Material Failure Mechanisms of Alkaline Zn Rechargeable Conversion Electrodes

D’Ambrose, Michael J.; Turney, Damon E.; Yadav, Gautam G.; Nyce, Michael; Banerjee, Sanjoy

doi:10.1021/acsaem.0c03144

Material Failure Mechanisms of Alkaline Zn Rechargeable Conversion Electrodes

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.0c03144· OSTI ID:1847079

^[1]; ^[2]; ^[2]; Nyce, Michael ^[2]; Banerjee, Sanjoy ^[2]

The City College of New York, NY (United States); City College of New York
The City College of New York, NY (United States)

Zinc (Zn) alkaline electrodes hold great importance and promise in the battery technology community, yet their behavior in real-world applications is still poorly understood. Here, we report a study of failure mechanisms and material evolution during cycling of 27 zinc–manganese dioxide (Zn–MnO₂) cells wherein the percent utilization of the Zn electroactive material is systematically varied between 1 and 16%. Cell fabrication is kept typical of the prevailing industrial cell design. The cycle life ranges from 2800 to 60, depending inversely on the Zn utilization. In all cases, the Zn material microstructure sheds the polytetrafluoroethylene (PTFE) binder and forms zinc oxide (ZnO) rods, with longer rods formed by lower current per Zn mass. Irreversible side reactions such as the hydrogen evolution reaction (HER), short circuits, or gas crossover cause the Zn anode’s charging efficiency to average 92% (as low as 86%), which in turn causes the baseload of metallic Zn to gradually disappear. Cell failure occurs after the baseload of metallic Zn is exhausted. The total lifetime discharge capacity remains constant near 12 ± 5 Ah/g Zn invariant of Zn utilization, which suggests that the aforementioned processes of Zn microstructural evolution and side-reaction destruction of baseload metallic zinc both progress linearly with cell capacity throughput. Manual reproduction of individual Zn failure mechanisms is performed in 22 fresh cells. Tight packing of the microstructure can lead to poor mass transfer, which causes supersaturation of soluble Zn and finally produces a high overvoltage during discharge. Here, the low charging current density yields poor coulombic efficiency due either to the competitive HER or soft short circuits.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Electricity (OE)

