High-Entropy Solvation Chemistry towards Affordable and Practical Ah-level Zinc Metal Battery | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article High-Entropy Solvation Chemistry towards Affordable and Practical Ah-level Zinc Metal Battery Kangning Zhao, Linhui Chang, Hongwei Cheng, Jiamin Li, Lei Zhang, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4870452/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 03 Jul, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Aqueous zinc-ion batteries offer sustainable large-scale storage potential with inherent safety and low cost, yet suffer from limited energy density and cycle life due to aqueous electrolyte constraints. Here, we introduce affordable, stable electrolyte (0.33 $·kg −1 ) incorporating minimal multi-halogen anions (Cl - , Br - , and I - ) to create a high-entropy solvation structure enabling high-performance zinc batteries. Despite the small amount, the diversified mono-halogenated contact ion pair and multi-halogenated aggregate solvation structures create the unique high-entropy solvation structure, to form the lean water halogenated interfacial environment, suppressing the hydrogen evolution reaction, while facilitating cascade desolvation. Multi-halogen additives generate diverse contact ion pairs (Zn-X, X=Cl/Br/I) with compact solvation shells accelerating ion transport. In this way, the high-entropy solvation structure breaks the trade-off between plating overpotential (energy efficiency) and plating/stripping reversibility (Coulombic efficiency). As a result, the high-entropy solvation-based electrolyte enables practical zinc metal battery with 152.2 Wh kg -1 electrode for 120 cycles at lean electrolyte of 2.4 μL mg -1 and an Ah-level pouch cell is validated with high Coulombic efficiency of over 99.90% for over 250 cycles. Our findings emphasize the importance of electrolyte design for the precise control of anion-cation interactions for stable Zn/electrolyte interface and enable practical zinc metal battery with high energy and low cost. Physical sciences/Materials science/Materials for energy and catalysis Physical sciences/Chemistry/Energy Sustainable Zn-ion Batteries High-entropy solvation Halogen anions Energy dense Contact ion pair Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Full Text Additional Declarations There is NO Competing Interest. Supplementary Files InventoryofSupportingInformation.docx Inventory of Supporting Information SupplementaryInformation.pdf Supplementary Information SourceData.xlsx Source Data Cite Share Download PDF Status: Published Journal Publication published 03 Jul, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4870452","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":474050689,"identity":"7aa737b4-70d1-4d69-9eab-5570fad21301","order_by":0,"name":"Kangning Zhao","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAArUlEQVRIiWNgGAWjYDACZhBRYMPDz95AkhaDNBnJngMkWWVw2MbghgOxio8zP5P4YHCeh+EGA+OHjzlEmc9mJjnD4DYP4+wGZsmZ24jQItnMwybNA9TCLHOAjZmXaC1/DM7xsEkkEKmFnxmohcHgAA8PCVrYjC17DJJ5JHgONhPnFzb+ww9v/Kiws7c/3nzww0ditAABiwSEZmwgTj0QMH8gWukoGAWjYBSMTAAATiUsI7JkH2gAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0003-2916-4386","institution":"Great Bay University","correspondingAuthor":true,"prefix":"","firstName":"Kangning","middleName":"","lastName":"Zhao","suffix":""},{"id":474050690,"identity":"80a4b676-3f69-43a3-b7f8-d1a5ac488364","order_by":1,"name":"Linhui Chang","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Linhui","middleName":"","lastName":"Chang","suffix":""},{"id":474050691,"identity":"876f2e85-7e48-4ba1-867d-4c699292aace","order_by":2,"name":"Hongwei Cheng","email":"","orcid":"https://orcid.org/0000-0003-1403-6752","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Hongwei","middleName":"","lastName":"Cheng","suffix":""},{"id":474050692,"identity":"c99d722b-8393-4eb1-9bf7-ae969cd2e5f8","order_by":3,"name":"Jiamin Li","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Jiamin","middleName":"","lastName":"Li","suffix":""},{"id":474050693,"identity":"5e5f6bdb-a218-4d9c-be68-8a675b694cd3","order_by":4,"name":"Lei