In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an ...In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.展开更多
All-solid-state lithium batteries(ASSLBs) based on sulfide solid-state electrolytes and high voltage layered oxide cathode are regarded as one of the most promising candidates for energy storage systems with high ener...All-solid-state lithium batteries(ASSLBs) based on sulfide solid-state electrolytes and high voltage layered oxide cathode are regarded as one of the most promising candidates for energy storage systems with high energy density and high safety.However,they usually suffer poor cathode/electrolyte interfacial stability,severely limiting their practical applications.In this work,a core-shell cathode with uniformly nanosized Li0.5La0.5TiO3(LLTO) electrolyte coating on LiNi0.5Co0.3Mn0.2O2(NCM532) is designed to improve the cathode/electrolyte interface stability.Nanosized LLTO coating layer not only significantly boosts interfacial migration of lithium ions,but also efficiently alleviates space-charge layer and inhibits the electrochemical decomposition of electrolyte.As a result,the assembled ASSLBs with high mass loading(9 mg cm-2)LLTO coated NCM532(LLTO@NCM532) cathode exhibit high initial capacity(135 mAh g^(-1)) and excellent cycling performance with high capacity retention(80% after 200 cycles) at 0.1 C and 25℃.This nanosized LLTO coating layer design provides a facile and effective strategy for constructing high performance ASSLBs with superior interfacial stability.展开更多
The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/elec...The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/electrochemical side reactions are considered to be the origin of the interfacial deterioration.However,the influence of chemical and electrochemical side reactions on the interfacial deterioration is rarely studied specifically.In this work,the deterioration mechanism of the interface between LiNi0.85-xCo0.15AlxO2 and Li10GeP2S12 is investigated in detail by combining in/ex-situ Raman spectra and Electrochemical Impedance Spectroscopy(EIS).It can be determined that chemical side reaction between LiNi0.8Co0.15Al0.05O2 and Li10GeP2S12 will occur immediately once contacted,and the interfacial deterioration becomes more serious after charge-discharge process under the dual effects of chemical and electrochemical side reactions.Moreover,our research reveals that the interfacial stability and the cycle performance of ASSLB can be greatly enhanced by increasing Al-substitution for Ni in LiNi0.85-xCo0.15AlxO2.In particular,the capacity retention of LiNi0.6Co0.15Al0.25O2 cathode after 200 cycles can reach 81.9%,much higher than that of LiNi0.8Co0.15Al0.05O2 cathode(12.5%@200 cycles).This work gives an insight to study the interfacial issues between Ni-rich layered oxide cathode and sulfide electrolyte for ASSLBs.展开更多
FeS_(2)cathode is promising for all-solid-state lithium batteries due to its ultra-high capacity,low cost,and environmental friendliness.However,the poor performances,induced by limited electrode-electrolyte interface...FeS_(2)cathode is promising for all-solid-state lithium batteries due to its ultra-high capacity,low cost,and environmental friendliness.However,the poor performances,induced by limited electrode-electrolyte interface,severe volume expansion,and polysulfide shuttle,hinder the application of FeS_(2)in all-solid-state lithium batteries.Herein,an integrated 3D FeS_(2)electrode with full infiltration of Li6PS5Cl sulfide electrolytes is designed to address these challenges.Such a 3D integrated design not only achieves intimate and maximized interfacial contact between electrode and sulfide electrolytes,but also effectively buffers the inner volume change of FeS_(2)and completely eliminates the polysulfide shuttle through direct solid-solid conversion of Li2S/S.Besides,the vertical 3D arrays guarantee direct electron transport channels and horizontally shortened ion diffusion paths,endowing the integrated electrode with a remarkably reduced interfacial impedance and enhanced reaction kinetics.Benefiting from these synergies,the integrated all-solid-state lithium battery exhibits the largest reversible capacity(667 mAh g^(-1)),best rate performance,and highest capacity retention of 82%over 500 cycles at 0.1 C compared to both a liquid battery and non-integrated all-solid-state lithium battery.The cycling performance is among the best reported for FeS_(2)-based all-solid-state lithium batteries.This work presents an innovative synergistic strategy for designing long-cycling high-energy all-solid-state lithium batteries,which can be readily applied to other battery systems,such as lithium-sulfur batteries.展开更多
