Halide solid electrolytes(SEs)show high ionic conductivity and good compatibility with cathode active materials,providing long-life all-solid-state lithium-ion batteries(ASSLIBs).Liquid-phase synthesis technology is a...Halide solid electrolytes(SEs)show high ionic conductivity and good compatibility with cathode active materials,providing long-life all-solid-state lithium-ion batteries(ASSLIBs).Liquid-phase synthesis technology is a feasible option for the large-scale manufacturing of halide SEs.However,no leading liquid-phase synthesis method for halide SEs has been developed because of a limited understanding of the solvent effect on the formation of halide SEs.Herein,a scalable and universal liquid-phase synthesis method for halide SEs using organic solvents is reported.The Li₃₋ₓYCl₆₋ₓ SEs synthesized via pyridine transform trigonal structure to metastable orthorhombic structure as the Li concentration decreases,forming a highly pure orthorhombic phase with an ionic conductivity of 1.3×10⁻⁴S cm⁻¹ at 25℃ in the composition of x=1.Spectroscopic analysis indicates that pyridine acts as a reducing ligand,stabilizing the orthorhombic Li₂YCl₅by modulating the valence state of yttrium ions.Additionally,the developed synthesis method is extended to the synthesis of bromide SEs with high ionic conductivity.ASSLIBs using LiNi₀.₈Co₀.₁Mn₀.₁O₂-Li₂YCl₅ cathode composites demonstrate good cycling stability for 100 cycles.The liquid-phase synthesis technology reported here opens opportunities for the practical manufacturing of halide-based ASSLIBs.展开更多
Poly(ethylene oxide)-based polymer all-solid-state lithium-sulfur batteries(ASSLSBs)have been a prominent direction in new generation of energy storage devices due to their safety,low cost and high specific energy.How...Poly(ethylene oxide)-based polymer all-solid-state lithium-sulfur batteries(ASSLSBs)have been a prominent direction in new generation of energy storage devices due to their safety,low cost and high specific energy.However,the performance degradation arising from the“shuttle effect”and poor ion transport dynamics limit its further development.Herein,for the first time,we introduce the concepts of adsorption and catalysis into polymer ASSLSBs.By combining S@KB with g-C3N4,the polysulfides shuttling is significantly inhibited.Meanwhile,the kinetic process of the cathode is obviously improved,which is confirmed by in situ electrochemical impedance spectroscopy.The battery with g-C3N4 can provide a high reversible capacity 1078.5 mAh/g,and can be stabilized for 150 cycles with a final Coulombic efficiency of 97.47%,implying a superior electrochemical stability than previously reported.Furthermore,the intrinsic mechanisms of adsorption and catalysis are intensively studied by means of XPS,DFT calculations,and galvanostatic intermittent titration technique.Changes in electrode properties before and after cycling have also been used to study battery stability.Overall,this work will open the door to the novel polymer all-solid-state lithium-sulfur battery design for practical realization of high-energy batteries.展开更多
To improve the solid–solid interface performance of all solid-state lithium batteries(ASSLBs),a novel sandwich-structured solid electrolyte(SSE,total thickness of 0.7 mm)was investigated.It comprises a central layer ...To improve the solid–solid interface performance of all solid-state lithium batteries(ASSLBs),a novel sandwich-structured solid electrolyte(SSE,total thickness of 0.7 mm)was investigated.It comprises a central layer of perovskite-type Li0.37Sr0.44Zr0.25Ta0.75O3(LSZT)electrolyte(thickness of 0.5 mm)sandwiched between two layers of composite solid polymer electrolyte(CSPE,each with a thickness of 0.1 mm).The thin CSPE interlayer not only effectively reduces interfacial resistance between LSZT and electrodes,but also suppresses Li-induced reduction degradation of LSZT while ensuring uniform current density distribution across the interface.The SSE demonstrates an ionic conductivity of 8.76×10−5S·cm−1at 30℃,increasing to 1.13×10−3S·cm−1at 100℃,with an activation energy of 0.36 eV.In addition,SSE is stable for Li metal and achieves electrochemical stability up to 4.58 V vs.Li+/Li.SSE shows outstanding electrode/electrolyte interfacial compatibility and significant suppression of the growth of Li dendrite.Ascribing to these merits,Li|SSE|Li symmetric cell maintained stable operation for 500 h at a current density of 0.3 mA·cm−2without short circuit,confirming robust interfacial compatibility between SSE and Li electrode.The all-solid-state LiFePO4|Li battery with SSE has an initial reversible discharge capacity of 109.8 mAh·g−1and a reversible capacity of 118.1 mAh·g−1after 50 cycles at a charge/discharge rate of 0.1C(30℃),demonstrating good cycling performance.展开更多
Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate ...Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate Na-ion batteries(ASSNIBs),Here,we develop a series of LaCl3-based sodium superionic conductors engineered through cation vacancy-concentration modulation,which facilitates the formation of a threedimensional Na+transport network and increases the density of ion-hopping sites.The optimized Na0.4Ta0.236La0.472Cl3(NTLC)electrolyte achieves a Na+conductivity of 1.38×10-3 S/cm at 30℃,with a reduced activation energy of 0.26 eV.It also exhibits excellent mechanical deformation and moderate high-voltage stability,resulting in enhanced interfacial compatibility.When paired directly with an uncoated NaCrO2 cathode,the NTLC catholyte enables ASSNIBs to cycle stably over 300 cycles with89.7%capacity retention at 0.3 C and room temperature.This work underscores the potential of vacancy-rich LaCl3-based sodium superionic conductors for advancing high-performance ASSNIBs.展开更多
All-solid-state lithium-sulfur batteries(ASSLSBs)hold promise as a next-generation energy storage technology,yet their practical deployment is hindered by sluggish sulfur redox kinetics and restricted triplephase inte...All-solid-state lithium-sulfur batteries(ASSLSBs)hold promise as a next-generation energy storage technology,yet their practical deployment is hindered by sluggish sulfur redox kinetics and restricted triplephase interfaces.Here,we designed a high-entropy sulfide(HES)material with mixed ionic-electronic conductivity as a multifunctional mediator to engineer robust ion/electron transport pathways and abundant catalytic sites within the cathode.This unique structural configuration significantly enhances charge transport and optimizes interfacial kinetics,dramatically reducing polarization.Critically,HESincorporated ASSLSBs exhibit superior performance at room temperature,achieving 84.0%capacity retention over 160 cycles at 1 C,a high capacity of 683.7 mAh g-1at 5.4 mA cm-2,and an exceptional areal capacity of 5.8 m Ah cm-2with a sulfur loading of 6 mg cm-2.This work demonstrates that highentropy-driven design principles can fundamentally address ion and electron transport challenges in sulfur cathodes,offering a viable strategy toward advanced ASSLSBs.展开更多
