Lithium-sulfur(Li-S)batteries are considered highly promising as next-generation energy storage systems due to high theoretical capacity(2600 Wh kg^(-1))and energy density(1675 mA h g^(-1))as well as the abundant natu...Lithium-sulfur(Li-S)batteries are considered highly promising as next-generation energy storage systems due to high theoretical capacity(2600 Wh kg^(-1))and energy density(1675 mA h g^(-1))as well as the abundant natural reserves,low cost of elemental sulfur,and environmentally friendly properties.However,several challenges impede its commercialization including low conductivity of sulfur itself,the severe“shuttle effect”caused by lithium polysulfides(LiPSs)during charge–discharge processes,volume expansion effects and sluggish reaction kinetics.As a solution,polar metal particles and their compounds have been introduced as the main hosts for sulfur cathode due to their robust catalytic activity and adsorption capability,effectively suppressing the“shuttle effect”of Li PSs.Bimetallic alloys and their compounds with multi-functional properties exhibit remarkable electrochemical performance more readily when compared to single-metal materials.Well-designed bimetallic materials demonstrate larger specific surface areas and richer active sites,enabling simultaneous high adsorption capability and strong catalytic properties.The synergistic effect of the“adsorption-catalysis”sites accelerates the adsorptiondiffusion-conversion process of Li PSs,ultimately achieving a long-lasting Li-S battery.Herein,the latest progress and performance of bimetallic materials in cathodes,separators,and interlayers of Li-S batteries are systematically reviewed.Firstly,the principles and challenges of Li-S batteries are briefly analyzed.Then,various mechanisms for suppressing“shuttle effects”of Li PSs are emphasized at the microscale.Subsequently,the performance parameters of various bimetallic materials are comprehensively summarized,and some improvement strategies are proposed based on these findings.Finally,the future prospects of bimetallic materials are discussed,with the hope of providing profound insights for the rational design and manufacturing of high-performance bimetallic materials for LSBs.展开更多
Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely comme...Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely commercial application and development of LSB is mainly hindered by serious“shuttle effect”of lithium polysulfides(Li PSs),slow reaction kinetics,notorious lithium dendrites,etc.In various structures of LSB materials,array structured materials,possessing the composition of ordered micro units with the same or similar characteristics of each unit,present excellent application potential for various secondary cells due to some merits such as immobilization of active substances,high specific surface area,appropriate pore sizes,easy modification of functional material surface,accommodated huge volume change,enough facilitated transportation for electrons/lithium ions,and special functional groups strongly adsorbing Li PSs.Thus many novel array structured materials are applied to battery for tackling thorny problems mentioned above.In this review,recent progresses and developments on array structured materials applied in LSBs including preparation ways,collaborative structural designs based on array structures,and action mechanism analyses in improving electrochemical performance and safety are summarized.Meanwhile,we also have detailed discussion for array structured materials in LSBs and constructed the structure-function relationships between array structured materials and battery performances.Lastly,some directions and prospects about preparation ways,functional modifications,and practical applications of array structured materials in LSBs are generalized.We hope the review can attract more researchers'attention and bring more studying on array structured materials for other secondary batteries including LSB.展开更多
Low-cost and flexible solid polymer electrolytes are promising in all-solid-state Li-metal batteries with high energy density and safety.However,both the low room-temperature ionic conductivities and the small Li^(+)t...Low-cost and flexible solid polymer electrolytes are promising in all-solid-state Li-metal batteries with high energy density and safety.However,both the low room-temperature ionic conductivities and the small Li^(+)transference number of these electrolytes significantly increase the internal resistance and overpotential of the battery.Here,we introduce Gd-doped CeO_(2) nanowires with large surface area and rich surface oxygen vacancies to the polymer electrolyte to increase the interaction between Gd-doped CeO_(2) nanowires and polymer electrolytes,which promotes the Li-salt dissociation and increases the concentration of mobile Li ions in the composite polymer electrolytes.The optimized composite polymer electrolyte has a high Li-ion conductivity of 5×10^(-4)4 S cm^(-1) at 30℃ and a large Li+transference number of 0.47.Moreover,the composite polymer electrolytes have excellent compatibility with the metallic lithium anode and high-voltage LiNi_(0.8)Mn _(0.1)Co_(0.1)O_(2)(NMC)cathode,providing the stable cycling of all-solid-state batteries at high current densities.展开更多
Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a cent...Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.展开更多