The interface instability between layered oxide cathode and sulfide electrolyte is a key point affecting the perform ance of sulfide-based all-solid-state lithium batteries.Coating with fast-ionic conductor and constr...The interface instability between layered oxide cathode and sulfide electrolyte is a key point affecting the perform ance of sulfide-based all-solid-state lithium batteries.Coating with fast-ionic conductor and constructing core-shell structure can effectively alleviate the interfacial side reactions and improve the interfacial stability between layered oxide and sulfide electrolyte.However,what have been neglected is the surface base(including Li_(2)CO_(3) and LiOH)of layered oxide can also affect the interfacial stability.To clarify this point clearly and improve the interfacial stability,the surface base of LiCoO_(2)(LCO)is regulated and investigated in this work.First,LCO with surface base Li_(2)CO_(3)(LCO@Li_(2)CO_(3))is prepared by the reaction of Co_(3)O_4 and excess Li_(2)CO_(3).Then,the bare LCO is obtained after LCO@Li_(2)CO_(3) is washed with deionized water and calcined again.Besides,LCO with surface base Li_(2)O(LCO@Li_(2)O)is also prepared with the bare LCO and LiOH.As a result,the electrochemical performances of LCO@Li_(2)O are significantly improved and much higher than those of LCO@Li_(2)CO_(3) and the bare LCO electrodes.In particular,LCO@Li_(2)O-2 cathode display the most outstanding electrochemical performances(discharge capacity138.4 mAh·g^(-1)at 0.2C,105 mAh·g^(-1)at 2C and a capacity retention of 95.4%after 150 cycles at 0.5C).The high discharge capacity and excellent cycle stability of LCO@Li_(2)O electrode confirm the effectiveness of regulating the surface base of layered oxide from Li_(2)CO_(3) to Li_(2)O.The surface base regulating is expected to be a simple but effective strategy to construct the stable interface between the cathode and the sulfide electrolyte of the all-solid-state lithium batteries.展开更多
Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid ele...Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.展开更多
All-solid-state lithium batteries(ASSLBs)based on sulfide solid electrolytes(SEs)are one of the most promising strategies for next-generation energy storage systems and electronic devices.However,the poor chemical/ele...All-solid-state lithium batteries(ASSLBs)based on sulfide solid electrolytes(SEs)are one of the most promising strategies for next-generation energy storage systems and electronic devices.However,the poor chemical/electrochemical stability of sulfide SEs with oxide cathode materials and high interfacial impedance,particularly due to physical contact failure,are the major limiting factors to the development of sulfide SEs in ASSLBs.Herein,the composite cathode of MOF-derived Fe_(7)S_(8)@C and Li_(6)PS_(5)Br fabricated by an infiltration method(IN-Fe_(7)S_(8))with dissoluble sulfide electrolyte(dissoluble SE)is reported.Dissoluble SE can easily infiltrate the porous sheet-type Fe_(7)S_(8)@C cathode to homogeneously contact with Fe_(7)S_(8)nanoparticles that are embedded in the surrounding carbon matrixes and form a fast ionic transport network.Benefiting from applying dissoluble SE and Fe_(7)S_(8)@C,the IN-Fe_(7)S_(8)-based cells displayed a reversible capacity of 510 mAh g^(-1)after 180 cycles at 0.045 mA cm^(-2)at 30℃.This work demonstrates a novel and practical method for the development of high-performance all-sulfide-based solid state batteries.展开更多
Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorgani...Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.展开更多
All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for t...All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.展开更多
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a th...Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.展开更多
All-solid-state lithium batteries(ASSLBs)have attracted increasing attention due to their high safety and energy density.Among all corresponding solid electrolytes,sulfide electrolytes are considered to be the most pr...All-solid-state lithium batteries(ASSLBs)have attracted increasing attention due to their high safety and energy density.Among all corresponding solid electrolytes,sulfide electrolytes are considered to be the most promising ion conductors due to high ionic conductivities.Despite this,many challenges remain in the application of ASSLBs,including the stability of sulfide electrolytes,complex interfacial issues between sulfide electrolytes and oxide electrodes as well as unstable anodic interfaces.Although oxide cathodes remain the most viable electrode materials due to high stability and industrialization degrees,the matching of sulfide electrolytes with oxide cathodes is challenging for commercial use in ASSLBs.Based on this,this review will present an overview of emerging ASSLBs based on sulfide electrolytes and oxide cathodes and high-light critical properties such as compatible electrolyte/electrode interfaces.And by considering the current challenges and opportunities of sulfide electrolyte-based ASSLBs,possible research directions and perspectives are discussed.展开更多
