Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithi...Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithium metal anode limits their development.Hence,a hybrid SEI(LICl/Li F/Li Zn)was constructed at the interface between Li_(5.5)PS_(4.5)Cl_(1.5)sulfide electrolyte and lithium metal.The Li Cl and Li F interface phases with high interface energy effectively induce the uniform deposition of Li^(+)and reduce the overpotential of Li^(+)deposition,while the Li Zn alloy interface phase accelerates the diffusion of lithium ions.The synergistic effect of the above functional interface phases inhibits the growth of lithium dendrites and stabilizes the interface between the sulfide electrolyte and lithium metal.The hybrid SEI strategy exhibits excellent electrochemical performance on symmetric batteries and all-solid-state batteries.The symmetrical cell exhibits stable cycling performance over long duration over 500 h at 1.0 mA cm^(-2).Moreover,the LiNbO_(3)@NCM712/Li_(5.5)PS_(4.5)Cl_(1.5)/Li-10%Zn F_(2)battery exhibits excellent cycle stability at a high rate of 0.5 C,with a capacity retention rate of 76.4%after 350 cycles.展开更多
Lithium argyrodites Li_(6)PS_(5)X(X=Cl,Br,I)show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility.However,the relati...Lithium argyrodites Li_(6)PS_(5)X(X=Cl,Br,I)show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility.However,the relatively low conductivity of Li_(6)PS_(5)I(10^(-6)m S/cm)compared to the other two compositions limits its applications.Herein,Si-doped Li_(6.5)P_(0.5)Si_(0.5)S_(5)I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm.Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping.However,the poor interfacial stability between layered oxide cathode Li Ni_(0.6)Co_(0.2)Mn_(0.2)O_(2)and Li_(6.5)P_(0.5)Si_(0.5)S_(5)I inhibits its battery performance.By introducing Li_(3)InCl6electrolyte in the configuration,the corresponding battery delivers high initial discharge capacity of 150.2m Ah/g and superior cyclability during 250 cycles at 0.5 C.This work offers design strategy to obtain Li_(6)PS_(5)I-based electrolytes for high performance solid-state batteries.展开更多
FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron ...FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron conductivity and large volume variation effect of FeS_(2) inhibit its practical applications.Here,the influence of particle size of FeS_(2) on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS_(2) size.Moreover,low operating temperature is chosen to mitigate the large volume changes during cycling in the battery.S-FeS_(2) with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS_(2) in Li_(5.5)PS_(4.5)Cl_(1.5)-based ASSLBs under different operating temperatures.S-FeS_(2) shows stable discharge capacities during 50 cycles with a current density of 0.1 m A/cm^(2)under -20℃.When the current density rises to 1.0 m A/cm^(2),it delivers an initial discharge capacity of 146.9 m Ah/g and maintains 63% of the capacity after 100 cycles.This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.展开更多
LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. H...LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. However, the inferior interfacial stability between the bare NCA and sulfides limits its electrochemical performance. Hereien, the dual-electrolyte layer is proposed to mitigate this effect and enhance the battery performances of NCA-based ASSLIBs. The Li_(3)InCl_6 wih high conductivity and excellent electrochemcial stability act both as an ion additives to promote Li-ion diffusion across the interface in the cathode and as a buffer layer between the cathode layer and the solid electrolyte layer to avoid side reactions and improve the interface stability. The corresponding battery exhibits high discharge capacities and superior cyclabilities at both room and elevated temperatures. It exhibits discharge performance of 237.04 and216.07 m Ah/g at 0.1 and 0.5 C, respectively, when cycled at 60 ℃, and sustains 95.9% of the capacity after100 cycles at 0.5 C. The work demonstrates a simple strategy to ensure the superior performances of NCA in sulfide-based ASSLBs.展开更多
