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
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
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
This research discusses the core concepts,evolutionary trajectories,inherent differences and intrinsic interconnections between carbon-based and silicon-based life forms.On this basis,we further analyze the potential ...This research discusses the core concepts,evolutionary trajectories,inherent differences and intrinsic interconnections between carbon-based and silicon-based life forms.On this basis,we further analyze the potential risks brought by the unbalanced development of carbon and silicon economies.Then we point out a critical reality:although silicon-based life still depends on the assistance of carbon-based life for its evolution at present,the unconstrained growth of the silicon-based economy may ultimately undermine the survival and development of carbon-based economies and carbon-based life itself.We also give the solutions under our new theory,using the revenue and time saved from the silicon-based economy to subsidize the carbon-based economy,and producing more ecological products.The study proposes 6 strategic recommendations:(1)human society should establish a carbon-based life community;(2)environmental institutions produce more essential ecological products for the community,not only for human life;(3)all stakeholders take advantage of silicon-based life while also restricting its unlimited development;(4)countries and industries give full play to the positive role of the silicon-based economy in climate change mitigation and carbon-based life health;(5)relevant governance bodies enable AI to Participate in politics,assist in formulating policies and implement them fairly.(6)regions and economic entities develop diverse carbon-based economies based on the non-monetary trading system.展开更多
Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmemb...Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.展开更多
Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabrica...Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.展开更多
The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by alteri...The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.展开更多
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 practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present bi...The practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present binder-free holey wrinkled-multilayered graphene(HWMG)scaffolds for highperformance LMAs with long cycle life.Holey graphene oxide(HGO)sheets were restacked into particle-like holey wrinkled-multilayered graphene oxide(HWMGO)in a high-concentration GO suspension,in which few-layer HGOs were quickly stabilized and wrinkled during the drying process,and upon reduction,they transformed into HWMG.HWMG exhibited excellent adhesion due to chemical interactions via edge-located functional groups.Its particle-like morphology,with numerous nanopores and high porosity,conferred outstanding mechanical flexibility and low tortuosity,enabling uniform Li-ion flux,buffering volume expansion,and suppressing dendrite growth.As a result,excellent long-term stability over 800 cycles and a voltage hysteresis of ca.7 mV over 6000 h were realized for the HWMG scaffolds,and a high areal capacity of 3.34 mAh cm^(-2) at 0.3 C after 350 cycles was demonstrated in a full-cell configuration.This work promotes the practical application of LMAs by offering a scalable scaffold design that suppresses dendrites and enhances cycle life.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
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
Silicon(Si)is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging,greatly hindering its automobile applications.Electrolyte ...Silicon(Si)is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging,greatly hindering its automobile applications.Electrolyte engineering currently relies on conventional evaluation criteria of reducing coulombic consumption,which implicitly presume its equivalence to irreversible capacity loss and complicates battery development.We introduce the detrimental ratioρto quantify the fraction of parasitic species that permanently degrades active material.This metric is independent and crucially complements total coulombic consumption for accurate performance evaluation.We systematically investigate multiple electrolyte formulations using high-precision leakage current measurements,open-circuit-voltage experiments,and post-mortem characterizations.Although some electrolytes exhibit similarly low coulombic consumption,they diverge significantly in capacity retention andρ.Especially,dimethyl-carbonate-based localized-high concentration electrolyte can synergically achieve low coulombic consumption and detrimental ratioρduring calendar aging,owing to its chemically inert and structurally resilient solidelectrolyte interface with minimal isolated Si material.By contrast,increasing fluoroethylene carbonate(FEC)additive content suppresses electrolyte breakdown but suffers aggravated chemical degradation of more LixSi isolation for irreversible capacity loss with a risingρ.This study critically reveals that the chemistry-characteristic detrimental ratioρestablishes physically informed performance evaluation to pave the way for accelerating battery development.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
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
