The high specific capacity and low negative electrochemical potential of lithium metal anodes(LMAs),may allow the energy density threshold of Li metal batteries(LMBs)to be pushed higher.However,the existing detrimenta...The high specific capacity and low negative electrochemical potential of lithium metal anodes(LMAs),may allow the energy density threshold of Li metal batteries(LMBs)to be pushed higher.However,the existing detrimental issues,such as dendritic growth and volume expansion,have hindered the practical implementation of LMBs.Introducing three-dimensional frameworks(e.g.,copper and nickel foam),have been regarded as one of the fundamental strategies to reduce the local current density,aiming to extend the Sand'time.Nevertheless,the local environment far from the skeleton is almost the same as the typical plane Li,due to macroporous space of metal foam.Herein,we built a double-layered 3D current collector of Li alloy anchored on the metal foam,with micropores interconnected macropores,via a viable thermal infiltration and cooling strategy.Due to the excellent electronic and ionic conductivity coupled with favorable lithiophilicity,the Li alloy can effectively reduce the nucleation barrier and enhance the Li^(+)transportation rate,while the metal foam can role as the primary promotor to enlarge the surface area and buffer the dimensional variation.Synergistically,the Li composite anode with hierarchical structure of primary and secondary scaffolds realized the even deposition behavior and minimum volume expansion,outputting preeminent prolonged cycling performances under high rate.展开更多
Constructing a smart polymer film with favorable lithium(Li)transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy.Unfortunately,the porosity and the swelling of th...Constructing a smart polymer film with favorable lithium(Li)transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy.Unfortunately,the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film,severely deteriorating the cyclic performance.Herein,we propose a defectfree hybrid film that consists of Li+conductive lithium polyacrylate(LiPAA)polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film.The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches,enhancing the integrity of LiPAA film.Consequently,a defect-free hybrid film is nailed flat against the Li metal anode,exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect.This facile strategy produces a promising anode for next generation Li batteries.展开更多
Infinite volume expansion and uncontrolled lithium dendrite growth are the main bottlenecks that greatly hinder the commercial application of lithium metal anodes.Herein,derived from zeolitic imidazolate framework(ZIF...Infinite volume expansion and uncontrolled lithium dendrite growth are the main bottlenecks that greatly hinder the commercial application of lithium metal anodes.Herein,derived from zeolitic imidazolate framework(ZIF)-67,carbon nanotubes(CNTs)-wrapped and CoP/Co_(2)P uniformly distributed nitrogen-doped hollow porous polyhedron carbon(CNT-CoP@NC)is elaborately designed as lithium metal host.A hybrid of N-doping and metallic phosphides modifications improves the lithiophilicity and reduces the nucleation barrier,consequently leading to homogeneous nucleation and smooth deposition of metallic lithium,thus suppresses the growth of Li dendrites.Meanwhile,self-generated CNTs arrays efficiently reduce the local current density.Moreover,the reduced lithium is preferentially deposited into the hollow structure of CNT-CoP@NC and then filled the voids among the CNT-CoP@NC particles.This all-pervasive Li plating design can not only alleviate the volume effect,but also maximize the anode space utilization.Benefiting from these synergistic modulations,even with an ultra-thin(7.2μm)anode layer of CNT-CoP@NC host,a high Coulombic efficiency for more than 400 cycles and an extended lifespan of 1,700 h under 1 mA·cm^(−2)can be achieved.When paired with a competitive high mass loading(17.1 mg·cm^(−2))LiFePO4 cathode,a superb cycling stability(126.7 mAh·g^(−1)over 550 cycles)is recorded at 1 C.展开更多
The commercialization of rechargeable Li metal batteries is hindered by dendrite growth and volumetric variation. Herein, we report a Li-rich dual-phase Li-Cu alloy with built-in 3 D conductive skeleton to replace con...The commercialization of rechargeable Li metal batteries is hindered by dendrite growth and volumetric variation. Herein, we report a Li-rich dual-phase Li-Cu alloy with built-in 3 D conductive skeleton to replace conventional planar Li anode. The Li-Cu alloy is simply prepared by fusion of Li and Cu metals at a relatively low-temperature of 500 °C, followed by a cooling process where phase-segregation leads to metallic Li phase distributed in the network of LiCu_x solid solution phase. Different from the common Li alloy, the electrochemical alloying reaction between Li and Cu metals is not observed. Therefore, the lithiophilic LiCu_x nanowires guides conformal plating of Li and the porous framework provides superior dimensional stability for the anode. This unique ferroconcrete-like structure of Li-Cu alloy enables dendrite-free Li plating for an expanded cycling lifetime. Constructing a new type of Li alloy with in situ formed electrochemically inactive framework is a promising and easily scaled-up strategy toward practical application of Li metal anodes.展开更多
