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
The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC gl...The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC glasses are presented. The experimental methods for determination of some ion transport parameters viz ionic conductivity （σ）, ionic mobility （μ）, mobile ion concentration （n）, ionic drift velocity （Vd）, ionic transference number （tion） and activation energies of FIC glasses are explained. The solid state battery fabrication by using some FIC glasses is also reported.展开更多
A novel kind of polymeric solid electrolyte,PVAEO_16,which possesses both ion conduction and electrochromic characteristics,was synthesized.Its anion conductivity was 1.9× 10^(-6)S·cm^(-1)(25℃).PVAEO_(16)—...A novel kind of polymeric solid electrolyte,PVAEO_16,which possesses both ion conduction and electrochromic characteristics,was synthesized.Its anion conductivity was 1.9× 10^(-6)S·cm^(-1)(25℃).PVAEO_(16)—based ECD could display reversibly the color of yellow and bluish violet over 1.7 V.The color—changing response time was 0.6 s and 1.3 s(±2.0V),re- spectively.The storage time of bluish violet under open circuit was more than 16 hours.展开更多
Poly (oligoether methacrylate-co-acrylonitrile) s, P (MEOn- AN), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of...Poly (oligoether methacrylate-co-acrylonitrile) s, P (MEOn- AN), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of polymer structure. At proper copolymer composition, lithium concentration and pendant length, the ion conductivity reaches 7.0×10^(-5)S/cm at ambient temperature, together with improved mechanical strength. The ion transport in the polymer media is assisted by segmental relaxation, which is confirmed both by the consistency between ion conductivity and T_g and by the study of TSC.展开更多
The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migration...The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.展开更多
Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven ...Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.展开更多
Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dua...Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.展开更多
Solid-state electrolytes(SSEs)can address the safety issue of organic electrolyte in rechargeable lithium batteries.Unfortunately,neither polymer nor ceramic SSEs used alone can meet the demand although great progress...Solid-state electrolytes(SSEs)can address the safety issue of organic electrolyte in rechargeable lithium batteries.Unfortunately,neither polymer nor ceramic SSEs used alone can meet the demand although great progress has been made in the past few years.Composite solid electrolytes(CSEs)composed of flexible polymers and brittle but more conducting ceramics can take advantage of the individual system for solid-state lithium metal batteries(SSLMBs).CSEs can be largely divided into two categories by the mass fraction of the components:“polymer rich”(PR)and“ceramic rich”(CR)systems with different internal structures and electrochemical properties.This review provides a comprehensive and in-depth understanding of recent advances and limitations of both PR and CR electrolytes,with a special focus on the ion conduction path based on polymer-ceramic interaction mechanisms and structural designs of ceramic fillers/frameworks.In addition,it highlights the PR and CR which bring the leverage between the electrochemical property and the mechanical property.Moreover,it further prospects the possible route for future development of CSEs according to their rational design,which is expected to accelerate the practical application of SSLMBs.展开更多
Lead free 0.94(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)ceramics were prepared by conventional solid-state mixed oxide route with the A-site stoichiometry modified to incorporate donor-doping(through Bi-excess)and accept...Lead free 0.94(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)ceramics were prepared by conventional solid-state mixed oxide route with the A-site stoichiometry modified to incorporate donor-doping(through Bi-excess)and acceptor-doping(through Na-excess).Both stoichiometric and nonstoichiometric ceramics exhibited a single perovskite phase with pseudo-cubic symmetry.A significant improvement in the dielectric properties was observed in Bi-excess compositions and a deterioration in the dielectric properties was observed in Na-excess compositions.Impedance spectroscopy was utilized to analyze the effects of A-site nonstoichiometry on conduction mechanisms.Compositions with Bi-excess resulted in an electrically homogeneous microstructure with an increase in resistivity by3-4 orders of magnitude and an associated activation energy of 1.57 eV which was close to half of the optical bandgap.In contrast,an electrically heterogeneous microstructure was observed in both the stoichiometric and Na-excess compositions.In addition,the Na-excess compositions exhibited low resistivities(ρ-10^(3)Ω-cm)with characteristic peaks in the impedance data comparable to the recent observations of oxide ion conduction in(Bi_(0.5)Na_(0.5))TiO_(3).Long term annealing studies were also conducted at 800℃to identify changes in crystal structure and electrical properties.The results of this study demonstrates that the dielectric and electrical properties of 0.94(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)ceramics are very sensitive to Bi/Na stoichiometry.展开更多