Silicon(Si)is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium(Li)-ion batteries(LIBs)because it has a high theoretical gravimetric Li storage...Silicon(Si)is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium(Li)-ion batteries(LIBs)because it has a high theoretical gravimetric Li storage capacity,relatively low lithiation voltage,and abundant resources.Consequently,massive efforts have been exerted to improve its electrochemical performance.While some progress in this field has been achieved,a number of severe challenges,such as the element’s large volume change during cycling,low intrinsic electronic conductivity,and poor rate capacity,have yet to be solved.Methods to solve these problems have been attempted via the development of nanosized Si materials.Unfortunately,reviews summarizing the work on Si-based alloys are scarce.Herein,the recent progress related to Si-based alloy anode materials is reviewed.The problems associated with Si anodes and the corresponding strategies used to address these problems are first described.Then,the available Si-based alloys are divided into Si/Li-active and inactive systems,and the characteristics of these systems are discussed.Other special systems are also introduced.Finally,perspectives and future outlooks are provided to enable the wider application of Si-alloy anodes to commercial LIBs.展开更多
Silicon has attracted much attention as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and rich resource abundance. However, the practical battery use of Si is challen...Silicon has attracted much attention as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and rich resource abundance. However, the practical battery use of Si is challenged by its low conductivity and drastic volume variation during the Li uptake/release process. Tremendous efforts have been made on shrinking the particle size of Si into nanoscale so that the volume variation could be accommodated. However, the bare nano-Si material would still pulverize upon (de)lithiation. Moreover, it shows an excessive surface area to invite unlimited growth of solid electrolyte interface that hinders the transportation of charge carriers, and an increased interparticle resistance. As a result, the Si nanoparticles gradually lose their electrical contact during the cycling process, which accounts for poor thermodynamic stability and sluggish kinetics of the anode reaction versus Li. To address these problems and improve the Li storage performance of nano-Si anode, proper structural design should be applied on the Si anode. In this perspective, we will briefly review some strategies for improving the electrochemistry versus Li of nano-Si materials and their derivatives, and show opinions on the optimal design of nanostructured Si anode for advanced LIBs.展开更多
Conventional lithium-ion batteries(LIBs)with graphite anodes are approaching their theoretical limitations in energy density.Replacing the conventional graphite anodes with high-capacity Si-based anodes represents one...Conventional lithium-ion batteries(LIBs)with graphite anodes are approaching their theoretical limitations in energy density.Replacing the conventional graphite anodes with high-capacity Si-based anodes represents one of the most promising strategies to greatly boost the energy density of LIBs.However,the inherent huge volume expansion of Si-based materials after lithiation and the resulting series of intractable problems,such as unstable solid electrolyte interphase layer,cracking of electrode,and especially the rapid capacity degradation of cells,severely restrict the practical application of Sibased anodes.Over the past decade,numerous reports have demonstrated that polymer binders play a critical role in alleviating the volume expansion and maintaining the integrity and stable cycling of Si-based anodes.In this review,the state-of-the-art designing of polymer binders for Si-based anodes have been systematically summarized based on their structures,including the linear,branched,crosslinked,and conjugated conductive polymer binders.Especially,the comprehensive designing of multifunctional polymer binders,by a combination of multiple structures,interactions,crosslinking chemistries,ionic or electronic conductivities,soft and hard segments,and so forth,would be promising to promote the practical application of Si-based anodes.Finally,a perspective on the rational design of practical polymer binders for the large-scale application of Si-based anodes is presented.展开更多
Silicon(Si)-based solid-state batteries(Si-SSBs)are attracting tremendous attention because of their high energy density and unprecedented safety,making them become promising candidates for next-generation energy stor...Silicon(Si)-based solid-state batteries(Si-SSBs)are attracting tremendous attention because of their high energy density and unprecedented safety,making them become promising candidates for next-generation energy storage systems.Nevertheless,the commercialization of Si-SSBs is significantly impeded by enormous challenges including large volume variation,severe interfacial problems,elusive fundamental mechanisms,and unsatisfied electrochemical performance.Besides,some unknown electrochemical processes in Si-based anode,solid-state electrolytes(SSEs),and Si-based anode/SSE interfaces are still needed to be explored,while an in-depth understanding of solid–solid interfacial chemistry is insufficient in Si-SSBs.This review aims to summarize the current scientific and technological advances and insights into tackling challenges to promote the deployment of Si-SSBs.First,the differences between various conventional liquid electrolyte-dominated Si-based lithium-ion batteries(LIBs)with Si-SSBs are discussed.Subsequently,the interfacial mechanical contact model,chemical reaction properties,and charge transfer kinetics(mechanical–chemical kinetics)between Si-based anode and three different SSEs(inorganic(oxides)SSEs,organic–inorganic composite SSEs,and inorganic(sulfides)SSEs)are systemically reviewed,respectively.Moreover,the progress for promising inorganic(sulfides)SSE-based Si-SSBs on the aspects of electrode constitution,three-dimensional structured electrodes,and external stack pressure is highlighted,respectively.Finally,future research directions and prospects in the development of Si-SSBs are proposed.展开更多
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 (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.
