Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growt...Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.展开更多
High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte...High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte additive to enhance the cycling performances of graphite/LiNi0.6Co0.2Mn0.2O2 pouch cell.In comparison with the baseline electrolyte,a small dose of pTSF can significantly improve the cyclic stability of the cell.Theoretical calculations together with experimental results indicate that pTSF would be oxidized and reduced to construct protective interphase film on the surfaces of LiNi0.6Co0.2Mn0.2O2 cathode and graphite anode,respectively.These S-containing surface films derived from pTSF effectively mitigate the decomposition of electrolyte,reduce the interphasial impedance,as well as prevent the dissolution of transition metal ions from Ni-rich cathode upon cycling at high voltage.This finding is beneficial for the practical application of high energy density graphite/LiNi0.6Co0.2Mn0.2O2 cells.展开更多
Since the electrode/electrolyte interface(EEI)is the main redox center of electrochemical processes,proper manipulation of the EEI microenvironment is crucial to stabilize interfacial behaviors.Here,a finger-paint met...Since the electrode/electrolyte interface(EEI)is the main redox center of electrochemical processes,proper manipulation of the EEI microenvironment is crucial to stabilize interfacial behaviors.Here,a finger-paint method is proposed to enable quick physical modification of glass-fiber separator without complicated chemical technology to modulate EEI of bilateral electrodes for aqueous zinc-ion batteries(ZIBs).An elaborate biochar derived from Aspergillus Niger is exploited as the modification agent of EEI,in which the multi-functional groups assist to accelerate Zn^(2+)desolvation and create a hydrophobic environment to homogenize the deposition behavior of Zn anode.Importantly,the finger-paint interface on separator can effectively protect cathodes from abnormal capacity fluctuation and/or rapid attenuation induced by H_(2)O molecular on the interface,which is demonstrated in modified MnO_(2),V_(2)O_(5),and KMn HCF-based cells.The as-proposed finger-paint method opens a new idea of bilateral interface engineering to facilitate the access to the practical application of the stable zinc electrochemistry.展开更多
Si(111)electrode has been widely used in electrochemical and photoelectrochemical studies.The potential dependent measurements of the second harmonic generation(SHG)were performed to study Si(111)electrode interface.A...Si(111)electrode has been widely used in electrochemical and photoelectrochemical studies.The potential dependent measurements of the second harmonic generation(SHG)were performed to study Si(111)electrode interface.At different azimuthal angles of the Si(111)and under different polarization combinations,the curve of the intensity of SHG with extern potential has a different form of line or parabola.Quantitative analysis showed that these differences in the potential-dependence can be explained by the isotropic and anisotropic contribution of the Si(111)electrode.The change in the isotropic and anisotropic contribution of the Si(111)electrode may be attributed to the increase in the doping concentration of Si(111)electrodes.展开更多
The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercializ...The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercialization.The regular concentration(1_(M))electrolytes with suitable properties(viscosity,ionic conductivity,etc.)are cost-guaranteed,but undesired reactions would always occur and lead to battery degradation during long cycles.To promote the long-term cycle stability in a cost-effective way,this work constructs bidirectional fluorine-rich electrode/electrolyte interphase(EEI)by redistribution of solvents and electrochemical induction.The fluorinated effect with reasonable zoning planning restricts morphological disintegration,meanwhile,forms spatial confinement on cathode.In particular,the obtained cathode electrolyte interphase(CEI)gets the ample ability of Na^(+)transport,which benefits from the fluorinated organics arranged in the epitaxy and the hemi-carbonate content acting on the thickness.Thus,the electrochemical long cycling performance of F-NVPOFⅡF-CC full cells is significantly enhanced(the decay rate at 1 C per cycle is as low as 0.01%).Such a fluorine-rich EEI engineering is expected to take transitional layers against the degradation of cells and make ultra-long cycle batteries possible.展开更多
High-voltage sodium-ion batteries(SIBs)are emerging as promising candidates for large-scale energy storage systems due to their abundant sodium source and high energy density.However,the instability of the electrode e...High-voltage sodium-ion batteries(SIBs)are emerging as promising candidates for large-scale energy storage systems due to their abundant sodium source and high energy density.However,the instability of the electrode electrolyte interphase remains a critical barrier to the potential use of high-voltage SIBs.Herein,sodium difluorophosphate(NaDFP)and fluoroethylene carbonate(FEC)serve as functional electrolyte additives to stabilize the interface of the high-voltage cathode.The oxidative competition between FEC and NaDFP facilitates the robust formation of the cathode-electrolyte interface(CEI)layer,enriched with inorganic components such as NaF/NaPO_(x)F_(y).The highly conductive NaF/NaPO_(x)F_(y)and inorganics provide fast ion transport pathways and mechanical strength,thereby mitigating the decomposition of carbonates and NaPF_(6).The half-cell equipped with BE 2 F+0.5 DFP demonstrates 93.9%capacity retention at 4.3 V across 600 cycles,showcasing excellent cycling capability.Full HC||NVOPF cells exhibit sustained performance with 91.69%capacity retention and a capacity of 91.57 mA·h/g over 1000 cycles at a 5 C rate.This study is poised to garner increased scholarly interest in the domain of rational electrolyte formulation for practical applications.