{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,3]],"date-time":"2026-07-03T15:59:31Z","timestamp":1783094371235,"version":"3.54.6"},"reference-count":75,"publisher":"MDPI AG","issue":"19","license":[{"start":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T00:00:00Z","timestamp":1759881600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China","award":["NSFC-22209101"],"award-info":[{"award-number":["NSFC-22209101"]}]},{"name":"National Natural Science Foundation of China","award":["2019JLZ-10"],"award-info":[{"award-number":["2019JLZ-10"]}]},{"name":"National Natural Science Foundation of China","award":["2021L012"],"award-info":[{"award-number":["2021L012"]}]},{"DOI":"10.13039\/501100017596","name":"Natural Science Basic Research Plan in Shaanxi Province","doi-asserted-by":"publisher","award":["NSFC-22209101"],"award-info":[{"award-number":["NSFC-22209101"]}],"id":[{"id":"10.13039\/501100017596","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100017596","name":"Natural Science Basic Research Plan in Shaanxi Province","doi-asserted-by":"publisher","award":["2019JLZ-10"],"award-info":[{"award-number":["2019JLZ-10"]}],"id":[{"id":"10.13039\/501100017596","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100017596","name":"Natural Science Basic Research Plan in Shaanxi Province","doi-asserted-by":"publisher","award":["2021L012"],"award-info":[{"award-number":["2021L012"]}],"id":[{"id":"10.13039\/501100017596","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi","award":["NSFC-22209101"],"award-info":[{"award-number":["NSFC-22209101"]}]},{"name":"Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi","award":["2019JLZ-10"],"award-info":[{"award-number":["2019JLZ-10"]}]},{"name":"Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi","award":["2021L012"],"award-info":[{"award-number":["2021L012"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Aqueous zinc-ion batteries (ZIBs) have emerged as a promising candidate for large-scale energy storage due to their inherent safety, low cost, and environmental friendliness. However, manganese dioxide (MnO2)-based cathodes, which are widely studied for ZIBs owing to their high theoretical capacity and low cost, face severe capacity fading issues that hinder the commercialization of ZIBs. This performance degradation mainly stems from the weak van der Waals forces between MnO2 layers leading to structural collapse during repeated Zn2+ insertion and extraction; it is also exacerbated by irreversible Mn dissolution via Mn3+ disproportionation that depletes active materials, and further aggravated by dynamic electrolyte pH fluctuations promoting insulating zinc hydroxide sulfate (ZHS) formation to block ion diffusion channels. To address these interconnected challenges, in this study, a synergistic strategy was developed combining crystal engineering and pH buffer regulation. We synthesized three MnO2 polymorphs (\u03b1-, \u03b4-, \u03b3-MnO2), identified \u03b4-MnO2 with flower-like microspheres as optimal, and introduced sodium dihydrogen phosphate (NaH2PO4) as a pH buffer (stabilizing pH at 2.8 \u00b1 0.2). The modified electrolyte improved \u03b4-MnO2 wettability (contact angle of 17.8\u00b0 in NaH2PO4-modified electrolyte vs. 26.1\u00b0 in base electrolyte) and reduced charge transfer resistance (Rct = 78.17 \u03a9), enabling the optimized cathode to retain 117.25 mAh g\u22121 (82.16% retention) after 2500 cycles at 1 A g\u22121. This work provides an effective strategy for stable MnO2-based ZIBs, promoting their application in renewable energy storage.<\/jats:p>","DOI":"10.3390\/ma18194632","type":"journal-article","created":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T14:06:53Z","timestamp":1759932413000},"page":"4632","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Synergistic Regulation of \u03b4-MnO2 Cathode via Crystal Engineering and pH Buffering for Long-Cycle Aqueous Zinc-Ion Batteries"],"prefix":"10.3390","volume":"18","author":[{"given":"Fan","family":"Zhang","sequence":"first","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haotian","family":"Yu","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiongyue","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yahao","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haodong","family":"Ren","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huirong","family":"Liang","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinrui","family":"Li","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuanyuan","family":"Feng","sequence":"additional","affiliation":[{"name":"School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1755-8564","authenticated-orcid":false,"given":"Bin","family":"Zhao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Electrical