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supported by the Fund of China Scholarship Council(Grant No.202404180010).
文摘This research discusses the core concepts,evolutionary trajectories,inherent differences and intrinsic interconnections between carbon-based and silicon-based life forms.On this basis,we further analyze the potential risks brought by the unbalanced development of carbon and silicon economies.Then we point out a critical reality:although silicon-based life still depends on the assistance of carbon-based life for its evolution at present,the unconstrained growth of the silicon-based economy may ultimately undermine the survival and development of carbon-based economies and carbon-based life itself.We also give the solutions under our new theory,using the revenue and time saved from the silicon-based economy to subsidize the carbon-based economy,and producing more ecological products.The study proposes 6 strategic recommendations:(1)human society should establish a carbon-based life community;(2)environmental institutions produce more essential ecological products for the community,not only for human life;(3)all stakeholders take advantage of silicon-based life while also restricting its unlimited development;(4)countries and industries give full play to the positive role of the silicon-based economy in climate change mitigation and carbon-based life health;(5)relevant governance bodies enable AI to Participate in politics,assist in formulating policies and implement them fairly.(6)regions and economic entities develop diverse carbon-based economies based on the non-monetary trading system.
基金the financial support from the National Natural Science Foundation of China(22408182)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT24024)the Natural Science Foundation of Inner Mongolia Autonomous Region(2023QN02007 and 2025QN02009)。
文摘Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.
基金(partially)funded by the BK21 FOUR Program of Graduate School,Kyung Hee University(GS-1-JO-ON-info2120241890)。
文摘Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.
基金financially supported by the Science and Technology Foundation of Henan Province(252102230017)the Doctoral Foundation of Henan University of Technology(2019BS005)+2 种基金the Talent Research Start-up Fund Project of Tongling University(2021tlxyrc23)the Natural Science Research Project of the Anhui Educational Committee(2023AH040234)the Scientific Research Projects of Tongling University(2022tlxyszZD04)。
文摘The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.
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 National Research Foundation of Korea(NRF)grants funded by the Korean government(MSIT)(RS-2024-00409952,RS-2024-00347936,and RS-202400407282)supported by the GRRC Program of Gyeonggi Province(GRRCHanyang2020-B01)supported by the Commercialization Promotion Agency for R&D Outcomes(COMPA)grant funded by the Korean Government(MSIT)(RS-2023-00304763)。
文摘The practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present binder-free holey wrinkled-multilayered graphene(HWMG)scaffolds for highperformance LMAs with long cycle life.Holey graphene oxide(HGO)sheets were restacked into particle-like holey wrinkled-multilayered graphene oxide(HWMGO)in a high-concentration GO suspension,in which few-layer HGOs were quickly stabilized and wrinkled during the drying process,and upon reduction,they transformed into HWMG.HWMG exhibited excellent adhesion due to chemical interactions via edge-located functional groups.Its particle-like morphology,with numerous nanopores and high porosity,conferred outstanding mechanical flexibility and low tortuosity,enabling uniform Li-ion flux,buffering volume expansion,and suppressing dendrite growth.As a result,excellent long-term stability over 800 cycles and a voltage hysteresis of ca.7 mV over 6000 h were realized for the HWMG scaffolds,and a high areal capacity of 3.34 mAh cm^(-2) at 0.3 C after 350 cycles was demonstrated in a full-cell configuration.This work promotes the practical application of LMAs by offering a scalable scaffold design that suppresses dendrites and enhances cycle life.