1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained ...1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained attention.The performance of routine LIBs is approaching the ceiling,particularly in terms of energy density,making it difficult to meet the ever-increasing demand for energy density[1].展开更多
All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lit...All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lithium-ion batteries.Understanding and optimizing the complex chemistries and interfaces that underpin ASSB performance present significant challenges from both experimental and modeling perspectives.In particular,atomistic simulations face difficulties in capturing the complex structure,disorder,and dynamic evolution of materials and interfaces under practically relevant conditions.While established methods such as density functional theory and classical force fields have provided valuable insights,some questions remain difficult to address,particularly those involving large system sizes or long timescales.Recently,machine learning interatomic potentials(MLIPs)have emerged as a transformative tool,enabling atomistic simulations at length and time scales that were previously challenging to access with conventional approaches.By delivering near first-principles accuracy with much greater efficiency,MLIPs open new avenues for large-scale,long-timescale,and high-throughput simulations of solid-state battery materials.In this review,we present a comparative overview of density functional theory,classical force fields,and MLIPs,highlighting their respective strengths and limitations in ASSB research.We then discuss how MLIPs enable simulations that reach longer timescales,larger system sizes,and support high-throughput calculations,providing unique insights into ion transport and interfacial evolution in ASSBs.Finally,we conclude with a summary and outlook on current challenges and future opportunities for expanding MLIP capabilities and accelerating their impact in solid-state battery research.展开更多
High-capacity silicon anodes hold great promise for safe and energy-dense all-solid-state lithium batteries(ASSLBs),yet their practical application is hindered by interfacial degradation and mechanical fracture,which ...High-capacity silicon anodes hold great promise for safe and energy-dense all-solid-state lithium batteries(ASSLBs),yet their practical application is hindered by interfacial degradation and mechanical fracture,which severely limit their cycle life.Herein,we unravel the particle-size-dependent electro-chemo-mechanical failure mechanisms of Si anodes in sulfide-based ASSLBs.The micro-sized Si(μm-Si)anode exhibits favorable initial Coulombic efficiency(ICE,79.15%)and reversible capacity(2260.5 mAh g-1)but succumbs to progressive particle fracture under prolonged cycling due to cumulative mechanical stress from large volume swings.By contrast,the nano-sized Si(nm-Si)anode suffers from severe interfacial side reactions and irreversible volume expansion due to its larger specific area and dense electrode structure,resulting in lower initial performance(ICE of 72.21%,1372.7 mAh g-1).In subsequent cycles,the nm-Si anode experiences continuous interfacial side reactions,leading to substantial accumulation of interfacial decomposition byproducts and sustained capacity decay.These contrasting failure pathways establish electro-chemo-mechanical coupling as the governing prin-ciple and provide a particle-size-dependent design framework for high-performance Si-based ASSLBs.展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O2(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O2(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g-1 at 0.2 C,160.9 mA h g-1 at 2.0 C and 112.3 mA h g-1 at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g-1 after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
All-solid-state batteries(ASSBs),which replace flammable liquid electrolytes with inorganic solid electrolytes(SEs),have attracted considerable attention as safer and higher-energy storage technologies.Among various c...All-solid-state batteries(ASSBs),which replace flammable liquid electrolytes with inorganic solid electrolytes(SEs),have attracted considerable attention as safer and higher-energy storage technologies.Among various candidates,sulfide-based SEs such as argyrodite-type Li6PS5Cl combine high ionic conductivity with excellent processability,facilitating the fabrication of dense and well-integrated composite cathodes.Nevertheless,the electrochemical performance of ASSBs remains largely constrained by interfacial and structural degradation occurring within the composite cathode.Understanding the degradation phenomena at the interface between the SE and the cathode active material is thus essential to improving the electrochemical performance and cycle life of these systems.Specifically,these degradation pathways can be broadly divided into(electro)chemical mechanisms—such as electrochemical decomposition of SE,transition-metal dissolution,oxygen-involving interfacial reactions,and surface reconstruction—and mechanical mechanisms,including particle cracking and interfacial contact loss driven by anisotropic stress and volume fluctuations.Acting synergistically,these processes reduce Li+mobility,increase interfacial impedance,and cause irreversible capacity loss.In this review,we systematically examine these degradation modes in sulfide-based ASSBs,with a particular focus on Ni-rich layered oxide/argyrodite composite cathodes.By organizing recent experimental findings,we aim to provide a comprehensive understanding of the limitations of current ASSB systems and to guide future efforts toward more stable and durable solid-state battery technologies.展开更多
