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
Lithium-sulfur(Li-S)battery is recognized for the high theoretical energy density and cost-effective raw materials.However,the instability of Li metal anodes limits the cycle life of Li-S batteries under practical con...Lithium-sulfur(Li-S)battery is recognized for the high theoretical energy density and cost-effective raw materials.However,the instability of Li metal anodes limits the cycle life of Li-S batteries under practical conditions.In this study,we propose a dual interface-passivating regulation strategy using nitrocellulose(NC),a macromolecular nitrate,to stabilize the interface/interphase between the electrolyte and Li metal anode.Specifically,the macromolecular crowding effect and the reduction in lithium polysulfides(LiPSs)activity through nitrate coordination endow NC desirable bifunctionality to simultaneously suppress the depletion of Li salts and LiPSs corrosion,leading to better interface passivation than mono-functional additives such as LiNO_(3)and carboxymethyl cellulose.Consequently,the cycle life of Li-S batteries under practically demanding conditions(50μm Li anodes;4.0 mg cm^(-2)S athodes)is extended to 180 cycles,outperforming those of additive-free or LiNO_(3)-containing commercial electrolytes.This study highlights the potential of bifunctional macromolecular additive design for effectively dual-passivating the anode/electrolyte interface towards highly stable practical Li-S batteries.展开更多
The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict betwe...The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.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
In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured ...In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured solutions. The experimental results indicated that the interfacial pH increased with the applied potential, first jumped to a maximum, then slowly decreased at the controlled potential during the electrodeposition process of functional ceramics.展开更多
Inorganic solid-state electrolytes(SSEs)are nonflammable alternatives to the commercial liquid-phase electrolytes.This enables the use of lithium(Li)metal as an anode,providing high-energy density and improved stabili...Inorganic solid-state electrolytes(SSEs)are nonflammable alternatives to the commercial liquid-phase electrolytes.This enables the use of lithium(Li)metal as an anode,providing high-energy density and improved stability by avoiding unwanted liquid-phase chemical reactions.Among the different types of SSEs,the garnet-type electrolytes witness a rapid development and are considered as one of the top candidates to pair with Li metal due to their high ionic conductivity,thermal,and electrochemical stability.However,the large resistances at the interface between garnet-type electrolytes and cathode/anode are the major bottlenecks for delivering desirable electrochemical performances of all-solid-state batteries(SSBs).The electrolyte/anode interface also suffers from metallic dendrite formation,leading to rapid performance degradation.This is a fundamental material challenge due to the poor contact and wettability between garnet-type electrolytes with electrode materials.Here,we summarize and analyze the recent contributions in mitigating such materials challenges at the interface.Strategies used to address these challenges are divided into different categories with regard to their working principles.On one hand,progress has been made in the anode/garnet interface,such as the successful application of Li-alloy anode and different artificial interlayers,significantly improving interfacial performance.On the other hand,the desired cathode/garnet interface is still hard to reach due to the complex chemical and physical structure at the cathode.The common methods used are nanostructured cathode host and sintering additives for increasing the contact area.On the basis of this information,we present our views on the remaining challenges and future research of electrode/garnet interface.This review not only motivates the need for further understanding of the fundamentals,stability,and modifications of the garnet/electrode interfaces but also provides guidelines for the future design of the interface for SSB.展开更多
All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The deve...All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.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
Reversible solid oxide cells(SOCs)are very efficient and clean for storage and regeneration of renewable electrical energy by switching between electrolysis and fuel cell modes.One of the most critical factors governi...Reversible solid oxide cells(SOCs)are very efficient and clean for storage and regeneration of renewable electrical energy by switching between electrolysis and fuel cell modes.One of the most critical factors governing the efficiency and durability of SOCs technology is the stability of the interface between oxygen electrode and electrolyte,which is conventionally formed by sintering at a high temperature of~1000–1250℃,and which suffers from delamination problem,particularly for reversibly operated SOCs.On the other hand,our recent studies have shown that the electrode/electrolyte interface can be in situ formed by a direct assembly approach under the electrochemical