P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries

P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries | 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 P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries Tianyi Ma, Yibo Ma, Kai Wang, Kewei Liu, Yang Guo, Yanan Xu, xianzhong sun, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6493639/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract It is known that there existing the "energy versus power dilemma" in electrochemical energy storage devices. Most conventional electrode materials, whether based on ion insertion-extraction or pseudo-capacitance, inevitably require a trade-off, enhancing one performance metric at the cost of another. For the high-theoretical-capacity (2596 mA h g - 1 ) black phosphorus (BP) electrode materials, the sluggish kinetics of multiphase phosphorus redox reactions (PRR) fundamentally constrain the fast-charging and high-power performance of BP-based batteries. Although catalytic strategies can accelerate redox kinetics, their application to BP’s complex solid-state transformations remains challenging. Here we report a catalytic approach through engineered P–N–P bridge bonds within the BP/carbon composite materials, which is first designed within the backbone of BP lattice, distinguishing it from previous studies on heteroatom-doped carbon materials. The formation of P-N-P bridge bonds within BP lattice can transform semi-conductive BP into a metallic state and reduce the energy barriers for Li-ions diffusion, improving PRR dynamics, structural stability and environmental stability. The resulting nitrogen-doped BP/carbon (N-BP/C) anode achieves ultrafast PRR kinetics and higher capacity, the N-BP/C anode shows the specific capacity of 1482 mA h g - 1 with a coulombic efficiency (CE) exceeding 99.6% after 200 cycles, more than twice the 687 mA h g - 1 of BP/C sample. Furthermore, an assembled LiFePO₄ ‖ N-BP/C pouch cell delivers 282 Wh kg⁻¹ energy density with 80% capacity retention within 10 minutes at a high current density of 10 A g⁻¹—meeting the U.S. Department of Energy’s Extreme Fast Charging (XFC) targets. This pouch cell also exhibits exceptional cyclability (> 3,400 cycles), more than 10 times longer than existing phosphorus-based LIBs. This work establishes a paradigm for catalytic enhancement in multiphase energy storage, advancing the design of new batteries with both high energy density and high power density. Physical sciences/Energy science and technology/Energy storage/Batteries Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry/Electrocatalysis black phosphorus P-N-P bridge bond "solid-liquid-solid" multiphase reaction solid-state catalysis fast-charging batteries Full Text Additional Declarations There is NO Competing Interest. Supplementary Files 4Supplementarymaterials.pdf P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries Cite Share Download PDF Status: Under Review 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-6493639","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":448774017,"identity":"d5c1f734-0253-4a99-b64d-8c5f02ac12af","order_by":0,"name":"Tianyi 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batteries","lastPublishedDoi":"10.21203/rs.3.rs-6493639/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6493639/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIt is known that there existing the \"energy versus power dilemma\" in electrochemical energy storage devices. Most conventional electrode materials, whether based on ion insertion-extraction or pseudo-capacitance, inevitably require a trade-off, enhancing one performance metric at the cost of another. For the high-theoretical-capacity (2596 mA h g\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e) black phosphorus (BP) electrode materials, the sluggish kinetics of multiphase phosphorus redox reactions (PRR) fundamentally constrain the fast-charging and high-power performance of BP-based batteries. Although catalytic strategies can accelerate redox kinetics, their application to BP\u0026rsquo;s complex solid-state transformations remains challenging. Here we report a catalytic approach through engineered P\u0026ndash;N\u0026ndash;P bridge bonds within the BP/carbon composite materials, which is first designed within the backbone of BP lattice, distinguishing it from previous studies on heteroatom-doped carbon materials. The formation of P-N-P bridge bonds within BP lattice can transform semi-conductive BP into a metallic state and reduce the energy barriers for Li-ions diffusion, improving PRR dynamics, structural stability and environmental stability. The resulting nitrogen-doped BP/carbon (N-BP/C) anode achieves ultrafast PRR kinetics and higher capacity, the N-BP/C anode shows the specific capacity of 1482 mA h g\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e with a coulombic efficiency (CE) exceeding 99.6% after 200 cycles, more than twice the 687 mA h g\u003csup\u003e-\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e of BP/C sample. Furthermore, an assembled LiFePO₄ ‖ N-BP/C pouch cell delivers 282 Wh kg⁻\u0026sup1; energy density with 80% capacity retention within 10 minutes at a high current density of 10 A g⁻\u0026sup1;\u0026mdash;meeting the U.S. Department of Energy\u0026rsquo;s Extreme Fast Charging (XFC) targets. This pouch cell also exhibits exceptional cyclability (\u0026gt;\u0026thinsp;3,400 cycles), more than 10 times longer than existing phosphorus-based LIBs. This work establishes a paradigm for catalytic enhancement in multiphase energy storage, advancing the design of new batteries with both high energy density and high power density.\u003c/p\u003e","manuscriptTitle":"P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-29 08:50:15","doi":"10.21203/rs.3.rs-6493639/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"c70ce33a-0335-4e86-b8e0-c42f6648135a","owner":[],"postedDate":"April 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":47751836,"name":"Physical sciences/Energy science and technology/Energy storage/Batteries"},{"id":47751837,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry/Electrocatalysis"}],"tags":[],"updatedAt":"2026-04-09T06:15:24+00:00","versionOfRecord":[],"versionCreatedAt":"2025-04-29 08:50:15","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6493639","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6493639","identity":"rs-6493639","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}