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due to their high industrial demands.However,the mechanistic understanding of C_(2) product formation remains unclear due to the lack of in situ or operando measurements that can observe the complex and instantaneous atomic evolutions of adsorbates at the electrode/electrolyte interface.Moreover,the sensitivity of ECR reactions to variations at the interface further widens the gap between mechanistic understanding and performance enhancement.To bridge this gap,first-principle studies provide insights into how the interface influences ECR.In this study,we present a review of mechanistic studies investigating the effects of various factors at the interface,with an emphasis on the C_(2) product formation.We begin by introducing ECR and the essential metrics.Next,we discuss the factors classified by their components at the interface,namely,electrocatalyst,electrolyte,and adsorbates,respectively,and their effects on the C_(2) product formation.Due to the interplay among these factors,we aim to deconvolute the influence of each factor and clearly demonstrate their impacts.Finally,we outline the promising directions for mechanistic studies of C_(2) products.展开更多
The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materia...The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materials for lithium-ion batteries.Silicon(Si),the second-largest element outside of Earth,has an exceptionally high specific capacity(3579 mAh g^(-1)),regarded as an excellent choice for the anode material in high-capacity lithium-ion batteries.However,it is low intrinsic conductivity and volume amplification during service status,prevented it from developing further.These difficulties can be successfully overcome by incorporating carbon into pure Si systems to form a composite anode and constructing a buffer structure.This review looks at the diffusion mechanism,various silicon-based anode material configurations(including sandwich,core-shell,yolk-shell,and other 3D mesh/porous structures),as well as the appropriate binders and electrolytes.Finally,a summary and viewpoints are offered on the characteristics and structural layout of various structures,metal/non-metal doping,and the compatibility and application of various binders and electrolytes for silicon-based anodes.This review aims to provide valuable insights into the research and development of silicon-based carbon anodes for high-performance lithium-ion batteries,as well as their integration with binders and electrolyte.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and elec...The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.展开更多
Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electroche...Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electrochemical interfaces was established exclusively based on the studies of liquid/solid electrochemical interfaces.Thus,similarities and differences of liquid and polymer electrolyte/electrode interfaces need to be mapped out to guide the design of device level electrochemical interfaces.In this work,we employ the sulfonate adsorption/desorption as a probe reaction to understand the electron-transfer steps in polymer and liquid electrolytes.Through cyclic voltametric investigations on the well-define single-crystal Pd_(ML)Pt(111)electrode,we demonstrate that the oxidative adsorption and reductive desorption of sulfonates at the polymer electrolyte/electrode interface are chemically distinct from those in liquid electrolytes,with the former occurring mostly via the proton-coupled pathway while the latter proceeding mainly through the solvation-mediated pathway.Importantly,the sulfonate adsorption/desorption behaviors of alkylsulfonates become increasingly similar to those in Nafion with longer alkyl chains,suggesting that the interfacial hydrophobicity and solvation environment conferred by the perfluorinated polymer play a decisive role in the electron-transfer mechanism.Results reported in this study highlight the mechanistic distinctions between electron-transfer processes at electrochemical interfaces involving polymer and liquid electrolytes,and provide a framework for understanding electron-transfer processes at polymer electrolyte/electrode interfaces.展开更多
The publisher regrets to inform that in the article of Advanced Powder Materials 4(2025)100261,the published Figs.3 and 5 belong to the initially submitted version,which should be replaced by the final version.The dif...The publisher regrets to inform that in the article of Advanced Powder Materials 4(2025)100261,the published Figs.3 and 5 belong to the initially submitted version,which should be replaced by the final version.The differences between the initial and final versions of these figures are described below.展开更多
Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interf...Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.展开更多
Metal coating is a prevalent strategy for enhancing surface properties.Among the numerous methods for preparing coatings,electrodeposition stands out due to its simplicity,cost-effectiveness,and high efficiency,making...Metal coating is a prevalent strategy for enhancing surface properties.Among the numerous methods for preparing coatings,electrodeposition stands out due to its simplicity,cost-effectiveness,and high efficiency,making it widely utilized in various metal coating applications.By meticulously selecting appropriate electrolytes and electrodeposition parameters,metal coatings with diverse structures and morphologies can be obtained,and tailored to meet specific performance requirements.As the demand for superior metal coating performance continues to rise,it is imperative to summarize and forecast electrodeposition techniques to meet the criteria for high quality and precision.This review delves into the electrodeposition preparation of several typical metal coatings in diverse electrolyte systems,including aqueous solutions,ionic liquids,deep eutectic solvents,and molten salts.We also examine the electrodeposition process on the cathode,elucidate the correlation between parameters and coating quality,and suggest future research directions.This review aims to provide valuable insights and guidance for the electrodeposition preparation of metal coatings.展开更多
