LiFePO4-Li3V2（PO4）3 composites were synthesized by solid-hydrothermal method and by ball milling,respectively.The electrochemical performance of the solid-hydrothermally obtained materials（C-LFVP） was significantl...LiFePO4-Li3V2（PO4）3 composites were synthesized by solid-hydrothermal method and by ball milling,respectively.The electrochemical performance of the solid-hydrothermally obtained materials（C-LFVP） was significantly improved compared with LiFePO4（LFP） and Li3V2（PO4）3（LVP）,and it was also much better than that of the ball-milled LiFePO4-Li3V2（PO4）3（P-LFVP）.C-LFVP and P-LFVP both had four REDOX peaks（voltage plateaus）,which coincided with that of LFP and LVP.Some new trace substances were found in C-LFVP which had more perfect morphology,this was responsible for the better electrochemical performance of C-LFVP than P-LFVP.展开更多
The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and lo...The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.展开更多
Various solid electrolytes,such as sulfides(10^-3-10^-2 S cm^-1)and oxides(10^-4–10^-3 S cm^-1)are explored and developed to solve the safety problems in commercial Li-ion batteries using liquid flammable electrolyte...Various solid electrolytes,such as sulfides(10^-3-10^-2 S cm^-1)and oxides(10^-4–10^-3 S cm^-1)are explored and developed to solve the safety problems in commercial Li-ion batteries using liquid flammable electrolytes.Metallic Li anode is required for pursuing high power density(>300 Wh kg^-1)for solid-state batteries[1,2].展开更多
Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrod...Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrode remain challenging due to the poor mechanical processibility and inferior electrochemical performance of metallic Li.Here,mechanico-chemical synthesis of robust ultrathin Li/Li_(3)P(LLP)composite foils(~15µm)is demonstrated by employing repeated mechanical rolling/stacking operations using red P and metallic Li as raw materials.The in-situ formed Li+-conductive Li_(3)P nanoparticles in metallic Li matrix and their tight bonding strengthen the mechanical durability and enable the successful fabrication of free-standing ultrathin Li metal composite foil.Besides,it also reduces the electrochemical Li nucleation barrier and homogenizes Li plating/stripping behavior.When matching to high-voltage LiCoO_(2),the full cell with a low negative/positive(N/P)capacity ratio of~1.5 offers a high energy density of~522 W·h·kg^(-1) at 0.5 C based on the mass of cathode and anode.Taking into account its facile manufacturing,potentially low cost,and good electrochemical performance,we believe that such an ultrathin composite Li metal foil design with nanoparticle-dispersion-strengthened mechanism may boost the development of high energy density Li metal batteries.展开更多
Lithium(Li)metal is believed to be the“Holy Grail”among all anode materials for next-generation Li-based batteries due to its high theoretical specific capacity(3860 mAh/g)and lowest redox potential(−3.04 V).Disappo...Lithium(Li)metal is believed to be the“Holy Grail”among all anode materials for next-generation Li-based batteries due to its high theoretical specific capacity(3860 mAh/g)and lowest redox potential(−3.04 V).Disappointingly,uncontrolled dendrite formation and“hostless”deposition impede its further development.It is well accepted that the construction of three-dimensional(3D)composite Li metal anode could tackle the above problems to some extent by reducing local current density and maintaining electrode volume during cycling.However,most strategies to build 3D composite Li metal anode require either electrodeposition or melt-infusion process.In spite of their effectiveness,these procedures bring multiple complex processing steps,high temperature,and harsh experimental conditions which cannot meet the actual production demand in consideration of cost and safety.Under this condition,a novel method to construct 3D composite anode via simple mechanical modification has been recently proposed which does not involve harsh conditions,fussy procedures,or fancy equipment.In this mini review,a systematic and in-depth investigation of this mechanical deformation technique to build 3D composite Li metal anode is provided.First,by summarizing a number of recent studies,different mechanical modification approaches are classified clearly according to their specific procedures.Then,the effect of each individual mechanical modification approach and its working mechanisms is reviewed.Afterwards,the merits and limits of different approaches are compared.Finally,a general summary and perspective on construction strategies for next-generation 3D composite Li anode are presented.展开更多