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 U.S.Department of Energy(DOE),Office of Energy Efficiency and Renewable Energy(EERE),Vehicle Technologies Office(VTO)under the Silicon Consortium Seedling project received by Z.H.Coperated for the DOE Office of Science by UChicago Argonne,LLC,under Contract DE-AC02-06CH11357+2 种基金Pacific Northwest National Laboratory(PNNL)was supported by the U.S.DOE,Office of Advanced Research Projects Agency-Energy(ARPA-E)under the EVs4ALL Program with the contract number DE-AC05-76RL01830operated by Battelle for the DOE under Contract DE-AC0576RL01830performed at the Oak Ridge National Laboratory(GMV)and supported by U.S.DOE’s VTO under the Silicon Consortium Program received by G.M.V.and directed by Carine Steinway,Nicolas Eidson Thomas,Thomas Do。
文摘Silicon(Si)is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging,greatly hindering its automobile applications.Electrolyte engineering currently relies on conventional evaluation criteria of reducing coulombic consumption,which implicitly presume its equivalence to irreversible capacity loss and complicates battery development.We introduce the detrimental ratioρto quantify the fraction of parasitic species that permanently degrades active material.This metric is independent and crucially complements total coulombic consumption for accurate performance evaluation.We systematically investigate multiple electrolyte formulations using high-precision leakage current measurements,open-circuit-voltage experiments,and post-mortem characterizations.Although some electrolytes exhibit similarly low coulombic consumption,they diverge significantly in capacity retention andρ.Especially,dimethyl-carbonate-based localized-high concentration electrolyte can synergically achieve low coulombic consumption and detrimental ratioρduring calendar aging,owing to its chemically inert and structurally resilient solidelectrolyte interface with minimal isolated Si material.By contrast,increasing fluoroethylene carbonate(FEC)additive content suppresses electrolyte breakdown but suffers aggravated chemical degradation of more LixSi isolation for irreversible capacity loss with a risingρ.This study critically reveals that the chemistry-characteristic detrimental ratioρestablishes physically informed performance evaluation to pave the way for accelerating battery development.
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 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.
基金financially supported by the National Natural Science Foundation of China(No.52074360)the Natural Science Foundation for Distinguished Young Scholars of Hunan Province(No.2020JJ2047)+1 种基金the Program of Huxiang Young Talents(No.2019RS2002)the Innovation-Driven Project of Central South University(No.2020CX027).
文摘Silicon(Si)is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium(Li)-ion batteries(LIBs)because it has a high theoretical gravimetric Li storage capacity,relatively low lithiation voltage,and abundant resources.Consequently,massive efforts have been exerted to improve its electrochemical performance.While some progress in this field has been achieved,a number of severe challenges,such as the element’s large volume change during cycling,low intrinsic electronic conductivity,and poor rate capacity,have yet to be solved.Methods to solve these problems have been attempted via the development of nanosized Si materials.Unfortunately,reviews summarizing the work on Si-based alloys are scarce.Herein,the recent progress related to Si-based alloy anode materials is reviewed.The problems associated with Si anodes and the corresponding strategies used to address these problems are first described.Then,the available Si-based alloys are divided into Si/Li-active and inactive systems,and the characteristics of these systems are discussed.Other special systems are also introduced.Finally,perspectives and future outlooks are provided to enable the wider application of Si-alloy anodes to commercial LIBs.
基金the financial support of this work by the National Natural Science Foundation of China (No.21773078)the Fundamental Research Funds for the Central Universities of China (Nos.2662015PY163 and 2662017JC025).
文摘Silicon has attracted much attention as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and rich resource abundance. However, the practical battery use of Si is challenged by its low conductivity and drastic volume variation during the Li uptake/release process. Tremendous efforts have been made on shrinking the particle size of Si into nanoscale so that the volume variation could be accommodated. However, the bare nano-Si material would still pulverize upon (de)lithiation. Moreover, it shows an excessive surface area to invite unlimited growth of solid electrolyte interface that hinders the transportation of charge carriers, and an increased interparticle resistance. As a result, the Si nanoparticles gradually lose their electrical contact during the cycling process, which accounts for poor thermodynamic stability and sluggish kinetics of the anode reaction versus Li. To address these problems and improve the Li storage performance of nano-Si anode, proper structural design should be applied on the Si anode. In this perspective, we will briefly review some strategies for improving the electrochemistry versus Li of nano-Si materials and their derivatives, and show opinions on the optimal design of nanostructured Si anode for advanced LIBs.
