The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assiste...The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.展开更多
Li2MnSiO4 has an extremely high theoretical capacity of 332 mAh?g?1. However, only around half of this capacity has been realized in practice and the capacity retention during cycling is also low. In this study, Li2Mn...Li2MnSiO4 has an extremely high theoretical capacity of 332 mAh?g?1. However, only around half of this capacity has been realized in practice and the capacity retention during cycling is also low. In this study, Li2MnSiO4/carbon composite nanofibers were prepared by a combination of electrospinning and heat treatment. The one-dimensional continuous carbon nanofiber matrix serves as long-distance conductive pathways for both electrons and ions. The composite nanofiber structure avoids the aggregation of Li2MnSiO4 particles, which in turn enhances the electrode conductivity and promotes the reaction kinetics. The resultant Li2MnSiO4/carbon composite nanofibers were used as the cathode material for Li-ion batteries, and they delivered high charge and discharge capacities of 218 and 185 mAh?g?1, respectively, at the second cycle. In addition, the capacity retention of Li2MnSiO4 at the first 20th cycles increased from 37% to 54% in composite nanofibers.展开更多
The lithium-ion(Li-ion)battery has received considerable attention in the field of energy conversion and storage due to its high energy density and eco-friendliness.Significant academic and commercial progress has bee...The lithium-ion(Li-ion)battery has received considerable attention in the field of energy conversion and storage due to its high energy density and eco-friendliness.Significant academic and commercial progress has been made in Li-ion battery technologies.One area of advancement has been the addition of nanofiber materials to Li-ion batteries due to their unique and desirable structural features including large aspect ratios,high surface areas,controllable chemical compositions,and abundant composite forms.In the past few decades,considerable research efforts have been devoted to constructing advanced nanofiber materials possessing conductive networks to facilitate efficient electron transport and large specific surface areas to support catalytically active sites,both for the purpose of boosting electrochemical performance.Herein,we focus on recent advancements of nanofiber materials with carefully designed structures and enhanced electrochemical properties for use in Li-ion batteries.The synthesis,structure,and properties of nanofiber cathodes,anodes,separators,and electrolytes,and their applications in Li-ion batteries are discussed.The research challenges and prospects of nanofiber materials in Li-ion battery applications are delineated.展开更多
Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolyte...Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.展开更多
Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost ...Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost for manufacturing fbered cathode.In this work,we demonstrated gamma manganese oxide(ɣ-MnO_(2))/reduced graphene oxide(rGO)fbered cathode fabrication using facile and cost-efective fber production and active material coating techniques.Specifcally,rGO fbers were fabricated via wet spinning,followed by chemical reduction with hydroiodic acid(HI).The synthesized rGO fber bundle was then dip-coated with a mixture ofɣ-MnO_(2),carbon black or multi-walled carbon nanotubes,and xanthan gum or polyvinylidene fuoride binder to obtainɣ-MnO_(2)/rGO fbered cathode.We studied the efect of binders and conductive materials on physical properties and electrochemical performance of the fbered cathode.It was found that hydrophobic binder had more benefts than hydrophilic binder by providing higher active material loading,better coating layer homogeneity,and more stable electrochemical performance.Cable-shaped Zn-ion batteries(CSZIBs)were then assembled by using theɣ-MnO_(2)/rGO fbered cathode,Zn wire anode,and xanthan gum polymeric gel electrolyte with 2 M ZnSO_(4) and 0.2 M MnSO_(4) salts without a separator.We investigated the battery assembling procedure on a glass slide(prototype ZIB)and in a plastic tube(cable-shaped ZIB),and evaluated their electrochemical performance.The CSZIB showed promising maximum capacity of~230 mAh/g with moderate cycling stability(80%capacity retention after 200 cycles)and high fexibility by maintaining the potential after consecutive pressing for 200 times under controlled pressing distance,duration,and testing speed.Finally,we explored ion intercalation behaviours and proposed a H^(+)/Zn^(2+)co-intercalation mechanism in ZIB withɣ-MnO_(2) active material.展开更多