The silicon-graphite(Si-C)composite electrode is considered a promising candidate for next-generation commercial electrodes due to its high capacity.However,lithium-ion batteries with silicon electrodes often experien...The silicon-graphite(Si-C)composite electrode is considered a promising candidate for next-generation commercial electrodes due to its high capacity.However,lithium-ion batteries with silicon electrodes often experience capacity fading and poor cyclic performance,primarily due to the mechanical degradation of the solid-electrolyte interphase(SEI).In this work,we present a homogenized constitutive model for Si-C composite electrodes under finite deformation,incorporating lithium-ion concentration-dependent properties.We perform a wrinkling analysis and systematically examine the influence of key parameters,such as modulus and thickness ratios,on the critical conditions for instability.Additionally,we investigate the ratcheting effect across varying silicon contents.Our findings reveal that maintaining the silicon content within an optimal range effectively reduces plastic accumulation during charge–discharge cycles.These insights provide crucial guidance for optimizing the design and fabrication of Si–C electrode systems,enhancing their durability and performance.展开更多
The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable informat...The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable information of interfacial phenomena during battery operation. In situ scanning probe microscopy （SPM） is a powerful technique used for the interfacial investigation of the Li-ion batteries. The versatile SPM techniques and their various operation modes have been utilized to measure the morphology and other properties of the electrode interface at high resolu- tion. Herein, we discuss the related SPM techniques to study the topography, mechanics and electrochemistry re- search of electrodes. Recent progresses of in situ SPM research on the electrode/electrolyte interface are summa- rized. Finally, the outlook of the technique is discussed.展开更多
Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of va...Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of vanadium species on conventional carbon electrodes remains a major limitation to their performance.We investigated the deposition of carbon black,carbon nanotubes,and electrochemically exfoliated graphene(Exf-Gr)onto thermally-activated carbon paper(ACP)by spray coating to increase the electrode electrocatalytic activity.The modified electrodes were characterized using scanning electron microscopy,X-ray diffraction,Raman spectroscopy,X-ray photoelectron microscopy,and surface area analysis,while their electrochemical properties were evaluated by cyclic voltammetry,electrochemical impedance spectroscopy,and singlecell VRFB testing.Among the modified electrodes,Exf-Gr/ACP had the best performance,achieving a 2.9-fold reduction in charge transfer resistance compared to pristine ACP and delivering 2.5 times the discharge capacity in single-cell tests.This improvement is attributed to Exf-Gr’s high surface area,favorable catalytic activity,and excellent dispersion on the ACP substrate.Surface modification with electrochemically exfoliated graphene is a highly effective strategy for improving the electrode performance in VRFB systems,with significant implications for large-scale energy storage.展开更多
The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.Howeve...The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.However,this pursuit has been fundamentally hindered by the absence of transformative battery materials capable of delivering the necessary electrochemical functions,robust interface adhesion,and,crucially,the suitable rheological properties required for on-demand shaping.In this work,we introduce a concept of a multifunctional plasticine electrode matrix(PEM)featuring nano-interpenetrating networks(nano-IPN)to address this challenge.Utilizing the nonflammable liquid-electrolyte hydration combined with conductive nanomaterials,we have realized a PEM in the form of a multifunctional nanocomposite that integrates ion and electron conduction,component binding,non-flammability,and plasticine-like moldability.With this PEM,we have successfully fabricated a variety of bulk-flexible electrodes with high mass loading of active material(AM)(>70 wt%)using industry-friendly extrusion and compression molding techniques.Moreover,these high AM-loading composite electrodes achieve an unparalleled bulk conformability and flexibility,remaining structurally intact even under severe mechanical stress.Ultimately,we have successfully produced shape-patternable and flexible batteries via extrusion molding.This study underscores the potential of the PEM to revolutionize battery microstructures,interfaces,manufacturing processes,and performance characteristics.展开更多
The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electr...The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li+.As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.展开更多
Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
基金support from the National Natural Science Foundation of China(22209089,22178187)Natural Science Foundation of Shandong Province(ZR2022QB048,ZR2021MB006)+2 种基金Excellent Youth Science Foundation of Shandong Province(Overseas)(2023HWYQ-089)the Taishan Scholars Program of Shandong Province(tsqn201909091)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.