polarization conditions at 800℃and lower.The direct assembly approach provides opportunities for significantly simplifying the cell fabrication procedures without the doped ceria barrier layer,enabling the utilization of a variety of high-performance oxygen electrode materials on barrier layer–free yttria-stabilized zirconia(YSZ)electrolyte.Most importantly,the in situ polarization induced interface shows a promising potential as highly active and durable interface for reversible SOCs.The objective of this progress report is to take an overview of the origin and research progress of in situ fabrication of oxygen electrodes based on the direct assembly approach.The prospect of direct assembly approach in the development of effective SOCs and in the fundamental studies of electrode/electrolyte interface reactions is discussed.展开更多
The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high in...The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.展开更多
Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stabil...Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.展开更多
Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode ...Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.展开更多
Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-...Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.展开更多
This article presents our experimental studies to unravel the dynamic photovoltaic processes occurring at donor:acceptor(D:A)and electrode:active layer(E:A)interfaces under device-operating conditions by using two uni...This article presents our experimental studies to unravel the dynamic photovoltaic processes occurring at donor:acceptor(D:A)and electrode:active layer(E:A)interfaces under device-operating conditions by using two unique magneto-optical measurements,namely photo-induced capacitance and magnetic field effect measurement.First,we have found that a higher surface polarization of dielectric thin film can decrease the surface charge accumulation at E:A interface.The photo-induced capacitance results indicate that dielectric thin film plays a crucial role in the charge collection in generating photocurrent in organic solar cells.Second,our experimental results from magnetic field effect show that the binding energies of charge transfer(CT)states at D:A interface can be evaluated by using the critical bias required to completely dissociate the CT states.This is the first experimental demonstration that the binding energies of CT states can be measured under deviceoperating conditions.Furthermore,we use our measurement of magnetic field effect to investigate the most popular organic photovoltaic solar cells,organometal halide perovskite photovoltaic devices.The results of magneto-photoluminescence show that the photogenerated electrons and holes are inevitably recombined into electron–hole pairs through a spin-dependent process in the perovskites.Therefore,using spin polarizations can present a new design to control the photovoltaic loss in perovskites-based photovoltaic devices.Also,we found that introducing D:A interface can largely affect the bulk charge dissociation and recombination in perovskite solar cells.This indicates that the interfacial and bulk photovoltaic processes are internally coupled in developing photovoltaic actions in perovskite devices.Clearly,these magneto-optical measurements show a great potential to unravel the deeper photovoltaic processes occurring at D:A and E:A interfaces in both organic bulk-heterojunction and perovskite solar cells under device-operating conditions.展开更多
The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herei...The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.展开更多
The energy supply of rising electronic textile can resort to gel-based fibre batteries attributed to their flexibility and safety.However,their electrochemical performance is plagued by the poor electrolyte–electrode...The energy supply of rising electronic textile can resort to gel-based fibre batteries attributed to their flexibility and safety.However,their electrochemical performance is plagued by the poor electrolyte–electrode interface.Recently,Peng et al.designed channel structures to accommodate gel electrolyte yielding intimate and stable interfaces for high-performance fibre batteries.Encompassing excellent electrochemical performance,stability,safety and large-scale productivity,the as-fabricated fibre lithium-ion batteries(FLBs)demonstrated the potential to supply energy for textile electronics.展开更多
Solid oxide electrolysis cell(SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion.However,the degradation of SOEC is a significant barrier to commercial viability.In this...Solid oxide electrolysis cell(SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion.However,the degradation of SOEC is a significant barrier to commercial viability.In this review paper,the typical degradation phenomena of SOEC are summarized,with great attention into the anodes/oxygen electrodes,including the commonly used and newly developed anode materials.Meanwhile,mechanistic investigations on the electrode/electrolyte interfaces are provided to unveil how the intrinsic factor,oxygen partial pressure pO2,and the electrochemical operation conditions,affect the interracial stability of SOEC.At last,this paper also presents some emerging mitigation strategies to circumvent long-term degradation,which include novel infiltration method,development of new anode materials and engineering of the microstructure.展开更多