Single-ion conducting polymer electrolytes(SIPEs)can be formed by anchoring charge delocalized anions on the side chains of a crosslinked polymer matrix,thereby eliminating the severe concentration polarization efect ...Single-ion conducting polymer electrolytes(SIPEs)can be formed by anchoring charge delocalized anions on the side chains of a crosslinked polymer matrix,thereby eliminating the severe concentration polarization efect in conventional dual-ion polymer electrolytes.Addition of a plasticizer into the polymer matrix confers advantages of both liquid and solid electrolytes.However,plasticized SIPEs usually face a trade-of between conductivity and mechanical strength.With insufcient strength,potentially there is short-circuiting failure during cycling.To address this challenge,a simple and mechanicallyrobust SIPE was developed by crosslinking monomer lithium(4-styrenesulfonyl)(trifuoromethylsulfonyl)imide(LiSTFSI)and crosslinker poly(ethylene glycol)diacrylate(PEGDA),with plasticizer propylene carbonate(PC),on electrospun polyacrylonitrile nanofbers(PAN-NFs).The well-fabricated polymer matrix provided fast and efective Li^(+) conductive pathways with a remarkable ionic conductivity of 8.09×10^(-4) S cm^(−1) and a superior lithium-ion transference number close to unity(t_(Li+)=0.92).The introduction of PAN-NFs not only improved the mechanical strength and fexibility but also endowed the plasticized SIPE with a wide electrochemical stability window(4.9 V vs.Li^(+)/Li)and better cycling stability.Superior longterm lithium cycling stability and dynamic interfacial compatibility were demonstrated by lithium symmetric cell testing.Most importantly,the assembled all-solid-state Li metal batteries showed stable cycling performance and remarkable rate capability both in low and high current densities.Therefore,this straightforward and mechanically reinforced SIPE exhibits great potential in the development of advanced all-solid-state Li-metal batteries.展开更多
Carbon cloth(CC)-based electrodes have attracted extensive attention for next-generation wearable energy-storage devices due to their excellent electrical conductivity and mechanical flexibility.However,the applicatio...Carbon cloth(CC)-based electrodes have attracted extensive attention for next-generation wearable energy-storage devices due to their excellent electrical conductivity and mechanical flexibility.However,the application of conventional CC-based electrodes for zinc(Zn)storage severely hinders Zn ion transport and induces deleterious Zn dendrite growth,resulting in poor electrochemical reliability.Herein,a novel oxygen plasma-treated carbon cloth(OPCC)is rationally designed as a current collector for flexible hybrid Zn ion supercapacitors(ZISs).The modified interface of OPCC with abundant oxygenated groups enables enhanced electrolyte wettability and uniform superficial electric field distribution.A prolonged working lifespan for Zn electrodeposition is achieved by the OPCC due to the improved interfacial kinetics and homogenized ion gradient.The as-prepared hybrid ZIS also delivers excellent cycling endurance(98.5%capacity retention for 1500 cycles)with outstanding operation stability under various extreme conditions.This facile surface modification strategy provides a new way for developing future flexible electrodes for wearable electronic products.展开更多
CONSPECTUS:Lithium−sulfur(Li−S)batteries have been extensively studied because both S and Li have high theoretical capacities,and S is abundant and environmentally friendly.However,their practical applications have be...CONSPECTUS:Lithium−sulfur(Li−S)batteries have been extensively studied because both S and Li have high theoretical capacities,and S is abundant and environmentally friendly.However,their practical applications have been hindered by several challenges,including poor conductivity of S and its intermediates,shuttle effects of polysulfides,Li dendrite growth,etc.Tremendous efforts have been taken to tackle these issues by developing functional S host materials,separators and interlayers,solid-state electrolytes,etc.,during the past decade.Compared to structurally complicated materials and intricate preparation approaches,electrospun nanofibers have obtained tremendous interests since they have played an extremely crucial role in improving the overall performance of Li−S cells due to their unique features such as easy-setup,substantial surface area,outstanding flexibility,high porosity,excellent mechanical properties,etc.展开更多
基金financial support from the National Key Research and Development Project (2017YFB0308200)the CAS Key Laboratory of Carbon Materials (KLCMKFJJ2011)。
文摘The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.
