Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic condu...Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.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
In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of...In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).展开更多
Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promo...Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt.Thus,TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries.However,the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains,which greatly reduces the dissociation of lithium salts.Herein,a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate)(PEGDA)in fully dispersed TPU.Hence a stretchable solid-state electrolyte(denoted as TELL and the contrast sample was denoted as TLL)with high ionic conductivity of 7.18×10^(-4) S/cm was obtained at room temperature.The Li^(+)transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of O.1 mA/cm^(2),while the contrast sample is short-circuited after 634 h of cycling.The LiFePO_(4)|TELL|Li cell achieves a capacity retention of 78.93%after 200 cycles at 2 C.The LiFePO_(4) TLL Li cellonly gains the capacity retention of 51.9%after 50 cyclesat the same current density.So,the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.展开更多
Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their prac...Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their practical applications,includ-ing dendrite formation,unstable solid electrolyte interphase(SEI),side reactions with electrolytes,and associated safety risks.This review systematically explores the mechanisms of lithium nucleation,growth,and stripping in both liquid and solid-state battery systems,analyzing critical theoretical concepts like heterogeneous nucleation thermodynamics,surface diffusion kinetics,space charge effects,and SEI-induced nucleation,which are crucial for understanding the genesis of dendrite growth.Additionally,the review discusses the electrochemical-mechanical coupling failures that lead to SEI degra-dation and the formation of dead lithium.For liquid systems,the review proposes strategies to mitigate dendrite formation and SEI instability,which include electrolyte optimization,artificial SEI design,and electrode framework design.In solid-state batteries,the review offers a granular analysis of the interface challenges associated with polymer,sulfide,and halide electrolytes and summarizes different solutions for different solid-state electrolytes.Meanwhile,the review emphasizes the importance of advanced characterization techniques and computational modeling in understanding and regulating the interface between lithium metal and electrolytes.Looking ahead,the review highlights future research directions that emp-hasize the integration of cross-disciplinary approaches to tackle these interconnected challenges.By addressing these issues,the path will be clear for the rapid commercialization and widespread application of lithium metal batteries,bringing us closer to realizing stable,high-energy-density batteries that can satisfy the escalating demands of modern energy storage applications across various industries.展开更多
This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,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-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,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 O_(2)-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 O_(2)source 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
High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions wit...High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions with the solid-state electrolytes.To circumvent these issues,a continuous uniform layer polyacrylonitrile(PAN)was introduced on the surface of LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) via in situ polymerization of acrylonitrile(AN).Furthermore,the partial-cyclized treatment of PAN(cPAN)coating layer presents high ionic and electron conductivity,which can accelerate interfacial Li+and electron diffusion simultaneously.And the thermodynamically stabilized cPAN coating layer cannot only effectively inhibit detrimental side reactions between cathode and solid-state electrolytes but also provide a homogeneous stress to simultaneously address the problems of bulk structural degradation,which contributes to the exceptional mechanical and electrochemical stabilities of the modified electrode.Besides,the coordination bond interaction between the cPAN and NCM811 can suppress the migration of Ni to elevate the stability of the crystal structure.Benefited from these,the In-cPAN-260@NCM811 shows excellent cycling performance with a retention of 86.8%after 300 cycles and superior rate capability.And endow the solid-state battery with thermal safety stability even at hightemperature extreme environment.This facile and scalable surface engineering represents significant progress in developing high-performance solid-state lithium metal batteries.展开更多
With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety a...With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li^(+)ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.展开更多
Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storag...Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.展开更多
Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to add...Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to address these issues.However,the high interfacial resistance of rigid ceramic electrolytes and the limited ionic conductivity of polymer electrolytes remain significant challenges,further complicated by the substantial volume expansion of Si.In this work,we chemically grafted a flame-retardant,self-healing polyurethane-thiourea polymer onto Li_(7)P_(3)S_(11)(SHPUSB-40%LPS)via nucleophilic addition,creating an electrolyte with exceptional ionic conductivity,high elasticity,and strong compatibility with Si anodes.We observed that FSI^(-)was strongly adsorbed onto the LPS surface through electrostatic interactions with sulfur vacancies,enhancing Li^(+)transport.Furthermore,SHPUSB-40%LPS exhibits dynamic covalent disulfide bonds and hydrogen bonds,enabling self-assembly of the electrolyte at the interface.This dynamic bonding provides a self-healing mechanism that mitigates structural changes during Si expansion and contraction cycles.As a result,the Si anode with SHPUSB-40%LPS presents excellent cycling stability,retaining nearly 53.5%of its capacity after 300 cycles.The practical applicability of this design was validated in a 2 Ah all-solid-state Si‖LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)pouch cell,which maintained a stable Li-ion storage capacity retention of 76.3%after 350cycles at 0.5C.This novel solid-state electrolyte with selfhealing properties offers a promising strategy to address fundamental interfacial and performance challenges associated with Si anodes.展开更多
Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transf...Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.展开更多
Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched wi...Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.展开更多
Poly(vinyl alcohol)(PVA)/1-butyl-3-methylimidazolium trifluoromethanesulfonate(BMIMOTf)/Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)solid-state composite electrolyte(SSCE)membranes were synthesized for solid-state lith...Poly(vinyl alcohol)(PVA)/1-butyl-3-methylimidazolium trifluoromethanesulfonate(BMIMOTf)/Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)solid-state composite electrolyte(SSCE)membranes were synthesized for solid-state lithium metal battery application.The garnet-type LLZTO nanoparticles were surface-coated with the polydopamine layer of 8-10 nm thickness to enhance the dispersion status of LLZTO particles in the PVA matrix.The hydrophilic BMIMOTf ionic liquid(IL)was added along with LLZTO nanoparticles to enhance the ionic conductivity and electrochemical stability of the SSCE membranes.The synthesized composite electrolyte membrane containing 7 wt%of LLZTO and 60 wt%of BMIMOTf showed the outstanding Li+conductivity of 2×10^(-3)S cm^(-1)and the lithium transference number of 0.76 at room temperature in the firm and flexible solid state with the tensile strength of 8 MPa.Such a high single ion conduction characteristic led to the quite low interfacial resistance of 39Ωbetween the composite electrolyte and the lithium anode.Owing to these superior properties of composite membranes,the LiFePO_(4)|SSCE|Li cell exhibited an excellent discharge capacity of 165 mAh g^(-1)at 0.2 C,maintaining the coulombic efficiency of 98%after 100 cycles at room temperature.展开更多
Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular st...Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular structure and luminescence properties,TADF molecules are far from meeting the needs of practical applications in terms of variety and number.In this paper,three twisted TADF molecules are studied and their photophysical properties are theoretically predicted based on the thermal vibrational correlation function method combined with multiscale calculations.The results show that all the molecules exhibit fast reverse intersystem crossing(RISC)rates(kRISC),predicting their TADF luminescence properties.In addition,the binding of DHPAzSi as the donor unit with different acceptors can change the dihedral angle between the ground and excited states,and the planarity of the acceptors is positively correlated with the reorganization energy,a property that has a strong influence on the non-radiative process.Furthermore,a decrease in the energy of the molecular charge transfer state and an increase in the kRISC were observed in the films.This study not only provides a reliable explanation for the observed experimental results,but also offers valuable insights that can guide the design of future TADF molecules.展开更多
Electrocatalytic carbon dioxide reduction is a promising technology for addressing global energy and environmental crises. However, its practical application faces two critical challenges: the complex and energy-inten...Electrocatalytic carbon dioxide reduction is a promising technology for addressing global energy and environmental crises. However, its practical application faces two critical challenges: the complex and energy-intensive process of separat-ing mixed reduction products and the economic viability of the carbon sources (reactants) used. To tackle these challenges simultaneously, solid-state electrolyte (SSE) reactors are emerging as a promising solution. In this review, we focus on the feasibility of applying SSE for tandem electrochemical CO_(2) capture and conversion. The configurations and fundamental principles of SSE reactors are first discussed, followed by an introduction to its applications in these two specific areas, along with case studies on the implementation of tandem electrolysis. In comparison to conventional H-type cell, flow cell and membrane electrode assembly cell reactors, SSE reactors incorporate gas diffusion electrodes and utilize