Hollow carbon-based nanostructures(HCNs)have found broad applications in various fields,particularly rechargeable batteries.However,the syntheses of HCNs usually rely on template methods,which are time-consuming,low-y...Hollow carbon-based nanostructures(HCNs)have found broad applications in various fields,particularly rechargeable batteries.However,the syntheses of HCNs usually rely on template methods,which are time-consuming,low-yield,and environmentally detrimental.Metal-organic frameworks(MOFs),constructed by organic ligands and inorganic metal nodes,have been identified as effective platforms for preparing HCNs without adding extra templates.This review summarized the recent progress in template-free synthesis of HCNs enabled by MOFs and their applications in rechargeable batteries.Different template-free strategies were introduced first with mechanistic insights into the hollowing mechanism.Then the electrochemical performances of the HCNs were discussed with highlight on the structure-function correlation.It is found that the built-in cavities and nonporous for HCNs is of critical importance to increase the storage sites for high capacity,to enhance charge and mass transport kinetics for high-rate capability,and to ensure the resilient electrode structure for stable cycling.Finally,the challenges and opportunities regarding MOFs-derived HCNs and their applications in rechargeable batteries were discussed.展开更多
Charging the LiCoO_(2)(LCO)cathode to a higher voltage,for example 4.5 V compared to the commonly used 4.2 V,is now intensively pursued so as to achieve a higher specific capacity.However,it suffers severe surface str...Charging the LiCoO_(2)(LCO)cathode to a higher voltage,for example 4.5 V compared to the commonly used 4.2 V,is now intensively pursued so as to achieve a higher specific capacity.However,it suffers severe surface structural degradation and detrimental interfacial side reactions between cathode and electrolyte,which lead to the fast capacity fading during long-term cycling.Here,a surface coating strategy was developed for the protection of 4.5 V LCO by constructing a manganese oxides(MOs)nanoshell around LCO particles,which was achieved through a solution-based coating process with success in controlling the growth kinetics of the coating species.We found that the introduction of the MOs nanoshell is highly effective in alleviating the organic electrolyte decomposition at the cathode surface,thus ensuring a much more stable LiF-rich cathode-electrolyte interface and an obvious lower interfacial resistance during electrochemical cycling.Meanwhile,this protection layer can effectively improve the structural stability of the cathode by hindering the cracks formation and structural degradation of LCO particles.Therefore,the MOs modified LCO exhibited excellent rate performance and a high discharge capacity retention of 81.5%after 100 cycles at 1 C compared with the untreated LCO(55.2%),as well as the improved thermal stability and cyclability at the elevated temperature.It is expected that this discovery and fundamental understanding of the surface chemistry regulation strategy provide promising insights into improving the reversibility and stability of LCO cathode at the cut-off voltage of 4.5 V.展开更多
All-solid-state batteries(ASSBs) hold great promise for next-generation energy storage technologies owing to their advantage in different aspects such as energy density,safety,and wide temperature tolerance.However,th...All-solid-state batteries(ASSBs) hold great promise for next-generation energy storage technologies owing to their advantage in different aspects such as energy density,safety,and wide temperature tolerance.However,the use of solid-state electrolytes(SSEs) instead of liquid ones meanwhile brings serious concerns related to the point-to-point contact between SSEs and electrodes,which is known to result in high interface resistance and inhomogeneous distribution of charges during the Li^(+)plating/stripping process,eventually leading to a premature failure of ASSBs.This review focuses on the garnet-type SSEs in the formula of Li_(7)La_(3)Zr_(2)O_(12)(LLZO),and discusses the structure-performance relationship of this ceramic electrolyte in detail to achieve a clear understanding of its Li^(+)transmission mechanism.Meanwhile,the challenges of cubic phase LLZO(c-LLZO) for their application in solidstate batteries(SSBs) are demonstrated by the Li/LLZO interface,which features the importance of Li metal wettability and dendrite suppression for sustainable performance.Furthermore,this review summarizes the recent research strategies to combat these contact issues at the Li/LLZO interface,highlighting the essential role played by surface modification of LLZO electrolytes.Following the obtained insights,perspectives for future research on LLZO to accelerate its potential development of SSBs in commercialized applications are also provided.展开更多
Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a co...Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a composite oxide seriously limits its practical capacity,which becomes a serious concern especially when a high rate charge/discharge capability is expected.Here,using a modified template-assisted synthesis protocol,which features an in-situ entrapment of both titanium and niobium species during the formation of polymeric microsphere followed by a pyrolysis process,we succeed in preparing hollow microspheres of titanium niobium oxide with high efficiency in structural control.When used as an anode material,the structurally-controlled hollow sample delivers high reversible capacity(103.7 m A h g^(-1)at 50 C)and extraordinary cycling capability especially at high charge/discharge currents(164.7 m A h g^(-1)after 500 cycles at 10 C).展开更多
Core-shell nanostructiKes have found broad potentials in a large variety of applications including catalysis, biomedicine, and energy conversion/storage devices [1,2]. The unique structural configuration endows the co...Core-shell nanostructiKes have found broad potentials in a large variety of applications including catalysis, biomedicine, and energy conversion/storage devices [1,2]. The unique structural configuration endows the compos让e a capability to combine advantages of both core and shell materials, and deliver optimized properties through a rational design of the components [3]. Accordingly, numerous research efforts have been directed to the synthesis control of the coating materials to build desired nanoshells. Particularly, silica-based core-shell structures have witnessed enormous success benefiting from the flexible synthesis capability ensured by the Stober process, which provides favorable growth kinetics in solution to build precise configuration of silica nanoshells su让ed for their applications, for example, silica-based nanocapsules for controlled drug delivery [4].展开更多
基金supported by the National Natural Science Foundation of China(21931012,22025507,22109052)Guangdong Basic and Applied Basic Research Foundation(2022B1515020001)+1 种基金Guangzhou Science and Technology Program(202201010703)the Fundamental Research Funds for the Central Universities(21621033)。
文摘Hollow carbon-based nanostructures(HCNs)have found broad applications in various fields,particularly rechargeable batteries.However,the syntheses of HCNs usually rely on template methods,which are time-consuming,low-yield,and environmentally detrimental.Metal-organic frameworks(MOFs),constructed by organic ligands and inorganic metal nodes,have been identified as effective platforms for preparing HCNs without adding extra templates.This review summarized the recent progress in template-free synthesis of HCNs enabled by MOFs and their applications in rechargeable batteries.Different template-free strategies were introduced first with mechanistic insights into the hollowing mechanism.Then the electrochemical performances of the HCNs were discussed with highlight on the structure-function correlation.It is found that the built-in cavities and nonporous for HCNs is of critical importance to increase the storage sites for high capacity,to enhance charge and mass transport kinetics for high-rate capability,and to ensure the resilient electrode structure for stable cycling.Finally,the challenges and opportunities regarding MOFs-derived HCNs and their applications in rechargeable batteries were discussed.
基金supported by the National Natural Science Foundation of China(Nos.22025507 and 21931012)the Key Research Program of Frontier Sciences,CAS(ZDBS-LY-SLH020)Beijing National Laboratory for Molecular Sciences(BNLMSCXXM-202010).
