The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the che...The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.展开更多
Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utiliz...Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.展开更多
The inferior conductivity and drastic volume expansion of silicon still remain the bottleneck in achieving high energy density Lithium-ion Batteries(LIBs).The design of the three-dimensional structure of electrodes by...The inferior conductivity and drastic volume expansion of silicon still remain the bottleneck in achieving high energy density Lithium-ion Batteries(LIBs).The design of the three-dimensional structure of electrodes by compositing silicon and carbon materials has been employed to tackle the above challenges,however,the exorbitant costs and the uncertainty of the conductive structure persist,leaving ample room for improvement.Herein,silicon nanoparticles were innovatively composited with eco-friendly biochar sourced from cotton to fabricate a 3D globally consecutive conductive network.The network serves a dual purpose:enhancing overall electrode conductivity and serving as a scaffold to maintain electrode integrity.The conductivity of the network was further augmented by introducing P-doping at the optimum doping temperature of 350℃.Unlike the local conductive sites formed by the mere mixing of silicon and conductive agents,the consecutive network can affirm the improvement of the conductivity at a macro level.Moreover,first-principle calculations further validated that the rapid diffusion of Li^(+)is attributed to the tailored electronic microstructure and charge rearrangement of the fiber.The prepared consecutive conductive Si@P-doped carbonized cotton fiber anode outperforms the inconsecutive Si@Graphite anode in both cycling performance(capacity retention of 1777.15 mAh g^(-1) vs.682.56 mAh g^(-1) after 150 cycles at 0.3 C)and rate performance(1244.24 mAh g^(-1) vs.370.28 mAh g^(-1) at 2.0 C).The findings of this study may open up new avenues for the development of globally interconnected conductive networks in Si-based anodes,thereby enabling the fabrication of high-performance LIBs.展开更多
Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a h...Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.展开更多
A flexible carbon fiber-confined yolk-shelled silicon-based composite is reported as an anode material for lithium storage applications.Silicon nanoparticles(Si NPs)are confined by the N-doped hollow carbon cages(SiNH...A flexible carbon fiber-confined yolk-shelled silicon-based composite is reported as an anode material for lithium storage applications.Silicon nanoparticles(Si NPs)are confined by the N-doped hollow carbon cages(SiNHC)and these uniform dispersed yolk-shell-structured Si-NHC units were encapsulated by the carbon fibers within an interconnected three-dimensional(3D)framework(Si-NHC@CNFs).For the encapsulated yolkshelled Si-NHC,the void space between the inner Si NPs and outer NHC can accommodate the structural changes of Si NPs during charging/discharging processes,leading to effectively improved structural stability and cycling life.More importantly,all the Si-NHC units were bridged together through a conductive CNFs"highway"to enhance the overall conductivity and tap density further.As observed,Si-NHC@CNFs exhibited an initial discharge capacity of 1364.1 mAh·g^(-1)at 1000 mA·g^(-1)and678.9 mAh·g^(-1)at 2000 mA·g^(-1).Furthermore,the reversible capacity was well maintained at 752.2 mAh·g^(-1)at500 mA·g^(-1)after 6000 ultra-long cycles.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
Photoelectrochemical(PEC)water splitting holds significant promise for sustainable energy harvesting that enables efficient conversion of solar energy into green hydrogen.Nevertheless,achievement of high performance i...Photoelectrochemical(PEC)water splitting holds significant promise for sustainable energy harvesting that enables efficient conversion of solar energy into green hydrogen.Nevertheless,achievement of high performance is often limited by charge carrier recombination,resulting in unsatisfactory saturation current densities.To address this challenge,we present a novel strategy for achieving ultrahigh current density by incorporating a bridge layer between the Si substrate and the NiOOH cocatalyst in this paper.The optimal photoanode(TCO/n-p-Si/TCO/Ni)shows a remarkably low onset potential of 0.92 V vs.a reversible hydrogen electrode and a high saturation current density of 39.6 mA·cm^(-2),which is about 92.7%of the theoretical maximum(42.7 mA·cm^(-2)).In addition,the photoanode demonstrates stable operation for 60 h.Our systematic characterizations and calculations demonstrate that the bridge layer facilitates charge transfer,enhances catalytic performance,and provides corrosion protection to the underlying substrate.Notably,the integration of this photoanode into a PEC device for overall water splitting leads to a reduction of the onset potential.These findings provide a viable pathway for fabricating highperformance industrial photoelectrodes by integrating a substrate and a cocatalyst via a transparent and conductive bridge layer.展开更多
