It is of significance to construct continuous multiphase percolation channels with fast lithium-ion pathway in hybrid solid electrolytes.3D ceramic nanostructure frameworks have attracted great attention in this field...It is of significance to construct continuous multiphase percolation channels with fast lithium-ion pathway in hybrid solid electrolytes.3D ceramic nanostructure frameworks have attracted great attention in this field.Herein,the three-dimensional perovskite Li_(0.33)La_(0.557)TiO_(3)nanotubes framework(3D-LLTO-NT)is fabricated via a facile coaxial electro-spinning process followed by a calcination process at 800°C.The hybrid polymer electrolyte of 3DLLTO-NT framework and poly(ethylene carbonate)(3D-LLTO-NT@PEC)shows improved ionic conductivity of 1.73×10^(-4)S cm^(-1)at ambient temperature,higher lithium-ion transference number(t_(Li)^(+))of 0.78 and electrochemical stability window up to 5.0 V vs Li/Li^(+).The all-solid-state cell of LiFePO_(4)/3D-LLTO-NT@PEC/Li delivers a high specific capacity of 140.2 mAh g^(-1)at 0.1 C at ambient temperature.This outstanding performance is attributed to the 3D ceramic nanotubes frameworks which provide fast lithium ion transfer pathway and stable interfaces.展开更多
Substituting liquid electrolytes with solid elec-trolytes is considered as an important strategy to solve the problem of flammability and explosion for traditional lithium-ion batteries(LIB).However,neither inorganic ...Substituting liquid electrolytes with solid elec-trolytes is considered as an important strategy to solve the problem of flammability and explosion for traditional lithium-ion batteries(LIB).However,neither inorganic solid electrolytes(ISE)nor solid polymer electrolytes(SPE)alone can meet the operating requirements for room-temperature(RT)all-solid-state lithium metal batteries(ASSLMB).Here,we report a three-dimensional(3D)nanofiber framework reinforced polyethylene oxide(PEO)-based composite polymer electrolytes(CPE)through con-structing a nanofiber framework combining polyacryloni-trile(PAN)and fast Li-ion conductor Li_(0.33)La_(0.557)TiO_(3)(LLTO)framework by electrospinning method.Mean-while,the PEO electrolyte filled in the pores of the PAN/LLTO nanofiber framework can effectively isolate the direct contact between the chemically active Ti^(4+)in LLTO with lithium metal,thereby avoiding the occurrence of interfacial reactions.Enhanced electrochemical stability makes a wide electrochemical window up to 4.8 V with an ionic conductivity of about 9.87×10^(-5)S·cm^(-1)at RT.Benefiting from the excellent lithium dendrite growth inhibition ability of 3D PAN/LLTO nanofiber framework,especially when the mass of LLTO reaches twice that of the PAN,Li/Li symmetric cell could cycle stably for 1000 h without a short circuit.In addition,under 30℃,the LiFePO_(4)/Li ASSLMB using such CPE delivers large capacities of 156.2 and 140 mAh·g^(-1)at 0.2C and 0.5C,respectively.These results provide a new insight for the development of the next generation of safe,high-perfor-mance ASSLMBs.展开更多
As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.H...As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.展开更多
Perovskite-type lithium lanthanum titanates(LLTO)display a high bulk ionic conductivity and are considered a promising electrolyte for building up to advanced solid-state Li-ion batteries.The LLTO crystals contain a h...Perovskite-type lithium lanthanum titanates(LLTO)display a high bulk ionic conductivity and are considered a promising electrolyte for building up to advanced solid-state Li-ion batteries.The LLTO crystals contain a high concentration of intrinsically formed 90ο-rotated domain boundaries(DBs)serving as barriers to bulk Li-ion conduction.However,the mechanism of how the DB concentration and DB resistance can compete with each other to determine the bulk conductivity of LLTO is still unknown.Here we report a comprehensive study of LLTO compounds,aimed to unravel the mechanism and hence explore new path(s)for further improving the conductivity of this material.Our results show that both the sintering temperature and chemical composition can affect significantly the domain structures in LLTO.It is found that a decrease in the DB concentration is always accompanied by increased DB resistance due to the increased lattice mismatch at DBs,and vice versa.By unifying the electrochemical impedance spectroscopy and transmission electron microscopy analysis,it is clearly shown that the high DB resistance,instead of DB concentration,acts as the dominant factor governing the bulk conductivity of LLTO.The results thus renew the conventional understanding of the bulk Li-ion conduction in LLTO and shed light on developing novel LLTO electrolyte materials with improved ionic conductivity.展开更多
Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolyte...Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.展开更多
基金financial support from Key Scientific and Technological Project of Wuhan City(Grant no.2018010401011279)Team Innovation Foundation of Hubei province(Grant no.T201935)National Natural Science Foundation of China(Grant nos.51872127,22209059 and 22139001)
文摘It is of significance to construct continuous multiphase percolation channels with fast lithium-ion pathway in hybrid solid electrolytes.3D ceramic nanostructure frameworks have attracted great attention in this field.Herein,the three-dimensional perovskite Li_(0.33)La_(0.557)TiO_(3)nanotubes framework(3D-LLTO-NT)is fabricated via a facile coaxial electro-spinning process followed by a calcination process at 800°C.The hybrid polymer electrolyte of 3DLLTO-NT framework and poly(ethylene carbonate)(3D-LLTO-NT@PEC)shows improved ionic conductivity of 1.73×10^(-4)S cm^(-1)at ambient temperature,higher lithium-ion transference number(t_(Li)^(+))of 0.78 and electrochemical stability window up to 5.0 V vs Li/Li^(+).The all-solid-state cell of LiFePO_(4)/3D-LLTO-NT@PEC/Li delivers a high specific capacity of 140.2 mAh g^(-1)at 0.1 C at ambient temperature.This outstanding performance is attributed to the 3D ceramic nanotubes frameworks which provide fast lithium ion transfer pathway and stable interfaces.