Grant/Contract Number:: NA0003525

OSTI ID:: 1847079

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 4 Vol. 4; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Development of long-lived high-performance zinc-calcium/nickel oxide cells Jain, R.; Adler, T. C.; McLarnon, F. R. Journal of Applied Electrochemistry, Vol. 22, Issue 11 https://doi.org/10.1007/BF01029582	journal	November 1992
The rechargeability of manganese dioxide in alkaline electrolyte Kordesch, K.; Gsellmann, J.; Peri, M. Electrochimica Acta, Vol. 26, Issue 10 https://doi.org/10.1016/0013-4686(81)90021-9	journal	October 1981
Passivation of zinc in concentrated alkaline solution—II. Role of various experimental factors and the distinction between the solid-state and dissolution—precipitation mechanisms Baugh, L. M.; Baikie, A. R. Electrochimica Acta, Vol. 30, Issue 9 https://doi.org/10.1016/0013-4686(95)80009-3	journal	September 1985
Long life sealed nickel-zinc cell using a new separator Sato, Yuichi; Kanda, Motoya; Niki, Hirokazu Journal of Power Sources, Vol. 9, Issue 2 https://doi.org/10.1016/0378-7753(83)80029-9	journal	January 1983
A study of calcium zincate as negative electrode materials for secondary batteries Yu, Jingxian; Yang, Hanxi; Ai, Xinping Journal of Power Sources, Vol. 103, Issue 1 https://doi.org/10.1016/S0378-7753(01)00833-3	journal	December 2001
Preparation and electrochemical performance of In-doped ZnO as anode material for Ni–Zn secondary cells Zeng, Dongqing; Yang, Zhanhong; Wang, Shengwei Electrochimica Acta, Vol. 56, Issue 11 https://doi.org/10.1016/j.electacta.2011.01.119	journal	April 2011
Accessing the second electron capacity of MnO2 by exploring complexation and intercalation reactions in energy dense alkaline batteries Yadav, Gautam G.; Wei, Xia; Huang, Jinchao International Journal of Hydrogen Energy, Vol. 43, Issue 17 https://doi.org/10.1016/j.ijhydene.2018.03.061	journal	April 2018
Translating Materials-Level Performance into Device-Relevant Metrics for Zinc-Based Batteries Parker, Joseph F.; Ko, Jesse S.; Rolison, Debra R. Joule, Vol. 2, Issue 12 https://doi.org/10.1016/j.joule.2018.11.007	journal	December 2018
Development and testing of an economic grid-scale flow-assisted zinc/nickel-hydroxide alkaline battery Turney, Damon E.; Shmukler, Michael; Galloway, Kevin Journal of Power Sources, Vol. 264 https://doi.org/10.1016/j.jpowsour.2014.04.067	journal	October 2014
Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling Ingale, Nilesh D.; Gallaway, Joshua W.; Nyce, Michael Journal of Power Sources, Vol. 276 https://doi.org/10.1016/j.jpowsour.2014.11.010	journal	February 2015
Operando identification of the point of [Mn2]O4 spinel formation during γ-MnO2 discharge within batteries Gallaway, Joshua W.; Hertzberg, Benjamin J.; Zhong, Zhong Journal of Power Sources, Vol. 321 https://doi.org/10.1016/j.jpowsour.2016.05.002	journal	July 2016
Effects of barium on the performance of secondary alkaline zinc electrode Zheng, Y.; Wang, J. M.; Chen, H. Materials Chemistry and Physics, Vol. 84, Issue 1 https://doi.org/10.1016/j.matchemphys.2003.11.015	journal	March 2004
Rapid electrochemical synthesis of δ-MnO2 from γ-MnO2 and unleashing its performance as an energy dense electrode Yadav, Gautam G.; Wei, Xia; Gallaway, Joshua W. Materials Today Energy, Vol. 6 https://doi.org/10.1016/j.mtener.2017.10.008	journal	December 2017
Effects of lanthanum and neodymium hydroxides on secondary alkaline zinc electrode No authors listed Journal of Power Sources, Vol. 69, Issue 1-2 https://doi.org/10.1016/s0378-7753(97)02569-x	journal	November 1997
Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage Turney, Damon E.; Gallaway, Joshua W.; Yadav, Gautam G. Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00754	journal	May 2017
Photocorrosion of ZnO Single Crystals during Electrochemical Water Splitting Dworschak, Dominik; Brunnhofer, Carina; Valtiner, Markus ACS Applied Materials & Interfaces, Vol. 12, Issue 46 https://doi.org/10.1021/acsami.0c15508	journal	November 2020