All-solid-state lithium metal batteries(ASSLMBs)promise high energy density and enhanced safety.Nevertheless,their performance is hindered by lithium dendrite growth at high current densities,which can induce internal...All-solid-state lithium metal batteries(ASSLMBs)promise high energy density and enhanced safety.Nevertheless,their performance is hindered by lithium dendrite growth at high current densities,which can induce internal short circuits with abrupt cell voltage drops.However,at intermediate current densities,“soft shorts”,namely partial and transient internal shorts,are more prevalent and difficult to interpret.In such a case,the cell voltage does not collapse to zero but instead fluctuates dynamically and fails to increase further during charge.To elucidate the electro-chemo-mechanical mechanisms underlying this unusual soft short behavior,we investigate the cycling of Li4Ti5O12(LTO)|Li6PS5Cl(LPSC)|Li in a three-electrode cell configuration equipped with operando pressure monitoring.An in situ lithiated Au/W reference electrode enables independent tracking of the working and counter electrode potentials and their impedance evolution.During galvanostatic cycling,we directly captured the formation of a soft short accompanied by a partial voltage recovery by simultaneously tracking electrode potentials and realtime cell pressure.By correlating pressure transients with the measured Faradaic currents,we reveal for the first time that the onset of a soft short fundamentally decouples the internal electrochemical reactions from the externally imposed current.This hidden current redistribution is further substantiated by impedance spectroscopy,which shows a pronounced drop in ohmic resistance following dendritic bridging,providing direct evidence for the emergence of electronically conductive pathways across the solid electrolyte.Building on these insights,we propose an equivalent circuit model describing the dynamic evolution of soft shorts and introduce quantitative methods to estimate dendrite dimensions,found to range from 100 to 102nm.Together,these advances provide the first quantitative link between soft-short electrochemical signatures and the underlying nanoscale morphology of dendritic filaments.展开更多
Because of their exceptional safety and thermal stability,all-solid-state sodium batteries are viable next-generation energy storage technologies,while borohydride-based solid electrolytes have garnered considerable i...Because of their exceptional safety and thermal stability,all-solid-state sodium batteries are viable next-generation energy storage technologies,while borohydride-based solid electrolytes have garnered considerable interest for their favorable electrochemical stability.Nevertheless,the poor room-temperature ionic conductivity of Na2B12H12 continues to be a significant obstacle that restricts its usefulness.To address this issue,this work proposes a simple mechanochemical compositing strategy.By introducing boron nitride(BN)as a multifunctional interfacial modifier,the ionic conduction performance is significantly enhanced.The Na2B12H12/BN composite electrolyte is prepared via high-energy ball milling.Structural characterizations reveal that the incorporation of BN induces a mechanochemistry-driven phase and structural transformation in Na2B12H12 and creates abundant heterointerfaces.Electrochemical measurements show that theoptimized composite electrolyte achieves a high room-temperature ionic conductivity of 2.2×10-4 S cm-1,almost an order of magnitude higher than that of ball-milled pristine Na2B12H12,with a reduced activation energy of 0.31 eV.Furthermore,the electrolyte exhibits excellent stability against a Na-Sn alloy,enabling symmetric cells to cycle stably for over 800 h.An all-solid-state sodium battery assembled with Na3V2(PO4)3 as the cathode and a Na-Sn alloy as the anode demonstrates outstanding cycling stability(80%capacity retention after 100 cycles at 0.5 C)and rate capability.This work offers new insights for the creation of sophisticated all-solid-state sodium batteries by rationalizing the design of high-performance borohydride-based solid electrolytes through interfacial engineering using inert nanomaterials.展开更多
Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.L...Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li+/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO3(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li2.5Y0.5Zr0.5Cl6(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm-1for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g-1over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g-1.Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.展开更多
Polymer-based solid-state electrolytes with high flexibility and excellent processability present great prospects in all-solid-state lithium batteries.However,when encountering interface stability problems,the applica...Polymer-based solid-state electrolytes with high flexibility and excellent processability present great prospects in all-solid-state lithium batteries.However,when encountering interface stability problems,the application of polymer-based solid-state electrolytes in all-solid-state lithium batteries is puzzling.In this work,we proposed a lithium crosslinking strategy to regulate the interfacial chemistry by tailoring an effective Li2O-rich solid electrolyte interphase layer attributed to introducing 15-crown-5 into the polymer matrix.Specifically,crosslinking the 15-crown-5 with Li+in polymer-based solid-state electrolytes boosts the Li+transport by weakening the coordination between Li+and polymer chains.The crosslinked 15-crown-5 moves along with the Li+to the anode and decomposes to form the Li2O-rich solid electrolyte interphase with faster Li+diffusion kinetics,resulting in uniform lithium deposition and suppressing the dendrite penetration.Therefore,the symmetric Li-Li cell could stably maintain cycling over 1100 h without short-circuiting.The LiFePO4||Li full battery presents high retention of capacity(92.75%)over 500 cycles at 1 C.Also,the NCM811||Li full battery can be well-operated in 300 cycles with the capacity retention of 81.44%at 1 C.This study inspires the development of high-performance all-solid-state lithium batteries by rationally tailoring interface chemistry components by regulating the coordinated structure of Li+at the molecular level.展开更多
