To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density...To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density.However,their practical deployment is hindered by accelerated interface degradation and capacity decay originating from surface oxygen release and lattice oxygen activation during prolonged cycling.In this study,Ti_(x)NbB_((1−x))C_(2)was successfully coated on the surface of LiNi_(0.94)Co_(0.05)Mn_(0.01)O_(2).Density functional theory(DFT)calculations first elucidate a“point-to-point”anchoring mechanism where each surface oxygen atom coordinates with single species(Ti/Nb/B)offered by Ti_(x)NbB_((1−x))C_(2),which forms robust O–M bonds and sustain a stable interface structure.The electron energy loss spectroscopy(EELS)reveals the segregation of Ti/Nb toward subsurface layers during cycling,creating an optimized lattice oxygen coordination environment and suppressing oxygen activation.The dual oxygen stabilization mechanism dramatically improves the reversibility of phase transition and the structural stability of the Ni-rich cathode materials.Moreover,Ti_(x)NbB_((1−x))C_(2)as the protective layer decreases mechanical strain and suppresses the parasitic reactions.Consequently,the engineered cathode delivers 91%capacity retention after 1000 cycles at 0.3 C,suggesting excellent cycling stability.The research delivers a new design philosophy for the coating layer that can stabilize surface oxygen.Furthermore,the atomistic understanding of the structure–property relationship of the Ni-rich cathode materials provides valuable guidance for the future design of new cathode materials with superior structural stability in ASSLBs.展开更多
Lithium-selenium(Li-Se)batteries have attracted considerable attentions for next-generation energy storage systems owing to high volumetric capacity of 3265 m Ah cm^(-3) and excellent electronic conductivity(~10^(-5)S...Lithium-selenium(Li-Se)batteries have attracted considerable attentions for next-generation energy storage systems owing to high volumetric capacity of 3265 m Ah cm^(-3) and excellent electronic conductivity(~10^(-5)S cm^(-1))of selenium.However,the shuttling effect and capacity fading prevent their wide applications.Herein we report a low-cost strategy for scalable fabrication of lignin derived hierarchical porous carbon(LHPC)as a new high-loading Se host for high-capacity and long-term cycling Li-Se batteries in carbonate electrolyte.The resulting LHPC exhibits three-dimensional(3D)hierarchically porous structure,high specific surface area of 1696 m^(2) g^(-1),and hetero-atom doping(O,S),which can effectively confine the Se particles into the micropores,and meanwhile,offer effective chemical binding sites for selenides from hetero-atoms(O,S).As a result,our Li-Se batteries based on Se@LHPC demonstrate high capacity of 450 m Ah g^(-1) at 0.5 C after 500 cycles,with a low capacity fading rate of only 0.027%.The theoretical simulation confirmed the strong affinity of selenides on the O and S sites of LHPC effectively mitigating the Se losing.Therefore,our strategy of using lignin as the low-cost precursor of hierarchically porous carbon for high-loading Se host offers new opportunities for high-capacity and long-life Li-Se batteries.展开更多
All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However,...All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However, PEO-based ASSLSBs face the dilemma of insufficient Coulombic efficiency and long-term stability caused by the coupling problems of dendrite growth of anode and polysulfide shuttle of cathode. In this work, 1,3,5-trioxane(TOX) is used as a functional additive to design a PEO-based composite solidstate electrolyte(denoted as TOX-CSE), which realizes the stable long-term cycle of an ASSLSB. The results show that TOX can in-situ decompose on the anode to form a composite solid electrolyte interphase(SEI) layer with rich-organic component. It yields a high average modulus of 5.0 GPa, greatly improving the mechanical stability of the SEI layer and thus inhibiting the growth of dendrites. Also,the robust SEI layer can act as a barrier to block the side reaction between polysulfides and lithium metal.As a result, a Li-Li symmetric cell assembled with a TOX-CSE exhibits prolonged cycling stability over 2000 h at 0.2 m A cm^(-2). The ASSLSB also shows a stable cycling performance of 500 cycles at 0.5 C.This work reveals the structure–activity relationship between the mechanical property of interface layer and the battery's cycling stability.展开更多
The lepidocrocite-type H_(1.07)Ti_(1.73)O_(4) microsized structures with a tap density of 0.88 g·cm^(-3) were prepared through the ion exchange method with K_(0.8)Li_(0.27)Ti_(1.73)O_(4) powder as the precursor,a...The lepidocrocite-type H_(1.07)Ti_(1.73)O_(4) microsized structures with a tap density of 0.88 g·cm^(-3) were prepared through the ion exchange method with K_(0.8)Li_(0.27)Ti_(1.73)O_(4) powder as the precursor,and they exhibited good rate performance and outstanding cycle stability as an anode material for lithium ion batteries(LIB).The ion exchange method provides favorable conditions for H_(1.07)Ti_(1.73)O_(4) as an anode electrode material for LIBs.X-ray photoelectron spectroscopy(XPS)result demonstrates the existence of defects in the nonstoichiometric H1.07Ti1.73O4,which have a beneficial effect on the LIB performance.The electrochemical performance test proves that the half-cell with microsized H_(1.07)Ti_(1.73)O_(4)as the anode electrode can maintain a specific capacity of 129.5 mAh·g^(-1) after 1100 cycles and 101 mAh·g^(-1)after 3000 long cycles at high current densities of 2.0 and 5.0 A·g^(-1),respectively.In addition,the small volume change rate of 3.6%in H_(1.07)Ti_(1.73)O_(4)during Li ion insertion was confirmed by real-time in situ transmission electron microscopy(TEM).The LiFePO_(4)||H_(1.07)Ti_(1.73)O_(4)full battery exhibits a longterm cycling stability with a specific capacity of73.8 mAh·g^(-1) at a current density of 500 mA·g^(-1) after 200 cycles.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility wit...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.展开更多
Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as...Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as they are exposed to air.In this study,we synthesized a composite electrolyte membrane filled with garnet material using a casting method and successfully applied it to Li-air batteries.The polymer electrolyte composed of poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)filled with garnet LLZTO as an active filler(15-PHL CPE),which exhibited excellent flexibility,wide electrochemical window,high ion conductivity and good thermal stability.Furthermore,symmetric Li‖15-PHL CPE‖Li cells stably operate over 3500h at 0.1 mA cm^(-2)and 25℃.The assembled 15-PHL CPE-based Li-air battery reaches a stable cycling performance of 97 cycles at 200 mA g^(-1)with a well-maintained potential gap of1.93 V,which demonstrates promising application in Li-air batteries.展开更多
In this work,we report a high-performance self-standing supercapacitor electrode of mixed nickel manganese sulfides (NMSs)with a cracked-bark shape grown by one-step electrochemical deposition on activated carbon clot...In this work,we report a high-performance self-standing supercapacitor electrode of mixed nickel manganese sulfides (NMSs)with a cracked-bark shape grown by one-step electrochemical deposition on activated carbon cloth (ACC).The electrode possesses outstanding electrochemical properties,including a high specific capacitance of up to 3142.8 F g^(-1)at 1.0 A g^(-1),the high-rate performance (~1206.8 F g^(-1)at 60.0 A g^(-1)),and cycle stability (~92.3%capacitance retention after 8000 cycles at8 A g^(-1)).An asymmetric supercapacitor assembled using NMSs on ACC as the cathode,activated carbon on carbon cloth as the anode and 1.0 mol L;KOH as the electrolyte delivers a high energy density of 111.2 W h kg^(-1)at 800.0 W kg^(-1)and the prominent cycling performance of~93.2%capacitance retention after 10000 cycles at 5 A g^(-1)with the Columbic efficiency of around 100%during these 10000 cycles.The high performance and facile preparation indicate that the NMSs on ACC hold a huge potential as the electrode for supercapacitors.展开更多
Supercapacitors display promising electrochemical performance with high power density and excellent cycle stability.However,their low energy density limits their advancement in a broader range of applications.To enhan...Supercapacitors display promising electrochemical performance with high power density and excellent cycle stability.However,their low energy density limits their advancement in a broader range of applications.To enhance their energy density,we proposed self-assembled spinel NiMn2S4nanoflakes grown on nickel foam which we successfully prepared by a facile hydrothermal method.The NiMn2S4electrode delivers a high capacitance of 2096.7 F g^(-1)at 1.0 A g^(-1),with an exceptional rate capability(~720.6 F g^(-1)at a very high current density of 100 A g^(-1))and good cycle stability(~85.1%retention of the initial capacitance after 7000 cycles with the Coulombic efficiency around 100%).The as-fabricated asymmetric supercapacitors based on NiMn2S4nanoflakes//active carbon demonstrate an energy density of 73.6 W h kg^(-1)at 800.5 W kg^(-1)and adequate cycling performance of~84.6%capacitance retention at 15 A g^(-1)after 10000 cycles.The results reveal that the nanostructured NiMn2S4is an excellent electrode material for high-performance energy storage applications.展开更多
基金supported by the National Natural Science Foundation of China(21203008,21975025,12274025,22372008,and 22179007)Hainan Province Science and Technology Special Fund(ZDYF2021SHFZ232 and ZDYF2023GXJS022)Hainan Province Postdoctoral Science Foundation(300333)。
文摘To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density.However,their practical deployment is hindered by accelerated interface degradation and capacity decay originating from surface oxygen release and lattice oxygen activation during prolonged cycling.In this study,Ti_(x)NbB_((1−x))C_(2)was successfully coated on the surface of LiNi_(0.94)Co_(0.05)Mn_(0.01)O_(2).Density functional theory(DFT)calculations first elucidate a“point-to-point”anchoring mechanism where each surface oxygen atom coordinates with single species(Ti/Nb/B)offered by Ti_(x)NbB_((1−x))C_(2),which forms robust O–M bonds and sustain a stable interface structure.The electron energy loss spectroscopy(EELS)reveals the segregation of Ti/Nb toward subsurface layers during cycling,creating an optimized lattice oxygen coordination environment and suppressing oxygen activation.The dual oxygen stabilization mechanism dramatically improves the reversibility of phase transition and the structural stability of the Ni-rich cathode materials.Moreover,Ti_(x)NbB_((1−x))C_(2)as the protective layer decreases mechanical strain and suppresses the parasitic reactions.Consequently,the engineered cathode delivers 91%capacity retention after 1000 cycles at 0.3 C,suggesting excellent cycling stability.The research delivers a new design philosophy for the coating layer that can stabilize surface oxygen.Furthermore,the atomistic understanding of the structure–property relationship of the Ni-rich cathode materials provides valuable guidance for the future design of new cathode materials with superior structural stability in ASSLBs.