The integration of solid-polymer electrolytes into all-solid-state lithium batteries is highly desirable to overcome the limitations of current battery configurations that have a low energy density and severe safety c...The integration of solid-polymer electrolytes into all-solid-state lithium batteries is highly desirable to overcome the limitations of current battery configurations that have a low energy density and severe safety concerns.Polyacrylonitrile is an appealing matrix for solid-polymer electrolytes;however,the practical utilization of such polymer electrolytes in all-solid-state cells is impeded by inferior ionic conductivity and instability against a lithium-metal anode.In this work,we show that a polymer-in-salt electrolyte based on polyacrylonitrile with a lithium salt as the major component exhibits a wide electrochemically stable window,a high ionic conductivity,and an increased lithium-ion transference number.The growth of dendrites from the lithium-metal anode was suppressed effectively by the polymer-in-salt electrolyte to increase the safety features of the batteries.In addition,we found that a stable interphase was formed between the lithium-metal anode and the polymer-in-salt electrolyte to restrain the uncontrolled parasitic reactions,and we demonstrated an all-solid-state battery configuration with a LiFePO4 cathode and the polymer-in-salt electrolyte,which exhibited a superior cycling stability and rate capability.展开更多
Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface are...Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface area and large pore size of few hundred micrometers.In this work,a network of Li_(x)Cu solid solution alloy nanowires is in situ formed via infiltrating molten Li-Cu alloy into Ni foam and subsequent cooling treatment,whereby a three-component composite anode consisting of Li metal,Li_(x)Cu alloy,and Ni foam is fabricated.The Li_(x)Cu nanowires nested as secondary frame split the macropores into micropores,enlarging the active surface area and inducing uniform Li deposition significantly.The lithiophilicity of the alloy wires and the shrunken void size built by the hierarchical architecture can further tune the nucleation and growth behavior of Li.The multiscale synergetic effect between the primary and secondary scaffold guarantees the composite anode sheet with extraordinarily long-term cycling stability even under high current rates.展开更多
Constructing a three-dimensional(3D)multifunctional hosting architecture and subsequent thermal infusion of molten Li to produce advanced Li composite is an effective strategy for stable Li metal anode.However,the pur...Constructing a three-dimensional(3D)multifunctional hosting architecture and subsequent thermal infusion of molten Li to produce advanced Li composite is an effective strategy for stable Li metal anode.However,the pure liquid Li is difficult to spread across the surface of various substrates due to its large surface tension and poor wettability,hindering the production and application of Li composite anode.Herein,heteroatomic Ca is doped into molten Li to generate Li-Ca alloy,which greatly regulates the surface tension of the molten alloy and improves the wettability against carbon cloth(CC).Moreover,a secondary network composed of CaLi2 intermetallic compound with interconnected ant-nest-like lithiophilic channels is in situ formed and across the primary scaffold of CC matrix by infiltrating molten Li-Ca alloy into CC and then cooling treatment(LCAC),which has a larger and lithiophilic surface to enable uniform Li deposition into interior space of the hybrid scaffold without Li dendrites.Therefore,LCAC exhibits a long-term lifespan for 1100 h under a current density of 5 mA cm^(-2)with fixed areal capacity of 5 mAh cm^(-2).Remarkably,full cells paired with practical-level LiFePO4 cathode of 2.45 mAh cm^(-2)deliver superior performance.展开更多
基金supported by Huzhou Natural Science Foundation Project(Nos.2022YZ04 and 2022YZ21)S&T Special Program of Huzhou(No.2023GZ03)National Natural Science Foundation of China(No.52172184)。