Lithium-sulfur(Li-S)batteries are considered as promising candidates for novel energy storage technology that achieves energy density of 500 Wh·kg^(−1).However,poor cycle stability resulting from notorious shuttl...Lithium-sulfur(Li-S)batteries are considered as promising candidates for novel energy storage technology that achieves energy density of 500 Wh·kg^(−1).However,poor cycle stability resulting from notorious shuttle effect and the safety concerns deriving from flammability of ether-based electrolyte hinder the practical application of Li-S batteries.Because of low solubility to polysulfide,high ionic conductivity,and safety property,sulfide-based electrolytes can fundamentally address above issues.It is widely known that the effective transports of both electrons and ions are basic requirement for redox reaction of active materials in cathode.Thereby,construction of fast and stable ionic and electronic transport paths in cathode is especially pivotal for cycle stability of solid-state Li-S batteries(SSLSBs).In this review,we provide research progresses on facilitating transport of charge carriers in composite cathode of SSLSBs.From perspective of materials,intrinsically conductivity of electrolyte and carbon shows dramatic effect on migration of charge carriers in cathode of SSLSBs,thereby the conductive additives are summarized in the manuscript.Additionally,the charge transport in cathode of SSLSBs fully depends on the physical contact between active materials and conductive additives,therefore we summarized the strategies optimizing interfacial contact and reducing interfacial resistance.Finally,potential future research directions and prospects for SSLSBs with improved energy density and cycle performance are also proposed.展开更多
Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes...Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes is promising to achieve higher energy density.However,the incompatible interfaces between sulfide SEs and high-voltage cathodes have been one of the key factors limiting their applications.Therefore,this review presents a critical summarization of the interfacial issues in all-solid-state lithium batteries based on sulfide SEs and high-voltage cathodes and proposes strategies to stabilize the electrolyte/cathode interfaces.Moreover,the future research direction of electrolyte/cathode interfaces and application prospects of powder technology in sulfide-based ASSLBs were also discussed.展开更多
Coupling with high-voltage oxide cathode is the key to achieve high-energy density sulfide-based all-solid-state lithium batteries.However,the complex interfacial issues including the space charge layer effect and und...Coupling with high-voltage oxide cathode is the key to achieve high-energy density sulfide-based all-solid-state lithium batteries.However,the complex interfacial issues including the space charge layer effect and undesirable side reaction between sulfide solid-state electrolytes and oxide cathode materials are the main constraints on the development of high-performance allsolid-state lithium batteries,which lead to the continuous decay of electrochemical performance.Herein,different from the complicated coating procedure,a LiPO_(2)F_(2)additive engineering was proposed to achieve high-performance all-solid-state lithium batteries.With the introduction of LiPO_(2)F_(2)additive,a protective cathode-electrolyte interphase consisting of LiPxOyFz,LiF,and Li_(3)PO_(4)could be in situ formed to improve the interfacial stability between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)and Li_(5.5)PS_(4.5)Cl_(1.5)(LPSC).Benefiting from this,the NCM811/LPSC/Li all-solid-state lithium battery exhibited impressive cyclic stability with a capacity retention of 85.5%after 600 cycles(at 0.5 C).Diverse and comprehensive characterization,combined with finite element simulation and density functional theory calculation fully demonstrated the effective component,interfacial stabilization function and enhanced kinetic of LiPO_(2)F_(2)-derived cathode-electrolyte interphase.This work provides not only a feasible and effective method to stabilize the cathodic interface but also worthy insight into interfacial design for high-performance all-solid-state lithium batteries.展开更多
Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of L...Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of Li_(2)S.Herein,a low-cost and environmentally friendly method is proposed to synthesize Li_(2)S by the carbothermal reduction reaction of Li_(2)SO_(4)in one step,and the effects of various factors are also discussed.As a result,a purity of 99.67%is obtained over the self-prepared Li_(2)S.More importantly,the cost of the self-prepared Li_(2)S is only about 50$/kg,which is significantly lower than that of the commercial counterpart(10000−15000 dollar/kg).Moreover,the ionic conductivity of Li_(5.5)PS_(4.5)Cl_(1.5)prepared using self-prepared Li_(2)S as raw materials is 4.19 mS/cm at room temperature,which is a little higher than that of Li_(5.5)PS_(4.5)Cl_(1.5)using commercial Li_(2)S(4.05 mS/cm).And the all-solid-state lithium batteries(ASSLBs)with the as-prepared electrolytes could maintain a discharge capacity of 109.9 mA·h/g with an average coulombic efficiency(CE)of 98%after 100 cycles at 0.2 C,which is equivalent to that using commercial Li_(2)S,demonstrating that the preparation strategy of Li_(2)S proposed in this work is feasible.展开更多
This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction pro...This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.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
Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reac...Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.展开更多
We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs)...We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs).SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries,owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes.However,the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges.Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity.By optimizing binder molecular weights,we effectively shield the active materials from degradation and mechanical stress,significantly boosting the functionality and longevity of SSBs.These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.展开更多
Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_...Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).展开更多
基金financially supported by the National Natural Science Foundation of China(No.22301151)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(No.2022QN05024)+1 种基金the Science and Technology Projects of Inner Mongolia Autonomous Region(No.2024SKYPT0011)the Science and Technology Planning Project of Hohhot,China(No.2024-JieBangGuaShuai-Gao-4)
文摘In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.
基金supported by the National Natural Science Foundation of China (51575030, 51532002 and 51872027)Natural Science Foundation of Beijing Municipality (L172023)。
文摘All-solid-state lithium batteries(ASSLBs) based on sulfide solid-state electrolytes and high voltage layered oxide cathode are regarded as one of the most promising candidates for energy storage systems with high energy density and high safety.However,they usually suffer poor cathode/electrolyte interfacial stability,severely limiting their practical applications.In this work,a core-shell cathode with uniformly nanosized Li0.5La0.5TiO3(LLTO) electrolyte coating on LiNi0.5Co0.3Mn0.2O2(NCM532) is designed to improve the cathode/electrolyte interface stability.Nanosized LLTO coating layer not only significantly boosts interfacial migration of lithium ions,but also efficiently alleviates space-charge layer and inhibits the electrochemical decomposition of electrolyte.As a result,the assembled ASSLBs with high mass loading(9 mg cm-2)LLTO coated NCM532(LLTO@NCM532) cathode exhibit high initial capacity(135 mAh g^(-1)) and excellent cycling performance with high capacity retention(80% after 200 cycles) at 0.1 C and 25℃.This nanosized LLTO coating layer design provides a facile and effective strategy for constructing high performance ASSLBs with superior interfacial stability.
基金financially supported partly by the National Key Research and Development Program of China(2018YFE0111600)Tianjin Sci.&Tech.Program(17YFZCGX00560,18ZXJMTG00040,19JCZDJC31800)。
文摘The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/electrochemical side reactions are considered to be the origin of the interfacial deterioration.However,the influence of chemical and electrochemical side reactions on the interfacial deterioration is rarely studied specifically.In this work,the deterioration mechanism of the interface between LiNi0.85-xCo0.15AlxO2 and Li10GeP2S12 is investigated in detail by combining in/ex-situ Raman spectra and Electrochemical Impedance Spectroscopy(EIS).It can be determined that chemical side reaction between LiNi0.8Co0.15Al0.05O2 and Li10GeP2S12 will occur immediately once contacted,and the interfacial deterioration becomes more serious after charge-discharge process under the dual effects of chemical and electrochemical side reactions.Moreover,our research reveals that the interfacial stability and the cycle performance of ASSLB can be greatly enhanced by increasing Al-substitution for Ni in LiNi0.85-xCo0.15AlxO2.In particular,the capacity retention of LiNi0.6Co0.15Al0.25O2 cathode after 200 cycles can reach 81.9%,much higher than that of LiNi0.8Co0.15Al0.05O2 cathode(12.5%@200 cycles).This work gives an insight to study the interfacial issues between Ni-rich layered oxide cathode and sulfide electrolyte for ASSLBs.