Ion conduction plays key roles in electrochemical systems,including fuel cells,lithium ion batteries,and metal-air batteries.Covalent organic frameworks(COFs),as a new class of porous polymers,constructed by pre-desig...Ion conduction plays key roles in electrochemical systems,including fuel cells,lithium ion batteries,and metal-air batteries.Covalent organic frameworks(COFs),as a new class of porous polymers,constructed by pre-designable building blocks,are ideal hosts to accommodate ionic carries for conduction because of their straightforward pore channels,tunable pore size,controllable pore environment,and good chemical and thermal stability.Different from proton conduction,how to achieve high lithium ion conduction is still a challenge as it is difficult to dissociate ionic bonds of the lithium salts.To facilitate the dissociation of lithium salts,COFs with different pores and skeletons are well designed and constructed.This review focuses on emerging developments of lithium ion conduction in COFs,and discusses the structures of these COFs and conductive performance to elucidate the structure-property correlations.Furthermore,we have concluded the remaining challenge and future direction in these COF-based lithium conductive areas.This review provides deeper insight into COFs for ionic conduction.展开更多
Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrim...Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrimental electron conduction preventing their application as ion conductors.Here,REH_(x)(RE=Nd,Ce,and Pr)with varied grain sizes,rich grain boundaries,and defects have been prepared by ball milling and subsequent sintering.The electronic conductivity of the ball-milled REH_(x)samples can be reduced by 2-4 orders of magnitude compared with the non-ball-milled samples.The relationship of electron conduction and miscrostructures in REH_(x)is studied and discussed based on experimental data and previously-proposed classical and quantum theories.The H-conductivity of all REH_(x)is about 10^(-4)to 10^(-3)S cm^(-1)at room temperature,showing promise for the development of H-conductors and their applications in clean energy storage and conversion.展开更多
Green method for preparation of ion-conducting membranes(ICM) based on bacterial cellulose nanofibers(CNF) modified by a copolymer of sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid was elaborated. FTIR ...Green method for preparation of ion-conducting membranes(ICM) based on bacterial cellulose nanofibers(CNF) modified by a copolymer of sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid was elaborated. FTIR and NMR data confirmed grafting of polyacrylate onto cellulose surface. Formation of porous structure of the ICM was controlled by SEM and AFM. The maximal ionic conductivity of the membranes reaches 1.5 and 3.1 mS·cm^(-1)(60 ℃ and 98% relative humidity) when they are saturated with water or H_2SO_4(1 mol·L^(-1)) electrolyte,respectively. Prepared ICM was tested as a separator in a symmetrical supercapacitor with electrodes based on polyaniline hydrogel. The assembled cell demonstrate ability to operate at high current density up to 100 A·g^(-1) maintaining specific capacitance 165 F·g^(-1). Maximal specific capacitance of 289 F·g^(-1) was achieved at current density 1 A·g^(-1). Retaining of 90% of initial capacitance after 10000 of charge-discharge cycles proves high electrochemical stability of prepared ICM.展开更多
Nanopipette based scanning probe technique is a versatile tool in non-contact imaging in biology.In addition to the topographic imaging,its capability of localized delivery of bio-active molecules is emerging.In this ...Nanopipette based scanning probe technique is a versatile tool in non-contact imaging in biology.In addition to the topographic imaging,its capability of localized delivery of bio-active molecules is emerging.In this mini review,we introduce the applications of nanopipette in single-cell researches with a focus on localized delivery.The working principles of three delivery modes including resistive pulse,pressure-driven flow,and electroosmotic flow-driven delivery are summarized and compared.Their applications in single-cell researches are reviewed.The current technical challenges in scanning ion conductance microscopy-based delivery,and their growing influence in medicine and pharmacologic researches are also discussed.展开更多
