All-solid-state batteries(ASSBs)are considered to be the most promising candidates for improving battery safety and energy density.Sulfide electrolytes have a narrow electrochemical window,which hinders their applicat...All-solid-state batteries(ASSBs)are considered to be the most promising candidates for improving battery safety and energy density.Sulfide electrolytes have a narrow electrochemical window,which hinders their applications coupled with high-voltage cathodes.Halide electrolytes with high-voltage endurance can help solve this problem.Herein,the combination of spraying and slurry-coating methods was adopted as a practical route to process a free-standing Li_(6)PS_5Cl(LPSCl)asymmetrical electrolyte membrane(19.23Ωcm~2,75μm)decorated with a 10μm Li_(3)In Cl_(6)(LICl)layer.The LICl-LPSCl asymmetrical electrolyte membranes enhanced the high-voltage stabilities to match those of LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)and Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LRMO)cathodes.The NCM811|LICl-LPSCl|n Si ASSB achieved an initial coulombic efficiency(ICE)of 85.13%and a capacity retention of 77.16%after 200 cycles.Compared with the LPSCl membrane,the LICl-LPSCl membrane displayed high stability with the LRMO cathode as the charging cut-off voltage increased to 4.7 V,which improved the initial charge capacity from 143 to 270 mAh g^(-1)and achieved stable cycling of 160 m Ah g^(-1)at 0.5 C.Additionally,we attempted continuous LICl-LPSCl membrane production and utilized the product to fabricate a pouch-type ASSB based on LRMO.The fabrication of the LICl-LPSCl electrolyte membrane demonstrated its potential for controllable and industryadaptable applications in ASSBs.展开更多
A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm ...A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.展开更多
All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the unde...All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the undesirable side reactions of sulfide-based solid electrolytes(SEs),resulting in poor electrochemical properties with increased interfacial resistance.Here,we propose a wet chemical method rationally designed to achieve a conformal coating of lithium-indium chloride(Li_(3)InCl_(6))onto vapor-grown carbon fibers(VGCFs)as conductive agents.First,with the advantage of the Li_(3)InCl_(6) protective layer,use of VGCF@Li_(3)InCl_(6) leads to enhanced interfacial stability and improved electrochemical properties,including stable cycle performance.These results indicate that the Li_(3)InCl_(6) protective layer suppresses the unwanted reaction between Li_(6)PS_(5)Cl(LPSCl)and VGCF.Second,VGCF@Li_(3)InCl_(6) effectively promotes polytetrafluoroethylene(PTFE)fibrillization,leading to a homogeneous electrode microstructure.The uniform distribution of the cathode active material(CAM)in the electrode results in reduced charge-transfer resistance(R_(ct))and enhanced Li-ion kinetics.As a result,a full cell with the LiNi_(x)Mn_(y)Co_(z)O_(2)(NCM)/VGCF@Li_(3)InCl_(6) electrode shows an areal capacity of 7.7mAhcm^(−2) at 0.05 C and long-term cycle stability of 77.9%over 400 cycles at 0.2 C.This study offers a strategy for utilizing stable carbon-based conductive agents in sulfide-based ASSBs to enhance their electrochemical performance.展开更多
Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical dur...Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical durability and humidity stability,hindering their large-scale applications.Here,we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene(PTFE)binder to encapsulate Li_(3)InCl_(6)(LIC)particles(the most representative HSSE).By manipulating the fibrillating process,only 0.5 wt%PTFE is sufficient to prepare free-standing LIC-PTFE(LIC-P)HSSEs.Additionally,LIC-P demonstrates excellent mechanical durability and humidity resistance.They can maintain their shapes after being exposed to humid atmosphere for 30 min,meanwhile still exhibit high ionic conductivity of>0.2m S/cm at 25℃.Consequently,the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 m Ah/g at0.1 C and long cyclability of 200 cycles at 0.2 C.More importantly,the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7%after 100 cycles under0.2 C.Furthermore,for the first time,we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.展开更多
Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.None...Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.展开更多
All-solid-state batteries(ASSBs) with inorganic solid-state-electrolytes(SSEs) have been regarded as the promising candidate for next-generation energy storage due to their high energy density and outstanding safety p...All-solid-state batteries(ASSBs) with inorganic solid-state-electrolytes(SSEs) have been regarded as the promising candidate for next-generation energy storage due to their high energy density and outstanding safety performance.However,the representative oxide and sulfide electrolytes suffer from low ionic conductivity and poor(electro)chemical stability,respectively.Herein,we report a series of new halide superionic conductors Li_(2+x)Hf_(1-x)In_(x)Cl_(6) with high ionic conductivity up to 1.05 mS cm^(-1) at 30 ℃ that are simultaneously stable to high voltage.By means of the characterization techniques and bond-valence site energy(BVSE) calculation,insights into the effect of the phase transformation and underlying ionic transport mechanism by In substitution for Hf in Li_(2)HfCl_(6) are provided.Importantly,with the increased amount of aliovalent substitution in Li_(2+x)Hf_(1-x)In_(x)Cl_(6) microcrystal framework,a gradual structure evolution from trigonal to monoclinic phase has been observed,which is accompanied by the redistribution of Li-ions to generate two dimensionally(2D) preferable diffusion pathways through octahedral-tetrahe dral-octahedral sites in In^(3+)-substituted Li_(2)HfCl_(6).Additionally,due to the oxidative stability of Insubstituted Li_(2)HfCl_(6),the bulk-type ASSBs with bare LiCoO_(2) deliver distinguished electrochemical performance.展开更多