With the rapid advancement of technology and the growing demand for renewable energy,lithium-ion batteries have become the cornerstone of modern energy storage,particularly in electric vehicles.However,traditional gra...With the rapid advancement of technology and the growing demand for renewable energy,lithium-ion batteries have become the cornerstone of modern energy storage,particularly in electric vehicles.However,traditional graphite anodes limit further improvements in energy density and charging speed.Silicon,with its ultrahigh theoretical capacity,low cost,and environmental compatibility,has emerged as a promising alternative anode material.Nevertheless,its practical application is hindered by severe volume expansion during lithiation,unstable Solid-Electrolyte Interphase(SEI)formation,and low electrical conductivity.This study reviews and analyzes three mainstream strategies developed to address these challenges:(1)the design of silicon–carbon composite anodes to improve conductivity and structural stability;(2)the application of nano-engineered silicon architectures(0D to 3D)to buffer mechanical stress and enhance cycling performance;and(3)electrolyte modification to form more flexible and robust SEI layers.Through comparative analysis of multiple research teams,this paper summarizes how composite engineering,structural optimization,and electrolyte innovation collectively enhance silicon anode performance in terms of capacity retention,rate capability,and long-term stability.The findings indicate that hybrid approaches—combining chemical compositing,nanostructural design,and interfacial engineering—represent the most promising direction for achieving practical,scalable silicon-based anodes.With continued progress in low-cost synthesis and interface stabilization,silicon is expected to play a crucial role in next-generation high-energy lithium-ion batteries,meeting the growing global demand for efficient and sustainable energy storage.展开更多
Silicon(Si)is considered a potential alternative anode for next-generation Li-ion batteries owing to its high theoretical capacity and abundance.However,the commercial use of Si anodes is hindered by their large volum...Silicon(Si)is considered a potential alternative anode for next-generation Li-ion batteries owing to its high theoretical capacity and abundance.However,the commercial use of Si anodes is hindered by their large volume expansion(~300%).Numerous efforts have been made to address this issue.Among these efforts,Si-graphite co-utilization has attracted attention as a reasonable alternative for high-energy anodes.A comparative study of representative commercial Si-based materials,such as Si nanoparticles,Si suboxides,and Si−Graphite composites(SiGC),was conducted to characterize their overall performance in high-energy lithium-ion battery(LIB)design by incorporating conventional graphite.Nano-Si was found to exhibit poor electrochemical performance,with severe volume expansion during cycling.Si suboxide provided excellent cycling stability in a full-cell evaluation with stable volume variation after 50 cycles,but had a large irreversible capacity and remarkable volume expansion during the first cycle.SiGC displayed a good initial Coulombic efficiency and the lowest volume change in the first cycle owing to the uniformly distributed nano-Si layer on graphite;however,its long-term cycling stability was relatively poor.To complement each disadvantage of Si suboxide and SiGC,a new combination of these Si-based anodes was suggested and a reasonable improvement in overall battery performance was successfully achieved.展开更多
Anode materials for Li-ion batteries(LIBs)utilized in electric vehicles,portable electronics,and other devices are mainly graphite(Gr)and its derivatives.However,the limited energy density of Gr-based anodes promotes ...Anode materials for Li-ion batteries(LIBs)utilized in electric vehicles,portable electronics,and other devices are mainly graphite(Gr)and its derivatives.However,the limited energy density of Gr-based anodes promotes the exploration of alternative anode materials such as silicon(Si)-based materials because of their abundance in nature and low cost.Specifically,Si can store 10 times more energy than Gr and also has the potential to enhance the energy density of LIBs.Despite the many advantages of Si-based anodes,such as high theoretical capacity and low price,their widespread use is hindered by two major issues:charge-induced volume expansion and unreliable solid electrolyte interphase(SEI)propagation.In this detailed review,we highlight the key issues,current advances,and prospects in the rational design of Si-based electrodes for practical applications.We first explain the fundamental electrochemistry of Si and the importance of Si-based anodes in LIBs.The excessive volume increase,relatively low charge efficiency,and inadequate areal capacity of Si-based anodes are discussed to identify the barriers in enhancing their performance in LIBs.Subsequently,the use of binders(e.g.,linear polymer binders,branched polymer binders,cross-linked polymer binders,and conjugated conductive polymer binders),material-based anode composites(such as carbon and its derivatives,metal oxides,and MXenes),and liquid electrolyte construction techniques are highlighted to overcome the identified barriers.Further,tailoring Si-based materials and reshaping their surfaces and interfaces,including improving binders and electrolytes,are shown to be viable approaches to address their drawbacks,such as volume expansion,low charge efficiency,and poor areal capacity.Finally,we highlight that research and development on Si-based anodes are indispensable for their use in commercial applications.展开更多
Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in...Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.展开更多
Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully syn...Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully synthesize nano-sized Wadsley-Roth FeNb_(11)O_(29)through Fe-driven phase transformation of Nb_(2)O_(5),which delivers a high specific capacity(280.5 mA h g^(−1)at 0.25 C)along with abundant redox-active sites.Moreover,the Wadsley-Roth shear structure of FeNb_(11)O_(29)facilitates rapid Li^(+)diffusion and guarantees exceptional structural stability.Theoretical calculations further confirm that FeNb_(11)O_(29)has a narrow band gap,which significantly enhances the conductivity.Owing to these merits,FeNb_(11)O_(29)achieves a full charge/discharge cycle within merely 25 s at 75 C rate and retains remarkable cycling stability over 2500 cycles.As a consequence,our assembled FeNb_(11)O_(29)||LiFePO_(4)full cell demonstrates ultra-long cyclability(>10000 cycles)and outstanding fast-charging capability(complete cycling within 2 min at 30 C).These findings highlight nano-sized FeNb_(11)O_(29)as a highly promising anode candidate for next-generation fast-charging LIBs.展开更多
Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we...Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.展开更多
The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventi...Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventional carbon anodes that cannot match the fast capacitive anion intercalation behavior of graphite cathodes constraints on improving power density of SDIBs.Herein,we present an ingenious carbon microdomain engineering strategy to fabricate high-performance carbon anode with ion-mediated high-activity nitrogen species and molecular-scale closed-pore architectures.Experimental characterizations and theoretical investigations demonstrate that Zn^(2+)-mediated structural engineering tailors oxidized nitrogen species,which proficiently accelerate the sodium-ion desolvation kinetics;meanwhile the acetate-mediated pore-forming process modulates closed pores,which synergistically afford abundant sodium storage sites for high plateau-region capacity.As a result,the optimized microdomain engineered carbon material(MEC_(3))tailored with the optimal amount of zinc acetate demonstrates an outstanding plateau-region capacity of 253 mAh g^(-1)even at 1 C,among the highest reported values.Consequently,the MEC_(3)||expanded graphite dual-ion battery exhibits an unprecedented cycling stability at high current rate,maintaining 80.6%capacity retention after 10,000 cycles at 10 C,among the best reports.This microdomain engineering strategy provides a new design principle for overcoming kinetic limitations of carbonaceous materials in plateau-dominated sodium storage systems.展开更多
Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on ...Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.展开更多
Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth...Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.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
Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.展开更多
基金supported by the National Natural Science Foundation of China (21875107, U1802256, and 22209204)Leading Edge Technology of Jiangsu Province (BK20220009), the Natural Science Foundation of Jiangsu Province (BK20221140)+2 种基金the China Postdoctoral Science Foundation (2022M713364)Jiangsu Specially Appointed Professors ProgramPriority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.
基金supported by the National Natural Science Foundation of China (51673017)the National Natural Science Foundation of China (21404005)+1 种基金the Fundamental Research Funds for the Central Universities (XK1802-2)the Natural Science Foundation of Jiangsu Province (BK20150273)。
文摘Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.
基金supported by the National Natural Science Foundation of China(No.12205252)the Basic Public Welfare Re-search Special Project of Zhejiang Province(No.LZY22B040001)+4 种基金the Quzhou Science and Technology Plan Project(No.2022K39)Science and Technology Project of Quzhou Research Institute,Zhejiang University(Nos.IZQ2021KJ2032,IZQ2022KJ3014,and IZQ2022KJ3002)Independent scientific Research Project of Quzhou Research Institute,Zhejiang University(No.IZQ2021RCZX007)New“115 talents”Project ofQuzhou,National Nature Science Foundation of China(No.52172244)Fundamental Research Funds for the Central University(No.226202200053).