Lithium halide electrolytes show great potential in constructing high-energy-density solid-state batteries with high-voltage cathode materials due to their high electrochemical stability and wide voltage windows.Howev...Lithium halide electrolytes show great potential in constructing high-energy-density solid-state batteries with high-voltage cathode materials due to their high electrochemical stability and wide voltage windows.However,the high cost and low conductivity of some compositions inhibit their applications.Moreover,the effect of electronic additives in the cathode mixture on the stability and capacity is unclear.Here,the Y3+doping strategy is applied to enhance the conductivity of low-cost Li_(2)ZrCl_(6)electrolytes.By tailoring the Y^(3+)dopant in the structure,the optimal Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)with high conductivity up to 1.19×10^(−3) S cm^(−1) is obtained.Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)@CNT/Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)/Li_(5.5)PS_(4.5)Cl_(1.5)/In-Li solid-state batteries with different carbon nanotube(CNT)contents in the cathode are fabricated.The stability and electrochemical performances of the cathode mixture as a function of CNT content are studied.The cathode mixture containing 2%(wt.)CNT exhibits the highest stability and almost no discharge capacity,while the cathode mixture consisting of Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)and 10%(wt.)CNT delivers a high initial discharge capacity of 199.0 mAh g^(−1)and reversible capacities in the following 100 cycles.Multiple characterizations are combined to unravel the working mechanism and confirm that the electrochemical reaction involves the 2-step reaction of Y^(3+)/Zr^(0),Zr^(4+)/Zr^(0),and Cl^(−)/Cl_(x)^(−)in the Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)electrolyte.This work provides insight into designing a lithium halide electrolyte-based cathode mixture with a high ionic/electronic conductive framework and good interfacial stability for solid-state batteries.展开更多
Solid-state batteries with excellent safety and high energy density display great potential as next-generation energy storage devices.However,few solid electrolytes simultaneously possess high ionic conductivity and g...Solid-state batteries with excellent safety and high energy density display great potential as next-generation energy storage devices.However,few solid electrolytes simultaneously possess high ionic conductivity and good chemical and electrochemical stability.Herein,pure argyrodite Li_(6.6)Si_(0.6)Sb_(0.4)S_(5)I electrolyte with high Li-ion conductivity(9.0 mS cm−1)and poor stability is successfully synthesized via the typical mechanochemical route.Interfacial instability of this electrolyte with different electrode materials is investigated.A highly conductive Li_(3)InCl_(6)electrolyte,with a wide voltage window and excellent chemical and electrochemical stability,active material,and conductive carbon are introduced in the battery configuration,resulting in superior electrochemical performances with the bare LiNi_(0.7)Mn_(0.2)Co_(0.1)O_(2)cathode.The corresponding battery delivers a discharge capacity of 162.1 mAh g^(−1)at 0.5C and maintains 83.8%of the capacity after 200 cycles at room temperature.Moreover,this battery with a cathode mass loading of 6.37 mg cm−2 displays discharge capacities of 197.5 and 73.4 mAh g^(−1)at the beginning when cycled at 0.5C and 0.1C under the operating temperature of 60 and−20℃,respectively.The battery also achieved superior stablecycling performances at both temperatures.Due to the fast ionic conductivity from Li_(6.6)Si_(0.6)Sb_(0.4)S_(5)I and high electronic conductivity from carbon in the cathode,the thick-electrode configurations with huge mass loadings of 50.96 and 76.43 mg cm^(−2)also exhibit good capacities and highly reversible cyclability.This work provides a guideline for enabling superior conducting sulfide electrolytes with poor stability in thick-electrode configuration solid-state batteries.展开更多