All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid elect...All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid electrolytes with favorable electrode/electrolyte interface compatibility and high ionic conductivity in a simple and scalable manner.Hence,the oxygen-vacancy-rich Gd-doped SnO_(2) nanotubes(GDS NTs)are innovatively prepared and applied to the electrolyte of all-solid-state lithium metal batteries for the first time.The addition of GDS NTs can validly construct long-range co ntinuous ion transport networks in the poly(ethylene oxide)(PEO)-based system and greatly improve the mechanical properties of the electrolyte.Compared to the PEO-based electrolyte,the composite electrolyte displays a higher lithium ion conductivity of 2.41×10^(-4) S cm^(-1) at 30℃,a higher lithium ion transference number up to 0.62 and a wider electrochemical window of 5 V at 50℃.In addition,the composite electrolyte manifests outstanding compatibility with high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)cathode,LiFePO4 cathode and lithium metal anode.The assembled Li/Li symmetric battery exhibits stable Li plating/stripping cycling performance,which can cycle steadily for 1500 h at a capacity of 0.3 mA h cm^(-2).And Li/LiFePO4 battery still maintains a high capacity of 131.54 mA h g^(-1) at 0.5C after 800 cycles,which has a superior capacity retention rate of 93.2%.The obtained novel composite electrolyte has promising application prospects in the field of all-solid-state lithium metal cells.展开更多
With the emergence of some solid electrolytes(SSEs)with high ionic conductivity being comparable to liquid electrolytes,solid-state lithium-sulfur batteries(SSLSBs)have been widely regarded as one of the most promisin...With the emergence of some solid electrolytes(SSEs)with high ionic conductivity being comparable to liquid electrolytes,solid-state lithium-sulfur batteries(SSLSBs)have been widely regarded as one of the most promising candidates for the next generation of power generation energy storage batteries,and have been extensively researched.Though many fundamental and technological issues still need to be resolved to develop commercially viable technologies,SSLSBs using SSEs are expected to address the present limitations and achieve high energy and power density while improving safety,which is very attractive to large-scale energy storage systems.SSLSBs have been developed for many years.However,there are few systematic discussions related to the working mechanism of action of various electrolytes in SSLSBs and the defects and the corresponding solutions of various electrolytes.To fill this gap,it is very meaningful to review the recent progress of SSEs in SSLSBs.In this review,we comprehensively investigate and summarize the application of SSEs in LSBs to determine the differences which still exist between current progresses and real-world requirements,and comprehensively describe the mechanism of action of SSLSBs,including lithium-ion transport,interfacial contact,and catalytic conversion mechanisms.More importantly,the selection of solid electrolyte materials and the novel design of structures are reviewed and the properties of various SSEs are elucidated.Finally,the prospects and possible future research directions of SSLSBs including designing high electronic/ionic conductivity for cathodes,optimizing electrolytes and developing novel electrolytes with excellent properties,improving electrode/-electrolyte interface stability and enhancing interfacial dynamics between electrolyte and anode,using more advanced test equipment and characterization techniques to analyze conduction mechanism of Li^(+)in SSEs are presented.It is hoped that this review can arouse people’s attention and enlighten the development of functional materials and novel structures of SSEs in the next step.展开更多
Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are wi...Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.展开更多
With the popularity and widespread applications of electronics,higher demands are being placed on the performance of battery materials.Due to the large difference in electronegativity between fluorine and carbon atoms...With the popularity and widespread applications of electronics,higher demands are being placed on the performance of battery materials.Due to the large difference in electronegativity between fluorine and carbon atoms,doping fluorine atoms in nanocarbon-based materials is considered an effective way to improve the performance of used battery.However,there is still a blank in the systematic review of the mechanism and research progress of fluorine-doped nanostructured carbon materials in various batteries.In this review,the synthetic routes of fluorinated/fluorine-doped nanocarbon-based(CF_x)materials under different fluorine sources and the function mechanism of CF_x in various batteries are reviewed in detail.Subsequently,judging from the dependence between the structure and electrochemical performance of nanocarbon sources,the progress of CF_x based on different dimensions(0D–3D)for primary battery applications is reviewed and the balance between energy density and power density is critically discussed.In addition,the roles of CF_x materials in secondary batteries and their current applications in recent years are summarized in detail to illustrate the effect of introducing F atoms.Finally,we envisage the prospect of CF_x materials and offer some insights and recommendations to facilitate the further exploration of CF_x materials for various high-performance battery applications.展开更多