文摘The inferior conductivity and drastic volume expansion of silicon still remain the bottleneck in achieving high energy density Lithium-ion Batteries(LIBs).The design of the three-dimensional structure of electrodes by compositing silicon and carbon materials has been employed to tackle the above challenges,however,the exorbitant costs and the uncertainty of the conductive structure persist,leaving ample room for improvement.Herein,silicon nanoparticles were innovatively composited with eco-friendly biochar sourced from cotton to fabricate a 3D globally consecutive conductive network.The network serves a dual purpose:enhancing overall electrode conductivity and serving as a scaffold to maintain electrode integrity.The conductivity of the network was further augmented by introducing P-doping at the optimum doping temperature of 350℃.Unlike the local conductive sites formed by the mere mixing of silicon and conductive agents,the consecutive network can affirm the improvement of the conductivity at a macro level.Moreover,first-principle calculations further validated that the rapid diffusion of Li^(+)is attributed to the tailored electronic microstructure and charge rearrangement of the fiber.The prepared consecutive conductive Si@P-doped carbonized cotton fiber anode outperforms the inconsecutive Si@Graphite anode in both cycling performance(capacity retention of 1777.15 mAh g^(-1) vs.682.56 mAh g^(-1) after 150 cycles at 0.3 C)and rate performance(1244.24 mAh g^(-1) vs.370.28 mAh g^(-1) at 2.0 C).The findings of this study may open up new avenues for the development of globally interconnected conductive networks in Si-based anodes,thereby enabling the fabrication of high-performance LIBs.
基金Department of Education of Gansu Province: Industrial Support Plan Project (2022CYZC-23)National Natural Science Foundation of China (22269012)Gansu Key Research and Development Program (23YFGA0053)。
文摘Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.
基金financially supported by the Key Research and Development Program in Shanxi Province of China (No.202102040201008)。
文摘A flexible carbon fiber-confined yolk-shelled silicon-based composite is reported as an anode material for lithium storage applications.Silicon nanoparticles(Si NPs)are confined by the N-doped hollow carbon cages(SiNHC)and these uniform dispersed yolk-shell-structured Si-NHC units were encapsulated by the carbon fibers within an interconnected three-dimensional(3D)framework(Si-NHC@CNFs).For the encapsulated yolkshelled Si-NHC,the void space between the inner Si NPs and outer NHC can accommodate the structural changes of Si NPs during charging/discharging processes,leading to effectively improved structural stability and cycling life.More importantly,all the Si-NHC units were bridged together through a conductive CNFs"highway"to enhance the overall conductivity and tap density further.As observed,Si-NHC@CNFs exhibited an initial discharge capacity of 1364.1 mAh·g^(-1)at 1000 mA·g^(-1)and678.9 mAh·g^(-1)at 2000 mA·g^(-1).Furthermore,the reversible capacity was well maintained at 752.2 mAh·g^(-1)at500 mA·g^(-1)after 6000 ultra-long cycles.
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 Multi-Year Research Grants from the University of Macao(MYRG-GRG2023-00010-IAPME,MYRG-GRG2024-00038-IAPME,MYRG2022-00026-IAPME)the Science and Technology Development Fund(FDCT)from Macao SAR(0023/2023/AFJ,0050/2023/RIB2,006/2022/ALC,0087/2024/AFJ,0111/2022/A2).
文摘Photoelectrochemical(PEC)water splitting holds significant promise for sustainable energy harvesting that enables efficient conversion of solar energy into green hydrogen.Nevertheless,achievement of high performance is often limited by charge carrier recombination,resulting in unsatisfactory saturation current densities.To address this challenge,we present a novel strategy for achieving ultrahigh current density by incorporating a bridge layer between the Si substrate and the NiOOH cocatalyst in this paper.The optimal photoanode(TCO/n-p-Si/TCO/Ni)shows a remarkably low onset potential of 0.92 V vs.a reversible hydrogen electrode and a high saturation current density of 39.6 mA·cm^(-2),which is about 92.7%of the theoretical maximum(42.7 mA·cm^(-2)).In addition,the photoanode demonstrates stable operation for 60 h.Our systematic characterizations and calculations demonstrate that the bridge layer facilitates charge transfer,enhances catalytic performance,and provides corrosion protection to the underlying substrate.Notably,the integration of this photoanode into a PEC device for overall water splitting leads to a reduction of the onset potential.These findings provide a viable pathway for fabricating highperformance industrial photoelectrodes by integrating a substrate and a cocatalyst via a transparent and conductive bridge layer.
