Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalys...Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalysis,its effectiveness and power have not been fully harnessed to elucidate complex interfacial processes.Herein,we use the frequency dispersion parameter,n,which is extracted from EIS measurements(C_(s)=af^(n+1),-2<n<-1),to describe the dispersion characteristics of capacitance and interfacial properties of Co_(3)O_(4) before the onset of oxygen evolution reaction(OER)in alkaline conditions.We first prove that the n-value is sensitive to the interfacial electronic changes associated with Co redox processes and surface reconstruction.The n-value decreases by increasing the specific/active surface area of the catalysts.We further modify the interfacial properties by changing different components,i.e.,replacing the proton with deuterium,adding ethanol as a new oxidant,and changing the cation in the electrolyte.Intriguingly,the n-value can identify different influences on the interfacial process of proton transfer,the decrease and blocking of oxidized Co species,and the interfacial water structure.We demonstrate that the n-value extracted from EIS measurements is sensitive to the kinetic isotope effect,electrolyte cation,adsorbate surface coverage of oxidized Co species,and the interfacial water structure.Thus,it can be helpful to differentiate the multiple factors affecting the catalyst interface.These findings convey that the frequency dispersion of capacitance is a convenient and useful method to uncover the interfacial properties under electrocatalytic conditions,which helps to advance the understanding of the interfaceactivity relationship.展开更多
This study systematically investigated the effects of experimental conditions,crystal phase,and microstructure on the preparation of V_(2)O_(3)for vanadium flow batteries by reducing ammonium metavanadate extracted fr...This study systematically investigated the effects of experimental conditions,crystal phase,and microstructure on the preparation of V_(2)O_(3)for vanadium flow batteries by reducing ammonium metavanadate extracted from waste catalyst.The optimized experimental conditions were determined as follows:the CO reduction temperature was set at 575℃,the reduction time was 1 hour,the CO flow rate was 50 mL/min,and furnace cooling was performed subsequently.Under these conditions,the samples obtained were predominantly composed of single-phase V_(2)O_(3).Microstructural analysis reveals tightly packed grain configurations exhibiting flake-like or block-like morphologies.Significantly,the as-synthesized V_(2)O_(3)demonstrates sufficient purity for fabricating high-performance electrolytes in all-vanadium flow batteries,showing promising electrochemical applicability.展开更多
Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)to formic acid is considered an economically viable avenue toward carbon neutrality.Indium-based catalysts have garnered considerable attention in CO_(2)RR o...Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)to formic acid is considered an economically viable avenue toward carbon neutrality.Indium-based catalysts have garnered considerable attention in CO_(2)RR owing to their elevated hydrogen evolution reaction(HER)overpotential and eco-friendly characteristics.We have synthesized In2O_(3)nanofibers rich in oxygen vacancies using the electrospinning technique.The resultant 500-In_(2)O_(3)exhibited superior performance in converting CO_(2)RR to HCOOH,achieving an impressive formate Faradaic efficiency(FE)of 92.1% at a current density of-600 mA cm^(-2).Moreover,it demonstrated remarkable stability,maintaining its performance over 100 h at a current density of-300 mA cm^(-2)under a neutral electrolyte.Density functio nal theory(DFT)calculations,in conjunction with spectroscopic characterizations,have revealed that a Cl-modified In catalyst exhibits a lowered energy barrier for the formation of*HCOOH,while simultaneously inhibiting the generation of*H,in contrast to its pristine In counterpart.Ultimately,we successfully engineered a dual-electrode system capable of simultaneously producing formate at both the cathode and the anode.At a current density of-100 mA cm^(-2),our system achieves a reduction in energy consumption by 12.5% and a significant enhancement in electrical energy conversion efficiency by 39.9%.展开更多
Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-dope...Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-doped cobalt molybdate(WDCMO)catalyst was synthesized for efficient and durable OER under neutral electrolyte.It is demonstrated that catalyst reconstruction is suppressed by W doping,which stabilizes the Co-O-Mo point-to-point connection in CoMoO_(4) architecture and stimulates to a lower valence state of active sites over the surface phase.Thereby,the surface structure maintains to avoid compound dissolution caused by over-oxidation during OER.Meanwhile,the WDCMO catalyst promotes charge transfer and optimizes*OH intermediate adsorption,which improves reaction kinetics and intrinsic activity.Consequently,the WDCMO electrode exhibits an overpotential of 302 mV at 10 mA cm^(-2) in neutral electrolyte with an improvement of 182 mV compared with CoMoO4 electrode.Furthermore,W doping significantly improves the electrode stability from 50 h to more than 320 h,with a suppressive potential attenuation from 2.82 to 0.29 mV h^(-1).This work will shed new light on designing rational electrocatalysts for neutral OER.展开更多
Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study em...Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study employs density functional theory(DFT)to analyze the oxygen reduction reaction(ORR)free energy profile,overpotential,and adsorption energy of two-dimensional Ti_(3)C_(2)T_(x) as a cathode catalyst.The optimal oxygen adsorption sites on Ti_(3)C_(2)T_(x) surfaces are identified,and the charge transfer,band structure,density of states,and bonding characteristics after oxygen adsorption are quantitatively analyzed.Results suggest that Ti_(3)C_(2)T_(x) exhibits low overpotentials when used as a HELAB cathode electrocatalyst,with oxygen preferentially adsorbing at the top and bridge sites of Ti_(3)C_(2) and Ti_(3)C_(2)F2,respectively.These findings offer valuable insights for the application of MXenes in HELABs.展开更多
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. Ho...Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.展开更多
This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature&l...This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.展开更多
This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5...This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/)_5Bi_(1/5))_(x)O_(2-δ)(GSEYB)system.This system holds promise as a solid electrolyte material for low and medium-temperature solid oxide fuel cells.The powders of Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/5)Bi_(1/5))_(x)O_(2-δ)(x=0,0.10,0.15,0.20,0.25,0.30)were synthesized using the solid-phase reaction method.The GSEYB electrolytes were comprehensively investigated for their phase structure,microstructure,oxygen vacancy concentration,and ionic conductivity using X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),and impedance spectroscopy.XRD diffraction patterns confirm a cubic fluorite-type structure with Fm3m space groups in all multi-doped systems.After sintering at 1400℃for 10 h,the relative density of doped samples exceeds 96%.In terms of electrical properties,the Ce_(0.75)Gd_(0.05)Sm_(0.05)Er_(0.05)Y_(0.05)Bi_(0.05)O_(2-δ)(x=0.25)electrolyte exhibits the highest ionic conductivity(σ_(t)=4.45×10^(-2)S/cm)and the lowest activation energy(E_(a)=0.79 eV)at 800℃.The coefficient of thermal expansion of the developed electrolyte aligns well with that of the commonly used electrode materials.This compatibility positions it as a highly promising candidate for utilization as an electrolyte material in solid oxide fuel cells(SOFCs).展开更多
The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design c...The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.展开更多
Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-form...Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-...Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-scale renewable hydrogen production system currently that can compete with conventional fossil fuel hydrogen production.Renewable energy electrocatalytic water splitting is an ideal production technology with environmental cleanliness protection and good hydrogen purity,which meet the requirements of future development.This review summarizes and introduces the current status of hydrogen production by water splitting from three aspects:electricity,catalyst and electrolyte.In particular,the present situation and the latest progress of the key sources of power,catalytic materials and electrolyzers for electrocatalytic water splitting are introduced.Finally,the problems of hydrogen generation from electrolytic water splitting and directions of next-generation green hydrogen in the future are discussed and outlooked.It is expected that this review will have an important impact on the field of hydrogen production from water.展开更多
Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storag...Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.展开更多
Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environme...Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environmental friendliness, which is extremely important for wearable energy storage applications. Given that HEs play a critical role in building flexible RZIBs, it is urgent to summarize the recent advances in this field and elucidate the design principles of HEs for practical applications. This review systematically presents the development history, recent advances in the material fundamentals, functional designs, challenges, and prospects of the HEs-based RZIBs. Firstly, the fundamentals, species, and flexible mechanisms of HEs are discussed, along with their compatibility with Zn anodes and various cathodes. Then, the functional designs of hydrogel electrolytes in harsh conditions are comprehensively discussed, including high/low/wide-temperature windows, mechanical deformations(e.g., bending, twisting, and straining), and damages(e.g., cutting, burning, and soaking). Finally, the remaining challenges and future perspectives for advancing HEs-based RZIBs are outlined.展开更多
Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium me...Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.展开更多
A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses the...A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.展开更多
To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In p...Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.展开更多
The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developi...The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.展开更多
Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testifie...Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.展开更多
基金Swiss National Science Foundation through its PRIM A grant(grant No.PR00P2_193111)the NCCR MARVEL,a National Centre of Competence in Researchfunded by the Swiss National Science Foundation。
文摘Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalysis,its effectiveness and power have not been fully harnessed to elucidate complex interfacial processes.Herein,we use the frequency dispersion parameter,n,which is extracted from EIS measurements(C_(s)=af^(n+1),-2<n<-1),to describe the dispersion characteristics of capacitance and interfacial properties of Co_(3)O_(4) before the onset of oxygen evolution reaction(OER)in alkaline conditions.We first prove that the n-value is sensitive to the interfacial electronic changes associated with Co redox processes and surface reconstruction.The n-value decreases by increasing the specific/active surface area of the catalysts.We further modify the interfacial properties by changing different components,i.e.,replacing the proton with deuterium,adding ethanol as a new oxidant,and changing the cation in the electrolyte.Intriguingly,the n-value can identify different influences on the interfacial process of proton transfer,the decrease and blocking of oxidized Co species,and the interfacial water structure.We demonstrate that the n-value extracted from EIS measurements is sensitive to the kinetic isotope effect,electrolyte cation,adsorbate surface coverage of oxidized Co species,and the interfacial water structure.Thus,it can be helpful to differentiate the multiple factors affecting the catalyst interface.These findings convey that the frequency dispersion of capacitance is a convenient and useful method to uncover the interfacial properties under electrocatalytic conditions,which helps to advance the understanding of the interfaceactivity relationship.
文摘This study systematically investigated the effects of experimental conditions,crystal phase,and microstructure on the preparation of V_(2)O_(3)for vanadium flow batteries by reducing ammonium metavanadate extracted from waste catalyst.The optimized experimental conditions were determined as follows:the CO reduction temperature was set at 575℃,the reduction time was 1 hour,the CO flow rate was 50 mL/min,and furnace cooling was performed subsequently.Under these conditions,the samples obtained were predominantly composed of single-phase V_(2)O_(3).Microstructural analysis reveals tightly packed grain configurations exhibiting flake-like or block-like morphologies.Significantly,the as-synthesized V_(2)O_(3)demonstrates sufficient purity for fabricating high-performance electrolytes in all-vanadium flow batteries,showing promising electrochemical applicability.
基金supported by the National Key R&D Program of China(2023YFA1508002)the National Natural Science Foundation of China(22472139,U23A2087,U22A20392,22227802,22372137,22172126 and 22102136)+3 种基金the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2022008)the Natural Science Foundation of Fujian Province of China(2022J01044)the XMU Training Program of Innovation and Entrepreneurship for Undergraduates(202410384030,S_(2)02310384242)Supporting Project Number(RSP2025R304),King Saud University,Riyadh,Saudi Arabia。
文摘Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)to formic acid is considered an economically viable avenue toward carbon neutrality.Indium-based catalysts have garnered considerable attention in CO_(2)RR owing to their elevated hydrogen evolution reaction(HER)overpotential and eco-friendly characteristics.We have synthesized In2O_(3)nanofibers rich in oxygen vacancies using the electrospinning technique.The resultant 500-In_(2)O_(3)exhibited superior performance in converting CO_(2)RR to HCOOH,achieving an impressive formate Faradaic efficiency(FE)of 92.1% at a current density of-600 mA cm^(-2).Moreover,it demonstrated remarkable stability,maintaining its performance over 100 h at a current density of-300 mA cm^(-2)under a neutral electrolyte.Density functio nal theory(DFT)calculations,in conjunction with spectroscopic characterizations,have revealed that a Cl-modified In catalyst exhibits a lowered energy barrier for the formation of*HCOOH,while simultaneously inhibiting the generation of*H,in contrast to its pristine In counterpart.Ultimately,we successfully engineered a dual-electrode system capable of simultaneously producing formate at both the cathode and the anode.At a current density of-100 mA cm^(-2),our system achieves a reduction in energy consumption by 12.5% and a significant enhancement in electrical energy conversion efficiency by 39.9%.