Solid-state electrolytes(SEs)are the“blood vessels”in all-solid-state batteries(ASSBs),providing essential ion channels.In past decades,SE design has been mainly carried out within ordered crystalline frameworks,whi...Solid-state electrolytes(SEs)are the“blood vessels”in all-solid-state batteries(ASSBs),providing essential ion channels.In past decades,SE design has been mainly carried out within ordered crystalline frameworks,which is understandable for achieving well-defined ion transport pathways.However,the large impedance,poor interfaces,and dendrite penetration brought about by polycrystalline grain boundaries have always been the inherent drawbacks of crystalline SEs.Recently,tailoring disorder in crystalline SEs to achieve local atomic disorder or amorphous-state lattice disorder has emerged as an interesting strategy.In this review,we outline the working mechanism of disorder in SEs and highlight the prospects for amorphous solid electrolytes(ASEs)in advanced ASSBs,especially low-temperature ASSBs.From atomic disorder to lattice disorder,we discuss in depth the disorder-induced ion-conduction mechanism as well as properties,applications,and preparation methods.An interesting ASE closed-loop design and prediction framework is provided to meet the requirements for future ASSBs.After presenting these insights,we offer our view on the future development of ASEs.展开更多
This study shows that sulfide solid-state electrolytes,β-Li3PS4and Li6PS5Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature&l...This study shows that sulfide solid-state electrolytes,β-Li3PS4and Li6PS5Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O2-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O2source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.展开更多
Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy densi...Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO2coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm-2,achieving an areal capacity of 17.90 mA h cm-2.These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.展开更多
With the rapid development of flexible equipment,high-energy/-power requirements have been proposed for energy storage devices.Nevertheless,the poor conductivities of metallic oxides and their low levels of transmissi...With the rapid development of flexible equipment,high-energy/-power requirements have been proposed for energy storage devices.Nevertheless,the poor conductivities of metallic oxides and their low levels of transmission of electrons/ions hinder their widespread application.Here,a sandwich-structured Co3O4-Fe3O4(CFO) composite with binder-free was synthesized on a carbon cloth substrate via co-precipitation and partial ion exchange.The appropriate substitution of Co3O4with Fe3O4is favorable in promoting the rapid transfer of electrolyte ions and alleviating changes in volume during the electrochemical studies.When the duration of the substitution reaction is 20 min,the obtained electrode delivers a maximum specific capacitance of 1196.2 Fg-1at a current density of 1 A g-1and a superior capacity retention of~71%when the current density varies from 1to 30 Ag-1.Furthermore,the fabricated CFO//activated carbon flexible all-solid-state supercapacitor exhibits arespective maximum energy and power density of 68.7Wh kg-1and 16,000 W kg-1and excellent flexibility.It also displays a specific capacity retention of 81.3%under four continuous bending states at a current density of 6A g-1over 10,000 cycles.These remarkable electrochemical char ac teristics suggest that the sandwich-structured CFO composite displays considerable potential for application in flexible high-energy/-power supercapacitors.展开更多
All-solid-state batteries(ASSBs)are pursued due to their potential for better safety and high energy density.However,the energy density of the cathode for ASSBs does not seem to be satisfactory due to the low utilizat...All-solid-state batteries(ASSBs)are pursued due to their potential for better safety and high energy density.However,the energy density of the cathode for ASSBs does not seem to be satisfactory due to the low utilization of active materials(AMs)at high loading.With small amount of solid electrolyte(SE)powder in the cathode,poor electrochemical performance is often observed due to contact loss and non-homogeneous distribution of AMs and SEs,leading to high tortuosity and limitation of lithium and electron transport pathways.Here,we propose a novel cathode design that can achieve high volumetric energy density of 1258 Wh L-1at high AM content of 85 wt%by synergizing the merits of AM@SE core–shell composite particles with conformally coated thin SE shell prepared from mechanofusion process and small SE particles.The core–shell structure with an intimate and thin SE shell guarantees high ionic conduction pathway while unharming the electronic conduction.In addition,small SE particles play the role of a filler that reduces the packing porosity in the cathode composite electrode as well as between the cathode and the SE separator layer.The systematic demonstration of the optimization process may provide understanding and guidance on the design of electrodes for ASSBs with high electrode density,capacity,and ultimately energy density.展开更多
Li6PS5Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its c...Li6PS5Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li6PS5Cl/Li interface and growth of lithium dendrites inside Li6PS5Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li6PS5Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi6PS5Cl@Li3OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li6PS5Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm-2to 1.6 mA cm-2,and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm-2or from 10 h to 900 h at the cycling current of 0.5 mA cm-2;2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi6PS5Cl@Li3OCl interface.展开更多
基金supported by JSPS KAKENHI Grant Number 25K18098.
摘要Halide solid electrolytes(SEs)show high ionic conductivity and good compatibility with cathode active materials,providing long-life all-solid-state lithium-ion batteries(ASSLIBs).Liquid-phase synthesis technology is a feasible option for the large-scale manufacturing of halide SEs.However,no leading liquid-phase synthesis method for halide SEs has been developed because of a limited understanding of the solvent effect on the formation of halide SEs.Herein,a scalable and universal liquid-phase synthesis method for halide SEs using organic solvents is reported.The Li₃₋ₓYCl₆₋ₓ SEs synthesized via pyridine transform trigonal structure to metastable orthorhombic structure as the Li concentration decreases,forming a highly pure orthorhombic phase with an ionic conductivity of 1.3×10⁻⁴S cm⁻¹ at 25℃ in the composition of x=1.Spectroscopic analysis indicates that pyridine acts as a reducing ligand,stabilizing the orthorhombic Li₂YCl₅by modulating the valence state of yttrium ions.Additionally,the developed synthesis method is extended to the synthesis of bromide SEs with high ionic conductivity.ASSLIBs using LiNi₀.₈Co₀.₁Mn₀.₁O₂-Li₂YCl₅ cathode composites demonstrate good cycling stability for 100 cycles.The liquid-phase synthesis technology reported here opens opportunities for the practical manufacturing of halide-based ASSLIBs.
