Lithium metal attracts growing attention as an ideal anode candidate for next generation lithium battery systems owing to its high capacity,low density,and low working potential.However,the volume expansion of the bul...Lithium metal attracts growing attention as an ideal anode candidate for next generation lithium battery systems owing to its high capacity,low density,and low working potential.However,the volume expansion of the bulk and dendrite growth on the surface of lithium anode limits its practical application.Herein,we fabricate a composite lithium host featuring both multiple scaled structure and lithiophilic property to address obstacles at both aspects of bulk and surface simultaneously.In which,the multiple scaled structure provides void space to accommodate lithium volume change while zinc and cobalt oxides sites derived from Zeolitic Imidazolate Frameworks can react with lithium and form a stable solid electrolyte interphase,leading to a stable cycling of lithium symmetrical cell for more than 500 cycles with voltage hysteresis of only 88 mV at 2 mAcm^-2 and 5 mAh cm^-2.Moreover,full cells paired with LiFePO4 cathode can realize 500 cycles with 99.2%capacity retention,showing great potential for practical applications.The excellent electrochemical performance of the composite lithium anode proves the effectiveness of our anode design with multiple scaled structure and lithiophilic feature,which can be also expanded to other metal anodes for batteries.展开更多
Metal skeletons,such as Nickel Foam(NF) has attracted worldwide interests as stable host for lithium metal anode because of its high stability,large specific surface area and high conductivity.However,most metal skele...Metal skeletons,such as Nickel Foam(NF) has attracted worldwide interests as stable host for lithium metal anode because of its high stability,large specific surface area and high conductivity.However,most metal skeletons have lithophobic surface and uneven current distribution that result in sporadic lithium nucleation and uncontrolled dendrites growth.Herein,we describe a sequential immersing strategy to generate interwoven Nickel(Ⅱ)-dimethylglyoxime(Ni-DMG) nanowires at NF to obtain composite skeleton(NDNF),which can be used as an stable host for Li metal storage.The Ni-DMG has proved effective to realize uniform lithium nucleation and dendrite-free lithium deposition.Combing with the three dimensional(3 D) hierarchical porous structure,the composite host shows a significantly improved coulombic efficiency(CE) than pristine commercial nickel foam.Moreover,the corresponding Li‖Li symmetrical cells can run more than 700 h with low voltage hysteresis 22 mV at 1.0 mA/cm^(2),and Li@NDNF‖LiFePO;full-cell exhibits a high capacity retention of 82.03% at 1.0 C during 630 cycles.These results proved the effectiveness of metal-organic complexes in governing Li metal growth and can be employed as a new strategy for dendrite-free Li metal anode and safe Li metal batteries(LMBs).展开更多
Polymer electrolytes a re essential for next-gene ration lithium batteries because of their excellent safety record.However,low ionic conductivity is the main obstacle restricting their commercial application.Composit...Polymer electrolytes a re essential for next-gene ration lithium batteries because of their excellent safety record.However,low ionic conductivity is the main obstacle restricting their commercial application.Composites with nanoparticles are a promising route to overcome this obstacle.In this work,lithium polystyrene sulfonate brushes(LiPSS)is anchored to silicon dioxide nanoparticles with chemical bonding using atom transfer radial polymerization(SI-ATRP).The composite polymer electrolytes are made by mixing vinylene carbonate and nanoparticles via a facile in situ polymerization process.The ionic conductivity of composite polymer electrolytes is improved to 7.2×10^-4 S/cm at room temperature,which is attributed to the low degree of crystallinity of polymer electrolyte and the fast ion transport on the surfaces of polymer brush layers that act as a conductive network.The composite polymer electrolytes show a wide electrochemical window of approximately 4.5 V vs.Li^+/Li and excellent cycling performance retention of approximately 95%after 100 cycles at ambient temperature.The results also prove that surface groups of ceramic na noparticles are an important way to increase the electrochemical properties of composite polymer electrolytes.展开更多