基金financially supported by the National Key R&D Program of China(Grants 2016YBF0100100,2016YFA0200200)the National Natural Science Foundation of China(Grants 51872283,21805273)+1 种基金the Liaoning Bai Qian Wan Talents Program,Natural Science Foundation of Liaoning Province,Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(Grant 20180510038)the Liao Ning Revitalization Talents Program(Grant XLYC1807153),DICP(DICP ZZBS201708,DICP ZZBS201802,DICP I202032),DNL Cooperation Fund,CAS(DNL180310,DNL180308,DNL201912,and DNL201915),DICP&QIBEBT(Grant DICP&QIBEBT UN201702)。
文摘Lithium-selenium(Li-Se)batteries have attracted considerable attentions for next-generation energy storage systems owing to high volumetric capacity of 3265 m Ah cm^(-3) and excellent electronic conductivity(~10^(-5)S cm^(-1))of selenium.However,the shuttling effect and capacity fading prevent their wide applications.Herein we report a low-cost strategy for scalable fabrication of lignin derived hierarchical porous carbon(LHPC)as a new high-loading Se host for high-capacity and long-term cycling Li-Se batteries in carbonate electrolyte.The resulting LHPC exhibits three-dimensional(3D)hierarchically porous structure,high specific surface area of 1696 m^(2) g^(-1),and hetero-atom doping(O,S),which can effectively confine the Se particles into the micropores,and meanwhile,offer effective chemical binding sites for selenides from hetero-atoms(O,S).As a result,our Li-Se batteries based on Se@LHPC demonstrate high capacity of 450 m Ah g^(-1) at 0.5 C after 500 cycles,with a low capacity fading rate of only 0.027%.The theoretical simulation confirmed the strong affinity of selenides on the O and S sites of LHPC effectively mitigating the Se losing.Therefore,our strategy of using lignin as the low-cost precursor of hierarchically porous carbon for high-loading Se host offers new opportunities for high-capacity and long-life Li-Se batteries.
基金National Natural Science Foundation of China (Grant Nos. 22178125 and 21875071)。
文摘All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However, PEO-based ASSLSBs face the dilemma of insufficient Coulombic efficiency and long-term stability caused by the coupling problems of dendrite growth of anode and polysulfide shuttle of cathode. In this work, 1,3,5-trioxane(TOX) is used as a functional additive to design a PEO-based composite solidstate electrolyte(denoted as TOX-CSE), which realizes the stable long-term cycle of an ASSLSB. The results show that TOX can in-situ decompose on the anode to form a composite solid electrolyte interphase(SEI) layer with rich-organic component. It yields a high average modulus of 5.0 GPa, greatly improving the mechanical stability of the SEI layer and thus inhibiting the growth of dendrites. Also,the robust SEI layer can act as a barrier to block the side reaction between polysulfides and lithium metal.As a result, a Li-Li symmetric cell assembled with a TOX-CSE exhibits prolonged cycling stability over 2000 h at 0.2 m A cm^(-2). The ASSLSB also shows a stable cycling performance of 500 cycles at 0.5 C.This work reveals the structure–activity relationship between the mechanical property of interface layer and the battery's cycling stability.