基金supported by the National Natural Science Foundation of China(Nos.22309027 and 52374301)the Natural Science Foundation of Hebei Province(No.E2024501010)+2 种基金the Shijiazhuang Basic Research Project(Nos.241790667A and 241790907A)the Fundamental Research Funds for the Central Universities(Nos.N2423054 and N2423052)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(No.22567627H)。
摘要Poly(ethylene oxide)-based polymer all-solid-state lithium-sulfur batteries(ASSLSBs)have been a prominent direction in new generation of energy storage devices due to their safety,low cost and high specific energy.However,the performance degradation arising from the“shuttle effect”and poor ion transport dynamics limit its further development.Herein,for the first time,we introduce the concepts of adsorption and catalysis into polymer ASSLSBs.By combining S@KB with g-C3N4,the polysulfides shuttling is significantly inhibited.Meanwhile,the kinetic process of the cathode is obviously improved,which is confirmed by in situ electrochemical impedance spectroscopy.The battery with g-C3N4 can provide a high reversible capacity 1078.5 mAh/g,and can be stabilized for 150 cycles with a final Coulombic efficiency of 97.47%,implying a superior electrochemical stability than previously reported.Furthermore,the intrinsic mechanisms of adsorption and catalysis are intensively studied by means of XPS,DFT calculations,and galvanostatic intermittent titration technique.Changes in electrode properties before and after cycling have also been used to study battery stability.Overall,this work will open the door to the novel polymer all-solid-state lithium-sulfur battery design for practical realization of high-energy batteries.
基金financial support providedby the National Natural Science Foundation of China (Nos.92475203 and 52474374)the Joint Fund of Henan Province Science and Technology R&D Program,China (No.225200810035)the Research Initiation Grant for High-Level Talents by the Henan Academy of Sciences,China(No.232007016).
摘要To improve the solid–solid interface performance of all solid-state lithium batteries(ASSLBs),a novel sandwich-structured solid electrolyte(SSE,total thickness of 0.7 mm)was investigated.It comprises a central layer of perovskite-type Li0.37Sr0.44Zr0.25Ta0.75O3(LSZT)electrolyte(thickness of 0.5 mm)sandwiched between two layers of composite solid polymer electrolyte(CSPE,each with a thickness of 0.1 mm).The thin CSPE interlayer not only effectively reduces interfacial resistance between LSZT and electrodes,but also suppresses Li-induced reduction degradation of LSZT while ensuring uniform current density distribution across the interface.The SSE demonstrates an ionic conductivity of 8.76×10−5S·cm−1at 30℃,increasing to 1.13×10−3S·cm−1at 100℃,with an activation energy of 0.36 eV.In addition,SSE is stable for Li metal and achieves electrochemical stability up to 4.58 V vs.Li+/Li.SSE shows outstanding electrode/electrolyte interfacial compatibility and significant suppression of the growth of Li dendrite.Ascribing to these merits,Li|SSE|Li symmetric cell maintained stable operation for 500 h at a current density of 0.3 mA·cm−2without short circuit,confirming robust interfacial compatibility between SSE and Li electrode.The all-solid-state LiFePO4|Li battery with SSE has an initial reversible discharge capacity of 109.8 mAh·g−1and a reversible capacity of 118.1 mAh·g−1after 50 cycles at a charge/discharge rate of 0.1C(30℃),demonstrating good cycling performance.
基金Financial supports from the National Natural Science Foundation of China(22479009)the National related project。
摘要Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate Na-ion batteries(ASSNIBs),Here,we develop a series of LaCl3-based sodium superionic conductors engineered through cation vacancy-concentration modulation,which facilitates the formation of a threedimensional Na+transport network and increases the density of ion-hopping sites.The optimized Na0.4Ta0.236La0.472Cl3(NTLC)electrolyte achieves a Na+conductivity of 1.38×10-3 S/cm at 30℃,with a reduced activation energy of 0.26 eV.It also exhibits excellent mechanical deformation and moderate high-voltage stability,resulting in enhanced interfacial compatibility.When paired directly with an uncoated NaCrO2 cathode,the NTLC catholyte enables ASSNIBs to cycle stably over 300 cycles with89.7%capacity retention at 0.3 C and room temperature.This work underscores the potential of vacancy-rich LaCl3-based sodium superionic conductors for advancing high-performance ASSNIBs.