Zhang","email":"","orcid":"","institution":"Wuhan University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Lei","middleName":"","lastName":"Zhang","suffix":""},{"id":474050694,"identity":"50e968f2-403b-44eb-9c4b-2e674e7b6ea0","order_by":5,"name":"Bomian Zhang","email":"","orcid":"","institution":"Wuhan University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Bomian","middleName":"","lastName":"Zhang","suffix":""},{"id":474050695,"identity":"64fcd770-b586-4779-8ffc-fff3d743ee6a","order_by":6,"name":"Lihen Zheng","email":"","orcid":"","institution":"Wuhan University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Lihen","middleName":"","lastName":"Zheng","suffix":""},{"id":474050696,"identity":"89a6b53f-acd3-454b-8da7-5a1b234595f9","order_by":7,"name":"Qiangchao Sun","email":"","orcid":"","institution":"Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Qiangchao","middleName":"","lastName":"Sun","suffix":""},{"id":474050697,"identity":"2f39dcf0-5edb-4701-bc95-f9979c69577c","order_by":8,"name":"Jiantao Li","email":"","orcid":"https://orcid.org/0000-0003-2277-849X","institution":"Argonne National Laboratory","correspondingAuthor":false,"prefix":"","firstName":"Jiantao","middleName":"","lastName":"Li","suffix":""},{"id":474050698,"identity":"ce0e9fe4-2123-41d6-ab4e-853ef7b070d2","order_by":9,"name":"Xionggang Lu","email":"","orcid":"","institution":"School of Materials Science and Engineering, Shanghai University","correspondingAuthor":false,"prefix":"","firstName":"Xionggang","middleName":"","lastName":"Lu","suffix":""}],"badges":[],"createdAt":"2024-08-06 19:35:22","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4870452/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4870452/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-61456-z","type":"published","date":"2025-07-03T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":85185104,"identity":"231556e1-1991-4f0a-9779-14d4b793c5d2","added_by":"auto","created_at":"2025-06-23 08:05:07","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":294547,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eProposed design framework and mechanism for HESE.\u003c/strong\u003e (a-b) Trade-off between overpotential and CEs. (c) Schematic diagram of solvation structure and plating process. (d) CE test results by \u003cem\u003eAurbach’s \u003c/em\u003emethod. (e) Average CEs of Zn||Cu asymmetric cell and (f) Voltage hysteresis of Zn||Zn symmetrical cell with single halogen ion electrolyte.\u003c/p\u003e","description":"","filename":"Slide1.png","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/e93020c0603dc34404c5bfab.png"},{"id":85183490,"identity":"4981ad5c-e7f6-46c2-af16-c124fb250624","added_by":"auto","created_at":"2025-06-23 07:49:07","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":325682,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMicroscopic and mesoscopic solvation structures. \u003c/strong\u003e(a) 3D snapshots of HESE and partially enlarged snapshots for the solvation structure of Zn\u003csup\u003e2+\u003c/sup\u003e. (b) Distribution of first solvation structures. (c) Zn K-\u003cem\u003eedge \u003c/em\u003eXANES spectra, (d) Wavelet transform contour plots of Zn K-edge at\u003cem\u003e R-space\u003c/em\u003e, and (e) EXAFS analysis of the \u003cem\u003ek-space\u003c/em\u003e spectrum. (f) The proportion of three types of \u003cem\u003eV-O-H\u003c/em\u003e bonds obtained from Raman spectral fitting. (g) The radial distribution functions and coordination number of Zn\u003csup\u003e2+\u003c/sup\u003e-O, (h) Average Zn\u003csup\u003e2+\u003c/sup\u003e cluster sizes at 300 K. (i) Wide-angle X-ray scattering (WAXS) curves. (j) The Zn-ion self-diffusion coefficient (D\u003csub\u003eZn\u003c/sub\u003e) means squared displacement collected from MD simulations in two electrolyte solutions. (k) A summary of image snapshot with side and frontal view of the anode-electrolyte interface of HESE at negative potential, zero potential, and positive potential, respectively.