文摘Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-doped cobalt molybdate(WDCMO)catalyst was synthesized for efficient and durable OER under neutral electrolyte.It is demonstrated that catalyst reconstruction is suppressed by W doping,which stabilizes the Co-O-Mo point-to-point connection in CoMoO_(4) architecture and stimulates to a lower valence state of active sites over the surface phase.Thereby,the surface structure maintains to avoid compound dissolution caused by over-oxidation during OER.Meanwhile,the WDCMO catalyst promotes charge transfer and optimizes*OH intermediate adsorption,which improves reaction kinetics and intrinsic activity.Consequently,the WDCMO electrode exhibits an overpotential of 302 mV at 10 mA cm^(-2) in neutral electrolyte with an improvement of 182 mV compared with CoMoO4 electrode.Furthermore,W doping significantly improves the electrode stability from 50 h to more than 320 h,with a suppressive potential attenuation from 2.82 to 0.29 mV h^(-1).This work will shed new light on designing rational electrocatalysts for neutral OER.
文摘Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study employs density functional theory(DFT)to analyze the oxygen reduction reaction(ORR)free energy profile,overpotential,and adsorption energy of two-dimensional Ti_(3)C_(2)T_(x) as a cathode catalyst.The optimal oxygen adsorption sites on Ti_(3)C_(2)T_(x) surfaces are identified,and the charge transfer,band structure,density of states,and bonding characteristics after oxygen adsorption are quantitatively analyzed.Results suggest that Ti_(3)C_(2)T_(x) exhibits low overpotentials when used as a HELAB cathode electrocatalyst,with oxygen preferentially adsorbing at the top and bridge sites of Ti_(3)C_(2) and Ti_(3)C_(2)F2,respectively.These findings offer valuable insights for the application of MXenes in HELABs.
基金supported by the National Natural Science Foundation of China (Nos. 22379121, 62005216)Basic Public Welfare Research Program of Zhejiang (No. LQ22F050013)+1 种基金Zhejiang Province Key Laboratory of Flexible Electronics Open Fund (2023FE005)Shenzhen Foundation Research Program (No. JCYJ20220530112812028)。
文摘Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.
文摘This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.
基金supported by the Guangdong Provincial Basic and Applied Basic Research Foundation(2021A1515010671,2020A1515011221)the Guangdong Provincial Key Discipline Research Capacity Enhancement Project(2021ZDJS071)the Guangdong Provincial College Innovation Project(2021KTSCX122,2022KQNCX077)。
文摘This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/)_5Bi_(1/5))_(x)O_(2-δ)(GSEYB)system.This system holds promise as a solid electrolyte material for low and medium-temperature solid oxide fuel cells.The powders of Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/5)Bi_(1/5))_(x)O_(2-δ)(x=0,0.10,0.15,0.20,0.25,0.30)were synthesized using the solid-phase reaction method.The GSEYB electrolytes were comprehensively investigated for their phase structure,microstructure,oxygen vacancy concentration,and ionic conductivity using X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),and impedance spectroscopy.XRD diffraction patterns confirm a cubic fluorite-type structure with Fm3m space groups in all multi-doped systems.After sintering at 1400℃for 10 h,the relative density of doped samples exceeds 96%.In terms of electrical properties,the Ce_(0.75)Gd_(0.05)Sm_(0.05)Er_(0.05)Y_(0.05)Bi_(0.05)O_(2-δ)(x=0.25)electrolyte exhibits the highest ionic conductivity(σ_(t)=4.45×10^(-2)S/cm)and the lowest activation energy(E_(a)=0.79 eV)at 800℃.The coefficient of thermal expansion of the developed electrolyte aligns well with that of the commonly used electrode materials.This compatibility positions it as a highly promising candidate for utilization as an electrolyte material in solid oxide fuel cells(SOFCs).
基金supported by the National Natural Science Foundation of China(Nos.22208221,22178221)the Natural Science Foundation of Guangdong Province(Nos.2024A1515011078,2024A1515011507)+1 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20220818095805012,JCYJ20230808105109019)the Start-up Research Funding of Shenzhen University(No.868-000001032522).
文摘The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.