基金supported by the National Natural Science Foundation of China (21573080)the Guangdong Program for Support of Distinguished Young Scholar (2017B030306013)the Science and Technology Planning Project of Guangdong Province (2017B090901020)。
文摘High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte additive to enhance the cycling performances of graphite/LiNi0.6Co0.2Mn0.2O2 pouch cell.In comparison with the baseline electrolyte,a small dose of pTSF can significantly improve the cyclic stability of the cell.Theoretical calculations together with experimental results indicate that pTSF would be oxidized and reduced to construct protective interphase film on the surfaces of LiNi0.6Co0.2Mn0.2O2 cathode and graphite anode,respectively.These S-containing surface films derived from pTSF effectively mitigate the decomposition of electrolyte,reduce the interphasial impedance,as well as prevent the dissolution of transition metal ions from Ni-rich cathode upon cycling at high voltage.This finding is beneficial for the practical application of high energy density graphite/LiNi0.6Co0.2Mn0.2O2 cells.
基金financial support from the National Natural Science Foundation of China (21571080 and 52202253)the Natural Science Foundation of Jiangsu Province (BK20220914)+2 种基金Project funded by China Postdoctoral Science Foundation (2022M721593)the Jiangsu Funding Program for Excellent Postdoctoral Talent (2022ZB193)the financial support from International Center of Future Science,Jilin University,Changchun,P.R.China (ICFS Seed Funding for Young Researchers)。
文摘Since the electrode/electrolyte interface(EEI)is the main redox center of electrochemical processes,proper manipulation of the EEI microenvironment is crucial to stabilize interfacial behaviors.Here,a finger-paint method is proposed to enable quick physical modification of glass-fiber separator without complicated chemical technology to modulate EEI of bilateral electrodes for aqueous zinc-ion batteries(ZIBs).An elaborate biochar derived from Aspergillus Niger is exploited as the modification agent of EEI,in which the multi-functional groups assist to accelerate Zn^(2+)desolvation and create a hydrophobic environment to homogenize the deposition behavior of Zn anode.Importantly,the finger-paint interface on separator can effectively protect cathodes from abnormal capacity fluctuation and/or rapid attenuation induced by H_(2)O molecular on the interface,which is demonstrated in modified MnO_(2),V_(2)O_(5),and KMn HCF-based cells.The as-proposed finger-paint method opens a new idea of bilateral interface engineering to facilitate the access to the practical application of the stable zinc electrochemistry.
基金supported by the National Natural Science Foundation of China(No.21673251,No.21773258,No.21873104,and No.91856121)the Chinese Academy of Sciences(No.JKYYQ20180014)。
文摘Si(111)electrode has been widely used in electrochemical and photoelectrochemical studies.The potential dependent measurements of the second harmonic generation(SHG)were performed to study Si(111)electrode interface.At different azimuthal angles of the Si(111)and under different polarization combinations,the curve of the intensity of SHG with extern potential has a different form of line or parabola.Quantitative analysis showed that these differences in the potential-dependence can be explained by the isotropic and anisotropic contribution of the Si(111)electrode.The change in the isotropic and anisotropic contribution of the Si(111)electrode may be attributed to the increase in the doping concentration of Si(111)electrodes.