Ionic conductivity and electro/chemical compatibility of Li_(10)SnP_(2)S_(12) electrolytes play crucial roles in achieving superior electrochemical performances of the corresponding solid-state batteries.However,the r...Ionic conductivity and electro/chemical compatibility of Li_(10)SnP_(2)S_(12) electrolytes play crucial roles in achieving superior electrochemical performances of the corresponding solid-state batteries.However,the relatively low Li-ion conductivity and poor stability of Li_(10)SnP_(2)S_(12) toward high-voltage layered oxide cathodes limit its applications.Here,a Br-substituted strategy has been applied to promote Li-ion conductivity.The optimal composition of Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) delivers high conductivity up to 6.0 mS cm^(−1).7Li static spin-lattice relaxation(T1)nuclear magnetic resonance(NMR)and density functional theory simulation are combined to unravel the improvement of Li-ion diffusion mechanism for the modified electrolytes.To mitigate the interfacial stability between the Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) electrolyte and the bare LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2) cathode,introducing Li_(2)ZrO_(3) coating layer and Li_(3)InCl_(6) isolating layer strategies has been employed to fabricate all-solid-state lithium batteries with excellent electrochemical performances.The Li_(3)InCl_(6)-LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2)/Li_(3)InCl_(6)/Li_(9.9)SnP_(2)S_(11.9)Br_(0.1)/Li-In battery delivers much higher discharge capacities and fast capacity degradations at different charge/discharge C rates,while the Li_(2)ZrO_(3)@LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2)/Li_(9.9)SnP_(2)S_(11.9)Br_(0.1)/Li-In battery shows slightly lower discharge capacities at the same C rates and superior cycling performances.Multiple characterization methods are conducted to reveal the differences of battery performance.The poor electrochemical performance of the latter battery configuration is associated with the interfacial instability between the Li_(3)InCl_(6) electrolyte and the Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) electrolyte.This work offers an effective strategy to constructing Li_(10)SnP_(2)S_(12)-based all-solid-state lithium batteries with high capacities and superior cyclabilities.展开更多
基金supported by the National Key Research and Development Program of China(2021YFB2500200)the National Natural Science Foundation of China(52177214)+1 种基金supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(21C-OP202211)HUST’s Analytical and Testing Center for the technical support。
文摘Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithium metal anode limits their development.Hence,a hybrid SEI(LICl/Li F/Li Zn)was constructed at the interface between Li_(5.5)PS_(4.5)Cl_(1.5)sulfide electrolyte and lithium metal.The Li Cl and Li F interface phases with high interface energy effectively induce the uniform deposition of Li^(+)and reduce the overpotential of Li^(+)deposition,while the Li Zn alloy interface phase accelerates the diffusion of lithium ions.The synergistic effect of the above functional interface phases inhibits the growth of lithium dendrites and stabilizes the interface between the sulfide electrolyte and lithium metal.The hybrid SEI strategy exhibits excellent electrochemical performance on symmetric batteries and all-solid-state batteries.The symmetrical cell exhibits stable cycling performance over long duration over 500 h at 1.0 mA cm^(-2).Moreover,the LiNbO_(3)@NCM712/Li_(5.5)PS_(4.5)Cl_(1.5)/Li-10%Zn F_(2)battery exhibits excellent cycle stability at a high rate of 0.5 C,with a capacity retention rate of 76.4%after 350 cycles.
基金supported by the National Key Research and Development Program(No.2021YFB2400300)the National Key Research and Development Program(No.2021YFB2500200)+1 种基金supported by the National Natural Science Foundation of China(No.52177214)China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(No.21COP202211)。
文摘Lithium argyrodites Li_(6)PS_(5)X(X=Cl,Br,I)show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility.However,the relatively low conductivity of Li_(6)PS_(5)I(10^(-6)m S/cm)compared to the other two compositions limits its applications.Herein,Si-doped Li_(6.5)P_(0.5)Si_(0.5)S_(5)I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm.Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping.However,the poor interfacial stability between layered oxide cathode Li Ni_(0.6)Co_(0.2)Mn_(0.2)O_(2)and Li_(6.5)P_(0.5)Si_(0.5)S_(5)I inhibits its battery performance.By introducing Li_(3)InCl6electrolyte in the configuration,the corresponding battery delivers high initial discharge capacity of 150.2m Ah/g and superior cyclability during 250 cycles at 0.5 C.This work offers design strategy to obtain Li_(6)PS_(5)I-based electrolytes for high performance solid-state batteries.
