All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,s...All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,sulfide solid electrolyte(SSE)Li_(6)PS_(5)Cl has garnered significant attention.However,its application is limited by its poor cyclability and low critical current density(CCD).In this study,we introduce a novel approach to enhance the performance of Li_(6)PS_(5)Cl by doping it with fluorine,using lithium fluoride nanoparticles(LiFs)as the doping precursor.The F-doped electrolyte Li_(6)PS_(5)Cl-0.2LiF(nano)shows a doubled CCD,from 0.5 to 1.0 mA/cm^(2) without compromising the ionic conductivity;in fact,conductivity is enhanced from 2.82 to 3.30 mS/cm,contrary to the typical performance decline seen in conventionally doped Li_(6)PS_(5)Cl electrolytes.In symmetric Li|SSE|Li cells,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is 4 times longer than that of Li_(6)PS_(5)Cl,achieving 1500 h vs.371 h under a charging/discharging current density of 0.2 mA/cm^(2).In Li|SSE|LiNbO_(3)@NCM721 full cells,which are tested under a cycling rate of 0.1 C at 30℃,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is four times that of Li_(6)PS_(5)Cl,reaching 100 cycles vs.26 cycles.Therefore,the doping of nano-LiF off ers a promising approach to developing high-performance Li_(6)PS_(5)Cl for ASSLMBs.展开更多
All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-impr...All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.展开更多
Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-clas...Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.展开更多
The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inade...The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).展开更多
Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective catho...Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective cathode material for high-energy all-solid-state rechargeable batteries.However,its wide use is hindered by large volume expansion and low utilization rate.In this work,Se-infused nitrogen-doped hierarchical meso-microporous carbon composites(Se/NHPC)are prepared by a melt-diffusion process.Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%.All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode,a Li-In alloy as the anode,and Li_(6)PS_(5)Cl as the solid-state electrolyte,deliver a highly reversible capacity of 621 m Ah/g(92%of theoretical capacity),a good rate capability and a high capacity retention value of 80.9%after 100 cycles.It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate,as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Senchains to Se8rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.展开更多
All-solid-state lithium metal batteries(ASSLMBs)that incorporate solid electrolyte(SE)and lithium metal anode suggest considerable potential in addressing the security concerns and energy density limitation of convent...All-solid-state lithium metal batteries(ASSLMBs)that incorporate solid electrolyte(SE)and lithium metal anode suggest considerable potential in addressing the security concerns and energy density limitation of conventional lithium-ion batteries(LIBs).However,the practical application of ASSLMBs is always restricted by the interfacial instability of lithium metal anode/electrolyte and inevitable lithium dendrites propagation in SE.Herein,a solvate ionic liquid is adopted to modify the interface stability of lithium metal anode/electrolyte and inhibit the growth of lithium dendrites via an in-situ formation of a robust solid electrolyte interphase(SEI)on the surface of lithium metal anode.Consequently,the ASSLMBs assembled with Li_(6)PS_(5)Cl(LPSCl)electrolyte,lithium metal anode that protected by robust SEI layer,and LiNbO_(3)@NCM622 cathode exhibit high initial capacity of 126.5 mAh·g^(−1)and improved cycling stability with a capacity retention of 80.3%over 60 cycles at 0.1 C.This work helps to provide a facile route for the design of robust SEI in the application of ASSLMBs.展开更多
Bulk-type all-solid-state batteries(ASSBs)using sulfide solid electrolyte are considered as a promising alternative to commercial lithium-ion batteries owing to their high energy density and safety.However,cell energy...Bulk-type all-solid-state batteries(ASSBs)using sulfide solid electrolyte are considered as a promising alternative to commercial lithium-ion batteries owing to their high energy density and safety.However,cell energy density is often comparatively low due to use of a thick solid electrolyte separator and a lithium alloy as anode.For achieving high-performance ASSBs,creating a thin free-standing electrolyte with high-conductivity and good cycling stability against lithium anode is essential.In this work,we present Li_(6)PS_(5)Cl/poly(vinylidene difluoride)(LPSCl/PVDF)composite electrolytes prepared by a slurry method.The influence of the PVDF content on the microstructure,morphology,ionic conductivity and activation energy of the LPSCl/PVDF electrolytes is systematically investigated.Free-standing LPSCl/PVDF membranes with a thickness of 100-120 mm and a high ionic conductivity of about 1·10^(-3) S cm^(-1) at 25℃ are obtained.After adding PVDF to the LPSCl electrolyte,the cycling stability of the LPSCl electrolyte against lithium metal improves significantly.Therefore,LPSCl/PVDF composite electrolytes are promising candidates to be used in ASSBs.展开更多
基金supported by the National Key Research and Development Program of China(No.2018YFE0111600)the Haihe Laboratory of Sustainable Chemical Transformations(No.CYZC202307)for financial support。
文摘All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,sulfide solid electrolyte(SSE)Li_(6)PS_(5)Cl has garnered significant attention.However,its application is limited by its poor cyclability and low critical current density(CCD).In this study,we introduce a novel approach to enhance the performance of Li_(6)PS_(5)Cl by doping it with fluorine,using lithium fluoride nanoparticles(LiFs)as the doping precursor.The F-doped electrolyte Li_(6)PS_(5)Cl-0.2LiF(nano)shows a doubled CCD,from 0.5 to 1.0 mA/cm^(2) without compromising the ionic conductivity;in fact,conductivity is enhanced from 2.82 to 3.30 mS/cm,contrary to the typical performance decline seen in conventionally doped Li_(6)PS_(5)Cl electrolytes.In symmetric Li|SSE|Li cells,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is 4 times longer than that of Li_(6)PS_(5)Cl,achieving 1500 h vs.371 h under a charging/discharging current density of 0.2 mA/cm^(2).In Li|SSE|LiNbO_(3)@NCM721 full cells,which are tested under a cycling rate of 0.1 C at 30℃,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is four times that of Li_(6)PS_(5)Cl,reaching 100 cycles vs.26 cycles.Therefore,the doping of nano-LiF off ers a promising approach to developing high-performance Li_(6)PS_(5)Cl for ASSLMBs.