High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and sol...High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.展开更多
Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible pro...Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.展开更多
The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high io...The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.展开更多
Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and t...Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.展开更多
Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably th...Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.展开更多
Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds...Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds with unique structures.In recent years,owing to their abundant physicochemical properties(including high ionic conductivity and reversible redox activity),POMs have shown great potential in becoming a new generation of solid-state electrolytes.In this review,an overview is investigated about how POMs have evolved as ion-conducting materials from basic research to novel solid-state electrolytes in energy devices.First,some expressive POM-based ion-conducting materials in recent years are introduced and classified,mainly inspecting their structural and functional relationship.After that,it is further focused on the application of these ionconducting electrolytes in the fields of proton exchange membranes,supercapacitors,and ion batteries.In addition,some properties of POMs(such as inherent dimension,capable of forming stable hydrogen bonds,and reversible bonding to water molecules)enable these functional POM-based electrolytes to be employed in innovative applications such as ion selection,humidity sensing,and smart materials.Finally,some fundamental recommendations are given on the current opportunities and challenges of POM-based ion-conducting electrolytes.展开更多
Applying mixed oxygen ionic and electronic conducting(MIEC)oxides as the cathode offers a promis-ing solution to enhance the performance of solid oxide fuel cells(SOFCs).However,the phase instability in CO_(2)-contain...Applying mixed oxygen ionic and electronic conducting(MIEC)oxides as the cathode offers a promis-ing solution to enhance the performance of solid oxide fuel cells(SOFCs).However,the phase instability in CO_(2)-containing air and sluggish oxygen reduction activity of MIEC cathodes remain a long-term chal-lenge for optimizing the electrochemical performance of SOFCs.Herein,a heterovalent co-doping strategy is proposed to enhance the oxygen reduction activity and CO_(2)tolerance of SOFCs cathodes,which can be demonstrated by developing a novel BaCo_(0.6)Fe_(0.4)O_(3)-δ(BCF)-based MIEC oxide,BaCo_(0.6)Fe_(0.2)Sn_(0.1) Y_(0.1)O_(3-δ)(BCFSY).In addition to improving the stability of BCF-based perovskites,this strategy achieves an opti-mized balance of ionic mobility and oxygen vacancies due to the synergies between the effects of the co-dopants.Compared with single-doped materials,BCFSY exhibits improved CO_(2)tolerance and consider-ably higher ORR activity,which is reflected in a significantly lower polarization resistance of 0.15Ωcm^(2) at 600℃.The results of this work provide an efficient tactic for designing electrode materials for SOFCs.展开更多
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DST,New Delhi for providing financial assistance through the Fast Track Young Scientist Research Project(No.SR/FTP/PS-23/2009)
文摘The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC glasses are presented. The experimental methods for determination of some ion transport parameters viz ionic conductivity （σ）, ionic mobility （μ）, mobile ion concentration （n）, ionic drift velocity （Vd）, ionic transference number （tion） and activation energies of FIC glasses are explained. The solid state battery fabrication by using some FIC glasses is also reported.
基金The project is supported by National Natural Seience Foundation of China.
文摘A novel kind of polymeric solid electrolyte,PVAEO_16,which possesses both ion conduction and electrochromic characteristics,was synthesized.Its anion conductivity was 1.9× 10^(-6)S·cm^(-1)(25℃).PVAEO_(16)—based ECD could display reversibly the color of yellow and bluish violet over 1.7 V.The color—changing response time was 0.6 s and 1.3 s(±2.0V),re- spectively.The storage time of bluish violet under open circuit was more than 16 hours.