The utilization of all-solid-state electrolytes is considered to be an effective way to enhance the safety performance of lithium metal batteries.However,the low ionic conductivity and poor interface compatibility gre...The utilization of all-solid-state electrolytes is considered to be an effective way to enhance the safety performance of lithium metal batteries.However,the low ionic conductivity and poor interface compatibility greatly restrict the development of all-solid-state battery.In this study,a composite electrolyte combining the electrospun polyamide 6(PA6)nanofiber membrane with hierarchical structure and the polyethylene oxide(PEO)polymer is investigated.The introduction of PA6 nanofiber membrane can effectively reduce the crystallinity of the polymer,so that the ionic conductivity of the electrolyte can be enhanced.Moreover,it is found that the presence of finely branched fibers in the hierarchical structure PA6 membrane allows the polar functional groups(C=O and N-H bonds)to be fully exposed,which provides sufficient functional sites for lithium ion transport and helps to regulate the uniform deposition of lithium metal.Moreover,the hierarchical structure can enhance the mechanical strength(9.2 MPa)of the electrolyte,thereby effectively improving the safety and cycle stability of the battery.The prepared Li/Li symmetric battery can be stably cycled for 1500 h under 0.3 mA cm^(-2) and 60℃.This study demonstrates that the prepared electrolyte has excellent application prospects in the next generation all-solid-state lithium metal batteries.展开更多
In this study,a versatile fluorine-bearing gel membrane with multi-scale nanofibers was rationally designed and synthesized via facile one-step blend electrospinning of nano-titanium dioxide(TiO_(2))particles and fluo...In this study,a versatile fluorine-bearing gel membrane with multi-scale nanofibers was rationally designed and synthesized via facile one-step blend electrospinning of nano-titanium dioxide(TiO_(2))particles and fluorinated poly-m-phenyleneisophthalamide(PMIA)polymer solution.The prepared multiscale TiO_(2)-assisted gel separator presented relatively high porosity,small aperture,giving rise to superior affinity to electrolyte and sufficient active sites to accelerate lithium ions migration.Meanwhile,the asfabricated multifunctional GPE also rendered outstanding heat-resistance and well-distributed lithiumions flux,and the mutual overlaps between the coarse fibers and the fine fibers within the multi-scale nanofiber membrane provided a strong skeleton support,which in turn laid a solid footing stone for high-security and dendrite-proof batteries.Particularly,the nano-TiO_(2) particles within PMIA membrane acted as"gatekeepers",which can not only resist the growth of lithium dendrites,but also intercept the dissolved polysulfide on cathode side.Based on these merits,the gel PMIA-based lithium cobalt(LCO)/lithium battery obtained the remarkably improved rate capability and cycle performances on account of superior ionic conductivity,steady anodic stability window and weakened polarization behavior.Meanwhile,the resultant lithium-sulfur cell also delivered the outstanding cycling stability with the aid of the greatly prevented"shuttle effect"of dissolved lithium polysulfides based on the physical trapping and chemical binding of the prepared GPE to polysulfides species.This work proved that the addition of functional inorganic nanoparticles similar with TiO_(2) in multi-scale gel PMIA membrane can enhance the lithium ions transport capability,resist the growth of lithium dendrites as well as inhibit the shuttle effect of polysulfides,which would prompt a great development for dendrite-blocking and polysulfideinhibiting lithium-metal cells.展开更多
Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibili...Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibility and slow ionic migration.In this study,Mg O nanofibers and MgF;nanofibers were prepared via the electro-blow spinning and high-temperature calcination methods,and were applied to all-solid-state lithium metal batteries for the first time.The organic-inorganic composite SSEs exhibited continuous conduction paths based on the virtue of the nanofibers with high length-to-diameter ratio,which were designed and prepared by mixing prepared fillers into the poly(ethylene oxide)(PEO)/lithium bis(trifluoromethane)sulfonilimide(Li TFSI)system.The effect of filler with different morphologies,doping ratios and component on ionic conductivity,electrochemical stability and cycle performance were explored under two kinds of[EO]/[Li^(+)]ratios and ambient temperatures.The ionic conductivities of electrolytes containing Mg O and MgF;nanofibers can reach up to 1.19×10^(-4) and 1.39×10^(-4) S cm^(-1) at 30℃,respectively.They were attributed to specific ionic conductive enhancement at the organicinorganic interface,reduced crystallinity and Lewis acid interaction,which can effectively promote the dissociation of the lithium salts.Especially MgF_(2) nanofiber,combining low electronic conductance,excellent electrochemical stability and outstanding inhibition for lithium dendrites of fluorides,endowed the battery with an initial specific capacity of 140.6 m Ah g^(-1) and capacity decay rate per cycle of 0.055%after500 cycles at 50℃.The work can provide an idea to design SSE with fast and multi-dimensional Li conductive paths and excellent interfacial compatibility.展开更多
Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspo...Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.展开更多