Breaking the 2 V Barrier in Aqueous Zinc Chemistry: Creating 2.45 and 2.8 V MnO ₂ –Zn Aqueous Batteries Yadav, Gautam G.; Turney, Damon; Huang, Jinchao ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01643	journal	August 2019
Electrochemical Energy Storage for Green Grid Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W. Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613 https://doi.org/10.1021/cr100290v	journal	May 2011
A Study of Alkaline Solutions of Zinc Oxide Dirkse, Thedford P.; Postmus, Clarence; Vandenbosch, Robert Journal of the American Chemical Society, Vol. 76, Issue 23 https://doi.org/10.1021/ja01652a041	journal	December 1954
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
Wiring zinc in three dimensions re-writes battery performance—dendrite-free cycling Parker, Joseph F.; Chervin, Christopher N.; Nelson, Eric S. Energy Environ. Sci., Vol. 7, Issue 3 https://doi.org/10.1039/c3ee43754j	journal	January 2014
Real-time materials evolution visualized within intact cycling alkaline batteries Gallaway, Joshua W.; Erdonmez, Can K.; Zhong, Zhong J. Mater. Chem. A, Vol. 2, Issue 8 https://doi.org/10.1039/c3ta15169g	journal	January 2014
Superior cycling stability and high rate capability of three-dimensional Zn/Cu foam electrodes for zinc-based alkaline batteries Yan, Zhao; Wang, Erdong; Jiang, Luhua RSC Advances, Vol. 5, Issue 102 https://doi.org/10.1039/c5ra16264e	journal	January 2015
A Zn–NiO rechargeable battery with long lifespan and high energy density Wang, Xiaowei; Li, Minxia; Wang, Yanfang Journal of Materials Chemistry A, Vol. 3, Issue 16 https://doi.org/10.1039/c5ta01947h	journal	January 2015
A conversion-based highly energy dense Cu ²⁺ intercalated Bi-birnessite/Zn alkaline battery Yadav, Gautam G.; Wei, Xia; Huang, Jinchao Journal of Materials Chemistry A, Vol. 5, Issue 30 https://doi.org/10.1039/c7ta05347a	journal	January 2017
Vibrational Spectra of Solutions of Zinc Oxide in Potassium Hydroxide Fordyce, J. Stuart; Baum, Ruth L. The Journal of Chemical Physics, Vol. 43, Issue 3 https://doi.org/10.1063/1.1696856	journal	August 1965
NMR Study of Complex Ions in the Aqueous ZnO–KOH System Newman, Gerald H.; Blomgren, George E. The Journal of Chemical Physics, Vol. 43, Issue 8 https://doi.org/10.1063/1.1697204	journal	October 1965
Zinc Electrode Cycle-Life Performance in Alkaline Electrolytes Having Reduced zinc Species Solubility Nichols, James T.; McLARNON, Frank R.; Cairns, Elton J. Chemical Engineering Communications, Vol. 38, Issue 3-6 https://doi.org/10.1080/00986448508911315	journal	November 1985
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion Parker, Joseph F.; Chervin, Christopher N.; Pala, Irina R. Science, Vol. 356, Issue 6336 https://doi.org/10.1126/science.aak9991	journal	April 2017
Morphology and Spatial Distribution of ZnO Formed in Discharged Alkaline Zn/MnO[sub 2] AA Cells Horn, Quinn C.; Shao-Horn, Yang Journal of The Electrochemical Society, Vol. 150, Issue 5 https://doi.org/10.1149/1.1566014	journal	January 2003
Zinc Electrode Shape Change Einerhand, R. E. F. Journal of The Electrochemical Society, Vol. 138, Issue 1 https://doi.org/10.1149/1.2085582	journal	January 1991
The Secondary Alkaline Zinc Electrode McLarnon, Frank R. Journal of The Electrochemical Society, Vol. 138, Issue 2 https://doi.org/10.1149/1.2085653	journal	January 1991
Pasted‐Rolled Zinc Electrodes Containing Calcium Hydroxide for Use in Zn / NiOOH Cells Gagnon, Eugene G.; Wang, Yar‐Ming Journal of The Electrochemical Society, Vol. 134, Issue 9 https://doi.org/10.1149/1.2100830	journal	September 1987
Effects of KOH Concentration on the Shape Change and Cycle Life of Zn / NiOOH Cells Gagnon, E. G. Journal of The Electrochemical Society, Vol. 133, Issue 10 https://doi.org/10.1149/1.2108327	journal	October 1986
Accelerated Testing of Additives in Zinc Plates of Nickel Zinc Cells Biegler, C.; Deutscher, R. L.; Fletcher, S. Journal of The Electrochemical Society, Vol. 130, Issue 12 https://doi.org/10.1149/1.2119575	journal	December 1983