文摘Poly (oligoether methacrylate-co-acrylonitrile) s, P (MEOn- AN), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of polymer structure. At proper copolymer composition, lithium concentration and pendant length, the ion conductivity reaches 7.0×10^(-5)S/cm at ambient temperature, together with improved mechanical strength. The ion transport in the polymer media is assisted by segmental relaxation, which is confirmed both by the consistency between ion conductivity and T_g and by the study of TSC.
基金supported by the National Natural Science Foundation of China(Grant No.22073034)。
文摘The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.
基金the financial support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2023R1A2C2007699 and 2022R1A6A1A0306303912)the Nano Material Technology Development Program through the NRF funded by the Ministry of Science and ICT (NRF-2015M3A7B6027970)the Technology Innovation Program by the Ministry of Trade, Industry & Energy (RS-202300236794)
文摘Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.
基金supported by the National Natural Science Foundation of China(21975091,22122902,and 52272208)the Fundamental Research Fund for the Central Universities of China(2662023LXPY001 and 2662021JC004).
文摘Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.
基金supported by the National Key R&D Program of China(Grant No.2021YFB2500100)the National Natural Science Foundation of China(Grant Nos.51872196 and 22109114).
文摘Solid-state electrolytes(SSEs)can address the safety issue of organic electrolyte in rechargeable lithium batteries.Unfortunately,neither polymer nor ceramic SSEs used alone can meet the demand although great progress has been made in the past few years.Composite solid electrolytes(CSEs)composed of flexible polymers and brittle but more conducting ceramics can take advantage of the individual system for solid-state lithium metal batteries(SSLMBs).CSEs can be largely divided into two categories by the mass fraction of the components:“polymer rich”(PR)and“ceramic rich”(CR)systems with different internal structures and electrochemical properties.This review provides a comprehensive and in-depth understanding of recent advances and limitations of both PR and CR electrolytes,with a special focus on the ion conduction path based on polymer-ceramic interaction mechanisms and structural designs of ceramic fillers/frameworks.In addition,it highlights the PR and CR which bring the leverage between the electrochemical property and the mechanical property.Moreover,it further prospects the possible route for future development of CSEs according to their rational design,which is expected to accelerate the practical application of SSLMBs.
文摘Lead free 0.94(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)ceramics were prepared by conventional solid-state mixed oxide route with the A-site stoichiometry modified to incorporate donor-doping(through Bi-excess)and acceptor-doping(through Na-excess).Both stoichiometric and nonstoichiometric ceramics exhibited a single perovskite phase with pseudo-cubic symmetry.A significant improvement in the dielectric properties was observed in Bi-excess compositions and a deterioration in the dielectric properties was observed in Na-excess compositions.Impedance spectroscopy was utilized to analyze the effects of A-site nonstoichiometry on conduction mechanisms.Compositions with Bi-excess resulted in an electrically homogeneous microstructure with an increase in resistivity by3-4 orders of magnitude and an associated activation energy of 1.57 eV which was close to half of the optical bandgap.In contrast,an electrically heterogeneous microstructure was observed in both the stoichiometric and Na-excess compositions.In addition,the Na-excess compositions exhibited low resistivities(ρ-10^(3)Ω-cm)with characteristic peaks in the impedance data comparable to the recent observations of oxide ion conduction in(Bi_(0.5)Na_(0.5))TiO_(3).Long term annealing studies were also conducted at 800℃to identify changes in crystal structure and electrical properties.The results of this study demonstrates that the dielectric and electrical properties of 0.94(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)ceramics are very sensitive to Bi/Na stoichiometry.