\u003c/p\u003e","description":"","filename":"Slide2.png","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/6d4a96666ada8252197251c0.png"},{"id":85184672,"identity":"6c150a7a-772b-4307-88a8-08ac48676c76","added_by":"auto","created_at":"2025-06-23 07:57:07","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":347335,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThe nucleation and deposition behavior of zinc. \u003c/strong\u003eExperimental dimensionless transients in comparison with the theoretical nucleation models of (a) baseline and (b) HESE solution. (c) Time-series SEM images of Zn in two electrolytes about Zn nucleation and initial growth. (d) Schematic illustration of the Zn nucleation and growth mechanisms. Surface flatness mapping of deposited zinc in (e) baseline and (f) HESE solution. \u003cem\u003eIn-situ\u003c/em\u003e Raman spectra of the Zn/electrolyte interface in HESE during (g) plating and (h) stripping. (i) SEM images of plated Zn on Cu (A-E) in baseline electrolyte and (F-J) in HESE with a plating capacity from 0.2 mAh cm\u003csup\u003e-2\u003c/sup\u003e to 5 mAh cm\u003csup\u003e-2\u003c/sup\u003e. In situ microscopy images of the Zn plating process in (k) baseline electrolyte and (k) in HESE at 10 mA cm\u003csup\u003e-2\u003c/sup\u003e. (l-m) Cross section SEM images of 10 mAh cm\u003csup\u003e-2 \u003c/sup\u003edeposited zinc in baseline electrolyte and HESE, respectively.\u003c/p\u003e","description":"","filename":"Slide3.png","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/3c03283b2af3ba2c29323ab1.png"},{"id":85183496,"identity":"b098e329-3758-4b3f-89f3-997aa8c92018","added_by":"auto","created_at":"2025-06-23 07:49:08","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":40656,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectrochemical performance of symmetric and asymmetric cells.\u003c/strong\u003e Galvanostatic cycling of Zn||Zn symmetric cells in different electrolytes at (a) 40 mA cm\u003csup\u003e-2\u003c/sup\u003e and 20 mAh cm\u003csup\u003e-2\u003c/sup\u003e (DOD=68.4%), and (b) 20 mA cm\u003csup\u003e-2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e-2\u003c/sup\u003e. (c) Coulombic efficiencies and time-voltage profiles of Zn||Cu cells using different electrolytes at 1 mA cm\u003csup\u003e-2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e-2\u003c/sup\u003e and (d) 5 mA cm\u003csup\u003e-2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e-2\u003c/sup\u003e. (e) Coulombic efficiencies of the Zn||Ti cells at 20 mA cm\u003csup\u003e-2\u003c/sup\u003e, 10 mA h cm\u003csup\u003e-2\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"Slide4.png","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/4d83aabf6ce82949d8a67ca4.png"},{"id":85185105,"identity":"434c63ab-ca52-4a88-9393-d96f3929951e","added_by":"auto","created_at":"2025-06-23 08:05:08","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":155230,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePractical Zinc Battery Demonstration.\u003c/strong\u003e (a) Long-cycling performance of Zn||NVO coin cell at 4 A g\u003csup\u003e-1\u003c/sup\u003e. (b) Cycling stability of the Zn||NVO cell under harsh conditions (mass loading of 37 mg cm\u003csup\u003e-2\u003c/sup\u003e, E/C = ~6 μL mAh\u003csup\u003e-1\u003c/sup\u003e), the insert show two cell models. (c) Dependence of energy density on N/P ratio in Zn||NVO full cell. (d) Comparison of the proposed Zn||NVO cell with other reported low N/P and E/C ratio cells. (e) SEM images of zinc anode after 200 cycles. (f) Rate performance of the Zn||NVO cell (mass loading of 19 mg cm\u003csup\u003e-2\u003c/sup\u003e, N/P = ~1.52) in two electrolytes. (g) CV curves of Zn||NVO full cell at 0.1 mV s\u003csup\u003e-1\u003c/sup\u003e. (h-i) DRT fitted curves of Zn||NVO full cell. (j) The cycle performance and (k) Ah-level multi-layer pouch cell model using HESE.