基金supported by the National Natural Science Foundation of China(No.91963118 and 52102213)Science Technology Program of Jilin Province(No.20200201066JC)the 111 Project(No.B13013).
文摘The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercialization.The regular concentration(1_(M))electrolytes with suitable properties(viscosity,ionic conductivity,etc.)are cost-guaranteed,but undesired reactions would always occur and lead to battery degradation during long cycles.To promote the long-term cycle stability in a cost-effective way,this work constructs bidirectional fluorine-rich electrode/electrolyte interphase(EEI)by redistribution of solvents and electrochemical induction.The fluorinated effect with reasonable zoning planning restricts morphological disintegration,meanwhile,forms spatial confinement on cathode.In particular,the obtained cathode electrolyte interphase(CEI)gets the ample ability of Na^(+)transport,which benefits from the fluorinated organics arranged in the epitaxy and the hemi-carbonate content acting on the thickness.Thus,the electrochemical long cycling performance of F-NVPOFⅡF-CC full cells is significantly enhanced(the decay rate at 1 C per cycle is as low as 0.01%).Such a fluorine-rich EEI engineering is expected to take transitional layers against the degradation of cells and make ultra-long cycle batteries possible.
基金Project(2023QNRC001)supported by the Young Elite Scientists Sponsorship Program by CAST,ChinaProject(51932011)supported by the National Natural Science Foundation of China+1 种基金Project(2023JJ10060)supported by the Natural Science Foundation of Hunan Province,ChinaProject(23A0003)supported by the Scientific Research Fund of Hunan Provincial Education Department,China。
文摘High-voltage sodium-ion batteries(SIBs)are emerging as promising candidates for large-scale energy storage systems due to their abundant sodium source and high energy density.However,the instability of the electrode electrolyte interphase remains a critical barrier to the potential use of high-voltage SIBs.Herein,sodium difluorophosphate(NaDFP)and fluoroethylene carbonate(FEC)serve as functional electrolyte additives to stabilize the interface of the high-voltage cathode.The oxidative competition between FEC and NaDFP facilitates the robust formation of the cathode-electrolyte interface(CEI)layer,enriched with inorganic components such as NaF/NaPO_(x)F_(y).The highly conductive NaF/NaPO_(x)F_(y)and inorganics provide fast ion transport pathways and mechanical strength,thereby mitigating the decomposition of carbonates and NaPF_(6).The half-cell equipped with BE 2 F+0.5 DFP demonstrates 93.9%capacity retention at 4.3 V across 600 cycles,showcasing excellent cycling capability.Full HC||NVOPF cells exhibit sustained performance with 91.69%capacity retention and a capacity of 91.57 mA·h/g over 1000 cycles at a 5 C rate.This study is poised to garner increased scholarly interest in the domain of rational electrolyte formulation for practical applications.
基金supported by the National Research Foundation Singapore Investigatorship Program(Grant No.NRF-NRFI08-2022-0009)A*STAR(Agency for Science,Technology and Research)LCER FI program(Award No.U2102d2002)the E-CO2RR CREATE Program.
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due to their high industrial demands.However,the mechanistic understanding of C_(2) product formation remains unclear due to the lack of in situ or operando measurements that can observe the complex and instantaneous atomic evolutions of adsorbates at the electrode/electrolyte interface.Moreover,the sensitivity of ECR reactions to variations at the interface further widens the gap between mechanistic understanding and performance enhancement.To bridge this gap,first-principle studies provide insights into how the interface influences ECR.In this study,we present a review of mechanistic studies investigating the effects of various factors at the interface,with an emphasis on the C_(2) product formation.We begin by introducing ECR and the essential metrics.Next,we discuss the factors classified by their components at the interface,namely,electrocatalyst,electrolyte,and adsorbates,respectively,and their effects on the C_(2) product formation.Due to the interplay among these factors,we aim to deconvolute the influence of each factor and clearly demonstrate their impacts.Finally,we outline the promising directions for mechanistic studies of C_(2) products.