Insulation and Power Equipment, School of Electrical Engineering, Xi\u2019an Jiaotong University, Xi\u2019an 710049, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaogang","family":"Han","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Electrical Insulation and Power Equipment, School of Electrical Engineering, Xi\u2019an Jiaotong University, Xi\u2019an 710049, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,10,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"3529","DOI":"10.1039\/C6CS00776G","article-title":"Sodium-ion batteries: Present and future","volume":"46","author":"Hwang","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2515","DOI":"10.1021\/acsenergylett.2c01152","article-title":"Regulating water activity for rechargeable zinc-ion batteries: Progress and perspective","volume":"7","author":"Yang","year":"2022","journal-title":"ACS Energy Lett."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"6140","DOI":"10.1007\/s12598-025-03373-0","article-title":"Manipulating the metal\u2013oxygen covalency through diminishing d-p band center difference for rechargeable zinc-air batteries","volume":"44","author":"Huang","year":"2025","journal-title":"Rare Met."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4593","DOI":"10.1002\/adma.200901710","article-title":"Research on advanced materials for Li-ion batteries","volume":"21","author":"Li","year":"2009","journal-title":"Adv. Mater."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2480","DOI":"10.1021\/acsenergylett.8b01426","article-title":"Recent advances in aqueous zinc-ion batteries","volume":"3","author":"Fang","year":"2018","journal-title":"ACS Energy Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"e202315257","DOI":"10.1002\/anie.202315257","article-title":"Preintercalation of ammonium ions in layered \u03b4-MnO2 nanosheets for high-performance aqueous zinc-ion batteries","volume":"62","author":"Yao","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2464","DOI":"10.1039\/D2EE03731A","article-title":"Elucidating a dissolution\u2013deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn\/MnO2 batteries","volume":"16","author":"Kankanallu","year":"2023","journal-title":"Energy Environ. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"100015","DOI":"10.1016\/j.nwnano.2023.100015","article-title":"Modified Scherrer equation to calculate crystal size by XRD with high accuracy, examples Fe2O3, TiO2 and V2O5","volume":"3","author":"Nasiri","year":"2023","journal-title":"Nano Trends"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2304303","DOI":"10.1002\/aenm.202304303","article-title":"Modulating the structure of interlayer\/layer matrix on \u03b4-MnO2 via cerium doping-engineering toward high-performance aqueous zinc ion batteries","volume":"14","author":"Chen","year":"2024","journal-title":"Adv. Energy Mater."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2301906","DOI":"10.1002\/smll.202301906","article-title":"Triggering high capacity and superior reversibility of manganese oxides cathode via magnesium modulation for Zn\/\/MnO2 batteries","volume":"19","author":"Xia","year":"2023","journal-title":"Small"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"e70014","DOI":"10.1002\/cey2.70014","article-title":"Synergistic molecular engineering strategies for enhancing diffusion kinetics and interfacial stability of the \u03b4-MnO2 cathode in aqueous zinc-ion batteries","volume":"7","author":"Ding","year":"2025","journal-title":"Carbon Energy"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2109092","DOI":"10.1002\/adma.202109092","article-title":"Reunderstanding the reaction mechanism of aqueous Zn\u2013Mn batteries with sulfate electrolytes: Role of the zinc sulfate hydroxide","volume":"34","author":"Chen","year":"2022","journal-title":"Adv. Mater."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1074","DOI":"10.1016\/j.ensm.2021.11.002","article-title":"Uniform distribution of zinc ions achieved by functional supramolecules for stable zinc metal anode with long cycling lifespan","volume":"45","author":"Liu","year":"2022","journal-title":"Energy Storage Mater."