Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid ele...Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.展开更多
A self-standing,flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion batteries.The multi-functional composite semi-interp...A self-standing,flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion batteries.The multi-functional composite semi-interpenetrating polymer network(referred to as“Cs-IPN”)electrolyte membrane was fabricated by combining a UV-cured ethoxylated trimethylolpropane triacrylate(ETPTA)macromer with alumina nanoparticles in the presence of liquid electrolyte and thermoplastic linear poly(ethylene oxide)(PEO).The polymer electrolyte membrane exhibits a semi-interpenetrating polymer network structure and a higher room temperature ionic conductivity,which impart the electrolyte with a significant cycling(120 mAh g^(-1)after 200 cycles)and a remarkable rate(137 mAh g^(-1)at 0.1℃,130 mAh g^(-1)at 0.5℃,119 mAh g^(-1)at 1℃ and 100 mAh g^(-1)at 2℃)performance in Li/LiFePO4 battery.More importantly,the polymer electrolyte possesses superior ability to inhibit the growth of lithium dendrites,which makes it promising for next generation lithium ion batteries.展开更多
Lithium metal battery is considered to be the most promising energy storage technologies due to its ultra-high theoretical capacity and extremely low standard potential.However,the infinite volume change during uneven...Lithium metal battery is considered to be the most promising energy storage technologies due to its ultra-high theoretical capacity and extremely low standard potential.However,the infinite volume change during uneven deposition/dissolution process and the growth of lithium dendrite resulting in severe capacity decay and high safety hazards,which hinders the application in next generation secondary batteries.In this paper,the three dimensional(3D)porous copper is prepared through an electrochemical etching CueZn alloy,and the pore walls are modified with lithiophilic layer of ZnO and fluorine.The as-prepared 3D Cu/ZnO/F can inhibit the growth of Li dendrite and mitigate the huge volume change of Li metal anode during cycling process,resulting in stable solid electrolyte interface(SEI)layer and electrode structure.The Li|3D Cu/ZnO/F cell can be stably cycled over 300 cycles with 98% of coulomb efficiency at 0.5 mA cm^(-2),1 mAh cm^(-2).The synergistic effects of both ZnO and fluorine on inducing the uniform deposition of lithium by providing bonding sites can inhibit the generation of lithium dendrites and thus improve the electrochemical performance of lithium metal batteries.展开更多
Moist air is a great challenge for manufacturing sulfide-based all-solid-state lithium batteries as the water in air will lead to severe decomposition of sulfide electrolytes and release H2S gas.However,different with...Moist air is a great challenge for manufacturing sulfide-based all-solid-state lithium batteries as the water in air will lead to severe decomposition of sulfide electrolytes and release H2S gas.However,different with direct reaction with water,short-period air exposure of Li_(10)GeP_(2)S_(12) sulfide electrolyte with controlled humidity can greatly enhance the stability of Li_(10)GeP_(2)S_(12) against lithium metal,thus realizing stable Li_(10)GeP_(2)S_(12) based all-solid-state lithium metal batteries.During air exposure,partial hydrolysis reaction occurs on the surface of Li_(10)GeP_(2)S_(12) pellets,rapidly generating a protective decomposition layer of Li4P2S6,GeS2 and Li2HPO3 in dozens of seconds.This ionically conductive but electronically insulation protecting layer can effectively prevent the severe interface reaction between Li_(10)GeP_(2)S_(12) and lithium metal during electrochemical cycling.The Li/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li cell shows long cycling stability for 1000 h.And the LiCoO_(2)/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li batteries present good rate capability and long cyclic performances,showing capacity retention of 80%after 100 cycles.展开更多
基金supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(U1964205,51872303,52172253)+3 种基金the Ningbo S&T Innovation 2025 Major Special Programme(2019B10044,2021Z122)the Zhejiang Provincial Key R&D Program of China(2022C01072)the Jiangsu Provincial S&T Innovation Special Programme for carbon peak and carbon neutrality(BE2022007)the Youth Innovation Promotion Association CAS(Y2021080)。
文摘Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(NSFCeNo.51202117)Natural Science Foundation of Beijing(No.2162037 and L182062),the Beijing Nova Program(Z171100001117077)+4 种基金the Beijing outstanding talent program(No.2015000020124G121)the Fundamental Research Funds for the Central Universities(No.2014QJ02)the State Key Laboratory of Coal Resources and Safe Mining(No.SKLCRSM16KFB04)the Key Laboratory of Advanced Materials of Ministry of Education(No.2018AML03)the Yue Qi Young Scholar Project of China University of Mining&Technology(Beijing)(No.2017QN17).