The development of the solid-state polymer electrolytes (SPEs) for Li-ion batteries (LIBs) can effectively address the hidden safety issues of commercially used liquid electrolytes.Nevertheless,the unsatisfactory room...The development of the solid-state polymer electrolytes (SPEs) for Li-ion batteries (LIBs) can effectively address the hidden safety issues of commercially used liquid electrolytes.Nevertheless,the unsatisfactory room temperature ion conductivity and inferior mechanical strength for linear PEO-based SPEs are still the immense obstacles impeding the further applications of SPEs for large-scale commercialization.Herein,we fabricate a series of semi-interpenetrating-network (semi-IPN) polymer electrolytes based on a novel liquid crystal (C6M LC) and poly(ethylene glycol) diglycidyl ether (PEGDE) via UV-irradiation at the first time.The LCs not only highly improve the mechanical properties of electrolyte membranes via the construction of network structure with PEGDE,but also create stable ion transport channels for ion conduction.As a result,a free-standing flexible SPE shows outstanding ionic conductivity(5.93×10^(-5) S cm^(-1) at 30℃),a very wide electrochemical stability window of 5.5 V,and excellent thermal stability at thermal decomposition temperatures above 360℃ as well as the capacity of suppressing lithium dendrite growth.Moreover,the LiFePO_(4)/Li battery assembled with the semi-IPN electrolyte membranes exhibits good cycle performance and admirable reversible specific capacity.This work highlights the obvious advantages of LCs applied to the electrolyte for the advanced solid lithium battery.展开更多
Despite promising characteristics such as high specific energy and low cost,current Li-S batteries fall short in cycle life.Improving the cycling stability of S cathodes requires immobilizing the lithium polysulfide ...Despite promising characteristics such as high specific energy and low cost,current Li-S batteries fall short in cycle life.Improving the cycling stability of S cathodes requires immobilizing the lithium polysulfide （LPS） intermediates as well as accelerating their redox kinetics.Although many materials have been explored for trapping LPS,the ability to promote LPS redox has attracted much less attention.Here,we report for the first time on transition metal phosphides as effective host materials to enhance both LPS adsorption and redox.Integrating MoP-nanoparticle-decorated carbon nanotubes with S deposited on graphene oxide,we enable Li-S battery cathodes with substantially improved cycling stability and rate capability.Capacity decay rates as low as 0.017% per cycle over 1,000 cycles can be realized.Stable and high areal capacity （〉 3 mAh＆#183;cm-2） can be achieved under high mass loading conditions.Comparable electrochemical performance can also be achieved with analogous material structures based on CoP,demonstrating the potential of metal phosphides for long-cycle Li-S batteries.展开更多
Li metal anodes have attracted tremendous attention in the last decade because of their high theoretical capacities and low electrochemical potentials.However,until now,there has only been limited success in improving...Li metal anodes have attracted tremendous attention in the last decade because of their high theoretical capacities and low electrochemical potentials.However,until now,there has only been limited success in improving the interfacial and structural stabilities and in realizing the highly controllable and large-scale fabrication of this emerging material;these limitations have posed great obstacles to further performing fundamental and applied studies in Li metal anodes.In this review,we focus on summarizing the existing challenges of Li metal anodes based on the leap from coin cells to pouch cells and on outlining typical methods for designing Li metal anodes on demand;we controllably engineer their surface protection layers and structure sizes by encapsulating structured Li metal inside a variety of synthetic protection layers.We aim to provide a comprehensive understanding and serve as a strategic guide for designing and fabricating practicable Li metal anodes for use in pouch batteries.Challenges and opportunities regarding this burgeoning field are critically evaluated at the end of this review.展开更多