基金supported by the National Natural Science Foundation of China(grant No.22309101,U22A20113,and52261135543)the Fundamental Research Funds for the Central Universities of Ministry of Education(grant No.AUGA5710012925)+1 种基金the Guizhou Provincial Central Guiding Local Science and Technology Development Fund Program[2025](No.018)the Guizhou Provincial Key Technology R&D Program(ZZSG[2024]002)。
摘要All-solid-state lithium-sulfur batteries(ASSLSBs)hold promise as a next-generation energy storage technology,yet their practical deployment is hindered by sluggish sulfur redox kinetics and restricted triplephase interfaces.Here,we designed a high-entropy sulfide(HES)material with mixed ionic-electronic conductivity as a multifunctional mediator to engineer robust ion/electron transport pathways and abundant catalytic sites within the cathode.This unique structural configuration significantly enhances charge transport and optimizes interfacial kinetics,dramatically reducing polarization.Critically,HESincorporated ASSLSBs exhibit superior performance at room temperature,achieving 84.0%capacity retention over 160 cycles at 1 C,a high capacity of 683.7 mAh g-1at 5.4 mA cm-2,and an exceptional areal capacity of 5.8 m Ah cm-2with a sulfur loading of 6 mg cm-2.This work demonstrates that highentropy-driven design principles can fundamentally address ion and electron transport challenges in sulfur cathodes,offering a viable strategy toward advanced ASSLSBs.
基金supported by the Beijing Natural Science Foundation(L243019)the National Natural Science Foundation of China(22393900,22393904)+3 种基金the National Key Research and Development Program(2021YFB2500300)the JBGS project from Ordos(JBGS2024001)the Tsinghua University Initiative Scientific Research Programthe“Shuimu Tsinghua Scholar Program of Tsinghua University”。
摘要1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained attention.The performance of routine LIBs is approaching the ceiling,particularly in terms of energy density,making it difficult to meet the ever-increasing demand for energy density[1].
摘要All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lithium-ion batteries.Understanding and optimizing the complex chemistries and interfaces that underpin ASSB performance present significant challenges from both experimental and modeling perspectives.In particular,atomistic simulations face difficulties in capturing the complex structure,disorder,and dynamic evolution of materials and interfaces under practically relevant conditions.While established methods such as density functional theory and classical force fields have provided valuable insights,some questions remain difficult to address,particularly those involving large system sizes or long timescales.Recently,machine learning interatomic potentials(MLIPs)have emerged as a transformative tool,enabling atomistic simulations at length and time scales that were previously challenging to access with conventional approaches.By delivering near first-principles accuracy with much greater efficiency,MLIPs open new avenues for large-scale,long-timescale,and high-throughput simulations of solid-state battery materials.In this review,we present a comparative overview of density functional theory,classical force fields,and MLIPs,highlighting their respective strengths and limitations in ASSB research.We then discuss how MLIPs enable simulations that reach longer timescales,larger system sizes,and support high-throughput calculations,providing unique insights into ion transport and interfacial evolution in ASSBs.Finally,we conclude with a summary and outlook on current challenges and future opportunities for expanding MLIP capabilities and accelerating their impact in solid-state battery research.
基金supported by the National Key Research and Development Program of China(grant No.2021YFB2500300)the National Natural Science Foundation of China(grant Nos.22479012,224B2901)+1 种基金the Beijing Municipal Natural Science Foundation(grant No.L223009)the Hebei Natural Science Foundation(grant No.E2024208084).
摘要High-capacity silicon anodes hold great promise for safe and energy-dense all-solid-state lithium batteries(ASSLBs),yet their practical application is hindered by interfacial degradation and mechanical fracture,which severely limit their cycle life.Herein,we unravel the particle-size-dependent electro-chemo-mechanical failure mechanisms of Si anodes in sulfide-based ASSLBs.The micro-sized Si(μm-Si)anode exhibits favorable initial Coulombic efficiency(ICE,79.15%)and reversible capacity(2260.5 mAh g-1)but succumbs to progressive particle fracture under prolonged cycling due to cumulative mechanical stress from large volume swings.By contrast,the nano-sized Si(nm-Si)anode suffers from severe interfacial side reactions and irreversible volume expansion due to its larger specific area and dense electrode structure,resulting in lower initial performance(ICE of 72.21%,1372.7 mAh g-1).In subsequent cycles,the nm-Si anode experiences continuous interfacial side reactions,leading to substantial accumulation of interfacial decomposition byproducts and sustained capacity decay.These contrasting failure pathways establish electro-chemo-mechanical coupling as the governing prin-ciple and provide a particle-size-dependent design framework for high-performance Si-based ASSLBs.
基金supported by the National Key R&D Program of China(2021YFB3800300).
摘要High-nickel cathode,LiNi0.8Co0.1Mn0.1O2(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g-1 at 0.2 C,160.9 mA h g-1 at 2.0 C and 112.3 mA h g-1 at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g-1 after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the Technology Innovation Program(No.20024249,“Development of mass manufacturing technology for high performance lithium iron phosphate composites”)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by the Technology Innovation Program(No.00427225,“Development of manufacturing process technology for 3.7 V high voltage lithium iron manganese phosphate cathode material”)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)。
摘要All-solid-state batteries(ASSBs),which replace flammable liquid electrolytes with inorganic solid electrolytes(SEs),have attracted considerable attention as safer and higher-energy storage technologies.Among various candidates,sulfide-based SEs such as argyrodite-type Li6PS5Cl combine high ionic conductivity with excellent processability,facilitating the fabrication of dense and well-integrated composite cathodes.Nevertheless,the electrochemical performance of ASSBs remains largely constrained by interfacial and structural degradation occurring within the composite cathode.Understanding the degradation phenomena at the interface between the SE and the cathode active material is thus essential to improving the electrochemical performance and cycle life of these systems.Specifically,these degradation pathways can be broadly divided into(electro)chemical mechanisms—such as electrochemical decomposition of SE,transition-metal dissolution,oxygen-involving interfacial reactions,and surface reconstruction—and mechanical mechanisms,including particle cracking and interfacial contact loss driven by anisotropic stress and volume fluctuations.Acting synergistically,these processes reduce Li+mobility,increase interfacial impedance,and cause irreversible capacity loss.In this review,we systematically examine these degradation modes in sulfide-based ASSBs,with a particular focus on Ni-rich layered oxide/argyrodite composite cathodes.By organizing recent experimental findings,we aim to provide a comprehensive understanding of the limitations of current ASSB systems and to guide future efforts toward more stable and durable solid-state battery technologies.