基金supported by National Natural Science Foundation of China(No.22205182)National Science Fund for Distinguished Young Scholars(No.52025034)+2 种基金China Postdoctoral Science Foundation(Nos.2022M722594/2024T171170)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011516)financially supported by Innovation Team of Shaanxi Sanqin Scholars。
文摘The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materials for lithium-ion batteries.Silicon(Si),the second-largest element outside of Earth,has an exceptionally high specific capacity(3579 mAh g^(-1)),regarded as an excellent choice for the anode material in high-capacity lithium-ion batteries.However,it is low intrinsic conductivity and volume amplification during service status,prevented it from developing further.These difficulties can be successfully overcome by incorporating carbon into pure Si systems to form a composite anode and constructing a buffer structure.This review looks at the diffusion mechanism,various silicon-based anode material configurations(including sandwich,core-shell,yolk-shell,and other 3D mesh/porous structures),as well as the appropriate binders and electrolytes.Finally,a summary and viewpoints are offered on the characteristics and structural layout of various structures,metal/non-metal doping,and the compatibility and application of various binders and electrolytes for silicon-based anodes.This review aims to provide valuable insights into the research and development of silicon-based carbon anodes for high-performance lithium-ion batteries,as well as their integration with binders and electrolyte.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
基金Fundamental Research Funds for the Central Universities of China(Grant No. SWU-KT22030)Scientific and Technological Research Program of Chongqing Municipal Education Commission of China (No.KJQN202300205)financial support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under the project of 457444676。
文摘The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.
基金supported by the National Key R&D Program of China(No.2021YFA1501003)。
文摘Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electrochemical interfaces was established exclusively based on the studies of liquid/solid electrochemical interfaces.Thus,similarities and differences of liquid and polymer electrolyte/electrode interfaces need to be mapped out to guide the design of device level electrochemical interfaces.In this work,we employ the sulfonate adsorption/desorption as a probe reaction to understand the electron-transfer steps in polymer and liquid electrolytes.Through cyclic voltametric investigations on the well-define single-crystal Pd_(ML)Pt(111)electrode,we demonstrate that the oxidative adsorption and reductive desorption of sulfonates at the polymer electrolyte/electrode interface are chemically distinct from those in liquid electrolytes,with the former occurring mostly via the proton-coupled pathway while the latter proceeding mainly through the solvation-mediated pathway.Importantly,the sulfonate adsorption/desorption behaviors of alkylsulfonates become increasingly similar to those in Nafion with longer alkyl chains,suggesting that the interfacial hydrophobicity and solvation environment conferred by the perfluorinated polymer play a decisive role in the electron-transfer mechanism.Results reported in this study highlight the mechanistic distinctions between electron-transfer processes at electrochemical interfaces involving polymer and liquid electrolytes,and provide a framework for understanding electron-transfer processes at polymer electrolyte/electrode interfaces.
文摘The publisher regrets to inform that in the article of Advanced Powder Materials 4(2025)100261,the published Figs.3 and 5 belong to the initially submitted version,which should be replaced by the final version.The differences between the initial and final versions of these figures are described below.
基金National Natural Science Foundation of China (52073253)。
文摘Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.
基金financial support from the Project supported by the Southern Marine Science and Engineering Guangdong Lab-oratory(Zhuhai)(No.SML2023SP242)the National Natural Sci-ence Foundation of China(Nos.52274291 and 52204305)the Beijing Institute of Technology Research Fund Program for Young Scholars(No.1740011182102).
文摘Metal coating is a prevalent strategy for enhancing surface properties.Among the numerous methods for preparing coatings,electrodeposition stands out due to its simplicity,cost-effectiveness,and high efficiency,making it widely utilized in various metal coating applications.By meticulously selecting appropriate electrolytes and electrodeposition parameters,metal coatings with diverse structures and morphologies can be obtained,and tailored to meet specific performance requirements.As the demand for superior metal coating performance continues to rise,it is imperative to summarize and forecast electrodeposition techniques to meet the criteria for high quality and precision.This review delves into the electrodeposition preparation of several typical metal coatings in diverse electrolyte systems,including aqueous solutions,ionic liquids,deep eutectic solvents,and molten salts.We also examine the electrodeposition process on the cathode,elucidate the correlation between parameters and coating quality,and suggest future research directions.This review aims to provide valuable insights and guidance for the electrodeposition preparation of metal coatings.
基金supported by the National Natural Science Foundation of China(Grants Nos.12172102 and 12372097)the Fundamental Research Funds for the Central Universities(Grant No.HIT.OCEF.2022013).