基金financial support from the Natural Science Foundation of Shanghai(20ZR1464000)supports from the National Natural Science Foundation of China(21878322,22075309)the Science and Technology Commission of Shanghai Municipality(19ZR1479200,22ZR1470100)。
文摘Ion conduction plays key roles in electrochemical systems,including fuel cells,lithium ion batteries,and metal-air batteries.Covalent organic frameworks(COFs),as a new class of porous polymers,constructed by pre-designable building blocks,are ideal hosts to accommodate ionic carries for conduction because of their straightforward pore channels,tunable pore size,controllable pore environment,and good chemical and thermal stability.Different from proton conduction,how to achieve high lithium ion conduction is still a challenge as it is difficult to dissociate ionic bonds of the lithium salts.To facilitate the dissociation of lithium salts,COFs with different pores and skeletons are well designed and constructed.This review focuses on emerging developments of lithium ion conduction in COFs,and discusses the structures of these COFs and conductive performance to elucidate the structure-property correlations.Furthermore,we have concluded the remaining challenge and future direction in these COF-based lithium conductive areas.This review provides deeper insight into COFs for ionic conduction.
基金supported by the National Key Research and Development Program of China(2021YFB4000602)the National Natural Science Foundation of China(21988101,22279130,21633011)+1 种基金the Dalian Science and Technology Innovation Fund(2023RJ016)the Liaoning Revitalization Talents Program(x LYC2002076)。
文摘Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrimental electron conduction preventing their application as ion conductors.Here,REH_(x)(RE=Nd,Ce,and Pr)with varied grain sizes,rich grain boundaries,and defects have been prepared by ball milling and subsequent sintering.The electronic conductivity of the ball-milled REH_(x)samples can be reduced by 2-4 orders of magnitude compared with the non-ball-milled samples.The relationship of electron conduction and miscrostructures in REH_(x)is studied and discussed based on experimental data and previously-proposed classical and quantum theories.The H-conductivity of all REH_(x)is about 10^(-4)to 10^(-3)S cm^(-1)at room temperature,showing promise for the development of H-conductors and their applications in clean energy storage and conversion.
文摘Green method for preparation of ion-conducting membranes(ICM) based on bacterial cellulose nanofibers(CNF) modified by a copolymer of sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid was elaborated. FTIR and NMR data confirmed grafting of polyacrylate onto cellulose surface. Formation of porous structure of the ICM was controlled by SEM and AFM. The maximal ionic conductivity of the membranes reaches 1.5 and 3.1 mS·cm^(-1)(60 ℃ and 98% relative humidity) when they are saturated with water or H_2SO_4(1 mol·L^(-1)) electrolyte,respectively. Prepared ICM was tested as a separator in a symmetrical supercapacitor with electrodes based on polyaniline hydrogel. The assembled cell demonstrate ability to operate at high current density up to 100 A·g^(-1) maintaining specific capacitance 165 F·g^(-1). Maximal specific capacitance of 289 F·g^(-1) was achieved at current density 1 A·g^(-1). Retaining of 90% of initial capacitance after 10000 of charge-discharge cycles proves high electrochemical stability of prepared ICM.
基金support from the National Institute of General Medical Sciences(1R35G M147172-01).
文摘Nanopipette based scanning probe technique is a versatile tool in non-contact imaging in biology.In addition to the topographic imaging,its capability of localized delivery of bio-active molecules is emerging.In this mini review,we introduce the applications of nanopipette in single-cell researches with a focus on localized delivery.The working principles of three delivery modes including resistive pulse,pressure-driven flow,and electroosmotic flow-driven delivery are summarized and compared.Their applications in single-cell researches are reviewed.The current technical challenges in scanning ion conductance microscopy-based delivery,and their growing influence in medicine and pharmacologic researches are also discussed.
基金supported by the Australian Research Council Discovery Projects(DP150104365 and DP160104835)the financial support by the China Scholarship Council(201808340038) for his visiting at Curtin University,Australiathe ARC Discovery Early Career Researcher Award(DE180100773)。
文摘High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.
基金financially supported by National Key R&D Program for International Cooperation(No.2021YFE0115100)the project of the National Natural Science Foundation of China(Nos.51872240,51972270 and 52172101)+4 种基金Key Research and Development Program of Shaanxi Province(No.2021ZDLGY14-08 and 2022KWZ-04)Natural Science Foundation of Shaanxi Province(2020JZ-07)the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(2021-TS-03)the Fundamental Research Funds for the Central Universities(No.3102019JC005 and G2022KY0604)the Research Fund of the State Key Laboratory of Solid Lubrication(CAS),China(LSL-2007)。
文摘Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.