As the next generation of commercial automotive power batteries begins replacing liquid lithium batteries,many look towards all-solid-state batteries to pioneer the future.All-so lid-state batteries have attracted the...As the next generation of commercial automotive power batteries begins replacing liquid lithium batteries,many look towards all-solid-state batteries to pioneer the future.All-so lid-state batteries have attracted the attention of countless researchers around the world because of their high safety and high energy density.In recent times,halide solid-state electrolytes have become a research hotspot within solid-state electrolytes because of their potentially superior properties.In this paper,in the framework of DFT,we investigated the atomic mechanisms of improving the ionic conductivity and stability of Li_(3)YbCl_(6).Our calculations show that both trigonal and orthorhombic Li_(3)YbCl_(6) exhibit wide electrochemical windows and metastable properties(100 meV/atom>Ehull>0 meV/atom).However,the orthorhombic Li_(3)YbCl_(6) can be stabilized at high temperatures by taking the vibrational entropy into account,which is supported by the experimental results.Moreover,it is expected that because of the Yb/Li synergistic interactions that,due to their strong mutual coulomb repulsion,influence the Li^(+)transport behavior,the orthorhombic Li_(3)YbCl_(6) might have superior ionic conductivities with appropriate Li+migration paths determined by the Yb^(3+) distribution.Also,higher ionic conductivities can be obtained by regulating the random distribution of Li^(+) ions.Further Li^(+)-deficiency can also largely increase the ionic conductivity by invoking vacancies.This study helps gain a deeper understanding of the laws that govern ionic conductivities and stabilities and provides a certain theoretical reference for the experimental development and design of halide solid-state electrolytes.展开更多
Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are co...Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.展开更多
Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage c...Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.展开更多
Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relat...Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.展开更多
Halide electrolytes in solid-state batteries with excellent oxidative stability and high ionic conductivity have been well reported recently.However,the high-cost rare-earth elements and long duration of highrotation ...Halide electrolytes in solid-state batteries with excellent oxidative stability and high ionic conductivity have been well reported recently.However,the high-cost rare-earth elements and long duration of highrotation milling procure are the major obstacles.Herein,we have successfully synthesized the low cost Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)electrolyte consisting of abundant elements with comparable Li-ion conductivity in a short milling duration of 4 h.Phase transition of the annealed sample was also carefully investigated.Li Ni_(0.6)Co_(0.2)Mn_(0.2)O_(2)/Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)/Li_(5.5)PS_(4.5)Cl_(1.5)/In-Li batteries using different halide electrolytes were constructed and cycled at different voltage windows.Solid-state battery using Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)electrolyte obtained from long milling duration delivers higher discharge capacities and superior capacity retention than shorter milling time between 3.0 and 4.3 V.It delivers much higher discharge capacity when cycled at elevated temperature(60℃)and suffers fast capacity degradation when the upper cut-off voltage increases to 4.5 V at the same current density.This work provides an efficiency synthesis strategy for halide solid electrolyte and studies its applications in all-solid-state batteries in a wide temperature range.展开更多
The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requiremen...The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requirements for battery systems.The high-energy lithium batteries are expected to respond or react under different environmental conditions.In this work,a tri-salt composite electrolyte is designed with a temperature switch function for intelligently temperature-controlled lithium batteries.Specifically,the halide Li_(3)YBr_(6)together with LiTFSI and LiNO_(3)works as active fillers in a low-melting-point polymer matrix(polyethyleneglycol dimethyl ether(PEGDME)and polyethylene oxide(PEO)),which is further filled into the pre-lithiated alumina fiber skeleton.Above 60°C,the composite electrolyte exists in the liquid state and fully contacts with the working electrodes on the liquid–solid interface,effectively minimizing the interfacial resistance and leading to high discharge capacity in the cell.The electrolyte is changed into a solid state below 30°C so that the ionic conductivity is significantly reduced and the interface resistance is increased dramatically on the solid–solid interface.Therefore,by simply adjusting the temperature,the cell can be turned“ON”or“OFF”intentionally.This novel function of the composite electrolyte has enlightening significance in developing intelligently temperature-controlled lithium batteries.展开更多