基金the financial support from the Swiss National Science Foundation(SNSF)(grant No.Sinergia CRSII5_202296)。
摘要All-solid-state lithium metal batteries(ASSLMBs)promise high energy density and enhanced safety.Nevertheless,their performance is hindered by lithium dendrite growth at high current densities,which can induce internal short circuits with abrupt cell voltage drops.However,at intermediate current densities,“soft shorts”,namely partial and transient internal shorts,are more prevalent and difficult to interpret.In such a case,the cell voltage does not collapse to zero but instead fluctuates dynamically and fails to increase further during charge.To elucidate the electro-chemo-mechanical mechanisms underlying this unusual soft short behavior,we investigate the cycling of Li4Ti5O12(LTO)|Li6PS5Cl(LPSC)|Li in a three-electrode cell configuration equipped with operando pressure monitoring.An in situ lithiated Au/W reference electrode enables independent tracking of the working and counter electrode potentials and their impedance evolution.During galvanostatic cycling,we directly captured the formation of a soft short accompanied by a partial voltage recovery by simultaneously tracking electrode potentials and realtime cell pressure.By correlating pressure transients with the measured Faradaic currents,we reveal for the first time that the onset of a soft short fundamentally decouples the internal electrochemical reactions from the externally imposed current.This hidden current redistribution is further substantiated by impedance spectroscopy,which shows a pronounced drop in ohmic resistance following dendritic bridging,providing direct evidence for the emergence of electronically conductive pathways across the solid electrolyte.Building on these insights,we propose an equivalent circuit model describing the dynamic evolution of soft shorts and introduce quantitative methods to estimate dendrite dimensions,found to range from 100 to 102nm.Together,these advances provide the first quantitative link between soft-short electrochemical signatures and the underlying nanoscale morphology of dendritic filaments.
基金supported by the National Natural Science Foundation of China(Nos.52222210,U24A2064,52502228).
摘要Because of their exceptional safety and thermal stability,all-solid-state sodium batteries are viable next-generation energy storage technologies,while borohydride-based solid electrolytes have garnered considerable interest for their favorable electrochemical stability.Nevertheless,the poor room-temperature ionic conductivity of Na2B12H12 continues to be a significant obstacle that restricts its usefulness.To address this issue,this work proposes a simple mechanochemical compositing strategy.By introducing boron nitride(BN)as a multifunctional interfacial modifier,the ionic conduction performance is significantly enhanced.The Na2B12H12/BN composite electrolyte is prepared via high-energy ball milling.Structural characterizations reveal that the incorporation of BN induces a mechanochemistry-driven phase and structural transformation in Na2B12H12 and creates abundant heterointerfaces.Electrochemical measurements show that theoptimized composite electrolyte achieves a high room-temperature ionic conductivity of 2.2×10-4 S cm-1,almost an order of magnitude higher than that of ball-milled pristine Na2B12H12,with a reduced activation energy of 0.31 eV.Furthermore,the electrolyte exhibits excellent stability against a Na-Sn alloy,enabling symmetric cells to cycle stably for over 800 h.An all-solid-state sodium battery assembled with Na3V2(PO4)3 as the cathode and a Na-Sn alloy as the anode demonstrates outstanding cycling stability(80%capacity retention after 100 cycles at 0.5 C)and rate capability.This work offers new insights for the creation of sophisticated all-solid-state sodium batteries by rationalizing the design of high-performance borohydride-based solid electrolytes through interfacial engineering using inert nanomaterials.
基金financially supported by Shenzhen Science and Technology Program(JCYJ20240813142900001)Guangdong Provincial Key Laboratory of New Energy Materials Service Safety。
摘要Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li+/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO3(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li2.5Y0.5Zr0.5Cl6(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm-1for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g-1over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g-1.Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.
基金supported by the National Key Research and Development Program of China(Grant No.2020YFA0715000)the National Natural Science Foundation of China(Grant No.52272234)+2 种基金the International Science and Technology Cooperation Program of Hubei Province(Grant No.2024EHA039)the Independent Innovation Project of Hubei Longzhong Laboratory(Grant No.2022ZZ-20)the Key Research and Development Program of Henan Province(Grant No.251111240100).
摘要Polymer-based solid-state electrolytes with high flexibility and excellent processability present great prospects in all-solid-state lithium batteries.However,when encountering interface stability problems,the application of polymer-based solid-state electrolytes in all-solid-state lithium batteries is puzzling.In this work,we proposed a lithium crosslinking strategy to regulate the interfacial chemistry by tailoring an effective Li2O-rich solid electrolyte interphase layer attributed to introducing 15-crown-5 into the polymer matrix.Specifically,crosslinking the 15-crown-5 with Li+in polymer-based solid-state electrolytes boosts the Li+transport by weakening the coordination between Li+and polymer chains.The crosslinked 15-crown-5 moves along with the Li+to the anode and decomposes to form the Li2O-rich solid electrolyte interphase with faster Li+diffusion kinetics,resulting in uniform lithium deposition and suppressing the dendrite penetration.Therefore,the symmetric Li-Li cell could stably maintain cycling over 1100 h without short-circuiting.The LiFePO4||Li full battery presents high retention of capacity(92.75%)over 500 cycles at 1 C.Also,the NCM811||Li full battery can be well-operated in 300 cycles with the capacity retention of 81.44%at 1 C.This study inspires the development of high-performance all-solid-state lithium batteries by rationally tailoring interface chemistry components by regulating the coordinated structure of Li+at the molecular level.