基金the National Natural Science Foundation of China(21503131 and 51711530162)the Shanghai Municipal Science and Technology Commission(19640770300)+2 种基金the Shanghai Engineering Research Center of New Materials and Application for Resources and Environment(18DZ2281400)the Professional and Technical Service Platform for Designing and Manufacturing of Advanced Composite Materials(Shanghai)(19DZ2293100)the Engineering Research Center of Material Composition and Advanced Dispersion Technology,Ministry of Education。
文摘The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.
基金Supported by the Joint Funds of NSFC-Guangdong of China(U0834004)the Natural Science Foundation of Guangdong Province(06025657)
文摘Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.
基金supported by the National Natural Science Foundation of China(Nos.21771164,U1804129)the Natural Science Foundation of Henan Province(No.222300420525)the Zhongyuan Youth Talent Support Program of Henan Province
文摘Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.
基金financial support from the National Natural Science Foundation of China(No.21871042,21471028,No.21671036,No.21673098,No.21975211)support from the Innovative Research Group Project of NSFC(22021001)+5 种基金the National Key Research and Development Program(2021YFA1502300)Changbai Mountain Scholarship,Natural Science Foundation of Jilin Province(No.20200201083JC)Natural Science Foundation of Department of Education of Jilin Province(No.JJKH20201169KJ)the Fundamental Research Funds for the Central Universities(20720190035)Nanqiang Young Top-notch Talent Fellowship in Xiamen Universitysupported by Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences.
文摘Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds with unique structures.In recent years,owing to their abundant physicochemical properties(including high ionic conductivity and reversible redox activity),POMs have shown great potential in becoming a new generation of solid-state electrolytes.In this review,an overview is investigated about how POMs have evolved as ion-conducting materials from basic research to novel solid-state electrolytes in energy devices.First,some expressive POM-based ion-conducting materials in recent years are introduced and classified,mainly inspecting their structural and functional relationship.After that,it is further focused on the application of these ionconducting electrolytes in the fields of proton exchange membranes,supercapacitors,and ion batteries.In addition,some properties of POMs(such as inherent dimension,capable of forming stable hydrogen bonds,and reversible bonding to water molecules)enable these functional POM-based electrolytes to be employed in innovative applications such as ion selection,humidity sensing,and smart materials.Finally,some fundamental recommendations are given on the current opportunities and challenges of POM-based ion-conducting electrolytes.
基金supported by the National Natural Science Foundation of China (No. 22078022)China Postdoctoral Science Foundation (No.2021M690379)
文摘Applying mixed oxygen ionic and electronic conducting(MIEC)oxides as the cathode offers a promis-ing solution to enhance the performance of solid oxide fuel cells(SOFCs).However,the phase instability in CO_(2)-containing air and sluggish oxygen reduction activity of MIEC cathodes remain a long-term chal-lenge for optimizing the electrochemical performance of SOFCs.Herein,a heterovalent co-doping strategy is proposed to enhance the oxygen reduction activity and CO_(2)tolerance of SOFCs cathodes,which can be demonstrated by developing a novel BaCo_(0.6)Fe_(0.4)O_(3)-δ(BCF)-based MIEC oxide,BaCo_(0.6)Fe_(0.2)Sn_(0.1) Y_(0.1)O_(3-δ)(BCFSY).In addition to improving the stability of BCF-based perovskites,this strategy achieves an opti-mized balance of ionic mobility and oxygen vacancies due to the synergies between the effects of the co-dopants.Compared with single-doped materials,BCFSY exhibits improved CO_(2)tolerance and consider-ably higher ORR activity,which is reflected in a significantly lower polarization resistance of 0.15Ωcm^(2) at 600℃.The results of this work provide an efficient tactic for designing electrode materials for SOFCs.