Solid-state lithium metal batteries are considered to be the next generation of energy storage systems due to the high energy density brought by the use of metal lithium anode and the safety features brought by the us...Solid-state lithium metal batteries are considered to be the next generation of energy storage systems due to the high energy density brought by the use of metal lithium anode and the safety features brought by the use of solid electrolytes(SEs).Unfortunately,besides the safety features,using SEs brings issues of interfacial contact of lithium anode and electrolytes.Recently,to realize the application of solid-state lithium metal batteries,significant achievements have been made in the interface engineering of solid-state batteries,and various new strategies have been proposed.In this review,from the interface failure perspective of solid-state lithium metal batteries,we summarize failure mechanisms in terms of poor physical contact,weak chemical/electrochemical stability,continuing contact degradation,and uncontrollable lithium deposition.We then focused on the latest strategies for solving interface issues,including advancing in improving the physical solid-solid contact,increasing the electrochemical/chemical stability,restrain-ing continuing contact degradation,and controlling homogeneous lithium deposition.The ultimate and paramount future developing directions of solid-state lithium metal battery interface engineering are proposed.展开更多
The metallic lithium(Li)is the ultimate option in the development of anodes for high-energy secondary batteries.Unfortunately,inferior cycling reversibility and Li dendrites growth of Li metal as anode enormously impe...The metallic lithium(Li)is the ultimate option in the development of anodes for high-energy secondary batteries.Unfortunately,inferior cycling reversibility and Li dendrites growth of Li metal as anode enormously impede its commercialization.Here,a uniform Li I protective layer is constructed on Li metal anode via a facile and direct solid-gas reaction of Li metal with iodine vapor.The pre-constructed Li I layer possesses more steadily and faster Li ion transport than the conventional SEI layer and contributes to a steady interface for the Li metal anode,which affords a smooth Li deposition morphology without Li dendrites formation.The symmetrical cell with the Li metal anode protected by Li I layer exhibits a longer cycling lifetime of over 700 h at a current density of 1 m A cm^(-2) with Li plating capacity of 1 m Ah cm^(-2).Moreover,the Li I layer protected Li metal anode can still remain high capacity retention of 74.6%after 500 cycles in the full cell paired with NCM523 cathode.The work proposes an easy and effective method to fabricate a uniform and stable protective layer on the Li metal anode and offers a practicable thinking for the commercial implementation of Li metal batteries.展开更多
Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications ofte...Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications often entail electrodes with complicated pore structures,theoretical studies are mostly restricted to EDLCs of simple geometry such as planar or slit pores ignoring the curvature effects of the electrode surface.Significant gaps exist regarding the EDLC performance and the interfacial structure.Herein the classical density functional theory(CDFT)is used to study the capacitance and interfacial behavior of spherical electric double layers within a coarse-grained model.The capacitive performance is associated with electrode curvature,surface potential,and electrolyte concentration and can be correlated with a regression-tree(RT)model.The combination of CDFT with machine-learning methods provides a promising quantitative framework useful for the computational screening of porous electrodes and novel electrolytes.展开更多
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.
基金supported by the National Natural Science Foundation of China(22379021 and 22479021)。
文摘Lithium-sulfur(Li-S)battery is recognized for the high theoretical energy density and cost-effective raw materials.However,the instability of Li metal anodes limits the cycle life of Li-S batteries under practical conditions.In this study,we propose a dual interface-passivating regulation strategy using nitrocellulose(NC),a macromolecular nitrate,to stabilize the interface/interphase between the electrolyte and Li metal anode.Specifically,the macromolecular crowding effect and the reduction in lithium polysulfides(LiPSs)activity through nitrate coordination endow NC desirable bifunctionality to simultaneously suppress the depletion of Li salts and LiPSs corrosion,leading to better interface passivation than mono-functional additives such as LiNO_(3)and carboxymethyl cellulose.Consequently,the cycle life of Li-S batteries under practically demanding conditions(50μm Li anodes;4.0 mg cm^(-2)S athodes)is extended to 180 cycles,outperforming those of additive-free or LiNO_(3)-containing commercial electrolytes.This study highlights the potential of bifunctional macromolecular additive design for effectively dual-passivating the anode/electrolyte interface towards highly stable practical Li-S batteries.
