Lithium metal is regarded as the ultimate negative electrode material for secondary batteries due to its high energy density.However,it suffers from poor cycling stability because of its high reactivity with liquid el...Lithium metal is regarded as the ultimate negative electrode material for secondary batteries due to its high energy density.However,it suffers from poor cycling stability because of its high reactivity with liquid electrolytes.Therefore,continuous efforts have been put into improving the cycling Coulombic efficiency(CE)to extend the lifespan of the lithium metal negative electrode.Herein,we report that using dual-salt additives of LiPF_(6) and LiNO_(3) in an ether solvent-based electrolyte can significantly improve the cycling stability and rate capability of a Li-carbon(Li-CNT)composite.As a result,an average cycling CE as high as 99.30% was obtained for the Li-CNT at a current density of 2.5 mA cm^(-2) and an negative electrode to positive electrode capacity(N/P)ratio of 2.The cycling stability and rate capability enhancement of the Li-CNT negative electrode could be attributed to the formation of a better solid electrolyte interphase layer that contains both inorganic components and organic polyether.The former component mainly originates from the decomposition of the LiNO_(3) additive,while the latter comes from the LiPF_(6)-induced ring-opening polymerization of the ether solvent.This novel surface chemistry significantly improves the CE of Li negative electrode,revealing its importance for the practical application of lithium metal batteries.展开更多
Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindra...Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindrances,particularly fast capacity degradation resulting from the migration of dissolved polysulfide intermediates,remain to be significant challenges prior to the practical applications.In this work,a composite interlayer of carbon nanofibers(CNFs)which are enriched by Co-based metal organic frameworks(ZIF-67)growth in-situ is exploited.Notably,physical blocking and chemical trapping abilities are obtained synergistically from the ZIF/CNFs interlayer,which enables to restrain the dissolution of polysulfides and alleviate shuttle effect.Moreover,the three-dimensional fiber networks provide an interconnected conductive framework between each ZIF microreactor to promote fast electron transfer during cycling,thus contributing to excellent rate and cycling performance.As a result,Li-S cells with ZIF/CNFs interlayer show a high specific capacity of 1334 mAh g^(-1) at 1 C with an excellent cycling stability over 300 cycles.Besides,this scalable and affordable electrospinning fabrication method provides a promising approach for the design of MOFs-derived carbon materials for high performance Li-S batteries.展开更多
Organic-based electrode materials for lithium-ion batteries (LIBs) are promising due to their high theoretical capacity,structure versatility and environmental benignity.However,the poor intrinsic electric conductivit...Organic-based electrode materials for lithium-ion batteries (LIBs) are promising due to their high theoretical capacity,structure versatility and environmental benignity.However,the poor intrinsic electric conductivity of most polymers results in slow reaction kinetics and hinders their application as electrode materials for LIBs.A binder-free self-supporting organic electrode with excellent redox kinetics is herein demonstrated via in situ polymerization of a uniform thin polyimide (PI) layer on a porous and highly conductive carbonized nanofiber (CNF) framework.The PI active material in the porous PI@CNF film has large physical contact area with both the CNF and the electrolyte thus obtains superior electronic and ionic conduction.As a result,the PI@CNF cathode exhibits a discharge capacity of 170 mAh·g^-1 at 1 C (175 mA·g^-1),remarkable rate-performance (70.5% of 0.5 C capacity can be obtained at a 100 C discharge rate),and superior cycling stability with 81.3% capacity retention after 1,000 cycles at 1 C.Last but not least,a four-electron transfer redox process of the PI polymer was realized for the first time thanks to the excellent redox kinetics of the PI@CNF electrode,showing a discharge capacity exceeding 300 mAh·g^-1 at a current of 175 mA·g^-1.展开更多
Li has been considered as the ultimate anode material for high energy density secondary Li batteries.However,its practical application has been limited due to its low Coulombic efficiency(CE)and the formation of lithi...Li has been considered as the ultimate anode material for high energy density secondary Li batteries.However,its practical application has been limited due to its low Coulombic efficiency(CE)and the formation of lithium dendrites.Recently,we have developed a microspherical Li-carbon nanotube(Li-CNT)composite material passivated with octadecylphosphonic acid(OPA)self-assembled monolayer(SAM)exhibiting suppressed lithium dendrite formation and improved environmental/electrochemical stability.In this work,we demonstrated the significantly enhanced passivation effects of a SAM using dihexadecanoalkyl phosphate(DHP),a molecule that is comprised of double hydrophobic alkyl chains and forms a denser SAM on surfaces with large curvature.As a result,the DHP SAM delivers superior environmental and electrochemical stability to the OPA passivated Li-CNT material.In specific,the DHP passivated Li-CNT composite(DHP-Li-CNT)delivers a high CE of 99.25%under a 33.3%depth of discharge(DOD)at 1 C,when it is paired with a LiFePO4 cathode.The evolution of the SAM during cycling and the effects of DOD and current density on the CE of the DHP-Li-CNT anode have also been investigated.The improved SAM passivation constitutes an important step in achieving the goal of practically applicable Li anodes.展开更多
基金supported by the National Natural Science Foundation of China(21625304,21733012,and 21772190)the Ministry of Science and Technology of China(2016YFB0100102)。
基金the National Natural Science Foundation of China(Grant nos.21625304 and 21733012)the Ministry of Science and Technology(Grant No.2016YFA0200703).