文摘Li2MnSiO4 has an extremely high theoretical capacity of 332 mAh?g?1. However, only around half of this capacity has been realized in practice and the capacity retention during cycling is also low. In this study, Li2MnSiO4/carbon composite nanofibers were prepared by a combination of electrospinning and heat treatment. The one-dimensional continuous carbon nanofiber matrix serves as long-distance conductive pathways for both electrons and ions. The composite nanofiber structure avoids the aggregation of Li2MnSiO4 particles, which in turn enhances the electrode conductivity and promotes the reaction kinetics. The resultant Li2MnSiO4/carbon composite nanofibers were used as the cathode material for Li-ion batteries, and they delivered high charge and discharge capacities of 218 and 185 mAh?g?1, respectively, at the second cycle. In addition, the capacity retention of Li2MnSiO4 at the first 20th cycles increased from 37% to 54% in composite nanofibers.
基金Samuel S.Walker Distinguished Professorship Fund of the Wilson College of Textiles,North Carolina State University,and the Natural Science Foundation of Hubei Province(No.2021CFB478),China.
文摘The lithium-ion(Li-ion)battery has received considerable attention in the field of energy conversion and storage due to its high energy density and eco-friendliness.Significant academic and commercial progress has been made in Li-ion battery technologies.One area of advancement has been the addition of nanofiber materials to Li-ion batteries due to their unique and desirable structural features including large aspect ratios,high surface areas,controllable chemical compositions,and abundant composite forms.In the past few decades,considerable research efforts have been devoted to constructing advanced nanofiber materials possessing conductive networks to facilitate efficient electron transport and large specific surface areas to support catalytically active sites,both for the purpose of boosting electrochemical performance.Herein,we focus on recent advancements of nanofiber materials with carefully designed structures and enhanced electrochemical properties for use in Li-ion batteries.The synthesis,structure,and properties of nanofiber cathodes,anodes,separators,and electrolytes,and their applications in Li-ion batteries are discussed.The research challenges and prospects of nanofiber materials in Li-ion battery applications are delineated.
基金the Department of Energy,Office of Energy Efficiency and Renewable Energy(EERE),under Award Number DE-EE0007806.
文摘Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.
基金This work was fnancially supported by Wilson College of Textiles,North Carolina State University,National Nanotechnology Center(NANOTEC),and National Energy Technology Center(ENTEC).
文摘Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost for manufacturing fbered cathode.In this work,we demonstrated gamma manganese oxide(ɣ-MnO_(2))/reduced graphene oxide(rGO)fbered cathode fabrication using facile and cost-efective fber production and active material coating techniques.Specifcally,rGO fbers were fabricated via wet spinning,followed by chemical reduction with hydroiodic acid(HI).The synthesized rGO fber bundle was then dip-coated with a mixture ofɣ-MnO_(2),carbon black or multi-walled carbon nanotubes,and xanthan gum or polyvinylidene fuoride binder to obtainɣ-MnO_(2)/rGO fbered cathode.We studied the efect of binders and conductive materials on physical properties and electrochemical performance of the fbered cathode.It was found that hydrophobic binder had more benefts than hydrophilic binder by providing higher active material loading,better coating layer homogeneity,and more stable electrochemical performance.Cable-shaped Zn-ion batteries(CSZIBs)were then assembled by using theɣ-MnO_(2)/rGO fbered cathode,Zn wire anode,and xanthan gum polymeric gel electrolyte with 2 M ZnSO_(4) and 0.2 M MnSO_(4) salts without a separator.We investigated the battery assembling procedure on a glass slide(prototype ZIB)and in a plastic tube(cable-shaped ZIB),and evaluated their electrochemical performance.The CSZIB showed promising maximum capacity of~230 mAh/g with moderate cycling stability(80%capacity retention after 200 cycles)and high fexibility by maintaining the potential after consecutive pressing for 200 times under controlled pressing distance,duration,and testing speed.Finally,we explored ion intercalation behaviours and proposed a H^(+)/Zn^(2+)co-intercalation mechanism in ZIB withɣ-MnO_(2) active material.