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4845","DOI":"10.1039\/c3ta00031a","article-title":"Hydrothermal synthesis of \u03b1-MnO2 and \u03b2-MnO2 nanorods as high capacity cathode materials for sodium ion batteries","volume":"1","author":"Su","year":"2013","journal-title":"J. Mater. Chem. A"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"187","DOI":"10.1038\/nnano.2014.6","article-title":"A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes","volume":"9","author":"Liu","year":"2014","journal-title":"Nat. Nanotechnol."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"17150","DOI":"10.1039\/D2DT02153F","article-title":"Characterisation of intergrowth in metal oxide materials using structure-mining: The case of \u03b3-MnO2","volume":"51","author":"Magnard","year":"2022","journal-title":"Dalton Trans."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"3609","DOI":"10.1021\/cm504717p","article-title":"Electrochemically Induced Structural Transformation in a \u03b3-MnO2 Cathode of a High Capacity Zinc-Ion Battery System","volume":"27","author":"Alfaruqi","year":"2015","journal-title":"Chem. Mater."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"2868","DOI":"10.1007\/s12598-023-02303-2","article-title":"Review of vanadium-based oxide cathodes as aqueous zinc-ion batteries","volume":"42","author":"Chen","year":"2023","journal-title":"Rare Met."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Guo, Z., Xiao, Z., Chen, H., Zhou, X., Wang, P., Luo, J., Gao, Y., and Shang, H. (2024). Review of cathodic protection technology for steel rebars in concrete structures in marine environments. Appl. Sci., 14.","DOI":"10.3390\/app14199062"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Ding, Y., Xue, W., Chen, K., Yang, C., Feng, Q., Zheng, D., Xu, W., Wang, F., and Lu, X. (2023). Sodium ion pre-intercalation of \u03b4-MnO2 nanosheets for high energy density aqueous zinc-ion batteries. Nanomaterials, 13.","DOI":"10.3390\/nano13061075"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"205","DOI":"10.1007\/s40820-022-00939-w","article-title":"Solid electrolyte interface in Zn-based battery systems","volume":"14","author":"Wang","year":"2022","journal-title":"Nano-Micro Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"712","DOI":"10.1016\/j.electacta.2016.10.168","article-title":"An efficient \u03b1-MnO2 nanorods forest electrode for electrochemical capacitors with neutral aqueous electrolytes","volume":"220","author":"Kumar","year":"2016","journal-title":"Electrochim. Acta"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"2000082","DOI":"10.1002\/adsu.202000082","article-title":"Challenges and strategies for constructing highly reversible zinc anodes in aqueous zinc-ion batteries: Recent progress and future perspectives","volume":"4","author":"Yu","year":"2020","journal-title":"Adv. Sustain. Syst."},{"key":"ref_24","first-page":"931","article-title":"pH buffer KH2PO4 boosts zinc ion battery performance via facilitating proton reaction of MnO2 cathode","volume":"657","author":"Liu","year":"2024","journal-title":"J. Alloys Compd."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"e202313163","DOI":"10.1002\/anie.202313163","article-title":"Hybrid superlattice-triggered selective proton grotthuss intercalation in \u03b4-MnO2 for high-performance zinc-ion battery","volume":"62","author":"Zhang","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2880","DOI":"10.1021\/ja0177105","article-title":"Selected-control hydrothermal synthesis of \u03b1-and \u03b2-MnO2 single crystal nanowires","volume":"124","author":"Wang","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1007\/s40820-020-0397-3","article-title":"Layered birnessite cathode with a displacement\/intercalation mechanism for high-performance aqueous zinc-ion batteries","volume":"12","author":"Zhai","year":"2020","journal-title":"Nano-Micro Lett."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"100663","DOI":"10.1016\/j.ijoes.2024.100663","article-title":"Facile fabrication of mesoporous Ag-doped \u03b3-MnO2 nanowires with rich oxygen defects for boosting performance of aqueous Zn-ion batteries","volume":"19","author":"Li","year":"2024","journal-title":"Int. J. Electrochem. Sci."