Lithium-ion(Li-ion) battery and lithium-sulfur(Li-S) battery have attracted significant attention as promising components for large-scale energy storage because of high theoretical capacity of Li,excellent energy dens...Lithium-ion(Li-ion) battery and lithium-sulfur(Li-S) battery have attracted significant attention as promising components for large-scale energy storage because of high theoretical capacity of Li,excellent energy density or environmental friendness for two kinds of batteries.However,there still exist some respective obstacles for commercial applications,such as limited theoretical capacity,high cost and low conductivity of Li-ion cells or shuttle effect of lithium polysulfides of Li-S cells.As typical twodimensional materials,layered double hydroxides(LDHs) exhibit excellent potential in the field of energy storage due to facile tunability of composition,structure and morphology as well as convenient composite and strong catalytic properties.Consequently,various LDHs toward novel separators or interlayers,cathodes,anodes,and interesting catalytic templates are researched to resolve these challenges.In this review,the recent progress for LDHs applied in Li-ion batteries and Li-S batteries including the synthesis methods,designs and applications is presented and reviewed.Meanwhile,the existing challenges and future perspectives associated with material designs and practical applications of LDHs for these two classes of cells are discussed.WeWe hope that the review can attract more attention and inspire more profound researches toward the LDH-based electrochemical materials for energy storage.展开更多
All-solid-state lithium batteries(ASSLBs),receiving extensive attentions and studies,exhibit better safety,environmental friendliness,stability,wider electrochemical stability window and higher energy density than tra...All-solid-state lithium batteries(ASSLBs),receiving extensive attentions and studies,exhibit better safety,environmental friendliness,stability,wider electrochemical stability window and higher energy density than traditionally liquid lithium batteries.In a variety of inorganic materials,with highly replaceable,the non-lithium metal elements emerge in endlessly and affect performances in diversiform ways.Due to facile preparation,convertible structures and excellent properties,the lithium-containing bimetallic granular materials are often applied as important components of electrolytes in lithium batteries.In this review,in terms of the properties of substituted elements,changing crystal structures,increasing vacancies or defects and improving the interfacial conductions,the roles of metal element substitutions of inorganic particles on the improvement of solid-state electrolytes are expounded.And the applications of substituted strategies in ASSLBs as the host of inorganic particles electrolytes and as fillers or modifications for composite electrolytes are also investigated and discussed.It also summarizes the current concerns and obstacles that need to be broken through,as well as provides a basis guide for the selection and optimization of inorganic particles.展开更多
基金supported by the National Natural Science Foundation of China (52203066,51973157,61904123)the Tianjin Natural Science Foundation (18JCQNJC02900)+3 种基金National innovation and entrepreneurship training program for college students (202310058007)Tianjin Municipal college students’innovation and entrepreneurship training program (202310058088)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education (Grant No.2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Lithium-sulfur(Li-S)batteries are considered highly promising as next-generation energy storage systems due to high theoretical capacity(2600 Wh kg^(-1))and energy density(1675 mA h g^(-1))as well as the abundant natural reserves,low cost of elemental sulfur,and environmentally friendly properties.However,several challenges impede its commercialization including low conductivity of sulfur itself,the severe“shuttle effect”caused by lithium polysulfides(LiPSs)during charge–discharge processes,volume expansion effects and sluggish reaction kinetics.As a solution,polar metal particles and their compounds have been introduced as the main hosts for sulfur cathode due to their robust catalytic activity and adsorption capability,effectively suppressing the“shuttle effect”of Li PSs.Bimetallic alloys and their compounds with multi-functional properties exhibit remarkable electrochemical performance more readily when compared to single-metal materials.Well-designed bimetallic materials demonstrate larger specific surface areas and richer active sites,enabling simultaneous high adsorption capability and strong catalytic properties.The synergistic effect of the“adsorption-catalysis”sites accelerates the adsorptiondiffusion-conversion process of Li PSs,ultimately achieving a long-lasting Li-S battery.Herein,the latest progress and performance of bimetallic materials in cathodes,separators,and interlayers of Li-S batteries are systematically reviewed.Firstly,the principles and challenges of Li-S batteries are briefly analyzed.Then,various mechanisms for suppressing“shuttle effects”of Li PSs are emphasized at the microscale.Subsequently,the performance parameters of various bimetallic materials are comprehensively summarized,and some improvement strategies are proposed based on these findings.Finally,the future prospects of bimetallic materials are discussed,with the hope of providing profound insights for the rational design and manufacturing of high-performance bimetallic materials for LSBs.
