Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.None...Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.展开更多
In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation proces...In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation process.However,conventional in-situ polymer electrolytes suffer from poor interface stability,low mechanical strength,low oxidation stability,and certain flammability.Herein,a silsesquioxane(POSS)-nanocage-crosslinked in-situ polymer electrolyte(POSS-DOL@PI-F)regulated by fluorinated plasticizer and enhanced by polyimide skeleton is fabricated by Li salt initiated in-situ polymerization.Polyimide skeleton and POSS-nanocage-crosslinked network significantly enhance the tensile strength(22.8 MPa)and thermal stability(200℃)of POSS-DOL@PI-F.Fluorinated plasticizer improves ionic conductivity(6.83×10^(-4)S cm^(-1)),flame retardance,and oxidation stability(5.0 V)of POSS-DOL@PI-F.The fluorinated plasticizer of POSS-DOL@PI-F constructs robust LiF-rich solid electrolyte interphases and cathode electrolyte interphases,thereby dramatically enhancing the interface stability of Li metal anodes and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)cathodes.POSS-DOL@PI-F enables stable,long-term(1200 h),and dendrite-free cycle of Li‖Li cells.POSS-DOL@PI-F significantly boosts the performance of Li‖NCM811cells,which display superior cycle stability under harsh conditions of high voltage(4.5 V),high temperature(60℃),low temperature(-20℃),and high areal capacity.This work provides a rational design strategy for safe and efficient polymer electrolytes.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
A suitable interface between the electrode and electrolyte is crucial in achieving highly stable electrochemical performance for Li-ion batteries,as facile ionic transport is required.Intriguing research and developme...A suitable interface between the electrode and electrolyte is crucial in achieving highly stable electrochemical performance for Li-ion batteries,as facile ionic transport is required.Intriguing research and development have recently been conducted to form a stable interface between the electrode and electrolyte.Therefore,it is essential to investigate emerging knowledge and contextualize it.The nanoengineering of the electrode-electrolyte interface has been actively researched at the electrode/electrolyte and interphase levels.This review presents and summarizes some recent advances aimed at nanoengineering approaches to build a more stable electrode-electrolyte interface and assess the impact of each approach adopted.Furthermore,future perspectives on the feasibility and practicality of each approach will also be reviewed in detail.Finally,this review aids in projecting a more sustainable research pathway for a nanoengineered interphase design between electrode and electrolyte,which is pivotal for high-performance,thermally stable Li-ion 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
Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte los...Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.展开更多
Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with elec...Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with electrolytes and preventing the dendritic propagation,both of which would lead to undesirable decrease in Coulombic efficiency.Polysulfone(PSf)membrane with high rigidity and free-volume cavities of approximately 0.3 nm was employed to provide a stable interface on the surface of anodic electrode.The isotropic channels were constructed by the interconnected and uniformly distributed free volumes in the polymer matrix,and were expected to be swelled by solvent molecules and anions of lithium salt and to allow Li+ions to pass through onto the electrode surface.As a result,dendrite-free morphology of deposited lithium was observed.The stabilized interface arose from the PSf film was verified by the promoted performances of Cu|Li cells and steady voltage polarization of Li|Li cells.The full cell with PSf coated anode exhibited excellent cyclability(85%capacity retention rate over 400 cycles at 1C)and an outstanding rate capability(117 m Ah g-1 at 5C).The beneficial performances were further verified by the EIS results.This work provides a new strategic idea to settle the dendritic problems of Li metal anodes.展开更多
Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lit...Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.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
Silicon-based materials are considered as the next generation anode to replace graphite due to their low cost and ultra-high theoretical capacity.However,significant volume expansion and contraction occur during charg...Silicon-based materials are considered as the next generation anode to replace graphite due to their low cost and ultra-high theoretical capacity.However,significant volume expansion and contraction occur during charging and discharging processes,leading to the instability of electrode structure and susceptibility to peeling and damage,limiting its application.Constructing controllable molecular artificial solid electrolyte interphase(CMASEI)is an effective approach to address the commercialization of silicon-based anode materials[1].Improving the performance of silicon-based anodes through CMASEI is a multifaceted outcome.展开更多
The polyvinyl carbonate(PVC)polymer solid electrolyte can be in-situ generated in the assembled lithium-ion battery(LIBs);however,its rigid characteristic leads to uneven interface contact between electrolyte and elec...The polyvinyl carbonate(PVC)polymer solid electrolyte can be in-situ generated in the assembled lithium-ion battery(LIBs);however,its rigid characteristic leads to uneven interface contact between electrolyte and electrodes.In this work,trimethyl phosphate(TMP)is introduced into the precursor solution for in-situ generation of flexible PVC solid electrolyte to improve the interfacial contact of elec-trolyte and electrodes together with ionic conductivity.The PVC-TMP electrolyte exhibits good interface compatibility with the lithium metal anode,and the lithium symmetric battery based on PVC-TMP electrolyte shows no obvious polarization within 1000 h cycle.As a consequence,the initial interfacial resistance of battery greatly decreases from 278Ω(LiFePO_(4)(LFP)/PVC/Li)to 93Ω(LFP/PVC-TMP/Li)at 50℃,leading to an improved cycling stability of the LFP/PVC-TMP/Li battery.Such in-situ preparation of solid electrolyte within the battery is demonstrated to be very significant for commercial application.展开更多
Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical applicati...Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.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
Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was de...Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.展开更多
Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at ro...Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.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 rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid elect...The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.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
Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated here...Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.展开更多
Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their o...Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.展开更多
基金supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)+3 种基金the Fundamental Research Funds for the Central Universities(no.N2523050)the Natural Science Foundation of Hebei Province(no.E2024501010)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)the 2024 Hebei Provincial Postgraduate Student Innovation Ability Training Funding Project(no.CXZZSS2025162)。
文摘Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.