文摘The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.
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.
文摘In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured solutions. The experimental results indicated that the interfacial pH increased with the applied potential, first jumped to a maximum, then slowly decreased at the controlled potential during the electrodeposition process of functional ceramics.
基金Engineering and Physical Sciences Research Council,Grant/Award Number:EP/S018204/1。
文摘Inorganic solid-state electrolytes(SSEs)are nonflammable alternatives to the commercial liquid-phase electrolytes.This enables the use of lithium(Li)metal as an anode,providing high-energy density and improved stability by avoiding unwanted liquid-phase chemical reactions.Among the different types of SSEs,the garnet-type electrolytes witness a rapid development and are considered as one of the top candidates to pair with Li metal due to their high ionic conductivity,thermal,and electrochemical stability.However,the large resistances at the interface between garnet-type electrolytes and cathode/anode are the major bottlenecks for delivering desirable electrochemical performances of all-solid-state batteries(SSBs).The electrolyte/anode interface also suffers from metallic dendrite formation,leading to rapid performance degradation.This is a fundamental material challenge due to the poor contact and wettability between garnet-type electrolytes with electrode materials.Here,we summarize and analyze the recent contributions in mitigating such materials challenges at the interface.Strategies used to address these challenges are divided into different categories with regard to their working principles.On one hand,progress has been made in the anode/garnet interface,such as the successful application of Li-alloy anode and different artificial interlayers,significantly improving interfacial performance.On the other hand,the desired cathode/garnet interface is still hard to reach due to the complex chemical and physical structure at the cathode.The common methods used are nanostructured cathode host and sintering additives for increasing the contact area.On the basis of this information,we present our views on the remaining challenges and future research of electrode/garnet interface.This review not only motivates the need for further understanding of the fundamentals,stability,and modifications of the garnet/electrode interfaces but also provides guidelines for the future design of the interface for SSB.
文摘All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.
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The authors thank the funding support by National Natural Science Foundation of China(21875038 and 22005055)Joint Independent Innovation Fund of Tianjin University and Fuzhou University(TF2020-10)and Australian Research Council(DP180100731 and DP180100568).
文摘Reversible solid oxide cells(SOCs)are very efficient and clean for storage and regeneration of renewable electrical energy by switching between electrolysis and fuel cell modes.One of the most critical factors governing the efficiency and durability of SOCs technology is the stability of the interface between oxygen electrode and electrolyte,which is conventionally formed by sintering at a high temperature of~1000–1250℃,and which suffers from delamination problem,particularly for reversibly operated SOCs.On the other hand,our recent studies have shown that the electrode/electrolyte interface can be in situ formed by a direct assembly approach under the electrochemical polarization conditions at 800℃and lower.The direct assembly approach provides opportunities for significantly simplifying the cell fabrication procedures without the doped ceria barrier layer,enabling the utilization of a variety of high-performance oxygen electrode materials on barrier layer–free yttria-stabilized zirconia(YSZ)electrolyte.Most importantly,the in situ polarization induced interface shows a promising potential as highly active and durable interface for reversible SOCs.The objective of this progress report is to take an overview of the origin and research progress of in situ fabrication of oxygen electrodes based on the direct assembly approach.The prospect of direct assembly approach in the development of effective SOCs and in the fundamental studies of electrode/electrolyte interface reactions is discussed.
基金the funding support from the National Natural Science Foundation of China(22222902,22209062)the Natural Science Foundation of Jiangsu Province(BK20200047)+2 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB150004)the Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China(JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program(202310320066Z)。
文摘The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.
基金financial support from the Natural Science Foundation of Hunan Province,China (No.2023JJ40759)the State Key Laboratory of Powder Metallurgy in Central South University,China。
文摘Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.
