Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12...Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.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
Li(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) solid garnet-type electrolyte has been widely reported due to its outstanding safety and electrochemical stability.However,the inherent rigidity and brittleness of LLZTO lead...Li(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) solid garnet-type electrolyte has been widely reported due to its outstanding safety and electrochemical stability.However,the inherent rigidity and brittleness of LLZTO lead to poor contact with anode/cathode and the operation failure of full cells.Herein,the dual-interlayers are constructed as the fast interfacial ion-migration channel by using Ti_(3)C_(2)T_(x)(MXene,Txis-O,-OH,-F) with trace ionic liquid(IL),which promote the intimate contact between LLZTO and anode/cathode and suppress Li-dendrites growth.Notably,IL can wet the cathode to promote intimate interface contact and be decomposed into some inorganic compounds(such as Li3N,LiF,and Li2Sx),resulting in reduced interfacial resistance and fast Li-ion transportation.Consequently,in the prepared Li-symmetric cell,the interfacial resistance on the anode side plunges to 33.1 Ω cm^(-2),and stably maintains over 1000 h without short circuit at 0.05 mA cm^(-2).The full cell of Li|LiFePO4delivers a high initial capacity of 158.52 mA h g^(-1)and outstanding retention of 90.18% after 100 cycles at 60℃ and 0.2 C.Our work provides an efficient strategy to design dual-interlayers between LLZTO and anode/cathode for the interfacial modification to enhance the performance of solid garnet batteries.展开更多
The garnet (Grt) and biotite (Bt) from gneisses of the Ji’ an Group are characterized by diffusion zoning at the rim, but equilibrium composition of metamorphic peak is usually remained in extensive interior area. Ga...The garnet (Grt) and biotite (Bt) from gneisses of the Ji’ an Group are characterized by diffusion zoning at the rim, but equilibrium composition of metamorphic peak is usually remained in extensive interior area. Garnet with growth zoning is also found in the kyanite zone.In the light of microarea compositional variation of Grt and Bt, the temperatuIe and pressuIe at the progressive, peak and post peak metamorphic stages are determined by correctly using GrtBt thermometer and GASP barometer. On this basis, a counterclockwise P-T-t path can be constructed, which reflects the closing process of an ensialic rift belt in this region during the Early Proterozoic.展开更多
Studies on the metamorphism and deformation conditions of rocks in the suture zone are good ways to discuss the orogenic process and mechanism. The microstructure and ultramicrostructure features of minerals are true ...Studies on the metamorphism and deformation conditions of rocks in the suture zone are good ways to discuss the orogenic process and mechanism. The microstructure and ultramicrostructure features of minerals are true embodiment of formation environment of the orogenic belt. Based on the study of microstructure, ultramicrostructure deformation characteristic and compositional zonation of garnets in garnets-mica schists in the Tongbai mountain, east section of the Shangdan fault zone, the results show that the three types of garnets have suffered various states of plastic deformation. The dynamic recrystallization of garnets is due to the subgrain growth and boundary migration. The dislocations are mainly free dislocation and dislocation walls. The free dislocation density ρ = 6.14 × 108/cm2, and dislocation movement are mainly slips;slip planes are 1/2 {110} and {001}. Garnet microprobe analysis shows that it belongs to almandine, and reflects it has undergone epidote-amphibolite to amphibolite facies metamorphism. Compositional zonation of garnet shows that the rocks had experienced progressive metamorphism. First metamorphic environment was continuous temperature-pressure and in mid-term there were two non-synchronous transient cooling and decompression processes, and it finally underwent decompression and warming process of the thermal relaxation environment. The formation condition of garnet-mica schist is estimated: T = 562°C - 617°C, and P = 0.77 - 1.02 GPa. The differential stress is 0.511 GPa and strain rate is 4.97536 × 10-10 m/s. After systemic analysis, a conclusion is drawn that the plastic deformation mode, deformation mechanism and formation environment of garnets are closely related to the formation and development of the Shangdan fault zone. It truly reflects that the Shangdan fault zone, as the suture zone of Yangtze and north China plate, has been subjected to early medium-grade metamorphism. With the continuous compression after the collision, the left-lateral shearing happened and caused the formation of high density dislocations and subgrains of the garnets;finally the plastic deformation happened and the bulging recrystallization formed in the period of heat relaxation had a relative low stress.展开更多
基金financially supported by the National Key R&D Program of China(Grant no.2016YFB0100100)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA17020404)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA09010203)R&D Projects in Key Areas of Guangdong Province(Grant no.2019B090908001)DICP&QIBEBT(Grant no.DICP&QIBEBT UN201702)。
文摘Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.