基金supported by the National Natural Science Foundation of China(Grant nos.52272201,52072136,52172229,52302303,and 51972257)Yanchang Petroleum-WHUT Joint Program(yc-whlg-2022ky-05)+1 种基金the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology,2022-KF-20)Fundamental Research Funds for the Central Universities(2023IVA106)for financial support
文摘FeS_(2)cathode is promising for all-solid-state lithium batteries due to its ultra-high capacity,low cost,and environmental friendliness.However,the poor performances,induced by limited electrode-electrolyte interface,severe volume expansion,and polysulfide shuttle,hinder the application of FeS_(2)in all-solid-state lithium batteries.Herein,an integrated 3D FeS_(2)electrode with full infiltration of Li6PS5Cl sulfide electrolytes is designed to address these challenges.Such a 3D integrated design not only achieves intimate and maximized interfacial contact between electrode and sulfide electrolytes,but also effectively buffers the inner volume change of FeS_(2)and completely eliminates the polysulfide shuttle through direct solid-solid conversion of Li2S/S.Besides,the vertical 3D arrays guarantee direct electron transport channels and horizontally shortened ion diffusion paths,endowing the integrated electrode with a remarkably reduced interfacial impedance and enhanced reaction kinetics.Benefiting from these synergies,the integrated all-solid-state lithium battery exhibits the largest reversible capacity(667 mAh g^(-1)),best rate performance,and highest capacity retention of 82%over 500 cycles at 0.1 C compared to both a liquid battery and non-integrated all-solid-state lithium battery.The cycling performance is among the best reported for FeS_(2)-based all-solid-state lithium batteries.This work presents an innovative synergistic strategy for designing long-cycling high-energy all-solid-state lithium batteries,which can be readily applied to other battery systems,such as lithium-sulfur batteries.
基金financially supported by the National Key Research and Development Program of China (No.2018YFE0111600)the National Natural Science Foundation of China (Nos.52172224 and 22279090)the Science and Technology Major Project of China National Machinery Industry Corporation (No.SINOMAST-ZDZX-2019-04)。
文摘The interface instability between layered oxide cathode and sulfide electrolyte is a key point affecting the perform ance of sulfide-based all-solid-state lithium batteries.Coating with fast-ionic conductor and constructing core-shell structure can effectively alleviate the interfacial side reactions and improve the interfacial stability between layered oxide and sulfide electrolyte.However,what have been neglected is the surface base(including Li_(2)CO_(3) and LiOH)of layered oxide can also affect the interfacial stability.To clarify this point clearly and improve the interfacial stability,the surface base of LiCoO_(2)(LCO)is regulated and investigated in this work.First,LCO with surface base Li_(2)CO_(3)(LCO@Li_(2)CO_(3))is prepared by the reaction of Co_(3)O_4 and excess Li_(2)CO_(3).Then,the bare LCO is obtained after LCO@Li_(2)CO_(3) is washed with deionized water and calcined again.Besides,LCO with surface base Li_(2)O(LCO@Li_(2)O)is also prepared with the bare LCO and LiOH.As a result,the electrochemical performances of LCO@Li_(2)O are significantly improved and much higher than those of LCO@Li_(2)CO_(3) and the bare LCO electrodes.In particular,LCO@Li_(2)O-2 cathode display the most outstanding electrochemical performances(discharge capacity138.4 mAh·g^(-1)at 0.2C,105 mAh·g^(-1)at 2C and a capacity retention of 95.4%after 150 cycles at 0.5C).The high discharge capacity and excellent cycle stability of LCO@Li_(2)O electrode confirm the effectiveness of regulating the surface base of layered oxide from Li_(2)CO_(3) to Li_(2)O.The surface base regulating is expected to be a simple but effective strategy to construct the stable interface between the cathode and the sulfide electrolyte of the all-solid-state lithium batteries.