基金supported by the National Natural Science Foundation of China(Nos.U1804132,51802288 and 11504331)Academic Improvement Program of Physics of Zhengzhou University(No.2018WLTJ02)Zhengzhou University Youth Talent Start-up Grant,Zhongyuan Youth Talent Support Program of Henan Province(No.ZYQR201912152)。
文摘The lepidocrocite-type H_(1.07)Ti_(1.73)O_(4) microsized structures with a tap density of 0.88 g·cm^(-3) were prepared through the ion exchange method with K_(0.8)Li_(0.27)Ti_(1.73)O_(4) powder as the precursor,and they exhibited good rate performance and outstanding cycle stability as an anode material for lithium ion batteries(LIB).The ion exchange method provides favorable conditions for H_(1.07)Ti_(1.73)O_(4) as an anode electrode material for LIBs.X-ray photoelectron spectroscopy(XPS)result demonstrates the existence of defects in the nonstoichiometric H1.07Ti1.73O4,which have a beneficial effect on the LIB performance.The electrochemical performance test proves that the half-cell with microsized H_(1.07)Ti_(1.73)O_(4)as the anode electrode can maintain a specific capacity of 129.5 mAh·g^(-1) after 1100 cycles and 101 mAh·g^(-1)after 3000 long cycles at high current densities of 2.0 and 5.0 A·g^(-1),respectively.In addition,the small volume change rate of 3.6%in H_(1.07)Ti_(1.73)O_(4)during Li ion insertion was confirmed by real-time in situ transmission electron microscopy(TEM).The LiFePO_(4)||H_(1.07)Ti_(1.73)O_(4)full battery exhibits a longterm cycling stability with a specific capacity of73.8 mAh·g^(-1) at a current density of 500 mA·g^(-1) after 200 cycles.
基金supported by the National Natural Science Foundation of China(52003293,51927806,52272258)the Fundamental Research Funds for the Central Universities(2023ZKPYJD07)the Beijing Nova Program(20220484214).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.
基金supported by the National Natural Science Foundation of China(U2330124,22411560292,U20A2072,52072352,21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)Sichuan Science and Technology Program(2023ZYD0026)。
文摘Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as they are exposed to air.In this study,we synthesized a composite electrolyte membrane filled with garnet material using a casting method and successfully applied it to Li-air batteries.The polymer electrolyte composed of poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)filled with garnet LLZTO as an active filler(15-PHL CPE),which exhibited excellent flexibility,wide electrochemical window,high ion conductivity and good thermal stability.Furthermore,symmetric Li‖15-PHL CPE‖Li cells stably operate over 3500h at 0.1 mA cm^(-2)and 25℃.The assembled 15-PHL CPE-based Li-air battery reaches a stable cycling performance of 97 cycles at 200 mA g^(-1)with a well-maintained potential gap of1.93 V,which demonstrates promising application in Li-air batteries.
基金supported by the Natural Science Foundation of Gansu,China(Grant No.20JR10RA611)。
文摘In this work,we report a high-performance self-standing supercapacitor electrode of mixed nickel manganese sulfides (NMSs)with a cracked-bark shape grown by one-step electrochemical deposition on activated carbon cloth (ACC).The electrode possesses outstanding electrochemical properties,including a high specific capacitance of up to 3142.8 F g^(-1)at 1.0 A g^(-1),the high-rate performance (~1206.8 F g^(-1)at 60.0 A g^(-1)),and cycle stability (~92.3%capacitance retention after 8000 cycles at8 A g^(-1)).An asymmetric supercapacitor assembled using NMSs on ACC as the cathode,activated carbon on carbon cloth as the anode and 1.0 mol L;KOH as the electrolyte delivers a high energy density of 111.2 W h kg^(-1)at 800.0 W kg^(-1)and the prominent cycling performance of~93.2%capacitance retention after 10000 cycles at 5 A g^(-1)with the Columbic efficiency of around 100%during these 10000 cycles.The high performance and facile preparation indicate that the NMSs on ACC hold a huge potential as the electrode for supercapacitors.
基金partly supported by the Natural Science Foundation of Gansu,China(Grant Nos.22YF7GA009 and 20JR10RA611)the Fundamental Research Funds for the Central Universities(Grant No.lzujbky-2021 sp54)。
文摘Supercapacitors display promising electrochemical performance with high power density and excellent cycle stability.However,their low energy density limits their advancement in a broader range of applications.To enhance their energy density,we proposed self-assembled spinel NiMn2S4nanoflakes grown on nickel foam which we successfully prepared by a facile hydrothermal method.The NiMn2S4electrode delivers a high capacitance of 2096.7 F g^(-1)at 1.0 A g^(-1),with an exceptional rate capability(~720.6 F g^(-1)at a very high current density of 100 A g^(-1))and good cycle stability(~85.1%retention of the initial capacitance after 7000 cycles with the Coulombic efficiency around 100%).The as-fabricated asymmetric supercapacitors based on NiMn2S4nanoflakes//active carbon demonstrate an energy density of 73.6 W h kg^(-1)at 800.5 W kg^(-1)and adequate cycling performance of~84.6%capacitance retention at 15 A g^(-1)after 10000 cycles.The results reveal that the nanostructured NiMn2S4is an excellent electrode material for high-performance energy storage applications.