基金supported by the National Key Research and Development Program(No.2021YFB2400300)the National Natural Science Foundation of China(No.52177214)supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(No.21C-OP202211)。
文摘FeS_(2) shows significant potential as cathode material for all-solid-state lithium batteries(ASSLBs)due to its high theoretical specific capacity,low cost,and environmental friendliness.However,the poor ion/electron conductivity and large volume variation effect of FeS_(2) inhibit its practical applications.Here,the influence of particle size of FeS_(2) on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS_(2) size.Moreover,low operating temperature is chosen to mitigate the large volume changes during cycling in the battery.S-FeS_(2) with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS_(2) in Li_(5.5)PS_(4.5)Cl_(1.5)-based ASSLBs under different operating temperatures.S-FeS_(2) shows stable discharge capacities during 50 cycles with a current density of 0.1 m A/cm^(2)under -20℃.When the current density rises to 1.0 m A/cm^(2),it delivers an initial discharge capacity of 146.9 m Ah/g and maintains 63% of the capacity after 100 cycles.This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.
基金supported by the National Key Research and Development Program (No.2021YFB2500200)the National Natural Science Foundation of China (No.52177214)supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund (No.21C-OP202211)。
文摘LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA) is a promising cathode for sulfide-based solid-state lithium batteries(ASSLBs)profiting from its high specific capacity and voltage plateau, which yielding high energy density. However, the inferior interfacial stability between the bare NCA and sulfides limits its electrochemical performance. Hereien, the dual-electrolyte layer is proposed to mitigate this effect and enhance the battery performances of NCA-based ASSLIBs. The Li_(3)InCl_6 wih high conductivity and excellent electrochemcial stability act both as an ion additives to promote Li-ion diffusion across the interface in the cathode and as a buffer layer between the cathode layer and the solid electrolyte layer to avoid side reactions and improve the interface stability. The corresponding battery exhibits high discharge capacities and superior cyclabilities at both room and elevated temperatures. It exhibits discharge performance of 237.04 and216.07 m Ah/g at 0.1 and 0.5 C, respectively, when cycled at 60 ℃, and sustains 95.9% of the capacity after100 cycles at 0.5 C. The work demonstrates a simple strategy to ensure the superior performances of NCA in sulfide-based ASSLBs.
基金National Key Research and Development Program(2021YFB2500200)National Natural Science Foundation of China(Nos.52177214 and 51821005).
文摘Lithium halide electrolytes show great potential in constructing high-energy-density solid-state batteries with high-voltage cathode materials due to their high electrochemical stability and wide voltage windows.However,the high cost and low conductivity of some compositions inhibit their applications.Moreover,the effect of electronic additives in the cathode mixture on the stability and capacity is unclear.Here,the Y3+doping strategy is applied to enhance the conductivity of low-cost Li_(2)ZrCl_(6)electrolytes.By tailoring the Y^(3+)dopant in the structure,the optimal Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)with high conductivity up to 1.19×10^(−3) S cm^(−1) is obtained.Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)@CNT/Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)/Li_(5.5)PS_(4.5)Cl_(1.5)/In-Li solid-state batteries with different carbon nanotube(CNT)contents in the cathode are fabricated.The stability and electrochemical performances of the cathode mixture as a function of CNT content are studied.The cathode mixture containing 2%(wt.)CNT exhibits the highest stability and almost no discharge capacity,while the cathode mixture consisting of Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)and 10%(wt.)CNT delivers a high initial discharge capacity of 199.0 mAh g^(−1)and reversible capacities in the following 100 cycles.Multiple characterizations are combined to unravel the working mechanism and confirm that the electrochemical reaction involves the 2-step reaction of Y^(3+)/Zr^(0),Zr^(4+)/Zr^(0),and Cl^(−)/Cl_(x)^(−)in the Li_(2.5)Zr_(0.5)Y_(0.5)Cl_(6)electrolyte.This work provides insight into designing a lithium halide electrolyte-based cathode mixture with a high ionic/electronic conductive framework and good interfacial stability for solid-state batteries.