},{"key":"ref_29","first-page":"5101","article-title":"Ion transport and tortuosity in two-dimensional materials for energy storage devices","volume":"20","author":"Tian","year":"2020","journal-title":"Nano Lett."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1803815","DOI":"10.1002\/aenm.201803815","article-title":"Defect engineering of oxygen-deficient manganese oxide to achieve high-performing aqueous zinc ion battery","volume":"9","author":"Xiong","year":"2019","journal-title":"Adv. Energy Mater."},{"key":"ref_31","first-page":"13645","article-title":"Towards high-performance aqueous Zn\u2013MnO2 batteries: Formation & alleviation of irreversible inert phases","volume":"9","author":"Zhang","year":"2021","journal-title":"J. Mater. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"e9120039","DOI":"10.26599\/NRE.2023.9120039","article-title":"Recent advances and perspectives for Zn-based batteries: Zn anode and electrolyte","volume":"2","author":"Ge","year":"2023","journal-title":"Nano Res. Energy"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"911","DOI":"10.1107\/S0021889804022551","article-title":"Size\u2013Strain Line-Broadening Analysis of the Ceria Round-Robin Sample","volume":"37","author":"Balzar","year":"2004","journal-title":"J. Appl. Crystallogr."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"18029","DOI":"10.1039\/D3TA03338D","article-title":"Recent advances in aqueous zinc\u2013sulfur batteries: Overcoming challenges for sustainable energy storage","volume":"11","author":"Feng","year":"2023","journal-title":"J. Mater. Chem. A"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"2620","DOI":"10.1021\/acsenergylett.8b01552","article-title":"Present and future perspective on electrode materials for rechargeable zinc-ion batteries","volume":"3","author":"Konarov","year":"2018","journal-title":"ACS Energy Lett."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"545","DOI":"10.1039\/D4EE04525D","article-title":"Strategies of interfacial chemistry manipulated zinc deposition towards high-energy and long-cycle-life aqueous anode-free zinc metal batteries","volume":"18","author":"Wang","year":"2025","journal-title":"Energy Environ. Sci."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"146901","DOI":"10.1016\/j.cej.2023.146901","article-title":"Unravelling the proton hysteresis mechanism in vacancy modified vanadium oxides for High-Performance aqueous zinc ion battery","volume":"477","author":"Li","year":"2023","journal-title":"Chem. Eng. J."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"5563","DOI":"10.1039\/D1EE01861B","article-title":"A progressive nucleation mechanism enables stable zinc stripping\u2013plating behavior","volume":"14","author":"Li","year":"2021","journal-title":"Energy Environ. Sci."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2325983","DOI":"10.1080\/17518253.2024.2325983","article-title":"Recent advances in MXene-based materials for high-performance metal-air batteries","volume":"17","author":"Worku","year":"2024","journal-title":"Green Chem. Lett. Rev."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"673","DOI":"10.1016\/j.jcis.2023.09.102","article-title":"Defective construction of vanadium-based cathode materials for high-rate long-cycle aqueous zinc ion batteries","volume":"653","author":"Ran","year":"2024","journal-title":"J. Colloid Interface Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"6610","DOI":"10.1039\/D3TA06778E","article-title":"A multifunctional phenylalanine additive stabilizing zinc anodes in aqueous zinc ion batteries","volume":"12","author":"Ni","year":"2024","journal-title":"J. Mater. Chem. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"103248","DOI":"10.1016\/j.ensm.2024.103248","article-title":"Strategies for pH regulation in aqueous zinc-ion batteries","volume":"67","author":"Liu","year":"2024","journal-title":"Energy Storage Mater."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"102","DOI":"10.1107\/S0021889878012844","article-title":"Scherrer after Sixty Years: A Survey and Some New Results in the Determination of Crystallite Size","volume":"11","author":"Langford","year":"1978","journal-title":"J. Appl. Crystallogr."