Lithium metal solid-state batteries(LMSBs)have attracted extensive attention over the past decades,due to their fascinating advantages of safety and potential for high energy density.Solid-state electrolytes(SEs)with ...Lithium metal solid-state batteries(LMSBs)have attracted extensive attention over the past decades,due to their fascinating advantages of safety and potential for high energy density.Solid-state electrolytes(SEs)with fast ionic transport and excellent stability are indispensable components in LMSBs.Heretofore,a series of inorganic SEs have been extensively explored,such as sulfide-and oxide-based electrolytes.Unfortunately,they both have difficulty in achieving a satisfactory balance of conductivity and stability,and oxides suffer from a high impedance of grain boundaries,while sulfides encounter poor stability.Halide-based solid electrolytes are gradually emerging as one of the most promising candidates for LMSBs due to their advantages of decent room temperature ionic conductivity(>10^(−3)S cm^(−1)),good compatibility with oxide cathode materials,good chemical stability,and scalability.Herein,research and development of the widely studied metal halide SEs including fluorides,chlorides,bromides,and iodides are reviewed,mainly focusing on the structures and ionic conductivities as well as preparation methods and electrochemical/chemical stabilities.And then,based on typical metal halide solid electrolytes,we emphasize the interface issues(grain boundaries,cathode−electrolyte and electrolyte–anode interfaces)that exist in the corresponding LMSBs and summarize the related work on understanding and engineering these interfaces.Furthermore,the typical(or in situ)characterization tools widely used for solid-state interfaces are reviewed.Finally,a perspective on the future direction for developing high-performance LMSBs based on the halide electrolyte family is put out.展开更多
All-solid-state Li batteries(ASSLBs) with solid-state electrolytes(SSEs) are exciting candidates for nextgeneration energy storage and receive considerable attention owing to their reliability. Halide SSEs are promisi...All-solid-state Li batteries(ASSLBs) with solid-state electrolytes(SSEs) are exciting candidates for nextgeneration energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li3InCl6or Li_(3)ScCl_(6), the low ionic conductivity of Li_(2)ZrCl_(6)(LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li_(2+2x)Zr_(1–x)MxCl_(6), which can be used in highperformance ASSLBs owing to its high ionic conductivity(up to 0.62 mS cm^(-1)). The theoretical(ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitution with divalent metals to obtain Li-Richened LZC is effective in improving Li^(+)conductivity in SSEs. By combining Li_(2.1)Zr_(0.95)Mg_(0.05)Cl_(6)(Mg5-LZC) with a Li–In anode and a LiCoO_(2)cathode, a room-temperature ASSLBs with excellent long-term cycling stability(88% capacity retention at 0.3C for 100 cycles) and highrate capability(121 m A h g^(-1)at 1C) is reported. This exploratory work sheds light on improving the Li^(+)conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.展开更多
Tremendous studies have been engaged in exploring the application of solid-state electrolytes(SSEs)as it provides opportunities for next-generation batteries with excellent safety and high energy density.Among the exi...Tremendous studies have been engaged in exploring the application of solid-state electrolytes(SSEs)as it provides opportunities for next-generation batteries with excellent safety and high energy density.Among the existing SSEs,newly developed halide SSEs have become a hot spot owing to their high ionic conductivity up to 1 mS cm^(-1) and their stability against high-voltage cathode.As a result,halide SSEs have been shown to be promising candidates for all-solid-state lithium batteries(ASSLBs).Here,we review the progress of halide SSEs and available modification strategies of halide SSE-based batteries.First,halide SSEs are divided into four different categories,including halide SSEs with divalent metal,trivalent metal,tetravalent metal,and non-metal central elements,to overview their progress in the studies of their ionic conductivity,crystal structure,conductive mechanism,and electrochemical properties.Then,based on their existing drawbacks,three sorts of modification strategies,classified as chemical doping,interfacial modification,and composite electrolytes,along with their impacts on halide SSE-based batteries,are summarized.Finally,some perspectives toward halide SSE research are put forward,which will help promote the development of halide SSE-based batteries.展开更多
Rechargeable all-solid-state batteries(ASSBs)are considered to be the next generation of devices for electrochemical energy storage.The development of solid-state electrolytes(SSEs)is one of the most crucial subjects ...Rechargeable all-solid-state batteries(ASSBs)are considered to be the next generation of devices for electrochemical energy storage.The development of solid-state electrolytes(SSEs)is one of the most crucial subjects in the field of energy storage chemistry.The newly emerging halide SSEs have recently been intensively studied for application in ASSBs due to their favorable combination of high ionic conductivity,exceptional chemical and electrochemical stability,and superior mechanical deformability.In this review,a critical overview of the development,synthesis,chemical stability and remaining challenges of halide SSEs is given.The design strategies for optimizing the ionic conductivity of halide SSEs,such as element substitution and crystal structure design,are summarized in detail.Moreover,the associated chemical stability issues in terms of solvent compatibility,humid air stability and corresponding degradation mechanisms are discussed.In particular,advanced in situ/operando characterization techniques applied to halide-based ASSBs are highlighted.In addition,a comprehensive understanding of the interface issues,cost issues,and scalable processing challenges faced by halide-based ASSBs for practical application is provided.Finally,future perspectives on how to design high-performance electrode/electrolyte materials are given,which are instructive for guiding the development of halide-based ASSBs for energy conversion and storage.展开更多