基金supported by the National Natural Science Foundation of China(22375116,22001057)the Science Foundation of High-Level Talents of Wuyi University(2019AL017,2021AL002)Tianjin Lishen Battery Co.,Ltd。
文摘In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation process.However,conventional in-situ polymer electrolytes suffer from poor interface stability,low mechanical strength,low oxidation stability,and certain flammability.Herein,a silsesquioxane(POSS)-nanocage-crosslinked in-situ polymer electrolyte(POSS-DOL@PI-F)regulated by fluorinated plasticizer and enhanced by polyimide skeleton is fabricated by Li salt initiated in-situ polymerization.Polyimide skeleton and POSS-nanocage-crosslinked network significantly enhance the tensile strength(22.8 MPa)and thermal stability(200℃)of POSS-DOL@PI-F.Fluorinated plasticizer improves ionic conductivity(6.83×10^(-4)S cm^(-1)),flame retardance,and oxidation stability(5.0 V)of POSS-DOL@PI-F.The fluorinated plasticizer of POSS-DOL@PI-F constructs robust LiF-rich solid electrolyte interphases and cathode electrolyte interphases,thereby dramatically enhancing the interface stability of Li metal anodes and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)cathodes.POSS-DOL@PI-F enables stable,long-term(1200 h),and dendrite-free cycle of Li‖Li cells.POSS-DOL@PI-F significantly boosts the performance of Li‖NCM811cells,which display superior cycle stability under harsh conditions of high voltage(4.5 V),high temperature(60℃),low temperature(-20℃),and high areal capacity.This work provides a rational design strategy for safe and efficient polymer electrolytes.
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 funding from Bavarian Center for Battery Technology(Baybatt,Hightech Agenda Bayern)and Bayerisch-Tschechische Hochschulagentur(BTHA)(BTHA-AP-202245,BTHA-AP-2023-5,and BTHA-AP-2023-12)supported by the University of Bayreuth-Deakin University Joint Ph.D.Program+1 种基金supported by the Regional Innovation Strategy(RIS)through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(2021RIS-003)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS2023-00213749)
文摘A suitable interface between the electrode and electrolyte is crucial in achieving highly stable electrochemical performance for Li-ion batteries,as facile ionic transport is required.Intriguing research and development have recently been conducted to form a stable interface between the electrode and electrolyte.Therefore,it is essential to investigate emerging knowledge and contextualize it.The nanoengineering of the electrode-electrolyte interface has been actively researched at the electrode/electrolyte and interphase levels.This review presents and summarizes some recent advances aimed at nanoengineering approaches to build a more stable electrode-electrolyte interface and assess the impact of each approach adopted.Furthermore,future perspectives on the feasibility and practicality of each approach will also be reviewed in detail.Finally,this review aids in projecting a more sustainable research pathway for a nanoengineered interphase design between electrode and electrolyte,which is pivotal for high-performance,thermally stable Li-ion 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supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22179130,22379143,22479145)。
文摘Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.
基金supported by the Opening Project(SKLACPS-C-21)of the State Key Laboratory of Advanced Chemical Power Source,Guizhou Meiling Power Sources Co.Ltd.the Program for Innovative and Entrepreneurial team in Zhuhai(ZH01110405160007PWC)Key Laboratory of Advanced Chemical Power Sources,Guizhou Meiling Power Sources Co.Ltd.,Zunyi 563003,Guizhou,China,for funding the experiments.