基金supported by the National Natural Science Foundation of China(No.22075115)Natural Science Foundation of Jiangsu Province(No.BK20211352)+2 种基金Joint Funds of the National Natural Science Foundation of China(No.U2141201)Natural Science Foundation(No.22KJA430005)of Jiangsu Education Committee of ChinaPostgraduate Research and Practice Innovation Program of Jiangsu Normal University(No.2021XKT0296).
文摘Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.
基金Natural Science Foundation of the Jiangsu Higher Education Institutions of China,Grant/Award Number:22KJB150004Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200047+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:22209062,22222902Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China,Grant/Award Number:JSTJ-2022-023。
文摘Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.
基金supported by the National Science Foundation of the United States(ECCS-1102011,ECCS-0644945,and CBET-1438181)the support from Sustainable Energy Education and Research Center and Center for Materials Processing at the University of Tennessee+1 种基金This research was partially conducted at the Center for Nanophase Materials Sciences based on user project(CNMS2012-106,CNMS2012-107,CNMS-2012-108),which is sponsored at Oak Ridge National Laboratory by the Division of Scientific User Facilities,U.S.Department of Energythe University of Tennessee also acknowledge the project support from the National Natural Science Foundation of China(21161160445,61077020)
文摘This article presents our experimental studies to unravel the dynamic photovoltaic processes occurring at donor:acceptor(D:A)and electrode:active layer(E:A)interfaces under device-operating conditions by using two unique magneto-optical measurements,namely photo-induced capacitance and magnetic field effect measurement.First,we have found that a higher surface polarization of dielectric thin film can decrease the surface charge accumulation at E:A interface.The photo-induced capacitance results indicate that dielectric thin film plays a crucial role in the charge collection in generating photocurrent in organic solar cells.Second,our experimental results from magnetic field effect show that the binding energies of charge transfer(CT)states at D:A interface can be evaluated by using the critical bias required to completely dissociate the CT states.This is the first experimental demonstration that the binding energies of CT states can be measured under deviceoperating conditions.Furthermore,we use our measurement of magnetic field effect to investigate the most popular organic photovoltaic solar cells,organometal halide perovskite photovoltaic devices.The results of magneto-photoluminescence show that the photogenerated electrons and holes are inevitably recombined into electron–hole pairs through a spin-dependent process in the perovskites.Therefore,using spin polarizations can present a new design to control the photovoltaic loss in perovskites-based photovoltaic devices.Also,we found that introducing D:A interface can largely affect the bulk charge dissociation and recombination in perovskite solar cells.This indicates that the interfacial and bulk photovoltaic processes are internally coupled in developing photovoltaic actions in perovskite devices.Clearly,these magneto-optical measurements show a great potential to unravel the deeper photovoltaic processes occurring at D:A and E:A interfaces in both organic bulk-heterojunction and perovskite solar cells under device-operating conditions.
基金supported by the National Natural Science Foundation of China(Nos.21203008,21975025,12274025)the Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232,ZDYF2023GXJS022)the Hainan Province Postdoctoral Science Foundation(No.300333)。
文摘The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.
基金supported by the MOST(2022YFA1203302,2022YFA1203304 and 2018YFA0703502)NSFC(Grant Nos.52021006,T2188101)+1 种基金Gusu’s young leading talent(ZXL2021449)Key industry technology innovation project of Suzhou(SYG202108).
文摘The energy supply of rising electronic textile can resort to gel-based fibre batteries attributed to their flexibility and safety.However,their electrochemical performance is plagued by the poor electrolyte–electrode interface.Recently,Peng et al.designed channel structures to accommodate gel electrolyte yielding intimate and stable interfaces for high-performance fibre batteries.Encompassing excellent electrochemical performance,stability,safety and large-scale productivity,the as-fabricated fibre lithium-ion batteries(FLBs)demonstrated the potential to supply energy for textile electronics.