All solid-state lithium batteries(ASSLBs)are identified as the next-generation energy storage technology due to their prospects of nonflammability and improved energy density.Elevating the charging cutoff voltage of c...All solid-state lithium batteries(ASSLBs)are identified as the next-generation energy storage technology due to their prospects of nonflammability and improved energy density.Elevating the charging cutoff voltage of cathode materials is an effective strategy to improve the energy density of ASSLBs.However,the limited oxidative stability of solid-state electrolytes(SEs)and structural and chemically irreversible changes in the cathode active material result in inferior electrochemical performance.Here,we synthesized nano-Li_(1.2)Al_(0.1)Ta_(1.9)PO_(8)(LATPO)coatings on the surface of lithium cobalt oxide(LCO)by a facile ball-milling method combined with heat treatments.This artificial intermediate phase effectively enhances the structural stability and interfacial transport kinetics of the cathode and mitigates continuous side reactions at the cathode/solid electrolyte interface.As a result,the ASSLBs with modified LCO cathode exhibit a reversible capacity of 203.5 mAh g^(−1)at 0.1 C and 4.0 V(corresponding to the potential of 4.6 V vs.Li^(+)/Li),superior cycling stability(85.4%capacity retention after 500 cycles),a high areal capacity(4.6 mAh cm^(−2)),and a good rate capability(62 mAh g^(−1)at 3 C).This study emphasizes the importance of cathode surface modification in achieving stable cycling of halide-based ASSLBs at high voltages.展开更多
Zirconium-based halide electrolytes were created as prospective candidates for all-solid-state lithium batteries(ASSLBs)because of their low cost,wide electrochemical window,and superior compatibility with oxide catho...Zirconium-based halide electrolytes were created as prospective candidates for all-solid-state lithium batteries(ASSLBs)because of their low cost,wide electrochemical window,and superior compatibility with oxide cathodes.However,practical implementation is hindered by limitations such as suboptimal room-temperature(RT)ionic conductivity(<1mS cm^(−1))and poor interfacial compatibility with lithium metal.Herein,we report a new class of zirconium-based chlorides,Li_(2−x)Zr_(1−x)NbxCl_(6),synthesized by a high-valent Nb^(5+)doping method.The introduction of Nb^(5+)induces local lattice decrease,which simultaneously weakens the binding intensity of Li─Zr and optimizes ion migration pathways and defect concentrations.Therefore,the optimal composition,Li_(1.75)Zr_(0.75)Nb_(0.25)Cl_(6)(denoted as LZC-Nb),achieves a high RT ionic conductivity of 1.82 mS cm^(−1)and exceptional moisture resistance.Furthermore,the dynamic interfacial modulation of LZC-Nb forms a low-impedance passivation layer,enhancing Li^(+)transport kinetics.This improvement in interfacial stability enables symmetric batteries to exceed a critical current density of 1.3 mA cm^(−2).Combined with a LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)cathode,the resultant ASSLB retains 81.8%of its initial capacity(157.5 mAh g^(−1))after 600 cycles at 0.3 C.This study provides a proven strategy for developing inorganic ionic conductors with superior ionic transport and interfacial compatibility,offering a viable pathway toward high-performance ASSLBs.展开更多
基金financially supported by Hunan Provincial Key R&D Project(Grant No.2023GK2016)the National Key Research and Development Program of China(Grant No.2023YFC2909100)the National Natural Science Foundation of China(Grant Nos.52304376 and 22109084)。
文摘All-solid-state batteries(ASSBs)are considered to be the most promising candidates for improving battery safety and energy density.Sulfide electrolytes have a narrow electrochemical window,which hinders their applications coupled with high-voltage cathodes.Halide electrolytes with high-voltage endurance can help solve this problem.Herein,the combination of spraying and slurry-coating methods was adopted as a practical route to process a free-standing Li_(6)PS_5Cl(LPSCl)asymmetrical electrolyte membrane(19.23Ωcm~2,75μm)decorated with a 10μm Li_(3)In Cl_(6)(LICl)layer.The LICl-LPSCl asymmetrical electrolyte membranes enhanced the high-voltage stabilities to match those of LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)and Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LRMO)cathodes.The NCM811|LICl-LPSCl|n Si ASSB achieved an initial coulombic efficiency(ICE)of 85.13%and a capacity retention of 77.16%after 200 cycles.Compared with the LPSCl membrane,the LICl-LPSCl membrane displayed high stability with the LRMO cathode as the charging cut-off voltage increased to 4.7 V,which improved the initial charge capacity from 143 to 270 mAh g^(-1)and achieved stable cycling of 160 m Ah g^(-1)at 0.5 C.Additionally,we attempted continuous LICl-LPSCl membrane production and utilized the product to fabricate a pouch-type ASSB based on LRMO.The fabrication of the LICl-LPSCl electrolyte membrane demonstrated its potential for controllable and industryadaptable applications in ASSBs.