文摘The high specific capacity and low negative electrochemical potential of lithium metal anodes(LMAs),may allow the energy density threshold of Li metal batteries(LMBs)to be pushed higher.However,the existing detrimental issues,such as dendritic growth and volume expansion,have hindered the practical implementation of LMBs.Introducing three-dimensional frameworks(e.g.,copper and nickel foam),have been regarded as one of the fundamental strategies to reduce the local current density,aiming to extend the Sand'time.Nevertheless,the local environment far from the skeleton is almost the same as the typical plane Li,due to macroporous space of metal foam.Herein,we built a double-layered 3D current collector of Li alloy anchored on the metal foam,with micropores interconnected macropores,via a viable thermal infiltration and cooling strategy.Due to the excellent electronic and ionic conductivity coupled with favorable lithiophilicity,the Li alloy can effectively reduce the nucleation barrier and enhance the Li^(+)transportation rate,while the metal foam can role as the primary promotor to enlarge the surface area and buffer the dimensional variation.Synergistically,the Li composite anode with hierarchical structure of primary and secondary scaffolds realized the even deposition behavior and minimum volume expansion,outputting preeminent prolonged cycling performances under high rate.
基金partly supported by the National Natural Science Foundation of China(Nos.22379019 and 52172184)the Science and Technology Department of Sichuan Province of China(No.24GJHZ0444)and S&T Special Program of Huzhou(No.2023GZ03)。
文摘Constructing a smart polymer film with favorable lithium(Li)transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy.Unfortunately,the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film,severely deteriorating the cyclic performance.Herein,we propose a defectfree hybrid film that consists of Li+conductive lithium polyacrylate(LiPAA)polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film.The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches,enhancing the integrity of LiPAA film.Consequently,a defect-free hybrid film is nailed flat against the Li metal anode,exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect.This facile strategy produces a promising anode for next generation Li batteries.
基金supported by the National Natural Science Foundation of China(Nos.21673033 and 52172184)Suining Science and Technology Program(No.2019ZDCGZH003).
文摘Infinite volume expansion and uncontrolled lithium dendrite growth are the main bottlenecks that greatly hinder the commercial application of lithium metal anodes.Herein,derived from zeolitic imidazolate framework(ZIF)-67,carbon nanotubes(CNTs)-wrapped and CoP/Co_(2)P uniformly distributed nitrogen-doped hollow porous polyhedron carbon(CNT-CoP@NC)is elaborately designed as lithium metal host.A hybrid of N-doping and metallic phosphides modifications improves the lithiophilicity and reduces the nucleation barrier,consequently leading to homogeneous nucleation and smooth deposition of metallic lithium,thus suppresses the growth of Li dendrites.Meanwhile,self-generated CNTs arrays efficiently reduce the local current density.Moreover,the reduced lithium is preferentially deposited into the hollow structure of CNT-CoP@NC and then filled the voids among the CNT-CoP@NC particles.This all-pervasive Li plating design can not only alleviate the volume effect,but also maximize the anode space utilization.Benefiting from these synergistic modulations,even with an ultra-thin(7.2μm)anode layer of CNT-CoP@NC host,a high Coulombic efficiency for more than 400 cycles and an extended lifespan of 1,700 h under 1 mA·cm^(−2)can be achieved.When paired with a competitive high mass loading(17.1 mg·cm^(−2))LiFePO4 cathode,a superb cycling stability(126.7 mAh·g^(−1)over 550 cycles)is recorded at 1 C.
基金the National Natural Science Foundation of China (21673033 and 21473022)the Science and Technology Department of Sichuan Province of China (2019YFH0001)the Fundamental Research Funds for the Central Universities (ZYGX2019J024)。
文摘The commercialization of rechargeable Li metal batteries is hindered by dendrite growth and volumetric variation. Herein, we report a Li-rich dual-phase Li-Cu alloy with built-in 3 D conductive skeleton to replace conventional planar Li anode. The Li-Cu alloy is simply prepared by fusion of Li and Cu metals at a relatively low-temperature of 500 °C, followed by a cooling process where phase-segregation leads to metallic Li phase distributed in the network of LiCu_x solid solution phase. Different from the common Li alloy, the electrochemical alloying reaction between Li and Cu metals is not observed. Therefore, the lithiophilic LiCu_x nanowires guides conformal plating of Li and the porous framework provides superior dimensional stability for the anode. This unique ferroconcrete-like structure of Li-Cu alloy enables dendrite-free Li plating for an expanded cycling lifetime. Constructing a new type of Li alloy with in situ formed electrochemically inactive framework is a promising and easily scaled-up strategy toward practical application of Li metal anodes.
