society, Vol. 138, Issue 39 https://doi.org/10.1021/jacs.6b05958	journal	September 2016
FinalBulks_for_public_release.zip Carlson, Evan figshare https://doi.org/10.6084/m9.figshare.20303988	dataset	January 2022
Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery Wu, Chuan; Gu, Sichen; Zhang, Qinghua Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07980-7	journal	January 2019
Improving Energy Density and Structural Stability of Manganese Oxide Cathodes for Na-Ion Batteries by Structural Lithium Substitution de la Llave, Ezequiel; Talaie, Elahe; Levi, Elena Chemistry of Materials, Vol. 28, Issue 24 https://doi.org/10.1021/acs.chemmater.6b04078	journal	December 2016
Electrochemically Induced Structural Transformation in a γ-MnO ₂ Cathode of a High Capacity Zinc-Ion Battery System Alfaruqi, Muhammad H.; Mathew, Vinod; Gim, Jihyeon Chemistry of Materials, Vol. 27, Issue 10 https://doi.org/10.1021/cm504717p	journal	May 2015
Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane Birkner, Nancy; Navrotsky, Alexandra Proceedings of the National Academy of Sciences, Vol. 114, Issue 7 https://doi.org/10.1073/pnas.1620427114	journal	January 2017
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
Birnessite-type MnO ₂ Nanowalls and Their Magnetic Properties Zhu, H. T.; Luo, J.; Yang, H. X. The Journal of Physical Chemistry C, Vol. 112, Issue 44 https://doi.org/10.1021/jp804673n	journal	October 2008
Evaluating transition metal oxides within DFT-SCAN and $SCAN + U$ frameworks for solar thermochemical applications Sai Gautam, Gopalakrishnan; Carter, Emily A. Physical Review Materials, Vol. 2, Issue 9 https://doi.org/10.1103/PhysRevMaterials.2.095401	journal	September 2018
Manganese Cluster in Photosynthesis: Where Plants Oxidize Water to Dioxygen Yachandra, Vittal K.; Sauer, Kenneth; Klein, Melvin P. Chemical Reviews, Vol. 96, Issue 7 https://doi.org/10.1021/cr950052k	journal	January 1996
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
Effect of Multiple Cation Electrolyte Mixtures on Rechargeable Zn–MnO ₂ Alkaline Battery Hertzberg, Benjamin J.; Huang, An; Hsieh, Andrew Chemistry of Materials, Vol. 28, Issue 13 https://doi.org/10.1021/acs.chemmater.6b00232	journal	June 2016
Calibration of the DFT/GGA+U Method for Determination of Reduction Energies for Transition and Rare Earth Metal Oxides of Ti, V, Mo, and Ce Lutfalla, Suzanne; Shapovalov, Vladimir; Bell, Alexis T. Journal of Chemical Theory and Computation, Vol. 7, Issue 7 https://doi.org/10.1021/ct200202g	journal	June 2011
Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host Kim, Chunjoong; Phillips, Patrick J.; Key, Baris Advanced Materials, Vol. 27, Issue 22 https://doi.org/10.1002/adma.201500083	journal	April 2015
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I. Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808 https://doi.org/10.1088/0953-8984/9/4/002	journal	January 1997
Cation Vacancies in MnO[sub 2] and Their Influence on Electrochemical Reactivity Ruetschi, Paul Journal of The Electrochemical Society, Vol. 135, Issue 11 https://doi.org/10.1149/1.2095406	journal	January 1988
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
Manganese oxide minerals: Crystal structures and economic and environmental significance Post, J. E. Proceedings of the National Academy of Sciences, Vol. 96, Issue 7 https://doi.org/10.1073/pnas.96.7.3447	journal	March 1999
Energetics of ${MnO}_{2}$ polymorphs in density functional theory Kitchaev, Daniil A.; Peng, Haowei; Liu, Yun Physical Review B, Vol. 93, Issue 4 https://doi.org/10.1103/PhysRevB.93.045132	journal	January 2016
Ground-state properties of multivalent manganese oxides: Density functional and hybrid density functional calculations Franchini, C.; Podloucky, R.; Paier, J. Physical Review B, Vol. 75, Issue 19 https://doi.org/10.1103/PhysRevB.75.195128	journal	May 2007