基金financially supported by Hunan Provincial Science and Technology Department,China(No.2021JJ10058)Key Research and Development Program of Hunan Province,China(No.2023GK2016)。
文摘A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.
基金supported by the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korean Government(MOTIE)(RS-2024-00417730,HRD Program for Industrial Innovation)supported by the Technology Innovation Program(or Industrial Strategic Technology Development Program-Materials&Components Technology Development Program)(20024261),Development of thick film electrodes and cell manufacturing technology for a high-performance lithium iron phosphate battery with energy density of over 200 Wh/kg was funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the undesirable side reactions of sulfide-based solid electrolytes(SEs),resulting in poor electrochemical properties with increased interfacial resistance.Here,we propose a wet chemical method rationally designed to achieve a conformal coating of lithium-indium chloride(Li_(3)InCl_(6))onto vapor-grown carbon fibers(VGCFs)as conductive agents.First,with the advantage of the Li_(3)InCl_(6) protective layer,use of VGCF@Li_(3)InCl_(6) leads to enhanced interfacial stability and improved electrochemical properties,including stable cycle performance.These results indicate that the Li_(3)InCl_(6) protective layer suppresses the unwanted reaction between Li_(6)PS_(5)Cl(LPSCl)and VGCF.Second,VGCF@Li_(3)InCl_(6) effectively promotes polytetrafluoroethylene(PTFE)fibrillization,leading to a homogeneous electrode microstructure.The uniform distribution of the cathode active material(CAM)in the electrode results in reduced charge-transfer resistance(R_(ct))and enhanced Li-ion kinetics.As a result,a full cell with the LiNi_(x)Mn_(y)Co_(z)O_(2)(NCM)/VGCF@Li_(3)InCl_(6) electrode shows an areal capacity of 7.7mAhcm^(−2) at 0.05 C and long-term cycle stability of 77.9%over 400 cycles at 0.2 C.This study offers a strategy for utilizing stable carbon-based conductive agents in sulfide-based ASSBs to enhance their electrochemical performance.
基金supported by the 261 Project of MIITthe National Natural Science Foundation of China(Nos.52250010,52201242,U23A20574)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)。
文摘Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical durability and humidity stability,hindering their large-scale applications.Here,we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene(PTFE)binder to encapsulate Li_(3)InCl_(6)(LIC)particles(the most representative HSSE).By manipulating the fibrillating process,only 0.5 wt%PTFE is sufficient to prepare free-standing LIC-PTFE(LIC-P)HSSEs.Additionally,LIC-P demonstrates excellent mechanical durability and humidity resistance.They can maintain their shapes after being exposed to humid atmosphere for 30 min,meanwhile still exhibit high ionic conductivity of>0.2m S/cm at 25℃.Consequently,the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 m Ah/g at0.1 C and long cyclability of 200 cycles at 0.2 C.More importantly,the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7%after 100 cycles under0.2 C.Furthermore,for the first time,we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.
基金supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)+3 种基金the Fundamental Research Funds for the Central Universities(no.N2523050)the Natural Science Foundation of Hebei Province(no.E2024501010)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)the 2024 Hebei Provincial Postgraduate Student Innovation Ability Training Funding Project(no.CXZZSS2025162)。
文摘Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.
基金the financial support of 21C Innovation Laboratory, Contemporary Amperex Technology Ltd. (21COP-202212)the Foundation of Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), the Nankai University, Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2022-K15)+1 种基金the China University of Mining & Technology (Beijing), the Foundation of Top-notch Innovative Talents Cultivation (BBJ2023031) of China University of Mining & Technology (Beijing)the National Natural Science Foundation of China (51672029 and 51372271)。
文摘All-solid-state batteries(ASSBs) with inorganic solid-state-electrolytes(SSEs) have been regarded as the promising candidate for next-generation energy storage due to their high energy density and outstanding safety performance.However,the representative oxide and sulfide electrolytes suffer from low ionic conductivity and poor(electro)chemical stability,respectively.Herein,we report a series of new halide superionic conductors Li_(2+x)Hf_(1-x)In_(x)Cl_(6) with high ionic conductivity up to 1.05 mS cm^(-1) at 30 ℃ that are simultaneously stable to high voltage.By means of the characterization techniques and bond-valence site energy(BVSE) calculation,insights into the effect of the phase transformation and underlying ionic transport mechanism by In substitution for Hf in Li_(2)HfCl_(6) are provided.Importantly,with the increased amount of aliovalent substitution in Li_(2+x)Hf_(1-x)In_(x)Cl_(6) microcrystal framework,a gradual structure evolution from trigonal to monoclinic phase has been observed,which is accompanied by the redistribution of Li-ions to generate two dimensionally(2D) preferable diffusion pathways through octahedral-tetrahe dral-octahedral sites in In^(3+)-substituted Li_(2)HfCl_(6).Additionally,due to the oxidative stability of Insubstituted Li_(2)HfCl_(6),the bulk-type ASSBs with bare LiCoO_(2) deliver distinguished electrochemical performance.