A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle ...A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle life.The mechanism behind the enhanced electrochemical performance of the“salt-in-metal”composite is investigated,where KNO_(3) in metallic Li composite electrode would be sustainably released into the electrolyte.The presence of NO_(3)-stabilizes the solid electrolyte interphase by producing functional Li_(3)N,LiNxOy,and Li_(2)O species.K^(+)from KNO_(3) also helps to form an electrostatic shield after its adsorption on the electrode protrusions,which suppresses the dendritic growth of metallic Li.With the above advantages,uniform Li plating with dense and planar structure is realized for the LKNO electrode.These findings reveal a deep understanding of the effect of the“saltin-metal”anode and provide new insights into the use of nitrate additives for high-energy-density Li metal batteries.展开更多
The conductivities of polyethylene oxide (PEO)-based polymer electrolytes (PE) can be improved by the addition of inorganic inert powder. The composite polymer electrolytes (CPE) PEO10LiX (X=4ClO- or 322N(CFSO)-)-Li2T...The conductivities of polyethylene oxide (PEO)-based polymer electrolytes (PE) can be improved by the addition of inorganic inert powder. The composite polymer electrolytes (CPE) PEO10LiX (X=4ClO- or 322N(CFSO)-)-Li2TiO3 were prepared by solution casting with inorganic solid electrolyte Li2TiO3 powder as a filler. Results showed that the conductivities of PEO10LiClO4-3wt% Li2TiO3 and PEO10LiN(CF3SO2)2-10wt% Li2TiO3 at 30 ℃ were 8.6×10-6 and 5.6×10-5 S·cm-1, respectively. The conductivities of CPE increased with the decrease of filler抯 particle size. The ionic conduction mechanism analysis showed that there may be three conduction routes in the CPE, i.e., PEO bulk, polymer-filler interface and Li2TiO3 crystal.展开更多
Polymer-based solid electrolytes have been extensively studied for solid-state lithium metal batteries to achieve high energy density and reliable security.But,its practical application is severely limited by low ioni...Polymer-based solid electrolytes have been extensively studied for solid-state lithium metal batteries to achieve high energy density and reliable security.But,its practical application is severely limited by low ionic conductivity and slow Li+transference.Herein,based on the“binary electrolytes”of poly(vinylidene fluoride-chlorotrifluoroethylene)(P(VDF-CTFE))and lithium salt(LiTFSI),a kind of eutectogel hybrid electrolytes(EHEs)with high Li+transference number was developed via tuning the spontaneous coupling of charge and vacated space generated by Li-cation diffusion utilizing the Li6.4La3Zr1.4Ta0.6O12(LLZTO)dopant.LLZTO doping promotes the dissociation of lithium salt,increases Li+carrier density,and boosts ion jumping and the coordination/decoupling reactions of Li+.As a result,the optimized EHEs-10%possess a high Li-transference number of 0.86 and a high Li+conductivity of 3.2×10–4 S·cm–1 at room temperature.Moreover,the prepared EHEs-10%composite solid electrolyte presents excellent lithiumphilic and compatibility,and can be tested stably for 1,200 h at 0.3 mA·cm–2 with assembled lithium symmetric batteries.Likewise,the EHEs-10%films match well with high-loading LiFePO4 and LiCoO2 cathodes(>10 mg·cm–2)and exhibit remarkable interface stability.Particularly,the LiFePO4//EHEs-10%//Li and LiCoO2//EHEs-10%//Li cells deliver high rate performance of 118 mAh·g–1 at 1 C and 93.7 mAh·g–1 at 2 C with coulombic efficiency of 99.3%and 98.1%,respectively.This work provides an in-depth understanding and new insights into our design for polymer electrolytes with fast Li+diffusion.展开更多
基金Project (2007BAQ01055) supported by the National Key Technology R&D Programs of ChinaProject (50574063) supported by theNational Natural Science Foundation of China
文摘LiFePO4-Li3V2（PO4）3 composites were synthesized by solid-hydrothermal method and by ball milling,respectively.The electrochemical performance of the solid-hydrothermally obtained materials（C-LFVP） was significantly improved compared with LiFePO4（LFP） and Li3V2（PO4）3（LVP）,and it was also much better than that of the ball-milled LiFePO4-Li3V2（PO4）3（P-LFVP）.C-LFVP and P-LFVP both had four REDOX peaks（voltage plateaus）,which coincided with that of LFP and LVP.Some new trace substances were found in C-LFVP which had more perfect morphology,this was responsible for the better electrochemical performance of C-LFVP than P-LFVP.