基金financially supported by Zhejiang Provincial Natural Science Foundation of China (No. LR20E020002)the National Natural Science Foundation of China (Nos.U20A20253 and 21972127)
文摘Substituting liquid electrolytes with solid elec-trolytes is considered as an important strategy to solve the problem of flammability and explosion for traditional lithium-ion batteries(LIB).However,neither inorganic solid electrolytes(ISE)nor solid polymer electrolytes(SPE)alone can meet the operating requirements for room-temperature(RT)all-solid-state lithium metal batteries(ASSLMB).Here,we report a three-dimensional(3D)nanofiber framework reinforced polyethylene oxide(PEO)-based composite polymer electrolytes(CPE)through con-structing a nanofiber framework combining polyacryloni-trile(PAN)and fast Li-ion conductor Li_(0.33)La_(0.557)TiO_(3)(LLTO)framework by electrospinning method.Mean-while,the PEO electrolyte filled in the pores of the PAN/LLTO nanofiber framework can effectively isolate the direct contact between the chemically active Ti^(4+)in LLTO with lithium metal,thereby avoiding the occurrence of interfacial reactions.Enhanced electrochemical stability makes a wide electrochemical window up to 4.8 V with an ionic conductivity of about 9.87×10^(-5)S·cm^(-1)at RT.Benefiting from the excellent lithium dendrite growth inhibition ability of 3D PAN/LLTO nanofiber framework,especially when the mass of LLTO reaches twice that of the PAN,Li/Li symmetric cell could cycle stably for 1000 h without a short circuit.In addition,under 30℃,the LiFePO_(4)/Li ASSLMB using such CPE delivers large capacities of 156.2 and 140 mAh·g^(-1)at 0.2C and 0.5C,respectively.These results provide a new insight for the development of the next generation of safe,high-perfor-mance ASSLMBs.
基金This study was financially supported by the National Natural Science Funds of China(No.21905040)the Startup Funds from the University of Electronic Science and Technology of China,the National Key Research and Development Program of China(Nos.2017YFB0702802 and 2018YFB0905400)Shanghai Venus Project(No.18QB1402600).
文摘As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.
基金supported by the National Natural Science Foundation of China(22075003,U2030206)。
文摘Perovskite-type lithium lanthanum titanates(LLTO)display a high bulk ionic conductivity and are considered a promising electrolyte for building up to advanced solid-state Li-ion batteries.The LLTO crystals contain a high concentration of intrinsically formed 90ο-rotated domain boundaries(DBs)serving as barriers to bulk Li-ion conduction.However,the mechanism of how the DB concentration and DB resistance can compete with each other to determine the bulk conductivity of LLTO is still unknown.Here we report a comprehensive study of LLTO compounds,aimed to unravel the mechanism and hence explore new path(s)for further improving the conductivity of this material.Our results show that both the sintering temperature and chemical composition can affect significantly the domain structures in LLTO.It is found that a decrease in the DB concentration is always accompanied by increased DB resistance due to the increased lattice mismatch at DBs,and vice versa.By unifying the electrochemical impedance spectroscopy and transmission electron microscopy analysis,it is clearly shown that the high DB resistance,instead of DB concentration,acts as the dominant factor governing the bulk conductivity of LLTO.The results thus renew the conventional understanding of the bulk Li-ion conduction in LLTO and shed light on developing novel LLTO electrolyte materials with improved ionic conductivity.
基金the Department of Energy,Office of Energy Efficiency and Renewable Energy(EERE),under Award Number DE-EE0007806.
文摘Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.