文摘Charging the LiCoO_(2)(LCO)cathode to a higher voltage,for example 4.5 V compared to the commonly used 4.2 V,is now intensively pursued so as to achieve a higher specific capacity.However,it suffers severe surface structural degradation and detrimental interfacial side reactions between cathode and electrolyte,which lead to the fast capacity fading during long-term cycling.Here,a surface coating strategy was developed for the protection of 4.5 V LCO by constructing a manganese oxides(MOs)nanoshell around LCO particles,which was achieved through a solution-based coating process with success in controlling the growth kinetics of the coating species.We found that the introduction of the MOs nanoshell is highly effective in alleviating the organic electrolyte decomposition at the cathode surface,thus ensuring a much more stable LiF-rich cathode-electrolyte interface and an obvious lower interfacial resistance during electrochemical cycling.Meanwhile,this protection layer can effectively improve the structural stability of the cathode by hindering the cracks formation and structural degradation of LCO particles.Therefore,the MOs modified LCO exhibited excellent rate performance and a high discharge capacity retention of 81.5%after 100 cycles at 1 C compared with the untreated LCO(55.2%),as well as the improved thermal stability and cyclability at the elevated temperature.It is expected that this discovery and fundamental understanding of the surface chemistry regulation strategy provide promising insights into improving the reversibility and stability of LCO cathode at the cut-off voltage of 4.5 V.
基金financially supported by the National Natural Science Foundation of China (Nos. 22025507 and 21931012)the Key Research Program of Frontier Sciences, CAS (No. ZDBS-LY-SLH020)Beijing National Laboratory for Molecular Sciences (No. BNLMS-CXXM-202010)。
文摘All-solid-state batteries(ASSBs) hold great promise for next-generation energy storage technologies owing to their advantage in different aspects such as energy density,safety,and wide temperature tolerance.However,the use of solid-state electrolytes(SSEs) instead of liquid ones meanwhile brings serious concerns related to the point-to-point contact between SSEs and electrodes,which is known to result in high interface resistance and inhomogeneous distribution of charges during the Li^(+)plating/stripping process,eventually leading to a premature failure of ASSBs.This review focuses on the garnet-type SSEs in the formula of Li_(7)La_(3)Zr_(2)O_(12)(LLZO),and discusses the structure-performance relationship of this ceramic electrolyte in detail to achieve a clear understanding of its Li^(+)transmission mechanism.Meanwhile,the challenges of cubic phase LLZO(c-LLZO) for their application in solidstate batteries(SSBs) are demonstrated by the Li/LLZO interface,which features the importance of Li metal wettability and dendrite suppression for sustainable performance.Furthermore,this review summarizes the recent research strategies to combat these contact issues at the Li/LLZO interface,highlighting the essential role played by surface modification of LLZO electrolytes.Following the obtained insights,perspectives for future research on LLZO to accelerate its potential development of SSBs in commercialized applications are also provided.
基金supported by the National Natural Science Foundation of China (51672282, 21373238)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09010101)
文摘Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a composite oxide seriously limits its practical capacity,which becomes a serious concern especially when a high rate charge/discharge capability is expected.Here,using a modified template-assisted synthesis protocol,which features an in-situ entrapment of both titanium and niobium species during the formation of polymeric microsphere followed by a pyrolysis process,we succeed in preparing hollow microspheres of titanium niobium oxide with high efficiency in structural control.When used as an anode material,the structurally-controlled hollow sample delivers high reversible capacity(103.7 m A h g^(-1)at 50 C)and extraordinary cycling capability especially at high charge/discharge currents(164.7 m A h g^(-1)after 500 cycles at 10 C).
基金supported by the National Natural Science Foundation of China (51672282)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09010101)
文摘Core-shell nanostructiKes have found broad potentials in a large variety of applications including catalysis, biomedicine, and energy conversion/storage devices [1,2]. The unique structural configuration endows the compos让e a capability to combine advantages of both core and shell materials, and deliver optimized properties through a rational design of the components [3]. Accordingly, numerous research efforts have been directed to the synthesis control of the coating materials to build desired nanoshells. Particularly, silica-based core-shell structures have witnessed enormous success benefiting from the flexible synthesis capability ensured by the Stober process, which provides favorable growth kinetics in solution to build precise configuration of silica nanoshells su让ed for their applications, for example, silica-based nanocapsules for controlled drug delivery [4].