基金the United States Department of Energy,Office of Basic Energy Sciences(DE-SC0005397).J.B.G.also acknowledges support from the Robert A.Welch Foundation(F-1066).
文摘The integration of solid-polymer electrolytes into all-solid-state lithium batteries is highly desirable to overcome the limitations of current battery configurations that have a low energy density and severe safety concerns.Polyacrylonitrile is an appealing matrix for solid-polymer electrolytes;however,the practical utilization of such polymer electrolytes in all-solid-state cells is impeded by inferior ionic conductivity and instability against a lithium-metal anode.In this work,we show that a polymer-in-salt electrolyte based on polyacrylonitrile with a lithium salt as the major component exhibits a wide electrochemically stable window,a high ionic conductivity,and an increased lithium-ion transference number.The growth of dendrites from the lithium-metal anode was suppressed effectively by the polymer-in-salt electrolyte to increase the safety features of the batteries.In addition,we found that a stable interphase was formed between the lithium-metal anode and the polymer-in-salt electrolyte to restrain the uncontrolled parasitic reactions,and we demonstrated an all-solid-state battery configuration with a LiFePO4 cathode and the polymer-in-salt electrolyte,which exhibited a superior cycling stability and rate capability.
基金partly supported by the National Natural Science Foundation of China(21673033)Sichuan Science and Technology Program(2020071)the Fundamental Research Founds for the Central Universities(ZYGX2019J024).
文摘Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface area and large pore size of few hundred micrometers.In this work,a network of Li_(x)Cu solid solution alloy nanowires is in situ formed via infiltrating molten Li-Cu alloy into Ni foam and subsequent cooling treatment,whereby a three-component composite anode consisting of Li metal,Li_(x)Cu alloy,and Ni foam is fabricated.The Li_(x)Cu nanowires nested as secondary frame split the macropores into micropores,enlarging the active surface area and inducing uniform Li deposition significantly.The lithiophilicity of the alloy wires and the shrunken void size built by the hierarchical architecture can further tune the nucleation and growth behavior of Li.The multiscale synergetic effect between the primary and secondary scaffold guarantees the composite anode sheet with extraordinarily long-term cycling stability even under high current rates.
基金the National Natural Science Foundation of China(Nos.21673033 and 52172184)the Suining Science and Technology Program(2019ZDCGZH003)the Fundamental Research Funds for the Central Universities(ZYGX2019J024).
文摘Constructing a three-dimensional(3D)multifunctional hosting architecture and subsequent thermal infusion of molten Li to produce advanced Li composite is an effective strategy for stable Li metal anode.However,the pure liquid Li is difficult to spread across the surface of various substrates due to its large surface tension and poor wettability,hindering the production and application of Li composite anode.Herein,heteroatomic Ca is doped into molten Li to generate Li-Ca alloy,which greatly regulates the surface tension of the molten alloy and improves the wettability against carbon cloth(CC).Moreover,a secondary network composed of CaLi2 intermetallic compound with interconnected ant-nest-like lithiophilic channels is in situ formed and across the primary scaffold of CC matrix by infiltrating molten Li-Ca alloy into CC and then cooling treatment(LCAC),which has a larger and lithiophilic surface to enable uniform Li deposition into interior space of the hybrid scaffold without Li dendrites.Therefore,LCAC exhibits a long-term lifespan for 1100 h under a current density of 5 mA cm^(-2)with fixed areal capacity of 5 mAh cm^(-2).Remarkably,full cells paired with practical-level LiFePO4 cathode of 2.45 mAh cm^(-2)deliver superior performance.