基金supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(U1964205,51872303,52172253)+3 种基金the Ningbo S&T Innovation 2025 Major Special Programme(2019B10044,2021Z122)the Zhejiang Provincial Key R&D Program of China(2022C01072)the Jiangsu Provincial S&T Innovation Special Programme for carbon peak and carbon neutrality(BE2022007)the Youth Innovation Promotion Association CAS(Y2021080)。
文摘Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.
基金supported by the Guangdong“Pearl River Talents Plan”(no.2017GC010218)R&D Program in Key Areas of Guangdong Province(no.2020B0101030005)+2 种基金Guangdong Basic and Applied Basic Research Foundation(nos.2020B15151200492021A1515010153)the National Natural Science Foundation of China(no.NSFC51621001).
文摘All-solid-state lithium batteries(ASSLBs)based on sulfide solid electrolytes(SEs)are one of the most promising strategies for next-generation energy storage systems and electronic devices.However,the poor chemical/electrochemical stability of sulfide SEs with oxide cathode materials and high interfacial impedance,particularly due to physical contact failure,are the major limiting factors to the development of sulfide SEs in ASSLBs.Herein,the composite cathode of MOF-derived Fe_(7)S_(8)@C and Li_(6)PS_(5)Br fabricated by an infiltration method(IN-Fe_(7)S_(8))with dissoluble sulfide electrolyte(dissoluble SE)is reported.Dissoluble SE can easily infiltrate the porous sheet-type Fe_(7)S_(8)@C cathode to homogeneously contact with Fe_(7)S_(8)nanoparticles that are embedded in the surrounding carbon matrixes and form a fast ionic transport network.Benefiting from applying dissoluble SE and Fe_(7)S_(8)@C,the IN-Fe_(7)S_(8)-based cells displayed a reversible capacity of 510 mAh g^(-1)after 180 cycles at 0.045 mA cm^(-2)at 30℃.This work demonstrates a novel and practical method for the development of high-performance all-sulfide-based solid state batteries.
基金supported by the Enhancement of Performance and Production Technology of Lithium-based Next-generation Rechargeable Battery(project number 20012371)from the Ministry of Trade,Industry and Energy(MOTIE)of Koreasupported by project number KS2322-20(A Study on the Convergence Materials for Off-Grid Energy Conversion/Storage Integrated Devices)of the Korea Research Institute of Chemical Technology(KRICT).
文摘Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.
基金financially supported by the National Natural Science Foundation of China(52072036,52272187)the China Petroleum&Chemical Corporation(SINOPEC)project(223128).
文摘All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.
基金supported by grants from the National Natural Science Foundation of China(Nos.52072136,52172229,52272201,52302303,51972257)Yanchang Petroleum-WHUT Joint Program(No.yc-whlg-2022ky-05)Fundamental Research Funds for the Central Universities(Nos.104972024RSCrc0006,2023IVA106)for financial support。
文摘Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
基金supported by the National Key R&D Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant Nos.51872303,U1964205,51902321)+4 种基金the Zhejiang Provincial Natural Science Foundation of China(Grant No.LD18E020004,LY18E020018)the Ningbo S&T Innovation 2025 Major Special Programme(Grant Nos.2018B10061,2018B10087,2019B10044)the Natural Science Foundation of Ningbo(Grant Nos.2018A610010,2019A610007)the Jiangxi Provincial Key R&D Program of China(Grant No.20182ABC28007)the Youth Innovation Promotion Association CAS(2017342).