文摘With the rapid advancement of technology and the growing demand for renewable energy,lithium-ion batteries have become the cornerstone of modern energy storage,particularly in electric vehicles.However,traditional graphite anodes limit further improvements in energy density and charging speed.Silicon,with its ultrahigh theoretical capacity,low cost,and environmental compatibility,has emerged as a promising alternative anode material.Nevertheless,its practical application is hindered by severe volume expansion during lithiation,unstable Solid-Electrolyte Interphase(SEI)formation,and low electrical conductivity.This study reviews and analyzes three mainstream strategies developed to address these challenges:(1)the design of silicon–carbon composite anodes to improve conductivity and structural stability;(2)the application of nano-engineered silicon architectures(0D to 3D)to buffer mechanical stress and enhance cycling performance;and(3)electrolyte modification to form more flexible and robust SEI layers.Through comparative analysis of multiple research teams,this paper summarizes how composite engineering,structural optimization,and electrolyte innovation collectively enhance silicon anode performance in terms of capacity retention,rate capability,and long-term stability.The findings indicate that hybrid approaches—combining chemical compositing,nanostructural design,and interfacial engineering—represent the most promising direction for achieving practical,scalable silicon-based anodes.With continued progress in low-cost synthesis and interface stabilization,silicon is expected to play a crucial role in next-generation high-energy lithium-ion batteries,meeting the growing global demand for efficient and sustainable energy storage.
基金the Technology Innovation Program(No.20010542,Development of Petroleum Pitch Based Conductive Material and Binder for Lithium Ion Secondary Battery and Their Application)funded by the Ministry of Trade,Industry&Energy(MOTIE,Republic of Korea)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.2021R1A2C1095408).
文摘Silicon(Si)is considered a potential alternative anode for next-generation Li-ion batteries owing to its high theoretical capacity and abundance.However,the commercial use of Si anodes is hindered by their large volume expansion(~300%).Numerous efforts have been made to address this issue.Among these efforts,Si-graphite co-utilization has attracted attention as a reasonable alternative for high-energy anodes.A comparative study of representative commercial Si-based materials,such as Si nanoparticles,Si suboxides,and Si−Graphite composites(SiGC),was conducted to characterize their overall performance in high-energy lithium-ion battery(LIB)design by incorporating conventional graphite.Nano-Si was found to exhibit poor electrochemical performance,with severe volume expansion during cycling.Si suboxide provided excellent cycling stability in a full-cell evaluation with stable volume variation after 50 cycles,but had a large irreversible capacity and remarkable volume expansion during the first cycle.SiGC displayed a good initial Coulombic efficiency and the lowest volume change in the first cycle owing to the uniformly distributed nano-Si layer on graphite;however,its long-term cycling stability was relatively poor.To complement each disadvantage of Si suboxide and SiGC,a new combination of these Si-based anodes was suggested and a reasonable improvement in overall battery performance was successfully achieved.
基金supported by the Fundamental Research Funds for the Central Universities(No.2232023D-02,2232023Y-01,and 2232021A-02)the National Natural Science Foundation of China(No.52202361,No.92163121,and No.52122312).
文摘Anode materials for Li-ion batteries(LIBs)utilized in electric vehicles,portable electronics,and other devices are mainly graphite(Gr)and its derivatives.However,the limited energy density of Gr-based anodes promotes the exploration of alternative anode materials such as silicon(Si)-based materials because of their abundance in nature and low cost.Specifically,Si can store 10 times more energy than Gr and also has the potential to enhance the energy density of LIBs.Despite the many advantages of Si-based anodes,such as high theoretical capacity and low price,their widespread use is hindered by two major issues:charge-induced volume expansion and unreliable solid electrolyte interphase(SEI)propagation.In this detailed review,we highlight the key issues,current advances,and prospects in the rational design of Si-based electrodes for practical applications.We first explain the fundamental electrochemistry of Si and the importance of Si-based anodes in LIBs.The excessive volume increase,relatively low charge efficiency,and inadequate areal capacity of Si-based anodes are discussed to identify the barriers in enhancing their performance in LIBs.Subsequently,the use of binders(e.g.,linear polymer binders,branched polymer binders,cross-linked polymer binders,and conjugated conductive polymer binders),material-based anode composites(such as carbon and its derivatives,metal oxides,and MXenes),and liquid electrolyte construction techniques are highlighted to overcome the identified barriers.Further,tailoring Si-based materials and reshaping their surfaces and interfaces,including improving binders and electrolytes,are shown to be viable approaches to address their drawbacks,such as volume expansion,low charge efficiency,and poor areal capacity.Finally,we highlight that research and development on Si-based anodes are indispensable for their use in commercial applications.