基金Financial supports from the National Natural Science Foundation of China (51575030, 51532002 and 51872027)Beijing Natural Science Foundation (L172023)National Basic Research Program of China (2017YFE0113500)。
文摘The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.
基金financially supported by Ganfeng Lithium Co., Ltd.
文摘Various solid electrolytes,such as sulfides(10^-3-10^-2 S cm^-1)and oxides(10^-4–10^-3 S cm^-1)are explored and developed to solve the safety problems in commercial Li-ion batteries using liquid flammable electrolytes.Metallic Li anode is required for pursuing high power density(>300 Wh kg^-1)for solid-state batteries[1,2].
基金Y.S.acknowledges the financial support by National Natural Science Foundation of China(No.52272207)L.F.thanks the financial support by National Natural Science Foundation of China(No.22209031)+1 种基金Guizhou Provincial Basic Research Program(Natural Science)(No.QKHJC-ZK[2023]YB046)Natural Science Special Foundation of Guizhou University(No.X2022122 Special Post B).
文摘Achievement of lithium(Li)metal anode with thin thickness(e.g.,≤30µm)is highly desirable for rechargeable high energy density batteries.However,the fabrication and application of such thin Li metal foil electrode remain challenging due to the poor mechanical processibility and inferior electrochemical performance of metallic Li.Here,mechanico-chemical synthesis of robust ultrathin Li/Li_(3)P(LLP)composite foils(~15µm)is demonstrated by employing repeated mechanical rolling/stacking operations using red P and metallic Li as raw materials.The in-situ formed Li+-conductive Li_(3)P nanoparticles in metallic Li matrix and their tight bonding strengthen the mechanical durability and enable the successful fabrication of free-standing ultrathin Li metal composite foil.Besides,it also reduces the electrochemical Li nucleation barrier and homogenizes Li plating/stripping behavior.When matching to high-voltage LiCoO_(2),the full cell with a low negative/positive(N/P)capacity ratio of~1.5 offers a high energy density of~522 W·h·kg^(-1) at 0.5 C based on the mass of cathode and anode.Taking into account its facile manufacturing,potentially low cost,and good electrochemical performance,we believe that such an ultrathin composite Li metal foil design with nanoparticle-dispersion-strengthened mechanism may boost the development of high energy density Li metal batteries.
文摘Lithium(Li)metal is believed to be the“Holy Grail”among all anode materials for next-generation Li-based batteries due to its high theoretical specific capacity(3860 mAh/g)and lowest redox potential(−3.04 V).Disappointingly,uncontrolled dendrite formation and“hostless”deposition impede its further development.It is well accepted that the construction of three-dimensional(3D)composite Li metal anode could tackle the above problems to some extent by reducing local current density and maintaining electrode volume during cycling.However,most strategies to build 3D composite Li metal anode require either electrodeposition or melt-infusion process.In spite of their effectiveness,these procedures bring multiple complex processing steps,high temperature,and harsh experimental conditions which cannot meet the actual production demand in consideration of cost and safety.Under this condition,a novel method to construct 3D composite anode via simple mechanical modification has been recently proposed which does not involve harsh conditions,fussy procedures,or fancy equipment.In this mini review,a systematic and in-depth investigation of this mechanical deformation technique to build 3D composite Li metal anode is provided.First,by summarizing a number of recent studies,different mechanical modification approaches are classified clearly according to their specific procedures.Then,the effect of each individual mechanical modification approach and its working mechanisms is reviewed.Afterwards,the merits and limits of different approaches are compared.Finally,a general summary and perspective on construction strategies for next-generation 3D composite Li anode are presented.
