Dual electrode-free Zn-MnO2 battery as a future energy source

Sunny Nandi , Martin Pumera

InfoMat ›› 2026, Vol. 8 ›› Issue (1) : e70094

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InfoMat ›› 2026, Vol. 8 ›› Issue (1) :e70094 DOI: 10.1002/inf2.70094
REVIEW ARTICLE
Dual electrode-free Zn-MnO2 battery as a future energy source
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Abstract

Aqueous rechargeable Zn-MnO2 batteries are considered one of the most promising energy storage systems and have been extensively studied in recent years, owing to their high energy density, low cost, and intrinsic safety. However, the practical application of conventional Zn-MnO2 batteries is hindered by poor cycling stability, corrosion, and unwanted side reactions. Recently, dual electrode-free Zn-MnO2 batteries have emerged as a promising alternative. Their simplified battery configurations and lightweight design, achieved by eliminating the need for pre-fabricated bulk electrodes, offer higher energy density. Nevertheless, such designs can, in principle, suffer from limited cycle life due to the poor reversibility of the Zn-MnO2 deposition/stripping process. This review critically examines recent advances aimed at overcoming these challenges, highlighting the transition from conventional to anode-free, cathode-free, and ultimately dual electrode-free configurations. We also present key strategies including electrolyte engineering, current collector modification via 3D printing, and interfacial engineering to enable stable long-term cycling, along with insights from advanced in situ characterization techniques such as electrochemical quartz crystal microbalance (EQCM) and optical microscopy. Finally, we outline future opportunities required to advance this promising field toward practical applications.

Keywords

aqueous battery / current collectors / electrolyte engineering / energy storage / in situ monitoring

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Sunny Nandi, Martin Pumera. Dual electrode-free Zn-MnO2 battery as a future energy source. InfoMat, 2026, 8(1): e70094 DOI:10.1002/inf2.70094

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References

[1]

Kuznetsov OA, Mohanty S, Pigos E, Chen G, Cai W, Harutyunyan AR. High energy density flexible and ecofriendly lithium-ion smart battery. Energy Storage Mater. 2023;54:266-275.

[2]

Ren H, Du X, Liang J, Wei W. Optimization strategies for flexible aqueous rechargeable sodium-ion batteries (ARSIBs). J Mater Chem A. 2025;13(17):12009-12038.

[3]

Man P, He B, Zhang Q, et al. High-performance and Ultraflexible aqueous rechargeable lithium-ion batteries developed by constructing all binder-free electrode materials. Appl Mater Interfaces. 2020;12(23):25700-25708.

[4]

Wen Z, Wu F, Ng M-F, et al. Lean-water hydrogel with multipolar sites for flexible and high-performance aqueous aluminum-ion batteries. Adv Mater. 2025;37:2500695.

[5]

Reddy TB. Linden's Handbook of Batteries. 4th ed. McGraw Hill; 2010.

[6]

Winter M, Brodd RJ. What are batteries, fuel cells, and supercapacitors? Chem Rev. 2004;104(10):4245-4270.

[7]

Abdollahifar M, Cavers H, Scheffler S, Diener A, Lippke M, Kwade A. Insights into influencing electrode Calendering on the battery performance. Adv Energy Mater. 2023;13(40):2300973.

[8]

Tang K, Tian L, Zhang Y, Xu ZJ. Anode-free lithium metal batteries: a promising flexible energy storage system. J Mater Chem A. 2024;12(27):16268-16292.

[9]

Tian Y, An Y, Wei C, et al. Recent advances and perspectives of anode-free rechargeable batteries. Nano Energy. 2020;78:105344.

[10]

An Y, Zeng Y, Luan D, Lou XW(D). Materials design for high-energy-density anode-free batteries. Matter. 2024;7(4):1466-1502.

[11]

Zheng X, Liu Z, Sun J, et al. Constructing robust heterostructured interface for anode-free zinc batteries with ultrahigh capacities. Nat Commun. 2023;14(1):76.

[12]

An Y, Tian Y, Zhang K, et al. Stable aqueous anode-free zinc batteries enabled by interfacial engineering. Adv Funct Mater. 2021;31(26):2101886.

[13]

Nandi S, Pumera M. Anode-free zinc-metal batteries (AFZMBs): a new paradigm in energy storage. Small. 2025;21:2412161.

[14]

Liu Z, Yang Y, Liang S, Lu B, Zhou J. pH-buffer contained electrolyte for self-adjusted cathode-free Zn–MnO2 batteries with coexistence of dual mechanisms. Small Struct. 2021;2(11):2100119.

[15]

Gou L, Li J, Liang K, Zhao S, Li D, Fan X. Bi-MOF modulating MnO2 deposition enables ultra-stable cathode-free aqueous zinc-ion batteries. Small. 2023;19(17):2208233.