基金supported by the Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金supported by the Natural Sci-ence Foundation of Fujian Province (No.2024J011210)the High-Level Talent Start-Up Foundation of Xiamen Institute of Technology (No.YKJ23017R)。
文摘Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.
基金financially supported by the National Natural Science Foundation of China (52272209)
文摘Niobium-based oxides show great potential in anode materials for fast-charging lithium-ion batteries,but their practical application remains hindered by intrinsically low conductivity.In this study,we successfully synthesize nano-sized Wadsley-Roth FeNb_(11)O_(29)through Fe-driven phase transformation of Nb_(2)O_(5),which delivers a high specific capacity(280.5 mA h g^(−1)at 0.25 C)along with abundant redox-active sites.Moreover,the Wadsley-Roth shear structure of FeNb_(11)O_(29)facilitates rapid Li^(+)diffusion and guarantees exceptional structural stability.Theoretical calculations further confirm that FeNb_(11)O_(29)has a narrow band gap,which significantly enhances the conductivity.Owing to these merits,FeNb_(11)O_(29)achieves a full charge/discharge cycle within merely 25 s at 75 C rate and retains remarkable cycling stability over 2500 cycles.As a consequence,our assembled FeNb_(11)O_(29)||LiFePO_(4)full cell demonstrates ultra-long cyclability(>10000 cycles)and outstanding fast-charging capability(complete cycling within 2 min at 30 C).These findings highlight nano-sized FeNb_(11)O_(29)as a highly promising anode candidate for next-generation fast-charging LIBs.
基金the financial support from Research Institute for Smart Energy at the Hong Kong Polytechnic University(Grant No.CDB2)the support of the Hong Kong PhD Fellowship Scheme(Grant No.PF21-65328)。
文摘Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
基金support from the National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(52125105,52572282,52472269,52273312,22309200)+3 种基金Guangdong Basic and Applied Basic Research Foundation(2024A1515010201,2024A1515012379,2024A1515011670,2023A1515011519)Guangdong Special Support Program Outstanding Young Talents in Science and Technology Innovation(2021TQ05L894)Shenzhen Science and Technology Planning Project(JSGG20220831104004008,SGDX20230116092055008,KCXST20221021111606016)the NSRF via the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(B49G680115).
文摘Sodium-based dual-ion batteries(SDIBs)have been attracting increasing attention in recent years owing to their low cost,environmental benignancy,and high operating voltage.However,the sluggish ion kinetics of conventional carbon anodes that cannot match the fast capacitive anion intercalation behavior of graphite cathodes constraints on improving power density of SDIBs.Herein,we present an ingenious carbon microdomain engineering strategy to fabricate high-performance carbon anode with ion-mediated high-activity nitrogen species and molecular-scale closed-pore architectures.Experimental characterizations and theoretical investigations demonstrate that Zn^(2+)-mediated structural engineering tailors oxidized nitrogen species,which proficiently accelerate the sodium-ion desolvation kinetics;meanwhile the acetate-mediated pore-forming process modulates closed pores,which synergistically afford abundant sodium storage sites for high plateau-region capacity.As a result,the optimized microdomain engineered carbon material(MEC_(3))tailored with the optimal amount of zinc acetate demonstrates an outstanding plateau-region capacity of 253 mAh g^(-1)even at 1 C,among the highest reported values.Consequently,the MEC_(3)||expanded graphite dual-ion battery exhibits an unprecedented cycling stability at high current rate,maintaining 80.6%capacity retention after 10,000 cycles at 10 C,among the best reports.This microdomain engineering strategy provides a new design principle for overcoming kinetic limitations of carbonaceous materials in plateau-dominated sodium storage systems.
基金supported by the Foundation of Yunnan Province(Nos.202301AU070021,202201BE070001-027)the Test Foundation of KUST(No.2022T20210208).
文摘Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.
基金support from the Australian Research Council Discovery Program(DP220103416,DP240102177)Australian Research Council Future Fellowships(FT200100730,FT210100804).
文摘Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.
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 Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