基金Y.Sun acknowledges the financial support of the National Natural Science Foundation of China(No.52072137)Z.W.Seh acknowledges the support of the Singapore National Research Foundation(NRF-NRFF2017-04).
文摘A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle life.The mechanism behind the enhanced electrochemical performance of the“salt-in-metal”composite is investigated,where KNO_(3) in metallic Li composite electrode would be sustainably released into the electrolyte.The presence of NO_(3)-stabilizes the solid electrolyte interphase by producing functional Li_(3)N,LiNxOy,and Li_(2)O species.K^(+)from KNO_(3) also helps to form an electrostatic shield after its adsorption on the electrode protrusions,which suppresses the dendritic growth of metallic Li.With the above advantages,uniform Li plating with dense and planar structure is realized for the LKNO electrode.These findings reveal a deep understanding of the effect of the“saltin-metal”anode and provide new insights into the use of nitrate additives for high-energy-density Li metal batteries.
文摘The conductivities of polyethylene oxide (PEO)-based polymer electrolytes (PE) can be improved by the addition of inorganic inert powder. The composite polymer electrolytes (CPE) PEO10LiX (X=4ClO- or 322N(CFSO)-)-Li2TiO3 were prepared by solution casting with inorganic solid electrolyte Li2TiO3 powder as a filler. Results showed that the conductivities of PEO10LiClO4-3wt% Li2TiO3 and PEO10LiN(CF3SO2)2-10wt% Li2TiO3 at 30 ℃ were 8.6×10-6 and 5.6×10-5 S·cm-1, respectively. The conductivities of CPE increased with the decrease of filler抯 particle size. The ionic conduction mechanism analysis showed that there may be three conduction routes in the CPE, i.e., PEO bulk, polymer-filler interface and Li2TiO3 crystal.
基金This work was supported by the International Cooperation Projects of Sichuan Provincial Department of Science and Technology(No.2021YFH0126)Quzhou Science and Technology Bureau Project(No.2021D006)+2 种基金the Fundamental Research Funds for the Central Universities(No.A030202063008029)The China Postdoctoral Science Foundation(Nos.2021T140433,2020M683408)the Natural Science Foundation of Shaanxi Province(No.2021JQ-538).
文摘Polymer-based solid electrolytes have been extensively studied for solid-state lithium metal batteries to achieve high energy density and reliable security.But,its practical application is severely limited by low ionic conductivity and slow Li+transference.Herein,based on the“binary electrolytes”of poly(vinylidene fluoride-chlorotrifluoroethylene)(P(VDF-CTFE))and lithium salt(LiTFSI),a kind of eutectogel hybrid electrolytes(EHEs)with high Li+transference number was developed via tuning the spontaneous coupling of charge and vacated space generated by Li-cation diffusion utilizing the Li6.4La3Zr1.4Ta0.6O12(LLZTO)dopant.LLZTO doping promotes the dissociation of lithium salt,increases Li+carrier density,and boosts ion jumping and the coordination/decoupling reactions of Li+.As a result,the optimized EHEs-10%possess a high Li-transference number of 0.86 and a high Li+conductivity of 3.2×10–4 S·cm–1 at room temperature.Moreover,the prepared EHEs-10%composite solid electrolyte presents excellent lithiumphilic and compatibility,and can be tested stably for 1,200 h at 0.3 mA·cm–2 with assembled lithium symmetric batteries.Likewise,the EHEs-10%films match well with high-loading LiFePO4 and LiCoO2 cathodes(>10 mg·cm–2)and exhibit remarkable interface stability.Particularly,the LiFePO4//EHEs-10%//Li and LiCoO2//EHEs-10%//Li cells deliver high rate performance of 118 mAh·g–1 at 1 C and 93.7 mAh·g–1 at 2 C with coulombic efficiency of 99.3%and 98.1%,respectively.This work provides an in-depth understanding and new insights into our design for polymer electrolytes with fast Li+diffusion.
