The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We p...The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We propose a paradigm shift:reconfiguring random defects into engineered,monodisperse artificial micro-curves to homogenize electric fields and guide aligned zinc(Zn)deposition.Using moisture-assisted flash heating,we transform zincophilic silver(Ag)coatings on carbon fibers into uniformly dispersed micro-curved particles(Ag Particles@CC),creating identical nucleation sites with optimal zinc ion(Zn^(2+))adsorption energetics.Theoretical simulations confirm these structures eliminate localized field concentrations,enabling homogeneous plating/stripping.This design demonstrates remarkable performance,with ultrastable 1500 cycles at 10 mA cm^(-2)(98.6%avg.Coulombic efficiency)and symmetric cell operation>650 h(57.7 mV hysteresis).Crucially,interparticle discontinuities preserve intrinsic flexibility,enabling flexible pouch cells(Ag Particles@CC-Zn//NaV_(3)O_(8)·1,5H_(2)O)to successfully power wearable devices such as smartwatches and smartphones.This work establishes defect reconfiguration via artificial micro-curvature engineering as a universal strategy toward dendritesuppressed,flexible energy storage.展开更多
The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study intro...The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study introduces a molten salt electrochemical strategy for converting photovoltaic wSi into NiSi_(2)-silicon nanorods(NiSi_(2)-SiNRs)as high-performance anode materials for lithium-ion batteries.A stable oxidized passivation layer is formed on the wSi surface via controlled oxidation,and further in situ generated highly active NiSi_(2) droplets.The molten salt electric field modulates the surface energy of silicon,while particle integration drives localized directional growth,enabling the self-assembly of NiSi_(2)-SiNRs composites.These NiSi_(2)-SiNRs anodes exhibit rapid ion transport and effective strain buffering.The high aspect ratio of SiNRs and the presence of retained NiSi_(2) facilitate both longitudinal and transverse Li^(+) diffusion.Owing to their robust structural design,the NiSi_(2)-SiNRs anode achieves an excellent initial Coulombic efficiency of 91.61%and retains 72.99%of its capacity after 800 cycles at 2 A·g^(−1).This study establishes a model system for investigating silicide/silicon interfaces in molten salt electrochemical synthesis and provides an effective strategy for upcycling photovoltaic wSi into high-performance lithium-ion battery anodes.展开更多
Silicon(Si)-based anodes have emerged as promising candidates for the next-generation lithium-ion batteries(LIBs)due to their high theoretical capacity(4200 mAh g^(-1)).However,their further application is hindered by...Silicon(Si)-based anodes have emerged as promising candidates for the next-generation lithium-ion batteries(LIBs)due to their high theoretical capacity(4200 mAh g^(-1)).However,their further application is hindered by critical challenges,including severe volume expansion(~300%),formation of unstable solid electrolyte interphase(SEI),and inherently low conductivity.While extensive research has sought to alleviate the substantial internal stress caused by volume expansion through the rational design of Si-based anode structures,the underlying mechanisms that govern these improvements remain insufficiently understood,leaving significant gaps in mechanical and interface electrical failure.To build a comprehensive understanding relationship between structural design and performance enhancement of Si-based anodes,this review first analyzes the characteristics of various Sibased anode structures and their associated internal stresses.Subsequently,it summarizes effective strategies to optimize the performance of Si-based anodes,including doping design,novel electrolyte design,and fu nctional binder design.Additionally,we assess emerging technologies with high commercial potential for structural design and interfacial modification,such as porous carbon carriers,chemical vapor deposition(CVD),spray granulation,and pre-lithiation.Finally,this work provides perspectives on the structural design of Si-based anodes.Overall,this review systematically summarizes modification strategies for Si-based anodes through structural regulation and interface engineering,thereby providing a foundation for advanced structural and interfacial design.展开更多
Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the...Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.展开更多