文摘All-solid-state lithium batteries(ASSLBs)have attracted increasing attention due to their high safety and energy density.Among all corresponding solid electrolytes,sulfide electrolytes are considered to be the most promising ion conductors due to high ionic conductivities.Despite this,many challenges remain in the application of ASSLBs,including the stability of sulfide electrolytes,complex interfacial issues between sulfide electrolytes and oxide electrodes as well as unstable anodic interfaces.Although oxide cathodes remain the most viable electrode materials due to high stability and industrialization degrees,the matching of sulfide electrolytes with oxide cathodes is challenging for commercial use in ASSLBs.Based on this,this review will present an overview of emerging ASSLBs based on sulfide electrolytes and oxide cathodes and high-light critical properties such as compatible electrolyte/electrode interfaces.And by considering the current challenges and opportunities of sulfide electrolyte-based ASSLBs,possible research directions and perspectives are discussed.
基金supported by the Key Scientific and Technological Innovation Project of Shandong(No.2020CXGC010401)Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA22010602)+2 种基金the National Natural Science Foundation of China(Nos.52203150 and 52037006)CAS Key Technology Talent Program,Key Research and Development Plan of Shandong Province(No.2019GHZ009)Qingdao Key Laboratory of Solar Energy Utilization and Energy Storage Technology,and the Public Projects of Zhejiang Province(No.LGG19E020001).
文摘Lithium-sulfur(Li-S)batteries are considered as promising candidates for novel energy storage technology that achieves energy density of 500 Wh·kg^(−1).However,poor cycle stability resulting from notorious shuttle effect and the safety concerns deriving from flammability of ether-based electrolyte hinder the practical application of Li-S batteries.Because of low solubility to polysulfide,high ionic conductivity,and safety property,sulfide-based electrolytes can fundamentally address above issues.It is widely known that the effective transports of both electrons and ions are basic requirement for redox reaction of active materials in cathode.Thereby,construction of fast and stable ionic and electronic transport paths in cathode is especially pivotal for cycle stability of solid-state Li-S batteries(SSLSBs).In this review,we provide research progresses on facilitating transport of charge carriers in composite cathode of SSLSBs.From perspective of materials,intrinsically conductivity of electrolyte and carbon shows dramatic effect on migration of charge carriers in cathode of SSLSBs,thereby the conductive additives are summarized in the manuscript.Additionally,the charge transport in cathode of SSLSBs fully depends on the physical contact between active materials and conductive additives,therefore we summarized the strategies optimizing interfacial contact and reducing interfacial resistance.Finally,potential future research directions and prospects for SSLSBs with improved energy density and cycle performance are also proposed.
基金supported by the Beijing Natural Science Foundation(grant No.L223009)the National Natural Science Foundation of China(grant No.22075029)+1 种基金the National Key Research and Development Program of China(grant No.2021YFB2500300)the Key Research and Development(R&D)Projects of Shanxi Province(grant No.2021020660301013).
文摘Sulfide solid electrolytes(SEs)have attracted ever-increasing attention due to their superior roomtemperature ionic conductivity(~10^(-2) S cm^(-1)).Additionally,the integration of sulfide SEs and highvoltage cathodes is promising to achieve higher energy density.However,the incompatible interfaces between sulfide SEs and high-voltage cathodes have been one of the key factors limiting their applications.Therefore,this review presents a critical summarization of the interfacial issues in all-solid-state lithium batteries based on sulfide SEs and high-voltage cathodes and proposes strategies to stabilize the electrolyte/cathode interfaces.Moreover,the future research direction of electrolyte/cathode interfaces and application prospects of powder technology in sulfide-based ASSLBs were also discussed.
基金support by the Department of Science&Technology of Zhejiang Province under grant no.2024C01095Zhejiang Provincial Natural Science Foundation of China under grant nos.LD22E020006 and LBMHD24E020001the National Natural Science Foundation of China(NSFC)under grant nos.21972127,U20A20253,and 22279116.