基金Project supported by the GRINM Innovation Fund Project(2020TS0301)Jilin Province Science and Technology Major Project(20210301021GX)National Natural Science Foundation of China(U21A2080)。
文摘As the next generation of commercial automotive power batteries begins replacing liquid lithium batteries,many look towards all-solid-state batteries to pioneer the future.All-so lid-state batteries have attracted the attention of countless researchers around the world because of their high safety and high energy density.In recent times,halide solid-state electrolytes have become a research hotspot within solid-state electrolytes because of their potentially superior properties.In this paper,in the framework of DFT,we investigated the atomic mechanisms of improving the ionic conductivity and stability of Li_(3)YbCl_(6).Our calculations show that both trigonal and orthorhombic Li_(3)YbCl_(6) exhibit wide electrochemical windows and metastable properties(100 meV/atom>Ehull>0 meV/atom).However,the orthorhombic Li_(3)YbCl_(6) can be stabilized at high temperatures by taking the vibrational entropy into account,which is supported by the experimental results.Moreover,it is expected that because of the Yb/Li synergistic interactions that,due to their strong mutual coulomb repulsion,influence the Li^(+)transport behavior,the orthorhombic Li_(3)YbCl_(6) might have superior ionic conductivities with appropriate Li+migration paths determined by the Yb^(3+) distribution.Also,higher ionic conductivities can be obtained by regulating the random distribution of Li^(+) ions.Further Li^(+)-deficiency can also largely increase the ionic conductivity by invoking vacancies.This study helps gain a deeper understanding of the laws that govern ionic conductivities and stabilities and provides a certain theoretical reference for the experimental development and design of halide solid-state electrolytes.
基金supported by the National Key R&D Program of China(2022YFB3803505)National Natural Scientific Foundation of China(U21A2080&22479009)National Related Project and the Fundamental Research Funds for the Central Universities(FRF-TP-22-01C2)。
文摘Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.
基金financially supported by Natural Science Foundation of Hebei Province(Nos.B2020203037,F2021203097)Science Research Project of Hebei Education Department(No.JZX2024022)National Natural Science Foundation of China(Nos.52022088,51971245)。
文摘Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.
文摘Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.
基金supported by the National Key Research and Development Program(Nos.2021YFB2500200,2021YFB2400300)the National Natural Science Foundation of China(No.52177214)the Certificate of China Post-doctoral Science Foundation(No.2019M652634)。
文摘Halide electrolytes in solid-state batteries with excellent oxidative stability and high ionic conductivity have been well reported recently.However,the high-cost rare-earth elements and long duration of highrotation milling procure are the major obstacles.Herein,we have successfully synthesized the low cost Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)electrolyte consisting of abundant elements with comparable Li-ion conductivity in a short milling duration of 4 h.Phase transition of the annealed sample was also carefully investigated.Li Ni_(0.6)Co_(0.2)Mn_(0.2)O_(2)/Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)/Li_(5.5)PS_(4.5)Cl_(1.5)/In-Li batteries using different halide electrolytes were constructed and cycled at different voltage windows.Solid-state battery using Li_(2.25)Zr_(0.75)Fe_(0.25)Cl_(6)electrolyte obtained from long milling duration delivers higher discharge capacities and superior capacity retention than shorter milling time between 3.0 and 4.3 V.It delivers much higher discharge capacity when cycled at elevated temperature(60℃)and suffers fast capacity degradation when the upper cut-off voltage increases to 4.5 V at the same current density.This work provides an efficiency synthesis strategy for halide solid electrolyte and studies its applications in all-solid-state batteries in a wide temperature range.
基金Financial support from the National Natural Science Foundation of China(22279065 and 21935006)is gratefully acknowledged.
文摘The intense research of lithium-ion batteries has been motivated by their successful applications in mobile devices and electronic vehicles.The emerging of intelligent control in kinds of devices brings new requirements for battery systems.The high-energy lithium batteries are expected to respond or react under different environmental conditions.In this work,a tri-salt composite electrolyte is designed with a temperature switch function for intelligently temperature-controlled lithium batteries.Specifically,the halide Li_(3)YBr_(6)together with LiTFSI and LiNO_(3)works as active fillers in a low-melting-point polymer matrix(polyethyleneglycol dimethyl ether(PEGDME)and polyethylene oxide(PEO)),which is further filled into the pre-lithiated alumina fiber skeleton.Above 60°C,the composite electrolyte exists in the liquid state and fully contacts with the working electrodes on the liquid–solid interface,effectively minimizing the interfacial resistance and leading to high discharge capacity in the cell.The electrolyte is changed into a solid state below 30°C so that the ionic conductivity is significantly reduced and the interface resistance is increased dramatically on the solid–solid interface.Therefore,by simply adjusting the temperature,the cell can be turned“ON”or“OFF”intentionally.This novel function of the composite electrolyte has enlightening significance in developing intelligently temperature-controlled lithium batteries.