基金This work was supported by the National Natural Science Foundation of China(52203066,51973157,61904123)the Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金the National innovation and entrepreneurship training program for college students(202310058007)the Tianjin Municipal college students’innovation and entrepreneurship training program(202310058088)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(Grant No.2018KJ196)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University.
文摘Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely commercial application and development of LSB is mainly hindered by serious“shuttle effect”of lithium polysulfides(Li PSs),slow reaction kinetics,notorious lithium dendrites,etc.In various structures of LSB materials,array structured materials,possessing the composition of ordered micro units with the same or similar characteristics of each unit,present excellent application potential for various secondary cells due to some merits such as immobilization of active substances,high specific surface area,appropriate pore sizes,easy modification of functional material surface,accommodated huge volume change,enough facilitated transportation for electrons/lithium ions,and special functional groups strongly adsorbing Li PSs.Thus many novel array structured materials are applied to battery for tackling thorny problems mentioned above.In this review,recent progresses and developments on array structured materials applied in LSBs including preparation ways,collaborative structural designs based on array structures,and action mechanism analyses in improving electrochemical performance and safety are summarized.Meanwhile,we also have detailed discussion for array structured materials in LSBs and constructed the structure-function relationships between array structured materials and battery performances.Lastly,some directions and prospects about preparation ways,functional modifications,and practical applications of array structured materials in LSBs are generalized.We hope the review can attract more researchers'attention and bring more studying on array structured materials for other secondary batteries including LSB.
基金This work was supported by the National Natural Science Foundation of China (51973157,61904123)the Tianjin Natural Science Foundation (18JCQNJC02900)+3 种基金the Special Grade of the Financial Support from the China Postdoctoral Science Foundation (2020T130469)the Sci-ence and Technology Plans of Tianjin (19PTSYJC00010)the Science&Technol-ogy Development Fund of Tianjin Education Commission for Higher Education (2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University.
文摘Low-cost and flexible solid polymer electrolytes are promising in all-solid-state Li-metal batteries with high energy density and safety.However,both the low room-temperature ionic conductivities and the small Li^(+)transference number of these electrolytes significantly increase the internal resistance and overpotential of the battery.Here,we introduce Gd-doped CeO_(2) nanowires with large surface area and rich surface oxygen vacancies to the polymer electrolyte to increase the interaction between Gd-doped CeO_(2) nanowires and polymer electrolytes,which promotes the Li-salt dissociation and increases the concentration of mobile Li ions in the composite polymer electrolytes.The optimized composite polymer electrolyte has a high Li-ion conductivity of 5×10^(-4)4 S cm^(-1) at 30℃ and a large Li+transference number of 0.47.Moreover,the composite polymer electrolytes have excellent compatibility with the metallic lithium anode and high-voltage LiNi_(0.8)Mn _(0.1)Co_(0.1)O_(2)(NMC)cathode,providing the stable cycling of all-solid-state batteries at high current densities.
基金supported by the National Natural Science Foundation of China,China(52203066,51973157,51673148 and 51678411)the Science and Technology Plans of Tianjin,China(19PTSYJC00010)+3 种基金China Postdoctoral Science Foundation Grant,China(2019M651047)the Tianjin Research Innovation Project for Postgraduate Students,China(2020YJSB062)the Tianjin Municipal College Student’Innovation And Entrepreneurship Training Program,China(202110058052)the National Innovation and Entrepreneurship Training Program for College Students,China(202110058017)。
文摘Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.
基金supported by the National Natural Science Foundation of China(52203066,51973157,61904123,51873152)the Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金the Science and Technology Plans of Tianjin(19PTSYJC00010)the Tianjin Research Innovation Project for Postgraduate Students(2021YJSB234)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid electrolytes with favorable electrode/electrolyte interface compatibility and high ionic conductivity in a simple and scalable manner.Hence,the oxygen-vacancy-rich Gd-doped SnO_(2) nanotubes(GDS NTs)are innovatively prepared and applied to the electrolyte of all-solid-state lithium metal batteries for the first time.The addition of GDS NTs can validly construct long-range co ntinuous ion transport networks in the poly(ethylene oxide)(PEO)-based system and greatly improve the mechanical properties of the electrolyte.Compared to the PEO-based electrolyte,the composite electrolyte displays a higher lithium ion conductivity of 2.41×10^(-4) S cm^(-1) at 30℃,a higher lithium ion transference number up to 0.62 and a wider electrochemical window of 5 V at 50℃.In addition,the composite electrolyte manifests outstanding compatibility with high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)cathode,LiFePO4 cathode and lithium metal anode.The assembled Li/Li symmetric battery exhibits stable Li plating/stripping cycling performance,which can cycle steadily for 1500 h at a capacity of 0.3 mA h cm^(-2).And Li/LiFePO4 battery still maintains a high capacity of 131.54 mA h g^(-1) at 0.5C after 800 cycles,which has a superior capacity retention rate of 93.2%.The obtained novel composite electrolyte has promising application prospects in the field of all-solid-state lithium metal cells.