Solid-state Li metal battery has attracted increasing interests for its potentiallyhigh energy density and excellent safety assurance, which is a promising candidatefor next generation battery system. However, the low...Solid-state Li metal battery has attracted increasing interests for its potentiallyhigh energy density and excellent safety assurance, which is a promising candidatefor next generation battery system. However, the low ionic conductivityand Li^(+) transport number of solid-state polymer electrolytes limit their practicalapplication. Herein, a composite polymer electrolyte with self-insertedstructure is proposed using the layered double hydroxides (LDHs) as dopant toachieve a fast Li^(+) transport channel in poly(vinylidene-co-trifluoroethylene) [P(VDF-TrFE)] based polymer electrolyte. In such a composite electrolyte, P(VDF-TrFE) polymer has an all-trans conformation, in which all fluorineatoms locate on one side of the polymer chain, providing fast Li^(+) transporthighways. Meanwhile, the LDH can immobilize the anions of Li salts based onthe electrostatic interactions, promoting the dissociation of Li salts, therebyenhancing the ionic conductivity (6.4 × 10^(-4) S cm^(-1)) and Li^(+) transferencenumber (0.76). The anion immobilization effect can realize uniform electricfield distribution at the anode surface and suppress the dendritic Li growth.Moreover, the hydrogen bonding interaction between LDH and polymerchains also endows the composite electrolyte with strong mechanical properties.Thus, at room temperature, the Li jj Li symmetric cells can be stablycycled over 1000 h at a current density of 0.2 mA cm^(-2), and the full cells withLiFePO_(4) cathode deliver a high capacity retention (>95%) after 200 cycles. This work offers a promising route to construct solid-state polymer electrolytes withfast Li^(+) transport.展开更多
基金the National Natural Science Foundation of China(21771018,21875004)Beijing University of Chemical Technology(start-up grant buctrc201901,BUCT,China)Technology Innovation Project of New Energy Vehicles Industry and Pulead Technology Industry Co.Ltd。
文摘Lithium metal attracts growing attention as an ideal anode candidate for next generation lithium battery systems owing to its high capacity,low density,and low working potential.However,the volume expansion of the bulk and dendrite growth on the surface of lithium anode limits its practical application.Herein,we fabricate a composite lithium host featuring both multiple scaled structure and lithiophilic property to address obstacles at both aspects of bulk and surface simultaneously.In which,the multiple scaled structure provides void space to accommodate lithium volume change while zinc and cobalt oxides sites derived from Zeolitic Imidazolate Frameworks can react with lithium and form a stable solid electrolyte interphase,leading to a stable cycling of lithium symmetrical cell for more than 500 cycles with voltage hysteresis of only 88 mV at 2 mAcm^-2 and 5 mAh cm^-2.Moreover,full cells paired with LiFePO4 cathode can realize 500 cycles with 99.2%capacity retention,showing great potential for practical applications.The excellent electrochemical performance of the composite lithium anode proves the effectiveness of our anode design with multiple scaled structure and lithiophilic feature,which can be also expanded to other metal anodes for batteries.
基金financially supported by PULEAD Technology Industry Co.,Ltd.,the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB36000000)the National Key Research and Development Program of China (No. 2016YFA0200904)+3 种基金the National Natural Science Foundation of China (Nos. 21771018and 21875004)the Natural Science Foundation of Beijing (No.2192018)National Natural Science Foundation of China-Regional Innovation Joint Exploration Fund (No. U19A2019)Beijing University of Chemical Technology (Start-up grant No. buctrc201901,BUCT, China)。
文摘Metal skeletons,such as Nickel Foam(NF) has attracted worldwide interests as stable host for lithium metal anode because of its high stability,large specific surface area and high conductivity.However,most metal skeletons have lithophobic surface and uneven current distribution that result in sporadic lithium nucleation and uncontrolled dendrites growth.Herein,we describe a sequential immersing strategy to generate interwoven Nickel(Ⅱ)-dimethylglyoxime(Ni-DMG) nanowires at NF to obtain composite skeleton(NDNF),which can be used as an stable host for Li metal storage.The Ni-DMG has proved effective to realize uniform lithium nucleation and dendrite-free lithium deposition.Combing with the three dimensional(3 D) hierarchical porous structure,the composite host shows a significantly improved coulombic efficiency(CE) than pristine commercial nickel foam.Moreover,the corresponding Li‖Li symmetrical cells can run more than 700 h with low voltage hysteresis 22 mV at 1.0 mA/cm^(2),and Li@NDNF‖LiFePO;full-cell exhibits a high capacity retention of 82.03% at 1.0 C during 630 cycles.These results proved the effectiveness of metal-organic complexes in governing Li metal growth and can be employed as a new strategy for dendrite-free Li metal anode and safe Li metal batteries(LMBs).