基金National Natural Science Foundation of China,Grant/Award Numbers:21975276,52102329Shanghai Science and Technology Committee,Grant/Award Number:20520710800Program of Shanghai Academic Research Leader,Grant/Award Number:21XD1424400。
文摘Lithium metal solid-state batteries(LMSBs)have attracted extensive attention over the past decades,due to their fascinating advantages of safety and potential for high energy density.Solid-state electrolytes(SEs)with fast ionic transport and excellent stability are indispensable components in LMSBs.Heretofore,a series of inorganic SEs have been extensively explored,such as sulfide-and oxide-based electrolytes.Unfortunately,they both have difficulty in achieving a satisfactory balance of conductivity and stability,and oxides suffer from a high impedance of grain boundaries,while sulfides encounter poor stability.Halide-based solid electrolytes are gradually emerging as one of the most promising candidates for LMSBs due to their advantages of decent room temperature ionic conductivity(>10^(−3)S cm^(−1)),good compatibility with oxide cathode materials,good chemical stability,and scalability.Herein,research and development of the widely studied metal halide SEs including fluorides,chlorides,bromides,and iodides are reviewed,mainly focusing on the structures and ionic conductivities as well as preparation methods and electrochemical/chemical stabilities.And then,based on typical metal halide solid electrolytes,we emphasize the interface issues(grain boundaries,cathode−electrolyte and electrolyte–anode interfaces)that exist in the corresponding LMSBs and summarize the related work on understanding and engineering these interfaces.Furthermore,the typical(or in situ)characterization tools widely used for solid-state interfaces are reviewed.Finally,a perspective on the future direction for developing high-performance LMSBs based on the halide electrolyte family is put out.
基金the financial support from the Guangdong Natural Science Funds, China (2019A1515010675)the Science and Technology Project of Shenzhen, China (JCYJ20210324094206019)+5 种基金the financial support from the National Natural Science Foundation of China (52102284)the Department of Science and Technology of Guangxi Province, China (AB21220027, AD19110077)the Guangxi innovation research team project, China (Grant No.2018GXNSFGA281001)the Guangxi Natural Science Foundation, China (2018GXNSFAA138064, 2020GXNSFAA159037, and 2020GXNSFAA159059)the Guangxi Key Laboratory of Manufacturing Systems Foundation, China (20-065-40-005Z)the Engineering Research Center Foundation of Electronic Information Materials and Devices, China (EIMD-AA202005)。
文摘All-solid-state Li batteries(ASSLBs) with solid-state electrolytes(SSEs) are exciting candidates for nextgeneration energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li3InCl6or Li_(3)ScCl_(6), the low ionic conductivity of Li_(2)ZrCl_(6)(LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li_(2+2x)Zr_(1–x)MxCl_(6), which can be used in highperformance ASSLBs owing to its high ionic conductivity(up to 0.62 mS cm^(-1)). The theoretical(ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitution with divalent metals to obtain Li-Richened LZC is effective in improving Li^(+)conductivity in SSEs. By combining Li_(2.1)Zr_(0.95)Mg_(0.05)Cl_(6)(Mg5-LZC) with a Li–In anode and a LiCoO_(2)cathode, a room-temperature ASSLBs with excellent long-term cycling stability(88% capacity retention at 0.3C for 100 cycles) and highrate capability(121 m A h g^(-1)at 1C) is reported. This exploratory work sheds light on improving the Li^(+)conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.
基金supported by the National Natural Science Foundation of China(22179006)the Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JP134).
文摘Tremendous studies have been engaged in exploring the application of solid-state electrolytes(SSEs)as it provides opportunities for next-generation batteries with excellent safety and high energy density.Among the existing SSEs,newly developed halide SSEs have become a hot spot owing to their high ionic conductivity up to 1 mS cm^(-1) and their stability against high-voltage cathode.As a result,halide SSEs have been shown to be promising candidates for all-solid-state lithium batteries(ASSLBs).Here,we review the progress of halide SSEs and available modification strategies of halide SSE-based batteries.First,halide SSEs are divided into four different categories,including halide SSEs with divalent metal,trivalent metal,tetravalent metal,and non-metal central elements,to overview their progress in the studies of their ionic conductivity,crystal structure,conductive mechanism,and electrochemical properties.Then,based on their existing drawbacks,three sorts of modification strategies,classified as chemical doping,interfacial modification,and composite electrolytes,along with their impacts on halide SSE-based batteries,are summarized.Finally,some perspectives toward halide SSE research are put forward,which will help promote the development of halide SSE-based batteries.