The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and slugg...The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and sluggish oxygen evolution reaction kinetics.This work overcomes those challenges through a synergistic strategy that co-designs the hematite architecture and the surface reaction pathway.We introduce a textured and hierarchically porous Ti-doped Fe_(2)O_(3)(tp-Fe_(2)O_(3))photoanode,synthesized via multi-cycle growth and flame annealing method.This unique architecture features a high texture(110),enlarged surface area,and hierarchically porous structure,which enable significantly enhanced bulk charge transport and interfacial charge transfer compared to typical nanorod Ti-doped Fe_(2)O_(3)(nr-Fe_(2)O_(3)).As a result,the tp-Fe_(2)O_(3)photoanode achieves a photocurrent density of 3.1 mA cm^(-2)at 1.23 V vs.RHE with exceptional stability over 105 h,notably without any co-catalyst.By replacing the OER with the hydrazine oxidation reaction,the photocurrent further reaches a record-high level of 7.1 mA cm^(-2)at 1.23 V_(RHE).Finally,when we integrate the tp-Fe_(2)O_(3)with a commercial Si solar cell,it achieves a solar-to-hydrogen efficiency of 8.7%-the highest reported value for any Fe_(2)O_(3)-based PVtandem system.This work provides critical insights into rational Fe_(2)O_(3)photoanode design and highlights the potential of hydrazine as an efficient alternative anodic reaction,enabling waste valorization.展开更多
Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoa...Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoanodes via an interface-engineered hydrothermal growth followed by rapid thermal annealing(RTA).A TiO_(2)interfacial layer plays a crucial role in ensuring homogeneous precursor deposition,enhancing light absorption,and forming efficient heterojunctions with Sb_(2)S_(3),thereby significantly improving charge separation and transport.RTA further improves crystallinity and interfacial contact,resulting in dense and uniform Sb_(2)S_(3)films with enlarged grains and fewer defects.The optimized Sb_(2)S_(3)photoanode achieves a photocurrent density of 2.51 mA/cm^(2)at 1.23 V vs.the reversible hydrogen electrode(RHE),one of the highest reported for Sb_(2)S_(3)without additional catalysts or passivation layers.To overcome the limitations of oxygen evolution reaction(OER),we employ the iodide oxidation reaction(IOR)as an alternative,significantly lowering the overpotential and improving charge transfer kinetics.Consequently,it produces a record photocurrent density of 8.9 mA/cm^(2)at 0.54 V vs.RHE.This work highlights the synergy between TiO_(2)interfacial engineering,RTA-induced crystallization,and IOR-driven oxidation,offering a promising pathway for efficient and scalable PEC hydrogen production.展开更多
Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice dist...Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice distortions on hole extraction has been neglected.Herein,the crystal lattice of BiVO_(4) is distorted by doping with an inexpensive Cs metal;then,CoFe_(2)O_(4) is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode.Benefiting from the above design,the newly prepared CoFe_(2)O_(4)-Cs-BiVO_(4) photoanode achieved a photocurrent density of 5.66 mA cm^(–2) at 1.23 V vs.a reversible hydrogen electrode,indicating a 3.9-fold improvement in photocurrent density.Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO_(4) bulk-phase holes to the CoFe_(2)O_(4) layer.Additionally,the coupled CoFe_(2)O_(4) can be used as a hole extraction layer to further enhance the interfacial migration of carriers.The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO_(4) bulk phase to the active sites of the oxygen evolution reaction,thereby effectively inhibiting carrier recombination.This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion,thereby opening new avenues for the rational design of photoanodes.展开更多
Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius o...Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.展开更多
基金supported by the National Natural Science Foundation of China(52202218)the Fundamental Research Funds for the Central Universities(CUSF-DH-T-2023044)。
文摘The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We propose a paradigm shift:reconfiguring random defects into engineered,monodisperse artificial micro-curves to homogenize electric fields and guide aligned zinc(Zn)deposition.Using moisture-assisted flash heating,we transform zincophilic silver(Ag)coatings on carbon fibers into uniformly dispersed micro-curved particles(Ag Particles@CC),creating identical nucleation sites with optimal zinc ion(Zn^(2+))adsorption energetics.Theoretical simulations confirm these structures eliminate localized field concentrations,enabling homogeneous plating/stripping.This design demonstrates remarkable performance,with ultrastable 1500 cycles at 10 mA cm^(-2)(98.6%avg.Coulombic efficiency)and symmetric cell operation>650 h(57.7 mV hysteresis).Crucially,interparticle discontinuities preserve intrinsic flexibility,enabling flexible pouch cells(Ag Particles@CC-Zn//NaV_(3)O_(8)·1,5H_(2)O)to successfully power wearable devices such as smartwatches and smartphones.This work establishes defect reconfiguration via artificial micro-curvature engineering as a universal strategy toward dendritesuppressed,flexible energy storage.