基金supported by Beijing Natural Science Foundation(JQ22028)National Natural Science Foundation of China(U21A2080)+1 种基金Jilin Province Science and Technology Major Project(20210301021GX)Ministry of Science and Technology Rare Earth Special(2022YFB3506300).
文摘All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.
基金B.Tian acknowledges the financial support from the Science and Technology Project of Shenzhen(No.JCYJ20210324094206019)X.Huang acknowledges the financial support from the National Natural Science Foundation of China(No.52102284)+2 种基金Z.Yu acknowledges Department of Science and Technology of Guangxi Province(Nos.AB21220027,AD19110077)Guangxi Key Laboratory of Manufacturing Systems Foundation(No.20-065-40-005Z)Engineering Research Center Foundation of Electronic Information Materials and Devices(No.EIMD-AA202005).
文摘Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.
基金supported by the National Natural Science Foundation of China(No.T2241003)the National Key Research and Development Program of China(No.2022YFB4003500)the Key R&D project of Hubei Province,China(No.2021AAA006).
文摘The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).
基金supported by the National Natural Science Foundation of China(Nos.51902188,52272224)Innovation Capacity Improvement Project of Small and Medium-Sized Technology-Based Enterprise of Shandong Province(No.2021TSGC1149)+2 种基金Youth Innovation Team Project of Shandong Provincial Education Department(No.10000082295015)Natural Science Doctoral Foundation of Shandong Province(No.ZR2019BEM019)the Future Program for Young Scholar of Shandong University。
文摘Selenium,an element belonging to the same group in the periodic table as sulfur,has a high electronic conductivity(1×10^(-5)S/cm)and a high volumetric energy density(3253 mA h/cm^(3)),which is a prospective cathode material for high-energy all-solid-state rechargeable batteries.However,its wide use is hindered by large volume expansion and low utilization rate.In this work,Se-infused nitrogen-doped hierarchical meso-microporous carbon composites(Se/NHPC)are prepared by a melt-diffusion process.Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%.All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode,a Li-In alloy as the anode,and Li_(6)PS_(5)Cl as the solid-state electrolyte,deliver a highly reversible capacity of 621 m Ah/g(92%of theoretical capacity),a good rate capability and a high capacity retention value of 80.9%after 100 cycles.It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate,as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Senchains to Se8rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.
基金supported by the National Natural Science Foundation of China(No.U21A2080)Shanxi key research and development program(No.202102060301011)Key scientific research projects of colleges and universities in Henan Province(No.23A430044).
文摘All-solid-state lithium metal batteries(ASSLMBs)that incorporate solid electrolyte(SE)and lithium metal anode suggest considerable potential in addressing the security concerns and energy density limitation of conventional lithium-ion batteries(LIBs).However,the practical application of ASSLMBs is always restricted by the interfacial instability of lithium metal anode/electrolyte and inevitable lithium dendrites propagation in SE.Herein,a solvate ionic liquid is adopted to modify the interface stability of lithium metal anode/electrolyte and inhibit the growth of lithium dendrites via an in-situ formation of a robust solid electrolyte interphase(SEI)on the surface of lithium metal anode.Consequently,the ASSLMBs assembled with Li_(6)PS_(5)Cl(LPSCl)electrolyte,lithium metal anode that protected by robust SEI layer,and LiNbO_(3)@NCM622 cathode exhibit high initial capacity of 126.5 mAh·g^(−1)and improved cycling stability with a capacity retention of 80.3%over 60 cycles at 0.1 C.This work helps to provide a facile route for the design of robust SEI in the application of ASSLMBs.
基金supported by the Basic Science Center Program of NSFC under Grant No.51788104NSFC projects under Grant Nos.51532002,51572141,and 51625202financial support within the project 03XP0177A funded by BMBF with the cluster of competence FESTBATT.
文摘Bulk-type all-solid-state batteries(ASSBs)using sulfide solid electrolyte are considered as a promising alternative to commercial lithium-ion batteries owing to their high energy density and safety.However,cell energy density is often comparatively low due to use of a thick solid electrolyte separator and a lithium alloy as anode.For achieving high-performance ASSBs,creating a thin free-standing electrolyte with high-conductivity and good cycling stability against lithium anode is essential.In this work,we present Li_(6)PS_(5)Cl/poly(vinylidene difluoride)(LPSCl/PVDF)composite electrolytes prepared by a slurry method.The influence of the PVDF content on the microstructure,morphology,ionic conductivity and activation energy of the LPSCl/PVDF electrolytes is systematically investigated.Free-standing LPSCl/PVDF membranes with a thickness of 100-120 mm and a high ionic conductivity of about 1·10^(-3) S cm^(-1) at 25℃ are obtained.After adding PVDF to the LPSCl electrolyte,the cycling stability of the LPSCl electrolyte against lithium metal improves significantly.Therefore,LPSCl/PVDF composite electrolytes are promising candidates to be used in ASSBs.