[16]

Wang M, Chen N, Zhu Z, et al. Electrode-less MnO2-metal batteries with deposition and stripping chemistry. Small. 2021;17(44):2103921.

[17]

Li Y, Zheng X, Carlson EZ, et al. In situ formation of liquid crystal interphase in electrolytes with soft templating effects for aqueous dual-electrode-free batteries. Nat Energy. 2024;9(11):1350-1359.

[18]

Chen J, Xu W, Wang H, et al. Emerging two-dimensional nanostructured manganese-based materials for electrochemical energy storage: recent advances, mechanisms, challenges, and prospects. J Mater Chem A. 2022;10(40):21197-21250.

[19]

Gao Y, Yang H, Bai Y, Wu C. Mn-based oxides for aqueous rechargeable metal ion batteries. J Mater Chem A. 2021;9(19):11472-11500.

[20]

Li H, Zhang W, Sun K, et al. Manganese-based materials for rechargeable batteries beyond lithium-ion. Adv Energy Mater. 2021;11(25):2100867.

[21]

Sambandam B, Mathew V, Kim S, et al. An analysis of the electrochemical mechanism of manganese oxides in aqueous zinc batteries. Chem. 2022;8(4):924-946.

[22]

Zhang N, Wang JC, Guo YF, Wang PF, Zhu YR, Yi TF. Insights on rational design and energy storage mechanism of Mn-based cathode materials towards high performance aqueous zinc-ion batteries. Coordin Chem Rev. 2023;479:215009.

[23]

Chen W, Li G, Pei A, et al. A manganese–hydrogen battery with potential for grid-scale energy storage. Nat Energy. 2018;3(5):428-435.

[24]

Xu C, Li B, Du H, Kang F. Energetic zinc ion chemistry: the rechargeable zinc ion battery. Angew Chem Int Ed. 2012;51(4):933-935.

[25]

Alfaruqi MH, Mathew V, Gim J, et al. Electrochemically induced structural transformation in a γ-MnO2 cathode of a high capacity zinc-ion battery system. Chem Mater. 2015;27(10):3609-3620.

[26]

Zeng Y, Zhang X, Meng Y, et al. Achieving ultrahigh energy density and Long durability in a flexible rechargeable quasi-solid-state Zn–MnO2 battery. Adv Mater. 2017;29(26):1700274.

[27]

Zhu Y, Cui Y, Alshareef HN. An anode-free Zn–MnO2 battery. Nano Lett. 2021;21(3):1446-1453.

[28]

Luo S, Liu S, Yang G, et al. Electrode-free flexible batteries enabled by electro-deposition of both Zn and MnO2 from electrolytes. New J Chem. 2024;48(4):1462-1466.

[29]

Wang J, Zhou Y, Zhuo Y, et al. The challenges and strategies towards high-performance anode-free post-lithium metal batteries. Chem Sci. 2025;16(2):552-574.

[30]

Zhang X, Zhang L, Jia X, Song W, Liu Y. Design strategies for aqueous zinc metal batteries with high zinc utilization: from metal anodes to anode-free structures. Nano-Micro Lett. 2024;16(1):75.

[31]

Panda MR, El Meragawi S, Sharifzadeh Mirshekarloo M, Chen W, Shaibani M, Majumder M. Acidity-aided surface modification strategy to enhance in situ MnO2 deposition for high-performance Zn–MnO2 battery prototypes. Small. 2025;21(28):2311933.

[32]

Meng L, Zhu Y, Lu Y, et al. Rechargeable Zn–MnO2 batteries: Progress, challenges, rational design, and perspectives. ChemElectroChem. 2024;11(3):e202300495.

[33]

Song X, Ma Y, Hu W, et al. Recent progress and perspectives on anode-free aqueous zinc-metal batteries for higher energy density: a review. J Energy Chem. 2025;110:986-1005.

[34]

Perez-Antolin D, Sáez-Bernal I, Colina A, Ventosa E. Float-charging protocol in rechargeable Zn–MnO2 batteries: unraveling the key role of Mn2+ additives in preventing spontaneous pH changes. Electrochem Commun. 2022;138:107271.

[35]

Chao D, Zhou W, Ye C, et al. An electrolytic Zn–MnO2 battery for high-voltage and scalable energy storage. Angew Chem Int ed. 2019;58(23):7823-7828.

[36]

Mateos M, Makivic N, Kim Y-S, Limoges B, Balland V. Accessing the two-electron charge storage capacity of MnO2 in mild aqueous electrolytes. Adv Energy Mater. 2020;10:2000332.