The Behavior of the Zinc Electrode in Alkaline Solutions: V . Supersaturated Zincate Solutions Dirkse, T. P. Journal of The Electrochemical Society, Vol. 128, Issue 7 https://doi.org/10.1149/1.2127654	journal	July 1981
Observations of an Operating Zinc‐Pore Electrode Katan, T.; Savory, J. R.; Perkins, J. Journal of The Electrochemical Society, Vol. 126, Issue 11 https://doi.org/10.1149/1.2128811	journal	November 1979
The Zn ‐ KOH System: The Solution‐Precipitation Path for Anodic ZnO Formation Szpak, S.; Gabriel, C. J. Journal of The Electrochemical Society, Vol. 126, Issue 11 https://doi.org/10.1149/1.2128826	journal	November 1979
The Behavior of the Zinc Electrode in Alkaline Solutions: III . The Equilibrium Potential Dirkse, T. P. Journal of The Electrochemical Society, Vol. 126, Issue 9 https://doi.org/10.1149/1.2129306	journal	September 1979
Engineering Analysis of Shape Change in Zinc Secondary Electrodes Choi, King Wai Journal of The Electrochemical Society, Vol. 123, Issue 11 https://doi.org/10.1149/1.2132657	journal	January 1976
Supersaturated Zincate Solutions Van Doorne, W.; Dirkse, T. P. Journal of The Electrochemical Society, Vol. 122, Issue 1 https://doi.org/10.1149/1.2134149	journal	January 1975
Zinc Electrode Shape Change in Secondary Cells McBreen, James Journal of The Electrochemical Society, Vol. 119, Issue 12 https://doi.org/10.1149/1.2404060	journal	January 1972
The Mechanism of the Zinc(II)-Zinc Amalgam Electrode Reaction in Alkaline Media As Studied by Chronocoulometric and Voltammetric Techniques Payne, DeWitt A.; Bard, Allen J. Journal of The Electrochemical Society, Vol. 119, Issue 12 https://doi.org/10.1149/1.2404067	journal	January 1972
On the Deposition and Dissolution of Zinc in Alkaline Solutions Bockris, J. O'M.; Nagy, Z.; Damjanovic, A. Journal of The Electrochemical Society, Vol. 119, Issue 3 https://doi.org/10.1149/1.2404188	journal	January 1972
Exchange in the Zn, Zincate, ZnO System Dirkse, T. P.; Vander Lugt, L. A.; Hampson, N. A. Journal of The Electrochemical Society, Vol. 118, Issue 10 https://doi.org/10.1149/1.2407792	journal	January 1971
Film Formation and Hydrogen Evolution on the Alkaline Zinc Electrode Powers, R. W. Journal of The Electrochemical Society, Vol. 118, Issue 5 https://doi.org/10.1149/1.2408145	journal	January 1971
The Anodic Behavior of Zinc in KOH Solutions Dirkse, T. P.; De Wit, David; Shoemaker, R. Journal of The Electrochemical Society, Vol. 115, Issue 5 https://doi.org/10.1149/1.2411259	journal	January 1968
Anodic Films on Zinc and the Formation of Cobwebs Powers, R. W. Journal of The Electrochemical Society, Vol. 116, Issue 12 https://doi.org/10.1149/1.2411652	journal	January 1969
The Anodic Dissolution and Passivation of Zinc in Concentrated Potassium Hydroxide Solutions Powers, R. W.; Breiter, M. W. Journal of The Electrochemical Society, Vol. 116, Issue 6 https://doi.org/10.1149/1.2412040	journal	January 1969
Electrolytic Oxidation of Zinc in Alkaline Solutions Dirkse, Thedford P. Journal of The Electrochemical Society, Vol. 102, Issue 9 https://doi.org/10.1149/1.2430136	journal	January 1955
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
A Lateral Microfluidic Cell for Imaging Electrodeposited Zinc near the Shorting Condition Gallaway, Joshua W.; Desai, Divyaraj; Gaikwad, Abhinav Journal of The Electrochemical Society, Vol. 157, Issue 12 https://doi.org/10.1149/1.3491355	journal	January 2010
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO ₂ Gallaway, Joshua W.; Yadav, Gautam G.; Turney, Damon E. Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0221813jes	journal	January 2018
An In Situ Synchrotron Study of Zinc Anode Planarization by a Bismuth Additive Gallaway, Joshua W.; Gaikwad, Abhinav M.; Hertzberg, Benjamin Journal of The Electrochemical Society, Vol. 161, Issue 3 https://doi.org/10.1149/2.037403jes	journal	December 2013
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

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