文摘A self-standing,flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion batteries.The multi-functional composite semi-interpenetrating polymer network(referred to as“Cs-IPN”)electrolyte membrane was fabricated by combining a UV-cured ethoxylated trimethylolpropane triacrylate(ETPTA)macromer with alumina nanoparticles in the presence of liquid electrolyte and thermoplastic linear poly(ethylene oxide)(PEO).The polymer electrolyte membrane exhibits a semi-interpenetrating polymer network structure and a higher room temperature ionic conductivity,which impart the electrolyte with a significant cycling(120 mAh g^(-1)after 200 cycles)and a remarkable rate(137 mAh g^(-1)at 0.1℃,130 mAh g^(-1)at 0.5℃,119 mAh g^(-1)at 1℃ and 100 mAh g^(-1)at 2℃)performance in Li/LiFePO4 battery.More importantly,the polymer electrolyte possesses superior ability to inhibit the growth of lithium dendrites,which makes it promising for next generation lithium ion batteries.
基金the financial support from the Natural Science Foundation of Beijing(L182062)the Beijing Nova Program(Z171100001117077)+1 种基金the Yue Qi Young Scholar Project of China University of Mining&Technology(Beijing)(No.2017QN17)the Fundamental Research Funds for the Central Universities(No.2014QJ02).
文摘Lithium metal battery is considered to be the most promising energy storage technologies due to its ultra-high theoretical capacity and extremely low standard potential.However,the infinite volume change during uneven deposition/dissolution process and the growth of lithium dendrite resulting in severe capacity decay and high safety hazards,which hinders the application in next generation secondary batteries.In this paper,the three dimensional(3D)porous copper is prepared through an electrochemical etching CueZn alloy,and the pore walls are modified with lithiophilic layer of ZnO and fluorine.The as-prepared 3D Cu/ZnO/F can inhibit the growth of Li dendrite and mitigate the huge volume change of Li metal anode during cycling process,resulting in stable solid electrolyte interface(SEI)layer and electrode structure.The Li|3D Cu/ZnO/F cell can be stably cycled over 300 cycles with 98% of coulomb efficiency at 0.5 mA cm^(-2),1 mAh cm^(-2).The synergistic effects of both ZnO and fluorine on inducing the uniform deposition of lithium by providing bonding sites can inhibit the generation of lithium dendrites and thus improve the electrochemical performance of lithium metal batteries.
基金The work was supported by the National Key R&D Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant Nos.U1964205,51872303,51902321 and 52172253)+2 种基金Zhejiang Provincial Key R&D Program of China(Grant No.2022C01072)Ningbo S&T Innovation 2025 Major Special Programme(Grant Nos.2019B10044 and 2021Z122)Youth Innovation Promotion Association CAS(Y2021080).
文摘Moist air is a great challenge for manufacturing sulfide-based all-solid-state lithium batteries as the water in air will lead to severe decomposition of sulfide electrolytes and release H2S gas.However,different with direct reaction with water,short-period air exposure of Li_(10)GeP_(2)S_(12) sulfide electrolyte with controlled humidity can greatly enhance the stability of Li_(10)GeP_(2)S_(12) against lithium metal,thus realizing stable Li_(10)GeP_(2)S_(12) based all-solid-state lithium metal batteries.During air exposure,partial hydrolysis reaction occurs on the surface of Li_(10)GeP_(2)S_(12) pellets,rapidly generating a protective decomposition layer of Li4P2S6,GeS2 and Li2HPO3 in dozens of seconds.This ionically conductive but electronically insulation protecting layer can effectively prevent the severe interface reaction between Li_(10)GeP_(2)S_(12) and lithium metal during electrochemical cycling.The Li/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li cell shows long cycling stability for 1000 h.And the LiCoO_(2)/40s-air-exposed Li_(10)GeP_(2)S_(12)/Li batteries present good rate capability and long cyclic performances,showing capacity retention of 80%after 100 cycles.