文摘Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with electrolytes and preventing the dendritic propagation,both of which would lead to undesirable decrease in Coulombic efficiency.Polysulfone(PSf)membrane with high rigidity and free-volume cavities of approximately 0.3 nm was employed to provide a stable interface on the surface of anodic electrode.The isotropic channels were constructed by the interconnected and uniformly distributed free volumes in the polymer matrix,and were expected to be swelled by solvent molecules and anions of lithium salt and to allow Li+ions to pass through onto the electrode surface.As a result,dendrite-free morphology of deposited lithium was observed.The stabilized interface arose from the PSf film was verified by the promoted performances of Cu|Li cells and steady voltage polarization of Li|Li cells.The full cell with PSf coated anode exhibited excellent cyclability(85%capacity retention rate over 400 cycles at 1C)and an outstanding rate capability(117 m Ah g-1 at 5C).The beneficial performances were further verified by the EIS results.This work provides a new strategic idea to settle the dendritic problems of Li metal anodes.
基金support from the National Natural Science Foundation of China(52034011)the Fundamental Research Funds for the Science and Technology Program of Hunan Province(2019RS3002)+1 种基金the Central Universities of Central South University(Grant No.2018zzts133)Science and Technology Innovation Program of Hunan Province(2020RC2006).
文摘Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.
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 Nanxun Scholars Program for Young Scholars of ZJWEU(No.RC2023021315)the start-up funding for Scientific Research for High-level Talents(No.88106324004)the National Natural Science Foundation of China(No.62304070).
文摘Silicon-based materials are considered as the next generation anode to replace graphite due to their low cost and ultra-high theoretical capacity.However,significant volume expansion and contraction occur during charging and discharging processes,leading to the instability of electrode structure and susceptibility to peeling and damage,limiting its application.Constructing controllable molecular artificial solid electrolyte interphase(CMASEI)is an effective approach to address the commercialization of silicon-based anode materials[1].Improving the performance of silicon-based anodes through CMASEI is a multifaceted outcome.
基金financially supported by the National Natural Science Foundation of China (No.21676017)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources (No.SKL-ACPS-C-27)the Opening Project of State Key Laboratory of Organic-Inorganic Composites
文摘The polyvinyl carbonate(PVC)polymer solid electrolyte can be in-situ generated in the assembled lithium-ion battery(LIBs);however,its rigid characteristic leads to uneven interface contact between electrolyte and electrodes.In this work,trimethyl phosphate(TMP)is introduced into the precursor solution for in-situ generation of flexible PVC solid electrolyte to improve the interfacial contact of elec-trolyte and electrodes together with ionic conductivity.The PVC-TMP electrolyte exhibits good interface compatibility with the lithium metal anode,and the lithium symmetric battery based on PVC-TMP electrolyte shows no obvious polarization within 1000 h cycle.As a consequence,the initial interfacial resistance of battery greatly decreases from 278Ω(LiFePO_(4)(LFP)/PVC/Li)to 93Ω(LFP/PVC-TMP/Li)at 50℃,leading to an improved cycling stability of the LFP/PVC-TMP/Li battery.Such in-situ preparation of solid electrolyte within the battery is demonstrated to be very significant for commercial application.
基金support from the National Natural Science Foundation of China (No.51806072)。
文摘Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.
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.
基金conducted in a project within M-ERA.NET 3 with support from the European Union’s Horizon 2020 research,innovation program under grant agreement No.958174,Vinnova(Swedish Governmental Agency for Innovation Systems)the financial support from the LTU CREATERNITY program+1 种基金the J.Gust Richert Foundationthe National Natural Science Foundation of China(No.U23A20122)。
文摘Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.
基金supported by National Natural Science Foundation of China(No.22209075)。
文摘Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.
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 the National Natural Science Foundation of China (51773134)the Sichuan Science and Technology Program (2019YFH0112)+2 种基金the Fundamental Research Funds for the Central UniversitiesInstitutional Research Fund from Sichuan University (2021SCUNL201)the 111 Project (B20001)。
文摘The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.
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.
基金financially supported by the National Science Foundation of China, China (22179130, 91834301)the Foundation of the Key Laboratory of Chinese Academy of Sciences (CXJJ21S024)Dalian Institute of Chemical Physics, China (DICPI202023)。
文摘Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.
基金the financial support from the Brazilian funding agencies CNPq(301486/2016-6)FAEPEX(2426/17)+7 种基金FAPESP(2020/04431-0,2020/04281-8,2016/25082-8,2017/11986-5,2017/11958-1,2014/02163-7,2018/20756-6,2018/02713-8)CAPES(1740195)the financial support from CNPq(Processes 131234/2020-0 and 130741/2021-3)the Fundação ao AmparoàPesquisa do Estado de Minas Gerais(FAPEMIGCNPq for the PQ-2 grant(Process 310544/20190)the support of Shell,the strategic importance of the support given by Brazil’s National Oil,Natural Gas,and Biofuels Agency(ANP)through the R&D levy regulationthe Center for Innovation on New Energies(CINE)the LNLS/CNPEM。
文摘Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.