[37]

Mateos M, Harris KD, Limoges B, Balland V. Nanostructured electrode enabling fast and fully reversible MnO2-to-Mn2+ conversion in mild buffered aqueous electrolytes. ACS Appl Energy Mater. 2020;3(8):7610-7618.

[38]

Guo X, Zhou J, Bai C, Li X, Fang G, Liang S. Zn/MnO2 battery chemistry with dissolution-deposition mechanism. Mater Today Energy. 2020;16:100396.

[39]

Zhang W, Dai Y, Chen R, et al. Highly reversible zinc metal anode in a dilute aqueous electrolyte enabled by a pH buffer additive. Angew Chem Int ed. 2023;62(5):e202212695.

[40]

Fitz O, Wagner F, Pross-Brakhage J, et al. Introducing a concept for designing an aqueous electrolyte with pH buffer properties for Zn-MnO2 batteries with Mn2+/MnO2 deposition/dissolution. Energ Technol. 2023;11(12):2300723.

[41]

Molaei E, Doroodmand MM, Shaali R. Tartaric acid as a novel additive for approaching high-performance capacity retention in zinc-ion battery. Sci Rep. 2022;12(1):13301.

[42]

Wu J, Li Y, Huang J, Chi X, Yang J, Liu Y. Bromide–acetate co-mediated high-power density rechargeable aqueous zinc–manganese dioxide batteries. J Mater Chem A. 2021;9(38):21888-21896.

[43]

Ali M, Zheng X, Luo R, et al. Preventing electrolyte degradation through enhanced MnO2 deposition/dissolution in Zn–MnO2 battery using vanadium redox mediator. Chem Eng J. 2025;522:167404.

[44]

Liu X, Dong X, Passerini S. Operando pH measurements revealing the promoted Zn2+ intercalation kinetics of pre-intercalated V2O5 cathode in aqueous zinc metal batteries. J Power Sources. 2024;623:235401.

[45]

Aguilar I, Brown J, Godeffroy L, et al. A key advance toward practical aqueous Zn/MnO2 batteries via better electrolyte design. Joule. 2025;9(1):101784.

[46]

Fitz O, Bischoff C, Bauer M, et al. Electrolyte study with in operando pH tracking providing insight into the reaction mechanism of aqueous acidic Zn//MnO2 batteries. ChemElectroChem. 2021;8(18):3553-3566.

[47]

He Z-F, Lu Y-T, Wei T-C, Hu C-C. Complementary operando electrochemical quartz crystal microbalance and UV/Vis spectroscopic studies: acetate effects on zinc–manganese batteries. ChemSusChem. 2023;16(12):e202300259.

[48]

Rodríguez-Pérez IA, Chang HJ, Fayette M, et al. Mechanistic investigation of redox processes in Zn-MnO2 battery in mild aqueous electrolytes. J Mater Chem A. 2021;9(36):20766-20775.

[49]

Bischoff CF, Fitz OS, Burns J, et al. Revealing the local pH value changes of acidic aqueous zinc ion batteries with a manganese dioxide electrode during cycling. J Electrochem Soc. 2020;167(2):020545.

[50]

Rubel O, Nguyen Thanh Tran T, Gourley S, et al. Electrochemical stability of ZnMn2O4: understanding Zn-ion rechargeable battery capacity and degradation. J Phys Chem C. 2022;126(27):10957-10967.

[51]

Zhao D, Zhu Q, Zhou Q, et al. Enhancing I0/I conversion efficiency by starch confinement in zinc-iodine battery. Energy Environ Mater. 2024;7:e12522.

[52]

Zhang S-J, Hao J, Li H, et al. Polyiodide confinement by starch enables shuttle-free Zn–iodine batteries. Adv Mater. 2022;34:2201716.

[53]

Blumen O, Bergman G, Schwatrzman K, et al. Selection criteria for current collectors for highly efficient anode-free Zn batteries. J Mater Chem A. 2023;11(37):19970-19980.

[54]

Xu J, Li H, Jin Y, et al. Understanding the electrical mechanisms in aqueous zinc metal batteries: from electrostatic interactions to electric field regulation. Adv Energy Mater. 2024;36:2309726.

[55]

Chen J, Wang Y, Tian Z, Zhao J, Ma Y, Alshareef HN. Recent developments in three-dimensional Zn metal anodes for battery applications. InfoMat. 2024;6(1):e12485.

[56]

Zhu R, Xiong Z, Yang H, et al. Anode/cathode dual-purpose aluminum current collectors for aqueous zinc-ion batteries. Adv Funct Mater. 2023;33(8):2211274.

[57]

Chen C, Guo R, Ganapathy S, et al. Enhancing Zn deposition reversibility on MXene current collectors by forming ZnF2- containing solid-electrolyte interphase for anode-free zinc metal batteries. Small. 2025;2407226.