基金Beijing National Laboratory for Molecular Sciences,Grant/Award Number:2019BMS20022National Natural Science Foundation of China,Grant/Award Number:22005314+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences,Grant/Award Number:XDA21070300The China Postdoctoral Science Foundation,Grant/Award Number:2019M660805The National Key R&D Program of China,Grant/Award Number:2019YFA0705600The Special Financial Grant from the China Postdoctoral Science Foundation,Grant/Award Number:2020T130658。
文摘Conventional lithium-ion batteries(LIBs)with graphite anodes are approaching their theoretical limitations in energy density.Replacing the conventional graphite anodes with high-capacity Si-based anodes represents one of the most promising strategies to greatly boost the energy density of LIBs.However,the inherent huge volume expansion of Si-based materials after lithiation and the resulting series of intractable problems,such as unstable solid electrolyte interphase layer,cracking of electrode,and especially the rapid capacity degradation of cells,severely restrict the practical application of Sibased anodes.Over the past decade,numerous reports have demonstrated that polymer binders play a critical role in alleviating the volume expansion and maintaining the integrity and stable cycling of Si-based anodes.In this review,the state-of-the-art designing of polymer binders for Si-based anodes have been systematically summarized based on their structures,including the linear,branched,crosslinked,and conjugated conductive polymer binders.Especially,the comprehensive designing of multifunctional polymer binders,by a combination of multiple structures,interactions,crosslinking chemistries,ionic or electronic conductivities,soft and hard segments,and so forth,would be promising to promote the practical application of Si-based anodes.Finally,a perspective on the rational design of practical polymer binders for the large-scale application of Si-based anodes is presented.
基金supported by the National Natural Science Foundation of China(Grants Nos.52072323,52122211 and 21875155)the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Grant No.LAPS22005)+3 种基金the Frontier Exploration Projects of Longmen Laboratory(Grant No.LMQYTSKT008)the Shenzhen Technical Plan Project(No.JCYJ20220818101003008)the support of High-Tech Industrialization Project of Tan Kah Kee Innovation Laboratory(Grant No.RD2021010101)the“Double-First Class”Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University.L.Zhang and Q.Zhang acknowledge the support of the Nanqiang Young Top-notch Talent Fellowship at Xiamen University.
文摘Silicon(Si)-based solid-state batteries(Si-SSBs)are attracting tremendous attention because of their high energy density and unprecedented safety,making them become promising candidates for next-generation energy storage systems.Nevertheless,the commercialization of Si-SSBs is significantly impeded by enormous challenges including large volume variation,severe interfacial problems,elusive fundamental mechanisms,and unsatisfied electrochemical performance.Besides,some unknown electrochemical processes in Si-based anode,solid-state electrolytes(SSEs),and Si-based anode/SSE interfaces are still needed to be explored,while an in-depth understanding of solid–solid interfacial chemistry is insufficient in Si-SSBs.This review aims to summarize the current scientific and technological advances and insights into tackling challenges to promote the deployment of Si-SSBs.First,the differences between various conventional liquid electrolyte-dominated Si-based lithium-ion batteries(LIBs)with Si-SSBs are discussed.Subsequently,the interfacial mechanical contact model,chemical reaction properties,and charge transfer kinetics(mechanical–chemical kinetics)between Si-based anode and three different SSEs(inorganic(oxides)SSEs,organic–inorganic composite SSEs,and inorganic(sulfides)SSEs)are systemically reviewed,respectively.Moreover,the progress for promising inorganic(sulfides)SSE-based Si-SSBs on the aspects of electrode constitution,three-dimensional structured electrodes,and external stack pressure is highlighted,respectively.Finally,future research directions and prospects in the development of Si-SSBs are proposed.