基金supported by the Yunnan Province Basic Research General Program,China(No.202201BE070001-002)the Major Science and Technology Projects in Yunnan Province,China(No.202402AF 080005).
文摘The rapid expansion of the photovoltaic industry has generated heavily oxidized waste silicon(wSi),which hinders efficient recycling owing to its small particle size and uncontrolled surface oxidation.This study introduces a molten salt electrochemical strategy for converting photovoltaic wSi into NiSi_(2)-silicon nanorods(NiSi_(2)-SiNRs)as high-performance anode materials for lithium-ion batteries.A stable oxidized passivation layer is formed on the wSi surface via controlled oxidation,and further in situ generated highly active NiSi_(2) droplets.The molten salt electric field modulates the surface energy of silicon,while particle integration drives localized directional growth,enabling the self-assembly of NiSi_(2)-SiNRs composites.These NiSi_(2)-SiNRs anodes exhibit rapid ion transport and effective strain buffering.The high aspect ratio of SiNRs and the presence of retained NiSi_(2) facilitate both longitudinal and transverse Li^(+) diffusion.Owing to their robust structural design,the NiSi_(2)-SiNRs anode achieves an excellent initial Coulombic efficiency of 91.61%and retains 72.99%of its capacity after 800 cycles at 2 A·g^(−1).This study establishes a model system for investigating silicide/silicon interfaces in molten salt electrochemical synthesis and provides an effective strategy for upcycling photovoltaic wSi into high-performance lithium-ion battery anodes.
基金supported by the Science and Technology Plan of Fujian Provincial,China(2022G02020 and 2022H6002)the Collaborative Innovation Platform Project for Advanced Electrochemical Energy Storage Technology,Fuxiaquan National Independent Innovation Demonstration Zone,China(3502ZCQXT2022001)+1 种基金the Significant Science and Technology Project of Xiamen(the Future Industrial Area),China(3502Z20231058)the Scientific Research Startup Funding for Special Professor of Minjiang Scholars。
文摘Silicon(Si)-based anodes have emerged as promising candidates for the next-generation lithium-ion batteries(LIBs)due to their high theoretical capacity(4200 mAh g^(-1)).However,their further application is hindered by critical challenges,including severe volume expansion(~300%),formation of unstable solid electrolyte interphase(SEI),and inherently low conductivity.While extensive research has sought to alleviate the substantial internal stress caused by volume expansion through the rational design of Si-based anode structures,the underlying mechanisms that govern these improvements remain insufficiently understood,leaving significant gaps in mechanical and interface electrical failure.To build a comprehensive understanding relationship between structural design and performance enhancement of Si-based anodes,this review first analyzes the characteristics of various Sibased anode structures and their associated internal stresses.Subsequently,it summarizes effective strategies to optimize the performance of Si-based anodes,including doping design,novel electrolyte design,and fu nctional binder design.Additionally,we assess emerging technologies with high commercial potential for structural design and interfacial modification,such as porous carbon carriers,chemical vapor deposition(CVD),spray granulation,and pre-lithiation.Finally,this work provides perspectives on the structural design of Si-based anodes.Overall,this review systematically summarizes modification strategies for Si-based anodes through structural regulation and interface engineering,thereby providing a foundation for advanced structural and interfacial design.
基金supported by the National Natural Science Foundation of China(No.22179093 and 21905202)。
文摘Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.