[58]

Heo H, Lee J, Jo Y-R, An G-H. Industrial scalability of zinc-ion batteries: enhanced electrochemical performance with high mass loading electrodes on graphene-coated metal current collectors. Adv Energy Mater. 2025;15(22):2500261.

[59]

Huang W, Huang Y, Huang X, Shao F, Liu W, Kang F. 3D leaf-like copper–zinc alloy enables dendrite-free zinc anode for ultra-Long life aqueous zinc batteries. Small. 2024;20(47):2404294.

[60]

Mu Y, Li Z, Wu B-K, et al. 3D hierarchical graphene matrices enable stable Zn anodes for aqueous Zn batteries. Nat Commun. 2023;14(1):4205.

[61]

Xie S, Li Y, Dong L. Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface. J Energy Chem. 2023;76:32-40.

[62]

Xu K, Zheng X, Luo R, et al. A three-dimensional zincophilic nano-copper host enables dendrite-free and anode-free Zn batteries. Mater Today Energy. 2023;34:101284.

[63]

An Y, Xu B, Tian Y, et al. Reversible Zn electrodeposition enabled by interfacial chemistry manipulation for high-energy anode-free Zn batteries. Mater Today. 2023;70:93-103.

[64]

Zhang J, Mao L, Xia Z, Fan M, Deng Y, Chen Z. Zincophilic Design for Highly Stable and Dendrite-Free Zinc Metal Anodes in aqueous zinc-ion batteries. Adv Funct Mater. 2025;35(2):2412547.

[65]

Jeong DY, Chang WJ, Jang S, et al. Controlling dendrite growth and side reactions in anode-free Zn-ion aqueous batteries with PMMA:Zn coated electrode. J Energy Storage. 2024;76:109791.

[66]

Browne MP, Redondo E, Pumera M. 3D printing for electrochemical energy applications. Chem Rev. 2020;120(5):2783-2810.

[67]

Zhang G, Zhang X, Liu H, Li J, Chen Y, Duan H. 3D-printed Multi-Channel metal lattices enabling localized electric-field redistribution for dendrite-free aqueous Zn ion batteries. Adv Energy Mater. 2021;11(19):2003927.

[68]

Zhang F, Wei M, Viswanathan VV, et al. 3D printing technologies for electrochemical energy storage. Nano Energy. 2017;40:418-431.

[69]

Gao W, Michalička J, Pumera M. Hierarchical atomic layer deposited V2O5 on 3D printed nanocarbon electrodes for high-performance aqueous zinc-ion batteries. Small. 2022;18(1):2105572.

[70]

De P, Pumera M. Aqueous multivalent metal-ion batteries: toward 3D-printed architectures. Small. 2024;20(46):2404227.

[71]

Zeng L, He J, Yang C, et al. Direct 3D printing of stress-released Zn powder anodes toward flexible dendrite-free Zn batteries. Energy Storage Mater. 2023;54:469-477.

[72]

Mou C, Bai Y, Zhang Y, et al. A 3D-printed square-hole electrode for dendrite-free zinc–air batteries. Inorg Chem Front. 2023;10(22):6655-6663.

[73]

Ren Y, Meng F, Zhang S, et al. CNT@MnO2 composite ink toward a flexible 3D printed micro-zinc-ion battery. Carbon Energy. 2022;4(3):446-457.

[74]

Nie N, Wang F, Yao W. Fabrication of a 3D structure MnO2 electrode with high MnO2 mass loading as the cathode for high-performance aqueous zinc-ion batteries. Electrochim Acta. 2023;472:143423.

[75]

Yang H, Wan Y, Sun K, et al. Reconciling mass loading and gravimetric performance of MnO2 cathodes by 3D-printed carbon structures for zinc-ion batteries. Adv Funct Mater. 2023;33:2215076.

[76]

Chu T, Park S, Fu K. 3D printing-enabled advanced electrode architecture design. Carbon Energy. 2021;3(3):424-439.

[77]

Cheng W, Zhao M, Lai Y, et al. Recent advances in battery characterization using in situ XAFS, SAXS, XRD, and their combining techniques: from single scale to multiscale structure detection. Exploration. 2024;4(1):20230056.

[78]

Zheng M, You Y, Lu J. Understanding materials failure mechanisms for the optimization of lithium-ion battery recycling. Nat Rev Mater. 2025;10(5):355-368.

[79]

Singh A, Ouassi L, Allemang K, et al. Unlocking self-discharge: unveiling the mysteries of electrode-free Zn-MnO2 batteries with advanced in situ techniques in mild acid aqueous electrolytes. J Power Sources. 2025;625:235585.

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