基金supported by the National Natural Science Foundation of China(52203066,51973157,51673148,51678411)the Science and Technology Plans of Tianjin,China(19PTSYJC00010)+3 种基金the China Postdoctoral Science Foundation Grant(2019M651047)the Tianjin Research Innovation Project for Postgraduate Students,China(2020YJSB062)the Tianjin Municipal college student’innovation and entrepreneurship training program,China(202110058052)the National innovation and entrepreneurship training program for college students,China(202110058017)。
文摘With the emergence of some solid electrolytes(SSEs)with high ionic conductivity being comparable to liquid electrolytes,solid-state lithium-sulfur batteries(SSLSBs)have been widely regarded as one of the most promising candidates for the next generation of power generation energy storage batteries,and have been extensively researched.Though many fundamental and technological issues still need to be resolved to develop commercially viable technologies,SSLSBs using SSEs are expected to address the present limitations and achieve high energy and power density while improving safety,which is very attractive to large-scale energy storage systems.SSLSBs have been developed for many years.However,there are few systematic discussions related to the working mechanism of action of various electrolytes in SSLSBs and the defects and the corresponding solutions of various electrolytes.To fill this gap,it is very meaningful to review the recent progress of SSEs in SSLSBs.In this review,we comprehensively investigate and summarize the application of SSEs in LSBs to determine the differences which still exist between current progresses and real-world requirements,and comprehensively describe the mechanism of action of SSLSBs,including lithium-ion transport,interfacial contact,and catalytic conversion mechanisms.More importantly,the selection of solid electrolyte materials and the novel design of structures are reviewed and the properties of various SSEs are elucidated.Finally,the prospects and possible future research directions of SSLSBs including designing high electronic/ionic conductivity for cathodes,optimizing electrolytes and developing novel electrolytes with excellent properties,improving electrode/-electrolyte interface stability and enhancing interfacial dynamics between electrolyte and anode,using more advanced test equipment and characterization techniques to analyze conduction mechanism of Li^(+)in SSEs are presented.It is hoped that this review can arouse people’s attention and enlighten the development of functional materials and novel structures of SSEs in the next step.
基金supported by the National Natural Science Foundation of China(51973157,61904123,52103061,52203066)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)+3 种基金the project funded by China Postdoctoral Science Foundation(2021T140419)Tianjin Municipal College Student’Innovation and Entrepreneurship Training Program(202110058052)the National Innovation and Entrepreneurship Training Program for College Students(202110058017)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.
基金supported by the National Natural Science Foundation of China(51973157,61904123,52103061,52203066)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)+3 种基金the project funded by China Postdoctoral Science Foundation(2021T140419)Tianjin Municipal College Student’Innovation and Entrepreneurship Training Program(202110058052)the National Innovation and Entrepreneurship Training Program for College Students(202110058017)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘With the popularity and widespread applications of electronics,higher demands are being placed on the performance of battery materials.Due to the large difference in electronegativity between fluorine and carbon atoms,doping fluorine atoms in nanocarbon-based materials is considered an effective way to improve the performance of used battery.However,there is still a blank in the systematic review of the mechanism and research progress of fluorine-doped nanostructured carbon materials in various batteries.In this review,the synthetic routes of fluorinated/fluorine-doped nanocarbon-based(CF_x)materials under different fluorine sources and the function mechanism of CF_x in various batteries are reviewed in detail.Subsequently,judging from the dependence between the structure and electrochemical performance of nanocarbon sources,the progress of CF_x based on different dimensions(0D–3D)for primary battery applications is reviewed and the balance between energy density and power density is critically discussed.In addition,the roles of CF_x materials in secondary batteries and their current applications in recent years are summarized in detail to illustrate the effect of introducing F atoms.Finally,we envisage the prospect of CF_x materials and offer some insights and recommendations to facilitate the further exploration of CF_x materials for various high-performance battery applications.