基金financially supported by PULEAD Technology Industry Co.,Ltd.the National Natural Science Foundation of China(Nos.21771018,21875004)。
文摘Polymer electrolytes a re essential for next-gene ration lithium batteries because of their excellent safety record.However,low ionic conductivity is the main obstacle restricting their commercial application.Composites with nanoparticles are a promising route to overcome this obstacle.In this work,lithium polystyrene sulfonate brushes(LiPSS)is anchored to silicon dioxide nanoparticles with chemical bonding using atom transfer radial polymerization(SI-ATRP).The composite polymer electrolytes are made by mixing vinylene carbonate and nanoparticles via a facile in situ polymerization process.The ionic conductivity of composite polymer electrolytes is improved to 7.2×10^-4 S/cm at room temperature,which is attributed to the low degree of crystallinity of polymer electrolyte and the fast ion transport on the surfaces of polymer brush layers that act as a conductive network.The composite polymer electrolytes show a wide electrochemical window of approximately 4.5 V vs.Li^+/Li and excellent cycling performance retention of approximately 95%after 100 cycles at ambient temperature.The results also prove that surface groups of ceramic na noparticles are an important way to increase the electrochemical properties of composite polymer electrolytes.
基金supported by the National Natural Science Foundation of China(No.52073285 and No.11975238)。
文摘The development of the solid-state polymer electrolytes (SPEs) for Li-ion batteries (LIBs) can effectively address the hidden safety issues of commercially used liquid electrolytes.Nevertheless,the unsatisfactory room temperature ion conductivity and inferior mechanical strength for linear PEO-based SPEs are still the immense obstacles impeding the further applications of SPEs for large-scale commercialization.Herein,we fabricate a series of semi-interpenetrating-network (semi-IPN) polymer electrolytes based on a novel liquid crystal (C6M LC) and poly(ethylene glycol) diglycidyl ether (PEGDE) via UV-irradiation at the first time.The LCs not only highly improve the mechanical properties of electrolyte membranes via the construction of network structure with PEGDE,but also create stable ion transport channels for ion conduction.As a result,a free-standing flexible SPE shows outstanding ionic conductivity(5.93×10^(-5) S cm^(-1) at 30℃),a very wide electrochemical stability window of 5.5 V,and excellent thermal stability at thermal decomposition temperatures above 360℃ as well as the capacity of suppressing lithium dendrite growth.Moreover,the LiFePO_(4)/Li battery assembled with the semi-IPN electrolyte membranes exhibits good cycle performance and admirable reversible specific capacity.This work highlights the obvious advantages of LCs applied to the electrolyte for the advanced solid lithium battery.
文摘Despite promising characteristics such as high specific energy and low cost,current Li-S batteries fall short in cycle life.Improving the cycling stability of S cathodes requires immobilizing the lithium polysulfide （LPS） intermediates as well as accelerating their redox kinetics.Although many materials have been explored for trapping LPS,the ability to promote LPS redox has attracted much less attention.Here,we report for the first time on transition metal phosphides as effective host materials to enhance both LPS adsorption and redox.Integrating MoP-nanoparticle-decorated carbon nanotubes with S deposited on graphene oxide,we enable Li-S battery cathodes with substantially improved cycling stability and rate capability.Capacity decay rates as low as 0.017% per cycle over 1,000 cycles can be realized.Stable and high areal capacity （〉 3 mAh＆#183;cm-2） can be achieved under high mass loading conditions.Comparable electrochemical performance can also be achieved with analogous material structures based on CoP,demonstrating the potential of metal phosphides for long-cycle Li-S batteries.