文摘Lithium metal is regarded as the ultimate negative electrode material for secondary batteries due to its high energy density.However,it suffers from poor cycling stability because of its high reactivity with liquid electrolytes.Therefore,continuous efforts have been put into improving the cycling Coulombic efficiency(CE)to extend the lifespan of the lithium metal negative electrode.Herein,we report that using dual-salt additives of LiPF_(6) and LiNO_(3) in an ether solvent-based electrolyte can significantly improve the cycling stability and rate capability of a Li-carbon(Li-CNT)composite.As a result,an average cycling CE as high as 99.30% was obtained for the Li-CNT at a current density of 2.5 mA cm^(-2) and an negative electrode to positive electrode capacity(N/P)ratio of 2.The cycling stability and rate capability enhancement of the Li-CNT negative electrode could be attributed to the formation of a better solid electrolyte interphase layer that contains both inorganic components and organic polyether.The former component mainly originates from the decomposition of the LiNO_(3) additive,while the latter comes from the LiPF_(6)-induced ring-opening polymerization of the ether solvent.This novel surface chemistry significantly improves the CE of Li negative electrode,revealing its importance for the practical application of lithium metal batteries.
基金financially supported by the National Natural Science Foundation of China(51971080)the Natural Science Foundation of Guangdong Province,China(2018A030313182)+1 种基金Shenzhen Bureau of Science,Technology and Innovation Commission(JCYJ20170811154527927)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources。
文摘Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindrances,particularly fast capacity degradation resulting from the migration of dissolved polysulfide intermediates,remain to be significant challenges prior to the practical applications.In this work,a composite interlayer of carbon nanofibers(CNFs)which are enriched by Co-based metal organic frameworks(ZIF-67)growth in-situ is exploited.Notably,physical blocking and chemical trapping abilities are obtained synergistically from the ZIF/CNFs interlayer,which enables to restrain the dissolution of polysulfides and alleviate shuttle effect.Moreover,the three-dimensional fiber networks provide an interconnected conductive framework between each ZIF microreactor to promote fast electron transfer during cycling,thus contributing to excellent rate and cycling performance.As a result,Li-S cells with ZIF/CNFs interlayer show a high specific capacity of 1334 mAh g^(-1) at 1 C with an excellent cycling stability over 300 cycles.Besides,this scalable and affordable electrospinning fabrication method provides a promising approach for the design of MOFs-derived carbon materials for high performance Li-S batteries.
基金the "Strategic Priority Research Program:of the CAS (No.XDA09010600)the National Natural Science Foundation of China (Nos.21473242,21625304 and 21733012).
文摘Organic-based electrode materials for lithium-ion batteries (LIBs) are promising due to their high theoretical capacity,structure versatility and environmental benignity.However,the poor intrinsic electric conductivity of most polymers results in slow reaction kinetics and hinders their application as electrode materials for LIBs.A binder-free self-supporting organic electrode with excellent redox kinetics is herein demonstrated via in situ polymerization of a uniform thin polyimide (PI) layer on a porous and highly conductive carbonized nanofiber (CNF) framework.The PI active material in the porous PI@CNF film has large physical contact area with both the CNF and the electrolyte thus obtains superior electronic and ionic conduction.As a result,the PI@CNF cathode exhibits a discharge capacity of 170 mAh·g^-1 at 1 C (175 mA·g^-1),remarkable rate-performance (70.5% of 0.5 C capacity can be obtained at a 100 C discharge rate),and superior cycling stability with 81.3% capacity retention after 1,000 cycles at 1 C.Last but not least,a four-electron transfer redox process of the PI polymer was realized for the first time thanks to the excellent redox kinetics of the PI@CNF electrode,showing a discharge capacity exceeding 300 mAh·g^-1 at a current of 175 mA·g^-1.
基金supported by the National Natural Science Foundation of China(Nos.21625304,21733012)the"Strategic Priority Research Program”of Chinese Academy of Sciences(No.XDA09010600)the Ministry of Science and Technology(No.2016YFA0200703).
文摘Li has been considered as the ultimate anode material for high energy density secondary Li batteries.However,its practical application has been limited due to its low Coulombic efficiency(CE)and the formation of lithium dendrites.Recently,we have developed a microspherical Li-carbon nanotube(Li-CNT)composite material passivated with octadecylphosphonic acid(OPA)self-assembled monolayer(SAM)exhibiting suppressed lithium dendrite formation and improved environmental/electrochemical stability.In this work,we demonstrated the significantly enhanced passivation effects of a SAM using dihexadecanoalkyl phosphate(DHP),a molecule that is comprised of double hydrophobic alkyl chains and forms a denser SAM on surfaces with large curvature.As a result,the DHP SAM delivers superior environmental and electrochemical stability to the OPA passivated Li-CNT material.In specific,the DHP passivated Li-CNT composite(DHP-Li-CNT)delivers a high CE of 99.25%under a 33.3%depth of discharge(DOD)at 1 C,when it is paired with a LiFePO4 cathode.The evolution of the SAM during cycling and the effects of DOD and current density on the CE of the DHP-Li-CNT anode have also been investigated.The improved SAM passivation constitutes an important step in achieving the goal of practically applicable Li anodes.