Deposition of deep-sea manganese nodules Crerar, David A.; Barnes, H. L. Geochimica et Cosmochimica Acta, Vol. 38, Issue 2 https://doi.org/10.1016/0016-7037(74)90111-2	journal	February 1974
Alkali Metal Ions Insertion/Extraction Reactions with Hollandite-Type Manganese Oxide in the Aqueous Phase Feng, Qi; Kanoh, Hirofumi; Miyai, Yoshitaka Chemistry of Materials, Vol. 7, Issue 1 https://doi.org/10.1021/cm00049a023	journal	January 1995
Reversible Insertion Properties of Zinc Ion into Manganese Dioxide and Its Application for Energy Storage Xu, Chengjun; Du, Hongda; Li, Baohua Electrochemical and Solid-State Letters, Vol. 12, Issue 4 https://doi.org/10.1149/1.3065967	journal	January 2009
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
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies Stevanović, Vladan; Lany, Stephan; Zhang, Xiuwen Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/PhysRevB.85.115104	journal	March 2012
Rechargeable Lithium Batteries with Aqueous Electrolytes Li, W.; Dahn, J. R.; Wainwright, D. S. Science, Vol. 264, Issue 5162, p. 1115-1118 https://doi.org/10.1126/science.264.5162.1115	journal	May 1994
Tuning Magnetic Properties of α-MnO ₂ Nanotubes by K ⁺ Doping Luo, J.; Zhu, H. T.; Liang, J. K. The Journal of Physical Chemistry C, Vol. 114, Issue 19 https://doi.org/10.1021/jp1006928	journal	April 2010
Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures Yu, L. T. Journal of The Electrochemical Society, Vol. 144, Issue 3 https://doi.org/10.1149/1.1837492	journal	January 1997
Intercalated water in aqueous batteries Xiao, Biwei Carbon Energy, Vol. 2, Issue 2 https://doi.org/10.1002/cey2.55	journal	May 2020
Predicting aqueous stability of solid with computed Pourbaix diagram using SCAN functional Wang, Zhenbin; Guo, Xingyu; Montoya, Joseph npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-00430-3	journal	October 2020
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
Presentation of an Atlas of Chemical and Electrochemical Equilibria in the Precence of a Gaseous Phase Pourbaix, M.; Zhang, H.; Pourbaix, A. Materials Science Forum, Vol. 251-254 https://doi.org/10.4028/www.scientific.net/msf.251-254.143	journal	October 1997
Water in the interlayer region of birnessite: Importance in cation exchange and structural stability Johnson, E. A.; Post, J. E. American Mineralogist, Vol. 91, Issue 4 https://doi.org/10.2138/am.2006.2090	journal	April 2006
Manganese oxide porous crystals Feng, Qi; Kanoh, Hirofumi; Ooi, Kenta Journal of Materials Chemistry, Vol. 9, Issue 2 https://doi.org/10.1039/a805369c	journal	January 1999
Hydrothermal preparation and low temperature magnetic properties of Mn(OH)2 Christensen, A. Nørlund; Ollivier, G. Solid State Communications, Vol. 10, Issue 7 https://doi.org/10.1016/0038-1098(72)90602-3	journal	April 1972
Bond-length distributions for ions bonded to oxygen: results for the transition metals and quantification of the factors underlying bond-length variation in inorganic solids Gagné, Olivier Charles; Hawthorne, Frank Christopher IUCrJ, Vol. 7, Issue 4 https://doi.org/10.1107/S2052252520005928	journal	June 2020
Non-equilibrium crystallization pathways of manganese oxides in aqueous solution Sun, Wenhao; Kitchaev, Daniil A.; Kramer, Denis Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08494-6	journal	February 2019
Structural and electrochemical properties of the proton / γ-MnO2 system Chabre, Y.; Pannetier, J. Progress in Solid State Chemistry, Vol. 23, Issue 1 https://doi.org/10.1016/0079-6786(94)00005-2	journal	January 1995
Effects of interlayer confinement and hydration on capacitive charge storage in birnessite Boyd, Shelby; Ganeshan, Karthik; Tsai, Wan-Yu Nature Materials, Vol. 20, Issue 12 https://doi.org/10.1038/s41563-021-01066-4	journal	August 2021