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financially supported by the National Natural Science Foundation of China(NSFC)(52172096)。
文摘Li(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) solid garnet-type electrolyte has been widely reported due to its outstanding safety and electrochemical stability.However,the inherent rigidity and brittleness of LLZTO lead to poor contact with anode/cathode and the operation failure of full cells.Herein,the dual-interlayers are constructed as the fast interfacial ion-migration channel by using Ti_(3)C_(2)T_(x)(MXene,Txis-O,-OH,-F) with trace ionic liquid(IL),which promote the intimate contact between LLZTO and anode/cathode and suppress Li-dendrites growth.Notably,IL can wet the cathode to promote intimate interface contact and be decomposed into some inorganic compounds(such as Li3N,LiF,and Li2Sx),resulting in reduced interfacial resistance and fast Li-ion transportation.Consequently,in the prepared Li-symmetric cell,the interfacial resistance on the anode side plunges to 33.1 Ω cm^(-2),and stably maintains over 1000 h without short circuit at 0.05 mA cm^(-2).The full cell of Li|LiFePO4delivers a high initial capacity of 158.52 mA h g^(-1)and outstanding retention of 90.18% after 100 cycles at 60℃ and 0.2 C.Our work provides an efficient strategy to design dual-interlayers between LLZTO and anode/cathode for the interfacial modification to enhance the performance of solid garnet batteries.
文摘The garnet (Grt) and biotite (Bt) from gneisses of the Ji’ an Group are characterized by diffusion zoning at the rim, but equilibrium composition of metamorphic peak is usually remained in extensive interior area. Garnet with growth zoning is also found in the kyanite zone.In the light of microarea compositional variation of Grt and Bt, the temperatuIe and pressuIe at the progressive, peak and post peak metamorphic stages are determined by correctly using GrtBt thermometer and GASP barometer. On this basis, a counterclockwise P-T-t path can be constructed, which reflects the closing process of an ensialic rift belt in this region during the Early Proterozoic.
文摘Studies on the metamorphism and deformation conditions of rocks in the suture zone are good ways to discuss the orogenic process and mechanism. The microstructure and ultramicrostructure features of minerals are true embodiment of formation environment of the orogenic belt. Based on the study of microstructure, ultramicrostructure deformation characteristic and compositional zonation of garnets in garnets-mica schists in the Tongbai mountain, east section of the Shangdan fault zone, the results show that the three types of garnets have suffered various states of plastic deformation. The dynamic recrystallization of garnets is due to the subgrain growth and boundary migration. The dislocations are mainly free dislocation and dislocation walls. The free dislocation density ρ = 6.14 × 108/cm2, and dislocation movement are mainly slips;slip planes are 1/2 {110} and {001}. Garnet microprobe analysis shows that it belongs to almandine, and reflects it has undergone epidote-amphibolite to amphibolite facies metamorphism. Compositional zonation of garnet shows that the rocks had experienced progressive metamorphism. First metamorphic environment was continuous temperature-pressure and in mid-term there were two non-synchronous transient cooling and decompression processes, and it finally underwent decompression and warming process of the thermal relaxation environment. The formation condition of garnet-mica schist is estimated: T = 562°C - 617°C, and P = 0.77 - 1.02 GPa. The differential stress is 0.511 GPa and strain rate is 4.97536 × 10-10 m/s. After systemic analysis, a conclusion is drawn that the plastic deformation mode, deformation mechanism and formation environment of garnets are closely related to the formation and development of the Shangdan fault zone. It truly reflects that the Shangdan fault zone, as the suture zone of Yangtze and north China plate, has been subjected to early medium-grade metamorphism. With the continuous compression after the collision, the left-lateral shearing happened and caused the formation of high density dislocations and subgrains of the garnets;finally the plastic deformation happened and the bulging recrystallization formed in the period of heat relaxation had a relative low stress.