基金supported by the National Natural Science Foundation of China (51673148)National Basic Research Program of China (2014CB660813)+2 种基金National Key Technology Support Program (2015BAE01B03)Innovation Fund for Technology of China (14C26211200298)Innovation Fund for Technology of Tianjin (14TXGCCX00014,14ZXCXGX00776)~~
基金the National Natural Science Foundation of China(51973157,51673148 and 51678411),Chinathe China Postdoctoral Science Foundation Grant(2019 M651047),Chinathe Science and Technology Plans of Tianjin(No.17PTSYJC00040 and 18PTSYJC00180),China for the financial support。
文摘The utilization of all-solid-state electrolytes is considered to be an effective way to enhance the safety performance of lithium metal batteries.However,the low ionic conductivity and poor interface compatibility greatly restrict the development of all-solid-state battery.In this study,a composite electrolyte combining the electrospun polyamide 6(PA6)nanofiber membrane with hierarchical structure and the polyethylene oxide(PEO)polymer is investigated.The introduction of PA6 nanofiber membrane can effectively reduce the crystallinity of the polymer,so that the ionic conductivity of the electrolyte can be enhanced.Moreover,it is found that the presence of finely branched fibers in the hierarchical structure PA6 membrane allows the polar functional groups(C=O and N-H bonds)to be fully exposed,which provides sufficient functional sites for lithium ion transport and helps to regulate the uniform deposition of lithium metal.Moreover,the hierarchical structure can enhance the mechanical strength(9.2 MPa)of the electrolyte,thereby effectively improving the safety and cycle stability of the battery.The prepared Li/Li symmetric battery can be stably cycled for 1500 h under 0.3 mA cm^(-2) and 60℃.This study demonstrates that the prepared electrolyte has excellent application prospects in the next generation all-solid-state lithium metal batteries.
基金supported by the National Natural Science Foundation of China(51678411)the National Key Technology R&D Program(2016YFB0303300)the Science and Technology Plans of Tianjin(Nos.19PTSYJC00010 and 18PTSYJC00180)。
文摘In this study,a versatile fluorine-bearing gel membrane with multi-scale nanofibers was rationally designed and synthesized via facile one-step blend electrospinning of nano-titanium dioxide(TiO_(2))particles and fluorinated poly-m-phenyleneisophthalamide(PMIA)polymer solution.The prepared multiscale TiO_(2)-assisted gel separator presented relatively high porosity,small aperture,giving rise to superior affinity to electrolyte and sufficient active sites to accelerate lithium ions migration.Meanwhile,the asfabricated multifunctional GPE also rendered outstanding heat-resistance and well-distributed lithiumions flux,and the mutual overlaps between the coarse fibers and the fine fibers within the multi-scale nanofiber membrane provided a strong skeleton support,which in turn laid a solid footing stone for high-security and dendrite-proof batteries.Particularly,the nano-TiO_(2) particles within PMIA membrane acted as"gatekeepers",which can not only resist the growth of lithium dendrites,but also intercept the dissolved polysulfide on cathode side.Based on these merits,the gel PMIA-based lithium cobalt(LCO)/lithium battery obtained the remarkably improved rate capability and cycle performances on account of superior ionic conductivity,steady anodic stability window and weakened polarization behavior.Meanwhile,the resultant lithium-sulfur cell also delivered the outstanding cycling stability with the aid of the greatly prevented"shuttle effect"of dissolved lithium polysulfides based on the physical trapping and chemical binding of the prepared GPE to polysulfides species.This work proved that the addition of functional inorganic nanoparticles similar with TiO_(2) in multi-scale gel PMIA membrane can enhance the lithium ions transport capability,resist the growth of lithium dendrites as well as inhibit the shuttle effect of polysulfides,which would prompt a great development for dendrite-blocking and polysulfideinhibiting lithium-metal cells.