基金the National Key Research and Development Program(grant no.2021YFB2500200)the National Natural Science Foundation of China(grant no.52177214)+1 种基金the Department of Science and Technology of Guangdong Province(grant no.2017ZT07Z479)China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(grant no.21C-OP202211)。
文摘Solid-state batteries with excellent safety and high energy density display great potential as next-generation energy storage devices.However,few solid electrolytes simultaneously possess high ionic conductivity and good chemical and electrochemical stability.Herein,pure argyrodite Li_(6.6)Si_(0.6)Sb_(0.4)S_(5)I electrolyte with high Li-ion conductivity(9.0 mS cm−1)and poor stability is successfully synthesized via the typical mechanochemical route.Interfacial instability of this electrolyte with different electrode materials is investigated.A highly conductive Li_(3)InCl_(6)electrolyte,with a wide voltage window and excellent chemical and electrochemical stability,active material,and conductive carbon are introduced in the battery configuration,resulting in superior electrochemical performances with the bare LiNi_(0.7)Mn_(0.2)Co_(0.1)O_(2)cathode.The corresponding battery delivers a discharge capacity of 162.1 mAh g^(−1)at 0.5C and maintains 83.8%of the capacity after 200 cycles at room temperature.Moreover,this battery with a cathode mass loading of 6.37 mg cm−2 displays discharge capacities of 197.5 and 73.4 mAh g^(−1)at the beginning when cycled at 0.5C and 0.1C under the operating temperature of 60 and−20℃,respectively.The battery also achieved superior stablecycling performances at both temperatures.Due to the fast ionic conductivity from Li_(6.6)Si_(0.6)Sb_(0.4)S_(5)I and high electronic conductivity from carbon in the cathode,the thick-electrode configurations with huge mass loadings of 50.96 and 76.43 mg cm^(−2)also exhibit good capacities and highly reversible cyclability.This work provides a guideline for enabling superior conducting sulfide electrolytes with poor stability in thick-electrode configuration solid-state batteries.
基金National Key Research and Development Program(2021YFB2500200)National Natural Science Foundation of China(no.52177214)China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(no.21C-OP202211).
文摘Ionic conductivity and electro/chemical compatibility of Li_(10)SnP_(2)S_(12) electrolytes play crucial roles in achieving superior electrochemical performances of the corresponding solid-state batteries.However,the relatively low Li-ion conductivity and poor stability of Li_(10)SnP_(2)S_(12) toward high-voltage layered oxide cathodes limit its applications.Here,a Br-substituted strategy has been applied to promote Li-ion conductivity.The optimal composition of Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) delivers high conductivity up to 6.0 mS cm^(−1).7Li static spin-lattice relaxation(T1)nuclear magnetic resonance(NMR)and density functional theory simulation are combined to unravel the improvement of Li-ion diffusion mechanism for the modified electrolytes.To mitigate the interfacial stability between the Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) electrolyte and the bare LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2) cathode,introducing Li_(2)ZrO_(3) coating layer and Li_(3)InCl_(6) isolating layer strategies has been employed to fabricate all-solid-state lithium batteries with excellent electrochemical performances.The Li_(3)InCl_(6)-LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2)/Li_(3)InCl_(6)/Li_(9.9)SnP_(2)S_(11.9)Br_(0.1)/Li-In battery delivers much higher discharge capacities and fast capacity degradations at different charge/discharge C rates,while the Li_(2)ZrO_(3)@LiNi_(0.7)Co_(0.1)Mn_(0.2)O_(2)/Li_(9.9)SnP_(2)S_(11.9)Br_(0.1)/Li-In battery shows slightly lower discharge capacities at the same C rates and superior cycling performances.Multiple characterization methods are conducted to reveal the differences of battery performance.The poor electrochemical performance of the latter battery configuration is associated with the interfacial instability between the Li_(3)InCl_(6) electrolyte and the Li_(9.9)SnP_(2)S_(11.9)Br_(0.1) electrolyte.This work offers an effective strategy to constructing Li_(10)SnP_(2)S_(12)-based all-solid-state lithium batteries with high capacities and superior cyclabilities.