Catalytic Performance and in Situ Surface Chemistry of Pure α-MnO ₂ Nanorods in Selective Reduction of NO and N ₂ O with CO Shan, Junjun; Zhu, Yuan; Zhang, Shiran The Journal of Physical Chemistry C, Vol. 117, Issue 16 https://doi.org/10.1021/jp4018103	journal	April 2013
Density Functional Theory Modeling of MnO ₂ Polymorphs as Cathodes for Multivalent Ion Batteries Juran, Taylor R.; Young, Joshua; Smeu, Manuel The Journal of Physical Chemistry C, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcc.8b00918	journal	March 2018
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
The Nature of the Zinc-Containing Ion in Strongly Alkaline Solutions Dirkse, Thedford P. Journal of The Electrochemical Society, Vol. 101, Issue 6 https://doi.org/10.1149/1.2781254	journal	January 1954
Thermodynamics of Phase Selection in MnO ₂ Framework Structures through Alkali Intercalation and Hydration Kitchaev, Daniil A.; Dacek, Stephen T.; Sun, Wenhao Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b11301	journal	February 2017
Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides García-Mota, Mónica; Bajdich, Michal; Viswanathan, Venkatasubramanian The Journal of Physical Chemistry C, Vol. 116, Issue 39 https://doi.org/10.1021/jp306303y	journal	September 2012
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
Bismuth Enables the Formation of Disordered Birnessite in Rechargeable Alkaline Batteries Bruck, Andrea M.; Kim, Matthew A.; Ma, Lu Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/aba075	journal	July 2020
Formation enthalpies by mixing GGA and GGA $+$ $U$ calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Investigation of the Mechanism of Mg Insertion in Birnessite in Nonaqueous and Aqueous Rechargeable Mg-Ion Batteries Sun, Xiaoqi; Duffort, Victor; Mehdi, B. Layla Chemistry of Materials, Vol. 28, Issue 2 https://doi.org/10.1021/acs.chemmater.5b03983	journal	January 2016
Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD Gallaway, Joshua W.; Menard, Melissa; Hertzberg, Benjamin Journal of The Electrochemical Society, Vol. 162, Issue 1 https://doi.org/10.1149/2.0811501jes	journal	November 2014
Verwey-Type Transition and Magnetic Properties of the LiMn2O4Spinels Shimakawa, Y.; Numata, T.; Tabuchi, J. Journal of Solid State Chemistry, Vol. 131, Issue 1 https://doi.org/10.1006/jssc.1997.7366	journal	June 1997
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
Magnetic Properties of ${Mn}_{3}$ $O_{4}$ and the Canted Spin Problem Dwight, Kirby; Menyuk, Norman Physical Review, Vol. 119, Issue 5 https://doi.org/10.1103/PhysRev.119.1470	journal	September 1960
Neutron diffraction study of hydrogen in birnessite structures Post, J. E.; Heaney, P. J.; Cho, Y. American Mineralogist, Vol. 96, Issue 4 https://doi.org/10.2138/am.2011.3629	journal	March 2011
Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams Zeng, Zhenhua; Chan, Maria K. Y.; Zhao, Zhi-Jian The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b03169	journal	July 2015
Oxidation energies of transition metal oxides within the $GGA + U$ framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries Yadav, Gautam G.; Gallaway, Joshua W.; Turney, Damon E. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14424	journal	March 2017
A New Type of Antiferromagnetic Structure in the Rutile Type Crystal Yoshimori, Akio Journal of the Physical Society of Japan, Vol. 14, Issue 6 https://doi.org/10.1143/JPSJ.14.807	journal	June 1959

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ion insertion
electrochemistry
ionics
intercalation
ion selective electrode
manganese dioxide
polymorphs
density functional theory

Title: Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

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