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"24386","DOI":"10.1021\/acsami.2c03773","article-title":"Interface engineering to improve the rate performance and stability of the Mn-Cathode electrode for aqueous zinc-ion batteries","volume":"14","author":"Zhou","year":"2022","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"3553","DOI":"10.1002\/celc.202100888","article-title":"Electrolyte study with in operando pH tracking providing insight into the reaction mechanism of aqueous acidic Zn\/\/MnO2 batteries","volume":"8","author":"Fitz","year":"2021","journal-title":"ChemElectroChem"},{"key":"ref_46","first-page":"2111003","article-title":"Crystal structures, reaction mechanisms, and optimization strategies of MnO2 cathode for aqueous rechargeable zinc batteries","volume":"38","author":"Chen","year":"2022","journal-title":"Acta Phys.-Chim. Sin."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"103367","DOI":"10.1016\/j.ensm.2024.103367","article-title":"Electron-outflowing heterostructure hosts for high-voltage aqueous zinc-iodine batteries","volume":"68","author":"Kang","year":"2024","journal-title":"Energy Storage Mater."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"104523","DOI":"10.1016\/j.nanoen.2020.104523","article-title":"Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries","volume":"70","author":"Jia","year":"2020","journal-title":"Nano Energy"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"e202400095","DOI":"10.1002\/batt.202400095","article-title":"Insights into electrolyte strategies for suppressing side reactions towards aqueous zinc-ion batteries","volume":"7","author":"Gong","year":"2024","journal-title":"Batter. Supercaps"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"2301291","DOI":"10.1002\/adfm.202301291","article-title":"Developing cathode materials for aqueous zinc ion batteries: Challenges and practical prospects","volume":"34","author":"Li","year":"2024","journal-title":"Adv. Funct. Mater."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"133496","DOI":"10.1016\/j.seppur.2025.133496","article-title":"Revealing the pH-dependent dissolution mechanism of LiMn2O4\/\u03bb-MnO2 redox couple for selective electrochemical lithium extraction","volume":"372","author":"Wang","year":"2025","journal-title":"Sep. Purif. Technol."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2001769","DOI":"10.1002\/aenm.202001769","article-title":"Defect engineering in manganese-based oxides for aqueous rechargeable zinc-ion batteries: A review","volume":"10","author":"Xiong","year":"2020","journal-title":"Adv. Energy Mater."},{"key":"ref_53","doi-asserted-by":"crossref","unstructured":"Kamenskii, M.A., Volkov, F.S., Eliseeva, S.N., Tolstopyatova, E.G., and Kondratiev, V.V. (2023). Enhancement of electrochemical performance of aqueous zinc ion batteries by structural and interfacial design of MnO2 cathodes: The metal ion doping and introduction of conducting polymers. Energies, 16.","DOI":"10.3390\/en16073221"},{"key":"ref_54","unstructured":"(2021). JCPDS Card No. 44-0141 for \u03b1-MnO2, International Centre for Diffraction Data."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"18032","DOI":"10.1021\/acsomega.3c09725","article-title":"Preparation of Spherical \u03b4-MnO2 Nanoflowers by One-Step Coprecipitation Method as Electrode Material for Supercapacitor","volume":"9","author":"Zhang","year":"2024","journal-title":"ACS Omega"},{"key":"ref_56","unstructured":"(2021). JCPDS Card No. 72-1983 for \u03b3-MnO2, International Centre for Diffraction Data."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"e39656","DOI":"10.1016\/j.heliyon.2024.e39656","article-title":"Lithium extraction from geothermal brine using \u03b3-MnO2: A case study for Tuzla geothermal power plant","volume":"10","author":"Toprak","year":"2024","journal-title":"Heliyon"},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"4845","DOI":"10.1039\/D2CC00334A","article-title":"The back-deposition of dissolved Mn2+ to MnO2 cathodes for stable cycling in aqueous zinc batteries","volume":"58","author":"Yang","year":"2022","journal-title":"Chem. Commun."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1007\/s40820-023-01194-3","article-title":"Effectively Modulating Oxygen Vacancies in Flower-Like \u03b4-MnO2 Nanostructures for Large Capacity and High-Rate Zinc-Ion Storage","volume":"15","author":"Wang","year":"2023","journal-title":"Nano-Micro Lett."