文摘The silicon-graphite(Si-C)composite electrode is considered a promising candidate for next-generation commercial electrodes due to its high capacity.However,lithium-ion batteries with silicon electrodes often experience capacity fading and poor cyclic performance,primarily due to the mechanical degradation of the solid-electrolyte interphase(SEI).In this work,we present a homogenized constitutive model for Si-C composite electrodes under finite deformation,incorporating lithium-ion concentration-dependent properties.We perform a wrinkling analysis and systematically examine the influence of key parameters,such as modulus and thickness ratios,on the critical conditions for instability.Additionally,we investigate the ratcheting effect across varying silicon contents.Our findings reveal that maintaining the silicon content within an optimal range effectively reduces plastic accumulation during charge–discharge cycles.These insights provide crucial guidance for optimizing the design and fabrication of Si–C electrode systems,enhancing their durability and performance.
基金supported by the National Basic Research Program of China(2011YQ03012415,2011CB932304 and2011CB808701)the National Natural Science Foundation of China(21127901,21373237,21433011)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12020100)
文摘The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable information of interfacial phenomena during battery operation. In situ scanning probe microscopy （SPM） is a powerful technique used for the interfacial investigation of the Li-ion batteries. The versatile SPM techniques and their various operation modes have been utilized to measure the morphology and other properties of the electrode interface at high resolu- tion. Herein, we discuss the related SPM techniques to study the topography, mechanics and electrochemistry re- search of electrodes. Recent progresses of in situ SPM research on the electrode/electrolyte interface are summa- rized. Finally, the outlook of the technique is discussed.
基金supported by the University of Seoul’s 2025 Research Fund.
文摘Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of vanadium species on conventional carbon electrodes remains a major limitation to their performance.We investigated the deposition of carbon black,carbon nanotubes,and electrochemically exfoliated graphene(Exf-Gr)onto thermally-activated carbon paper(ACP)by spray coating to increase the electrode electrocatalytic activity.The modified electrodes were characterized using scanning electron microscopy,X-ray diffraction,Raman spectroscopy,X-ray photoelectron microscopy,and surface area analysis,while their electrochemical properties were evaluated by cyclic voltammetry,electrochemical impedance spectroscopy,and singlecell VRFB testing.Among the modified electrodes,Exf-Gr/ACP had the best performance,achieving a 2.9-fold reduction in charge transfer resistance compared to pristine ACP and delivering 2.5 times the discharge capacity in single-cell tests.This improvement is attributed to Exf-Gr’s high surface area,favorable catalytic activity,and excellent dispersion on the ACP substrate.Surface modification with electrochemically exfoliated graphene is a highly effective strategy for improving the electrode performance in VRFB systems,with significant implications for large-scale energy storage.
基金financial support from the National Natural Science Foundation of China(52473248,52203123,52125301,22279070 and U21A20170)the State Key Laboratory of Polymer Materials Engineering(Grant No:sklpme 2023-1-05 and sklpme 2024-2-04)+3 种基金the Ministry of Science and Technology of China(No.2019YFA0705703)the Sichuan Science and Technology Program(2023NSFSC0991 and 2025ZNSFSC1411)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University.
文摘The development of shape-customizable and bulk flexible electrochemical devices through processing technologies as versatile as those used for plastics promises to revolutionize the future of battery technology.However,this pursuit has been fundamentally hindered by the absence of transformative battery materials capable of delivering the necessary electrochemical functions,robust interface adhesion,and,crucially,the suitable rheological properties required for on-demand shaping.In this work,we introduce a concept of a multifunctional plasticine electrode matrix(PEM)featuring nano-interpenetrating networks(nano-IPN)to address this challenge.Utilizing the nonflammable liquid-electrolyte hydration combined with conductive nanomaterials,we have realized a PEM in the form of a multifunctional nanocomposite that integrates ion and electron conduction,component binding,non-flammability,and plasticine-like moldability.With this PEM,we have successfully fabricated a variety of bulk-flexible electrodes with high mass loading of active material(AM)(>70 wt%)using industry-friendly extrusion and compression molding techniques.Moreover,these high AM-loading composite electrodes achieve an unparalleled bulk conformability and flexibility,remaining structurally intact even under severe mechanical stress.Ultimately,we have successfully produced shape-patternable and flexible batteries via extrusion molding.This study underscores the potential of the PEM to revolutionize battery microstructures,interfaces,manufacturing processes,and performance characteristics.
基金supported by the National Natural Science Foundation of China(Nos.U21A20311 and 52400163).
文摘The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li+.As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