基金supported by the National Natural Science Foundation of China(Nos.52071227,22109025)the Key Scientific Research Project in Shanxi Province(Grant No.201805D121003)+5 种基金the Special Found Projects for Central Government Guidance to Local Science and Technology Developmentthe Science and Technology Major Projects of Shanxi Province(20191102004)the Fundamental Research Program of Shanxi Province(202103021222006)the Natural Science Foundation of Shanxi Province(2019D111102)the Research Project Supported by Shanxi Scholarship Council of China(HGKY2019085)the Natural Science Foundation of Fujian Province,China(2021J05121).
文摘Li metal anodes have attracted tremendous attention in the last decade because of their high theoretical capacities and low electrochemical potentials.However,until now,there has only been limited success in improving the interfacial and structural stabilities and in realizing the highly controllable and large-scale fabrication of this emerging material;these limitations have posed great obstacles to further performing fundamental and applied studies in Li metal anodes.In this review,we focus on summarizing the existing challenges of Li metal anodes based on the leap from coin cells to pouch cells and on outlining typical methods for designing Li metal anodes on demand;we controllably engineer their surface protection layers and structure sizes by encapsulating structured Li metal inside a variety of synthetic protection layers.We aim to provide a comprehensive understanding and serve as a strategic guide for designing and fabricating practicable Li metal anodes for use in pouch batteries.Challenges and opportunities regarding this burgeoning field are critically evaluated at the end of this review.
基金National Natural Science Foundation of China,Grant/Award Number:52071227Beijing Natural Science Foundation-Xiaomi Innovation Joint Foundation,Grant/Award Number:L223011+6 种基金Key Scientific Research Project in Shanxi Province,Grant/Award Number:201805D121003Special Found Projects for Central Government Guidance to Local Science and Technology Development,Science and Technology Major Projects of Shanxi Province,Grant/Award Number:20191102004Young Elite Scientists Sponsorship Program,Grant/Award Number:CAST(2022QNRC001)Fundamental Research Program of Shanxi Province,Grant/Award Number:202103021222006Shanxi Energy Internet Research Institute,Grant/Award Number:SXEI2023A004Shanxi Scholarship Council of China,Grant/Award Number:HGKY2019085Open Research Fund of Guangdong Advanced Carbon Materials Co.,Ltd,Grant/Award Number:Kargen-2024B0905。
文摘Solid-state Li metal battery has attracted increasing interests for its potentiallyhigh energy density and excellent safety assurance, which is a promising candidatefor next generation battery system. However, the low ionic conductivityand Li^(+) transport number of solid-state polymer electrolytes limit their practicalapplication. Herein, a composite polymer electrolyte with self-insertedstructure is proposed using the layered double hydroxides (LDHs) as dopant toachieve a fast Li^(+) transport channel in poly(vinylidene-co-trifluoroethylene) [P(VDF-TrFE)] based polymer electrolyte. In such a composite electrolyte, P(VDF-TrFE) polymer has an all-trans conformation, in which all fluorineatoms locate on one side of the polymer chain, providing fast Li^(+) transporthighways. Meanwhile, the LDH can immobilize the anions of Li salts based onthe electrostatic interactions, promoting the dissociation of Li salts, therebyenhancing the ionic conductivity (6.4 × 10^(-4) S cm^(-1)) and Li^(+) transferencenumber (0.76). The anion immobilization effect can realize uniform electricfield distribution at the anode surface and suppress the dendritic Li growth.Moreover, the hydrogen bonding interaction between LDH and polymerchains also endows the composite electrolyte with strong mechanical properties.Thus, at room temperature, the Li jj Li symmetric cells can be stablycycled over 1000 h at a current density of 0.2 mA cm^(-2), and the full cells withLiFePO_(4) cathode deliver a high capacity retention (>95%) after 200 cycles. This work offers a promising route to construct solid-state polymer electrolytes withfast Li^(+) transport.