基金supported by the National Natural Science Foundation of China(grant No.51973157)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(grant No.2020T130469)+2 种基金the Tianjin Municipal University Students’Innovation and Entrepreneurship Training Program Project(grant No.201910058036)the Science and Technology Plans of Tianjin(grant No.19PTSYJC00010)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(grant No.2018KJ196)。
文摘Solid-state electrolytes(SSEs),which replace flammable and toxic liquid electrolytes,have attracted widely attention.However,there exist still some challenges in actual application such as poor interfacial compatibility and slow ionic migration.In this study,Mg O nanofibers and MgF;nanofibers were prepared via the electro-blow spinning and high-temperature calcination methods,and were applied to all-solid-state lithium metal batteries for the first time.The organic-inorganic composite SSEs exhibited continuous conduction paths based on the virtue of the nanofibers with high length-to-diameter ratio,which were designed and prepared by mixing prepared fillers into the poly(ethylene oxide)(PEO)/lithium bis(trifluoromethane)sulfonilimide(Li TFSI)system.The effect of filler with different morphologies,doping ratios and component on ionic conductivity,electrochemical stability and cycle performance were explored under two kinds of[EO]/[Li^(+)]ratios and ambient temperatures.The ionic conductivities of electrolytes containing Mg O and MgF;nanofibers can reach up to 1.19×10^(-4) and 1.39×10^(-4) S cm^(-1) at 30℃,respectively.They were attributed to specific ionic conductive enhancement at the organicinorganic interface,reduced crystallinity and Lewis acid interaction,which can effectively promote the dissociation of the lithium salts.Especially MgF_(2) nanofiber,combining low electronic conductance,excellent electrochemical stability and outstanding inhibition for lithium dendrites of fluorides,endowed the battery with an initial specific capacity of 140.6 m Ah g^(-1) and capacity decay rate per cycle of 0.055%after500 cycles at 50℃.The work can provide an idea to design SSE with fast and multi-dimensional Li conductive paths and excellent interfacial compatibility.
基金the National Natural Science Foundation of China(51973157)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(2020T130469)+1 种基金the China Postdoctoral Science Foundation Grant(2019 M651047)the Science and Technology Plans of Tianjin(19PTSYJC00010)for their financial support。
文摘Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.
基金the National Natural Science Foundation of China(51973157,51673148 and 51678411)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(2020 T130469)+1 种基金the China Postdoctoral Science Foundation Grant(2019 M651047)the Science and Technology Plans of Tianjin(No.17PTSYJC00040 and18PTSYJC00180)for their financial support。
文摘Lithium-ion(Li-ion) battery and lithium-sulfur(Li-S) battery have attracted significant attention as promising components for large-scale energy storage because of high theoretical capacity of Li,excellent energy density or environmental friendness for two kinds of batteries.However,there still exist some respective obstacles for commercial applications,such as limited theoretical capacity,high cost and low conductivity of Li-ion cells or shuttle effect of lithium polysulfides of Li-S cells.As typical twodimensional materials,layered double hydroxides(LDHs) exhibit excellent potential in the field of energy storage due to facile tunability of composition,structure and morphology as well as convenient composite and strong catalytic properties.Consequently,various LDHs toward novel separators or interlayers,cathodes,anodes,and interesting catalytic templates are researched to resolve these challenges.In this review,the recent progress for LDHs applied in Li-ion batteries and Li-S batteries including the synthesis methods,designs and applications is presented and reviewed.Meanwhile,the existing challenges and future perspectives associated with material designs and practical applications of LDHs for these two classes of cells are discussed.WeWe hope that the review can attract more attention and inspire more profound researches toward the LDH-based electrochemical materials for energy storage.
基金This work was supported by the National Natural Science Foundation of China(grant No.51973157)the Special Grade of the Financial Support from the China Postdoctoral Science Foundation(grant No.2020T130469)+3 种基金Tianjin Municipal University Students'Innovation and Entrepreneurship Training Program Project(grant No.201910058036)the Science and Technology Plans of Tianjin(grant No.19PTSYJCO0010)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(grantNo.2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘All-solid-state lithium batteries(ASSLBs),receiving extensive attentions and studies,exhibit better safety,environmental friendliness,stability,wider electrochemical stability window and higher energy density than traditionally liquid lithium batteries.In a variety of inorganic materials,with highly replaceable,the non-lithium metal elements emerge in endlessly and affect performances in diversiform ways.Due to facile preparation,convertible structures and excellent properties,the lithium-containing bimetallic granular materials are often applied as important components of electrolytes in lithium batteries.In this review,in terms of the properties of substituted elements,changing crystal structures,increasing vacancies or defects and improving the interfacial conductions,the roles of metal element substitutions of inorganic particles on the improvement of solid-state electrolytes are expounded.And the applications of substituted strategies in ASSLBs as the host of inorganic particles electrolytes and as fillers or modifications for composite electrolytes are also investigated and discussed.It also summarizes the current concerns and obstacles that need to be broken through,as well as provides a basis guide for the selection and optimization of inorganic particles.