基金supported by the National Key R&D Program of China(2024YFA1211104)the National Natural Science Foundation of China(52572241 and 52272224)+1 种基金the Youth Student Fundamental Research Funds of Shandong University(SDUQM2528)the Science and Technology Project of the Construction System of Jiangsu Province(2024ZD076).
摘要Solid-state electrolytes(SEs)are the“blood vessels”in all-solid-state batteries(ASSBs),providing essential ion channels.In past decades,SE design has been mainly carried out within ordered crystalline frameworks,which is understandable for achieving well-defined ion transport pathways.However,the large impedance,poor interfaces,and dendrite penetration brought about by polycrystalline grain boundaries have always been the inherent drawbacks of crystalline SEs.Recently,tailoring disorder in crystalline SEs to achieve local atomic disorder or amorphous-state lattice disorder has emerged as an interesting strategy.In this review,we outline the working mechanism of disorder in SEs and highlight the prospects for amorphous solid electrolytes(ASEs)in advanced ASSBs,especially low-temperature ASSBs.From atomic disorder to lattice disorder,we discuss in depth the disorder-induced ion-conduction mechanism as well as properties,applications,and preparation methods.An interesting ASE closed-loop design and prediction framework is provided to meet the requirements for future ASSBs.After presenting these insights,we offer our view on the future development of ASEs.
摘要This study shows that sulfide solid-state electrolytes,β-Li3PS4and Li6PS5Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O2-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O2source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.
基金financially supported by the National Natural Science Foundation of China (52474338,22109084 and 52304338)the Hunan Provincial Key Research and Development Program (2024JK2093,2023GK2016)supported in part by the High Performance Computing Center of Central South University.
摘要Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO2coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm-2,achieving an areal capacity of 17.90 mA h cm-2.These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.
基金financially supported by the Fundamental Research Funds for the Central Universities,North Minzu University(No.2020KYQD18)the Key Research and Development Program(Talents Introduction Project)of Ningxia(No.2021BEB04027)+1 种基金the Fundamental Research Funds for the Central Universities,North Minzu University(No.2021KJCX04)the Natural Science Foundation of Ningxia Province(No.2022AAC05033)
摘要With the rapid development of flexible equipment,high-energy/-power requirements have been proposed for energy storage devices.Nevertheless,the poor conductivities of metallic oxides and their low levels of transmission of electrons/ions hinder their widespread application.Here,a sandwich-structured Co3O4-Fe3O4(CFO) composite with binder-free was synthesized on a carbon cloth substrate via co-precipitation and partial ion exchange.The appropriate substitution of Co3O4with Fe3O4is favorable in promoting the rapid transfer of electrolyte ions and alleviating changes in volume during the electrochemical studies.When the duration of the substitution reaction is 20 min,the obtained electrode delivers a maximum specific capacitance of 1196.2 Fg-1at a current density of 1 A g-1and a superior capacity retention of~71%when the current density varies from 1to 30 Ag-1.Furthermore,the fabricated CFO//activated carbon flexible all-solid-state supercapacitor exhibits arespective maximum energy and power density of 68.7Wh kg-1and 16,000 W kg-1and excellent flexibility.It also displays a specific capacity retention of 81.3%under four continuous bending states at a current density of 6A g-1over 10,000 cycles.These remarkable electrochemical char ac teristics suggest that the sandwich-structured CFO composite displays considerable potential for application in flexible high-energy/-power supercapacitors.
基金supported by the Technology Innovation Program(Grant no.20009985,Grant no.20026752)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)。
摘要All-solid-state batteries(ASSBs)are pursued due to their potential for better safety and high energy density.However,the energy density of the cathode for ASSBs does not seem to be satisfactory due to the low utilization of active materials(AMs)at high loading.With small amount of solid electrolyte(SE)powder in the cathode,poor electrochemical performance is often observed due to contact loss and non-homogeneous distribution of AMs and SEs,leading to high tortuosity and limitation of lithium and electron transport pathways.Here,we propose a novel cathode design that can achieve high volumetric energy density of 1258 Wh L-1at high AM content of 85 wt%by synergizing the merits of AM@SE core–shell composite particles with conformally coated thin SE shell prepared from mechanofusion process and small SE particles.The core–shell structure with an intimate and thin SE shell guarantees high ionic conduction pathway while unharming the electronic conduction.In addition,small SE particles play the role of a filler that reduces the packing porosity in the cathode composite electrode as well as between the cathode and the SE separator layer.The systematic demonstration of the optimization process may provide understanding and guidance on the design of electrodes for ASSBs with high electrode density,capacity,and ultimately energy density.
基金supported by the National Key Research and Development Program of China (2018YFE0111600)Haihe Laboratory of Sustainable Chemical Transformations for financial supportpartially supported by the Graduate Top-notch Innovation Award Plan in Liberal Arts and Science of Tianjin University for the Year of 2023 (B2-2023-012)
摘要Li6PS5Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li6PS5Cl/Li interface and growth of lithium dendrites inside Li6PS5Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li6PS5Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi6PS5Cl@Li3OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li6PS5Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm-2to 1.6 mA cm-2,and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm-2or from 10 h to 900 h at the cycling current of 0.5 mA cm-2;2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi6PS5Cl@Li3OCl interface.