\u003c/p\u003e","description":"","filename":"Slide5.png","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/4736c1e563d271c260adbc7b.png"},{"id":85999385,"identity":"cd0afd6c-ba4e-4290-9c4a-2249c95165e9","added_by":"auto","created_at":"2025-07-04 07:09:38","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":974845,"visible":true,"origin":"","legend":"","description":"","filename":"Mainmanusciptwithouttrackedchanges.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1_covered_3461ff54-9c47-4e02-9864-e7ed36063343.pdf"},{"id":85183489,"identity":"5fe7ba10-4e75-464a-bccf-e733cc9607ad","added_by":"auto","created_at":"2025-06-23 07:49:07","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":21971,"visible":true,"origin":"","legend":"Inventory of Supporting Information","description":"","filename":"InventoryofSupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/31ab56bd8cd94a947914dfbd.docx"},{"id":85183504,"identity":"0d5cc7f3-bdee-4394-8803-3eb3936c3e24","added_by":"auto","created_at":"2025-06-23 07:49:08","extension":"pdf","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":6379727,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SupplementaryInformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/3b7ad4dd293c5d42103f9740.pdf"},{"id":85183505,"identity":"d5b593f0-a683-411d-8171-313961545981","added_by":"auto","created_at":"2025-06-23 07:49:08","extension":"xlsx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":25390422,"visible":true,"origin":"","legend":"Source Data","description":"","filename":"SourceData.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-4870452/v1/eb8bd35e4657885117d69b08.xlsx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"High-Entropy Solvation Chemistry towards Affordable and Practical Ah-level Zinc Metal Battery","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"
[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Sustainable Zn-ion Batteries, High-entropy solvation, Halogen anions, Energy dense, Contact ion pair","lastPublishedDoi":"10.21203/rs.3.rs-4870452/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4870452/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eAqueous zinc-ion batteries offer sustainable large-scale storage potential with inherent safety and low cost, yet suffer from limited energy density and cycle life due to aqueous electrolyte constraints. Here, we introduce affordable, stable electrolyte (0.33 $·kg\u003csup\u003e−1\u003c/sup\u003e) incorporating minimal multi-halogen anions (Cl\u003csup\u003e-\u003c/sup\u003e, Br\u003csup\u003e-\u003c/sup\u003e, and I\u003csup\u003e-\u003c/sup\u003e) to create a high-entropy solvation structure enabling high-performance zinc batteries. Despite the small amount, the diversified mono-halogenated contact ion pair and multi-halogenated aggregate solvation structures create the unique high-entropy solvation structure, to form the lean water halogenated interfacial environment, suppressing the hydrogen evolution reaction, while facilitating cascade desolvation. Multi-halogen additives generate diverse contact ion pairs (Zn-X, X=Cl/Br/I) with compact solvation shells accelerating ion transport. In this way, the high-entropy solvation structure breaks the trade-off between plating overpotential (energy efficiency) and plating/stripping reversibility (Coulombic efficiency). As a result, the high-entropy solvation-based electrolyte enables practical zinc metal battery with 152.2 Wh kg\u003csup\u003e-1\u003c/sup\u003e\u003csub\u003eelectrode\u003c/sub\u003e for 120 cycles at lean electrolyte of 2.4 μL mg\u003csup\u003e-1\u003c/sup\u003e and an Ah-level pouch cell is validated with high Coulombic efficiency of over 99.90% for over 250 cycles. Our findings emphasize the importance of electrolyte design for the precise control of anion-cation interactions for stable Zn/electrolyte interface and enable practical zinc metal battery with high energy and low cost.\u003c/p\u003e","manuscriptTitle":"High-Entropy Solvation Chemistry towards Affordable and Practical Ah-level Zinc Metal Battery","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-23 07:49:03","doi":"10.21203/rs.3.rs-4870452/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"
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