基金financial support from the Department of Science and Technology of Jilin Province(20240304104SF,20240304103SF)the Research and Innovation Fund of the Beihua University for the Graduate Student(Major Project 2023012)。
文摘Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
基金supported by the National Natural Science Foundation of China(U23A20573,U23A20140,22109038)the Starting Research Funds of Hebei University of Science and Technology,Hebei Natural Science Foundation(D2022208001)+1 种基金the S&T Program of Hebei(23314401D)Hebei Pharmaceutical and Chemical Technology Innovation Center(225676121H).
文摘Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-scale renewable hydrogen production system currently that can compete with conventional fossil fuel hydrogen production.Renewable energy electrocatalytic water splitting is an ideal production technology with environmental cleanliness protection and good hydrogen purity,which meet the requirements of future development.This review summarizes and introduces the current status of hydrogen production by water splitting from three aspects:electricity,catalyst and electrolyte.In particular,the present situation and the latest progress of the key sources of power,catalytic materials and electrolyzers for electrocatalytic water splitting are introduced.Finally,the problems of hydrogen generation from electrolytic water splitting and directions of next-generation green hydrogen in the future are discussed and outlooked.It is expected that this review will have an important impact on the field of hydrogen production from water.
基金supported by the National Natural Science Foundation of China(Nos.22171102 and 22090044)the National Key R&D Program of China(Nos.2021YFF0500502 and 2023YFA1506304)+2 种基金the Jilin Province Science and Technology Development Plan(No.20230101024JC)the"Medicine+X"crossinnovation team of Bethune Medical Department of Jilin University"Leading the Charge with Open Competition"construction project(No.2022JBGS04)the Jilin University Graduate Training Office(Nos.2021JGZ08 and 2022YJSJIP20).
文摘Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.
基金supported by the National Natural Science Foundation of China (22379038)Science Research Project of Hebei Education Department (JZX2024015)+4 种基金Shijiazhuang Science and Technology Plan Project (241791357A)Central Guidance for Local Science and Technology Development Funds Project (246Z4408G)Excellent Youth Research Innovation Team of Hebei University (QNTD202410)High-level Talents Research Start-Up Project of Hebei University (521100224223)Hebei Province Innovation Capability Enhancement Plan Project (22567620H)。
文摘Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environmental friendliness, which is extremely important for wearable energy storage applications. Given that HEs play a critical role in building flexible RZIBs, it is urgent to summarize the recent advances in this field and elucidate the design principles of HEs for practical applications. This review systematically presents the development history, recent advances in the material fundamentals, functional designs, challenges, and prospects of the HEs-based RZIBs. Firstly, the fundamentals, species, and flexible mechanisms of HEs are discussed, along with their compatibility with Zn anodes and various cathodes. Then, the functional designs of hydrogel electrolytes in harsh conditions are comprehensively discussed, including high/low/wide-temperature windows, mechanical deformations(e.g., bending, twisting, and straining), and damages(e.g., cutting, burning, and soaking). Finally, the remaining challenges and future perspectives for advancing HEs-based RZIBs are outlined.
基金supported by the National Natural Science Foundation of China(52372249)support by the Program of Shanghai Academic Research Leader(21XD1424400)。
文摘Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.
基金supported by a National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(2021R1A2C1014294,2022R1A2C3003319)the BK21 FOUR(Fostering Outstanding Universities for Research)through the National Research Foundation(NRF)of Korea.
文摘A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金financial support by National Natural Science Foundation(NNSF)of China(Nos.52202269,52002248,U23B2069,22309162)Shenzhen Science and Technology program(No.20220810155330003)+1 种基金Shenzhen Basic Research Project(No.JCYJ20190808163005631)Xiangjiang Lab(22XJ01007).
文摘Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.
基金National Natural Science Foundation of China(NSFC)supported this work under Grant No.32250410309,11674086,51736006,and 51772080funding from Science and Technology Department of Jiangsu Province under Grant No.BE2022029Shenzhen University under Grant No.86902/000248 also supported part of this work.
文摘The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.
基金supported by the National Natural Science Foundation of China(No.92372123)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515012057,2022B1515020005,2023B1515130004)Guangzhou Basic and Applied Basic Research Foundation(No.202201011342).
文摘Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.