},{"key":"ref_60","doi-asserted-by":"crossref","unstructured":"Yadav, P., Putro, D., Kim, J., and Rai, A.K. (2023). Pom-Pom Flower-like Morphology of \u03b4-MnO2 with Superior Electrochemical Performances for Rechargeable Aqueous Zinc Ion Batteries. Batteries, 9.","DOI":"10.3390\/batteries9020133"},{"key":"ref_61","doi-asserted-by":"crossref","unstructured":"Tang, M., Liu, Q., Zou, X., Zhang, B., and An, L. (2025). High-energy-density aqueous zinc-ion batteries: Recent progress, design strategies, challenges, and perspectives. Adv. Mater., 2501361.","DOI":"10.1002\/adma.202501361"},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"2302655","DOI":"10.1002\/aenm.202302655","article-title":"Unveiling Ion-Exchange-Mediated Irreversible Zn2+ Intercalation for the \u03b4-MnO2 Cathode in Aqueous Zn-Ion Batteries","volume":"14","author":"Cui","year":"2024","journal-title":"Adv. Energy Mater."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"154578","DOI":"10.1016\/j.apsusc.2022.154578","article-title":"In situ synthesis of a self-supported MnO2-based cathode for high-performance zinc-ion batteries by K+ pre-intercalation","volume":"604","author":"Tan","year":"2022","journal-title":"Appl. Surf. Sci."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"e2401379","DOI":"10.1002\/smll.202401379","article-title":"Electrochemical Failure Mechanism of \u03b4-MnO2 in Zinc Ion Batteries Induced by Irreversible Layered-to-Spinel Phase Transition","volume":"20","author":"Zhao","year":"2024","journal-title":"Small"},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"128804","DOI":"10.1016\/j.colsurfa.2022.128804","article-title":"Robust structural stability of flower-like \u03b4-MnO2 as cathode for aqueous zinc ion battery","volume":"643","author":"Wang","year":"2022","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"1814","DOI":"10.1021\/acsenergylett.2c00777","article-title":"High-voltage manganese oxide cathode with two-electron transfer enabled by a phosphate proton reservoir for aqueous zinc batteries","volume":"7","author":"Liu","year":"2022","journal-title":"ACS Energy Lett."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"2300965","DOI":"10.1002\/smtd.202300965","article-title":"Understanding the Role of Zinc Hydroxide Sulfate in Aqueous Zn\u2013MnO2 Batteries","volume":"7","author":"Lim","year":"2024","journal-title":"Small Methods"},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"101784","DOI":"10.1016\/j.joule.2024.11.001","article-title":"A key advance toward practical aqueous Zn\/MnO2 batteries via better electrolyte design","volume":"9","author":"Aguilar","year":"2025","journal-title":"Joule"},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"2312894","DOI":"10.1002\/adma.202312894","article-title":"Addressing the carbonate issue: Electrocatalysts for acidic CO2 reduction reaction","volume":"37","author":"Wu","year":"2025","journal-title":"Adv. Mater."},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"e2300965","DOI":"10.1002\/smtd.202300965","article-title":"Understanding the Role of Zinc Hydroxide Sulfate and its Analogues in Mildly Acidic Aqueous Zinc Batteries: A Review","volume":"8","author":"Lim","year":"2024","journal-title":"Small Methods"},{"key":"ref_71","first-page":"2310497","article-title":"Distinguish MnO2\/Mn2+ Conversion\/Zn2+ Intercalation\/H+ Conversion Chemistries at Different Potentials in Aqueous Zn||MnO2 Batteries","volume":"20","author":"Li","year":"2024","journal-title":"Small"},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"e12575","DOI":"10.1002\/eem2.12575","article-title":"Recent advances on challenges and strategies of manganese dioxide cathodes for aqueous zinc-ion batteries","volume":"6","author":"Xu","year":"2023","journal-title":"Energy Environ. Mater."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"461","DOI":"10.1016\/0025-5408(83)90138-1","article-title":"Lithium insertion into manganese spinels","volume":"18","author":"Thackeray","year":"1983","journal-title":"Mater. Res. Bull."},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"e2201142","DOI":"10.1002\/smtd.202201142","article-title":"Suppressed Layered-to-Spinel Phase Transition in \u03b4-MnO2 via van der Waals Interaction for Highly Stable Zn\/MnO2 Batteries","volume":"6","author":"Qiu","year":"2022","journal-title":"Small Methods"},{"key":"ref_75","first-page":"e202403504","article-title":"Recent advances and perspectives on vanadium-and manganese-based cathode materials for aqueous zinc ion batteries","volume":"63","author":"Liu","year":"2024","journal-title":"Angew. Chem. Int. 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