基金the financial support of the Beijing National Laboratory for Condensed Matter Physics,21C Innovation Laboratory,Contemporary Amperex Technology Ltd.through project No.21C-OP-202212the Foundation of Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University+1 种基金the Foundation of State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering(Grant No.2022-K15),China University of Mining&Technology(Beijing)the National Natural Science Foundation of China(Nos.51672029,51372271).
文摘Rechargeable all-solid-state batteries(ASSBs)are considered to be the next generation of devices for electrochemical energy storage.The development of solid-state electrolytes(SSEs)is one of the most crucial subjects in the field of energy storage chemistry.The newly emerging halide SSEs have recently been intensively studied for application in ASSBs due to their favorable combination of high ionic conductivity,exceptional chemical and electrochemical stability,and superior mechanical deformability.In this review,a critical overview of the development,synthesis,chemical stability and remaining challenges of halide SSEs is given.The design strategies for optimizing the ionic conductivity of halide SSEs,such as element substitution and crystal structure design,are summarized in detail.Moreover,the associated chemical stability issues in terms of solvent compatibility,humid air stability and corresponding degradation mechanisms are discussed.In particular,advanced in situ/operando characterization techniques applied to halide-based ASSBs are highlighted.In addition,a comprehensive understanding of the interface issues,cost issues,and scalable processing challenges faced by halide-based ASSBs for practical application is provided.Finally,future perspectives on how to design high-performance electrode/electrolyte materials are given,which are instructive for guiding the development of halide-based ASSBs for energy conversion and storage.
基金supported by National Key Research and Development Program of China(Grant 2023YFB2503902)National Natural Science Foundation of China(Grants 22479009 and U21A2080).
文摘All solid-state lithium batteries(ASSLBs)are identified as the next-generation energy storage technology due to their prospects of nonflammability and improved energy density.Elevating the charging cutoff voltage of cathode materials is an effective strategy to improve the energy density of ASSLBs.However,the limited oxidative stability of solid-state electrolytes(SEs)and structural and chemically irreversible changes in the cathode active material result in inferior electrochemical performance.Here,we synthesized nano-Li_(1.2)Al_(0.1)Ta_(1.9)PO_(8)(LATPO)coatings on the surface of lithium cobalt oxide(LCO)by a facile ball-milling method combined with heat treatments.This artificial intermediate phase effectively enhances the structural stability and interfacial transport kinetics of the cathode and mitigates continuous side reactions at the cathode/solid electrolyte interface.As a result,the ASSLBs with modified LCO cathode exhibit a reversible capacity of 203.5 mAh g^(−1)at 0.1 C and 4.0 V(corresponding to the potential of 4.6 V vs.Li^(+)/Li),superior cycling stability(85.4%capacity retention after 500 cycles),a high areal capacity(4.6 mAh cm^(−2)),and a good rate capability(62 mAh g^(−1)at 3 C).This study emphasizes the importance of cathode surface modification in achieving stable cycling of halide-based ASSLBs at high voltages.
基金the National Natural Science Foundation of China(22479009&U21A2080)National related project are gratefully acknowledged.
文摘Zirconium-based halide electrolytes were created as prospective candidates for all-solid-state lithium batteries(ASSLBs)because of their low cost,wide electrochemical window,and superior compatibility with oxide cathodes.However,practical implementation is hindered by limitations such as suboptimal room-temperature(RT)ionic conductivity(<1mS cm^(−1))and poor interfacial compatibility with lithium metal.Herein,we report a new class of zirconium-based chlorides,Li_(2−x)Zr_(1−x)NbxCl_(6),synthesized by a high-valent Nb^(5+)doping method.The introduction of Nb^(5+)induces local lattice decrease,which simultaneously weakens the binding intensity of Li─Zr and optimizes ion migration pathways and defect concentrations.Therefore,the optimal composition,Li_(1.75)Zr_(0.75)Nb_(0.25)Cl_(6)(denoted as LZC-Nb),achieves a high RT ionic conductivity of 1.82 mS cm^(−1)and exceptional moisture resistance.Furthermore,the dynamic interfacial modulation of LZC-Nb forms a low-impedance passivation layer,enhancing Li^(+)transport kinetics.This improvement in interfacial stability enables symmetric batteries to exceed a critical current density of 1.3 mA cm^(−2).Combined with a LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)cathode,the resultant ASSLB retains 81.8%of its initial capacity(157.5 mAh g^(−1))after 600 cycles at 0.3 C.This study provides a proven strategy for developing inorganic ionic conductors with superior ionic transport and interfacial compatibility,offering a viable pathway toward high-performance ASSLBs.