基金supported by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.RS-2024-00335976)。
文摘The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and sluggish oxygen evolution reaction kinetics.This work overcomes those challenges through a synergistic strategy that co-designs the hematite architecture and the surface reaction pathway.We introduce a textured and hierarchically porous Ti-doped Fe_(2)O_(3)(tp-Fe_(2)O_(3))photoanode,synthesized via multi-cycle growth and flame annealing method.This unique architecture features a high texture(110),enlarged surface area,and hierarchically porous structure,which enable significantly enhanced bulk charge transport and interfacial charge transfer compared to typical nanorod Ti-doped Fe_(2)O_(3)(nr-Fe_(2)O_(3)).As a result,the tp-Fe_(2)O_(3)photoanode achieves a photocurrent density of 3.1 mA cm^(-2)at 1.23 V vs.RHE with exceptional stability over 105 h,notably without any co-catalyst.By replacing the OER with the hydrazine oxidation reaction,the photocurrent further reaches a record-high level of 7.1 mA cm^(-2)at 1.23 V_(RHE).Finally,when we integrate the tp-Fe_(2)O_(3)with a commercial Si solar cell,it achieves a solar-to-hydrogen efficiency of 8.7%-the highest reported value for any Fe_(2)O_(3)-based PVtandem system.This work provides critical insights into rational Fe_(2)O_(3)photoanode design and highlights the potential of hydrazine as an efficient alternative anodic reaction,enabling waste valorization.
基金supported by the National Research Foundation of Korea(NRF)grant fu nded by the Korean government(MSIT)(No.RS-2024-00335976)。
文摘Antimony sulfide(Sb_(2)S_(3))is a promising material for photoelectrochemical(PEC)devices that generate green hydrogen from sunlight and water.In this study,we present a synthesis of high-performance Sb_(2)S_(3)photoanodes via an interface-engineered hydrothermal growth followed by rapid thermal annealing(RTA).A TiO_(2)interfacial layer plays a crucial role in ensuring homogeneous precursor deposition,enhancing light absorption,and forming efficient heterojunctions with Sb_(2)S_(3),thereby significantly improving charge separation and transport.RTA further improves crystallinity and interfacial contact,resulting in dense and uniform Sb_(2)S_(3)films with enlarged grains and fewer defects.The optimized Sb_(2)S_(3)photoanode achieves a photocurrent density of 2.51 mA/cm^(2)at 1.23 V vs.the reversible hydrogen electrode(RHE),one of the highest reported for Sb_(2)S_(3)without additional catalysts or passivation layers.To overcome the limitations of oxygen evolution reaction(OER),we employ the iodide oxidation reaction(IOR)as an alternative,significantly lowering the overpotential and improving charge transfer kinetics.Consequently,it produces a record photocurrent density of 8.9 mA/cm^(2)at 0.54 V vs.RHE.This work highlights the synergy between TiO_(2)interfacial engineering,RTA-induced crystallization,and IOR-driven oxidation,offering a promising pathway for efficient and scalable PEC hydrogen production.
文摘Elemental doping of BiVO_(4) crystal lattices effectively enhances carrier separation,thereby facilitating efficient photoelectrochemical water splitting.However,the positive effect of elementally induced lattice distortions on hole extraction has been neglected.Herein,the crystal lattice of BiVO_(4) is distorted by doping with an inexpensive Cs metal;then,CoFe_(2)O_(4) is used as an efficient hole-extraction layer to further modify the surface of the doped photoanode.Benefiting from the above design,the newly prepared CoFe_(2)O_(4)-Cs-BiVO_(4) photoanode achieved a photocurrent density of 5.66 mA cm^(–2) at 1.23 V vs.a reversible hydrogen electrode,indicating a 3.9-fold improvement in photocurrent density.Detailed physicochemical characterization and density functional theory calculations showed that the lattice distortion induced by Cs doping promoted the directional migration of BiVO_(4) bulk-phase holes to the CoFe_(2)O_(4) layer.Additionally,the coupled CoFe_(2)O_(4) can be used as a hole extraction layer to further enhance the interfacial migration of carriers.The synergistic effect of the two effectively promotes the directional migration of photogenerated carriers from the BiVO_(4) bulk phase to the active sites of the oxygen evolution reaction,thereby effectively inhibiting carrier recombination.This study revealed the positive effect of the dual-hole extraction strategy on solar energy conversion,thereby opening new avenues for the rational design of photoanodes.
基金financially supported by the Natural Science Foundation of China(Nos.22208214,22005190,and 21938005)the Science&Technology Commission of Shanghai Municipality(Nos.20QB1405700,and 19DZ1205500)Zhejiang Key Research and Development Program(No.2020C01128)
文摘Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.