文摘Coupling with high-voltage oxide cathode is the key to achieve high-energy density sulfide-based all-solid-state lithium batteries.However,the complex interfacial issues including the space charge layer effect and undesirable side reaction between sulfide solid-state electrolytes and oxide cathode materials are the main constraints on the development of high-performance allsolid-state lithium batteries,which lead to the continuous decay of electrochemical performance.Herein,different from the complicated coating procedure,a LiPO_(2)F_(2)additive engineering was proposed to achieve high-performance all-solid-state lithium batteries.With the introduction of LiPO_(2)F_(2)additive,a protective cathode-electrolyte interphase consisting of LiPxOyFz,LiF,and Li_(3)PO_(4)could be in situ formed to improve the interfacial stability between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)and Li_(5.5)PS_(4.5)Cl_(1.5)(LPSC).Benefiting from this,the NCM811/LPSC/Li all-solid-state lithium battery exhibited impressive cyclic stability with a capacity retention of 85.5%after 600 cycles(at 0.5 C).Diverse and comprehensive characterization,combined with finite element simulation and density functional theory calculation fully demonstrated the effective component,interfacial stabilization function and enhanced kinetic of LiPO_(2)F_(2)-derived cathode-electrolyte interphase.This work provides not only a feasible and effective method to stabilize the cathodic interface but also worthy insight into interfacial design for high-performance all-solid-state lithium batteries.
基金Project(52374407)supported by the National Natural Science Foundation of China。
文摘Sulfide solid electrolytes(S-SEs)are widely preferred for their high ionic conductivity and processability.However,the further development of S-SEs is hindered by the excessive price of its critical raw materials of Li_(2)S.Herein,a low-cost and environmentally friendly method is proposed to synthesize Li_(2)S by the carbothermal reduction reaction of Li_(2)SO_(4)in one step,and the effects of various factors are also discussed.As a result,a purity of 99.67%is obtained over the self-prepared Li_(2)S.More importantly,the cost of the self-prepared Li_(2)S is only about 50$/kg,which is significantly lower than that of the commercial counterpart(10000−15000 dollar/kg).Moreover,the ionic conductivity of Li_(5.5)PS_(4.5)Cl_(1.5)prepared using self-prepared Li_(2)S as raw materials is 4.19 mS/cm at room temperature,which is a little higher than that of Li_(5.5)PS_(4.5)Cl_(1.5)using commercial Li_(2)S(4.05 mS/cm).And the all-solid-state lithium batteries(ASSLBs)with the as-prepared electrolytes could maintain a discharge capacity of 109.9 mA·h/g with an average coulombic efficiency(CE)of 98%after 100 cycles at 0.2 C,which is equivalent to that using commercial Li_(2)S,demonstrating that the preparation strategy of Li_(2)S proposed in this work is feasible.
基金Fiscal Year 2023-2024 High-Level and Growth Research and Development Subsidy for supporting the research and development activities for small and medium-size enterprise(SMEs),which is administered by Chiba Industry Advancement Center(Grant No.2066 and 2027)。
文摘This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.
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supported by the Basic Science Research Program through National Research Foundation of Korea(NRF)grant funded by the Ministry of Science and ICT(RS-2022-NR070534)supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(2710024139)。
文摘Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.
基金partially sponsored by the Office of Energy Efficiency and Renewable Energy(EERE)in the Vehicle Technologies Office(VTO)through the Advanced Battery Materials Research(BMR)Program,managed by DrsThe Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan(http://energy.gov/downloads/doe-public-access-plan).
文摘We demonstrate for the first time the critical influence of binder molecular weight on the performance of slurry-cast lithium nickel manganese cobalt oxide(NMC)cathodes in sulfide-based all-solid-state batteries(SSBs).SSBs are increasingly recognized as a safer and potentially more efficient alternative to traditional Li-ion batteries,owing to the superior ionic conductivities and inherent safety features of sulfide solid electrolytes.However,the integration of high-voltage NMC cathodes with sheet-type sulfide solid electrolytes presents significant fabrication challenges.Our findings reveal that higher molecular weight binders not only enhance the discharge capacity and cycle life of these cathodes but also ensure robust adhesion and structural integrity.By optimizing binder molecular weights,we effectively shield the active materials from degradation and mechanical stress,significantly boosting the functionality and longevity of SSBs.These results underscore the paramount importance of binder properties in advancing the practical application of high-performance all-solid-state batteries.
基金financial support from the Science and Technology Project of Shenzhen(Nos.JCYJ20210324094206019 and JCYJ20210324094000001).
文摘Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).