基金This work was supported by the Samuel S.Walker Distinguished Professorship in the Wilson College of Textiles at North Carolina State University。
文摘Single-ion conducting polymer electrolytes(SIPEs)can be formed by anchoring charge delocalized anions on the side chains of a crosslinked polymer matrix,thereby eliminating the severe concentration polarization efect in conventional dual-ion polymer electrolytes.Addition of a plasticizer into the polymer matrix confers advantages of both liquid and solid electrolytes.However,plasticized SIPEs usually face a trade-of between conductivity and mechanical strength.With insufcient strength,potentially there is short-circuiting failure during cycling.To address this challenge,a simple and mechanicallyrobust SIPE was developed by crosslinking monomer lithium(4-styrenesulfonyl)(trifuoromethylsulfonyl)imide(LiSTFSI)and crosslinker poly(ethylene glycol)diacrylate(PEGDA),with plasticizer propylene carbonate(PC),on electrospun polyacrylonitrile nanofbers(PAN-NFs).The well-fabricated polymer matrix provided fast and efective Li^(+) conductive pathways with a remarkable ionic conductivity of 8.09×10^(-4) S cm^(−1) and a superior lithium-ion transference number close to unity(t_(Li+)=0.92).The introduction of PAN-NFs not only improved the mechanical strength and fexibility but also endowed the plasticized SIPE with a wide electrochemical stability window(4.9 V vs.Li^(+)/Li)and better cycling stability.Superior longterm lithium cycling stability and dynamic interfacial compatibility were demonstrated by lithium symmetric cell testing.Most importantly,the assembled all-solid-state Li metal batteries showed stable cycling performance and remarkable rate capability both in low and high current densities.Therefore,this straightforward and mechanically reinforced SIPE exhibits great potential in the development of advanced all-solid-state Li-metal batteries.
基金This work was financially supported by Natural Science Foundation of Jiangsu Province(BK20210480)Hong Kong Scholars Program(P0035017).
文摘Carbon cloth(CC)-based electrodes have attracted extensive attention for next-generation wearable energy-storage devices due to their excellent electrical conductivity and mechanical flexibility.However,the application of conventional CC-based electrodes for zinc(Zn)storage severely hinders Zn ion transport and induces deleterious Zn dendrite growth,resulting in poor electrochemical reliability.Herein,a novel oxygen plasma-treated carbon cloth(OPCC)is rationally designed as a current collector for flexible hybrid Zn ion supercapacitors(ZISs).The modified interface of OPCC with abundant oxygenated groups enables enhanced electrolyte wettability and uniform superficial electric field distribution.A prolonged working lifespan for Zn electrodeposition is achieved by the OPCC due to the improved interfacial kinetics and homogenized ion gradient.The as-prepared hybrid ZIS also delivers excellent cycling endurance(98.5%capacity retention for 1500 cycles)with outstanding operation stability under various extreme conditions.This facile surface modification strategy provides a new way for developing future flexible electrodes for wearable electronic products.
文摘CONSPECTUS:Lithium−sulfur(Li−S)batteries have been extensively studied because both S and Li have high theoretical capacities,and S is abundant and environmentally friendly.However,their practical applications have been hindered by several challenges,including poor conductivity of S and its intermediates,shuttle effects of polysulfides,Li dendrite growth,etc.Tremendous efforts have been taken to tackle these issues by developing functional S host materials,separators and interlayers,solid-state electrolytes,etc.,during the past decade.Compared to structurally complicated materials and intricate preparation approaches,electrospun nanofibers have obtained tremendous interests since they have played an extremely crucial role in improving the overall performance of Li−S cells due to their unique features such as easy-setup,substantial surface area,outstanding flexibility,high porosity,excellent mechanical properties,etc.