基金This work is partially supported by U.S.Department of Energy under the contract number DE-EE0008378the Technology Managers Drs.Eric Miller and David Peterson for the technical guidance and financial support。
文摘Solid oxide electrolysis cell(SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion.However,the degradation of SOEC is a significant barrier to commercial viability.In this review paper,the typical degradation phenomena of SOEC are summarized,with great attention into the anodes/oxygen electrodes,including the commonly used and newly developed anode materials.Meanwhile,mechanistic investigations on the electrode/electrolyte interfaces are provided to unveil how the intrinsic factor,oxygen partial pressure pO2,and the electrochemical operation conditions,affect the interracial stability of SOEC.At last,this paper also presents some emerging mitigation strategies to circumvent long-term degradation,which include novel infiltration method,development of new anode materials and engineering of the microstructure.
基金Inner Mongolia Autonomous Region Science and Technology Program,Grant/Award Number:2023YFHH0061。
文摘Solid-state lithium metal batteries are considered to be the next generation of energy storage systems due to the high energy density brought by the use of metal lithium anode and the safety features brought by the use of solid electrolytes(SEs).Unfortunately,besides the safety features,using SEs brings issues of interfacial contact of lithium anode and electrolytes.Recently,to realize the application of solid-state lithium metal batteries,significant achievements have been made in the interface engineering of solid-state batteries,and various new strategies have been proposed.In this review,from the interface failure perspective of solid-state lithium metal batteries,we summarize failure mechanisms in terms of poor physical contact,weak chemical/electrochemical stability,continuing contact degradation,and uncontrollable lithium deposition.We then focused on the latest strategies for solving interface issues,including advancing in improving the physical solid-solid contact,increasing the electrochemical/chemical stability,restrain-ing continuing contact degradation,and controlling homogeneous lithium deposition.The ultimate and paramount future developing directions of solid-state lithium metal battery interface engineering are proposed.
基金financial support from the National Natural Science Foundation of China(Grant No.21875195)the Fundamental Research Funds for the Central Universities(20720190040)。
文摘The metallic lithium(Li)is the ultimate option in the development of anodes for high-energy secondary batteries.Unfortunately,inferior cycling reversibility and Li dendrites growth of Li metal as anode enormously impede its commercialization.Here,a uniform Li I protective layer is constructed on Li metal anode via a facile and direct solid-gas reaction of Li metal with iodine vapor.The pre-constructed Li I layer possesses more steadily and faster Li ion transport than the conventional SEI layer and contributes to a steady interface for the Li metal anode,which affords a smooth Li deposition morphology without Li dendrites formation.The symmetrical cell with the Li metal anode protected by Li I layer exhibits a longer cycling lifetime of over 700 h at a current density of 1 m A cm^(-2) with Li plating capacity of 1 m Ah cm^(-2).Moreover,the Li I layer protected Li metal anode can still remain high capacity retention of 74.6%after 500 cycles in the full cell paired with NCM523 cathode.The work proposes an easy and effective method to fabricate a uniform and stable protective layer on the Li metal anode and offers a practicable thinking for the commercial implementation of Li metal batteries.
基金sponsored by the National Natural Science Foundation of China(Nos.91834301,21908053,and 21808055)Shanghai Sailing Program(19YF1411700)financial support from the Fluid Interface Reactions,Structures and Transport(FIRST)Center,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Basic Energy Sciences。
文摘Understanding the microscopic structure and thermodynamic properties of electrode/electrolyte interfaces is central to the rational design of electric-double-layer capacitors(EDLCs).Whereas practical applications often entail electrodes with complicated pore structures,theoretical studies are mostly restricted to EDLCs of simple geometry such as planar or slit pores ignoring the curvature effects of the electrode surface.Significant gaps exist regarding the EDLC performance and the interfacial structure.Herein the classical density functional theory(CDFT)is used to study the capacitance and interfacial behavior of spherical electric double layers within a coarse-grained model.The capacitive performance is associated with electrode curvature,surface potential,and electrolyte concentration and can be correlated with a regression-tree(RT)model.The combination of CDFT with machine-learning methods provides a promising quantitative framework useful for the computational screening of porous electrodes and novel electrolytes.