a solid electro-lyte layer positioned between an anion exchange membrane (AEM) and a cation exchange membrane (CEM). A key inno-vation of this design is the sandwiched SSE layer, which enhances efficient ion transport and facilitates continuous product extraction through a stream of deionized water or humidified nitrogen, effectively separating ion conduction from product collection. During electrolysis, driven by an electric field and concentration gradient, electrochemically generated ions (e.g., HCOO- and CH3COO-) migrate through the AEM into the SSE layer, while protons produced from water oxidation at the anode traverse the CEM into the central chamber to maintain charge balance. Targeted products like HCOOH can form in the middle layer through ionic recombination and are efficiently carried away by the flowing medium through the porous SSE layer, in the absence of electrolyte salt impurities. As CO_(2)RR can generate a series of liquid products, advancements in catalyst discovery over the past several years have facilitated the industrial application of SSE for more efficient chemicals production. Also noteworthy, the cathode reduction reaction can readily consume protons from water, creating a highly al-kaline local environment. SSE reactors are thereby employed to capture acidic CO_(2), forming CO_(3)^(2-) from various gas sources including flue gases. Driven by the electric field, the formed CO_(3)^(2-) can traverse through the AEM and react with protons originating from the anode, thereby regenerating CO_(2). This CO_(2) can then be collected and utilized as a low-cost feedstock for downstream CO_(2) electrolysis. Based on this principle, several cell configurations have been proposed to enhance CO_(2) capture from diverse gas sources. Through the collaboration of two SSE units, tandem electrochemical CO_(2) capture and con-version has been successfully implemented. Finally, we offer insights into the future development of SSE reactors for prac-tical applications aimed at achieving carbon neutrality. We recommend that greater attention be focused on specific aspects, including the fundamental physicochemical properties of the SSE layer, the electrochemical engineering perspective related to ion and species fluxes and selectivity, and the systematic pairing of consecutive CO_(2) capture and conversion units. These efforts aim to further enhance the practical application of SSE reactors within the broader electrochemistry community.展开更多
Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc....Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc.However,achieving high Li+conductivity remains a major challenge,particularly at low temperatures.A key obstacle lies in the limited understanding of the complex interplay among amorphous components,including fillers,plasticizers,and residual solvents,which significantly hampers the rational design of high-performing CPEs.In this contribution,a polyvinylidene fluoride(PVDF)-based composite electrolyte has been developed,exhibiting high room-temperature ionic conductivity/mobility(>1 mS cm^(-1)/0.95×10^(-11)m^(2)s^(-1)),along with excellent electrochemical performances,including a wide stability window(4.8 V vs.Li/Li^(+)),superior charge/discharge capacity,and reversibility.By performing advanced solid-state nuclear magnetic resonance(ssNMR)techniques,in combination with systematic investigations into solid polymer electrolytes(SPEs),gel polymer electrolytes(GPEs),and CPEs,we establish an efficient NMR-based strategy for deconvoluting the structural and dynamic features of complex electrolyte systems.Notably,the simple1H magic-angle spinning(MAS)NMR spectroscopy enables the identification and monitoring of nearly all components in the composite matrix.Motion-sensitive1H-13C and1H-7Li correlation experiments further reveal that the rigidity of PVDF polymer chain segments and the presence of residual solvents are two critical factors governing Li+mobility.Moreover,we demonstrate that the order of the filler and plasticizer addition during the CPE fabrication significantly influences the performance of the electrolyte by regulating the retention of residual solvents.This work not only provides molecular-level insights into the structure-ion mobility relationships in the PVDF-based CPEs but also establishes a general NMR-based characterization approach for investigating other complex composite electrolyte materials.展开更多
The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defect...The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defects in the solid-state electrolyte,leading to internal short circuits that hinder practical application of SSLMB.While conventional experimental and finite element methods provide valuable insights,they are often costly,time-consuming,and inefficient for capturing the complicated stress evolution inside solid-state electrolyte.In this study,we propose a novel machine learning strategy that integrates prior knowledge and physics-informed constraints to predict the von Mises stress distribution induced by the internal defects of solid-state electrolyte.High-quality training datasets generated using a multiphysics simulation framework and key findings from previous studies were incorporated as physicsguided constraints to enhance prediction reliability and physical consistency of machine learning models.By employing a modified UNet architecture with squeeze-and-excitation module,it demonstrates remarkably high accuracy in stress prediction and exhibits excellent robustness and generalization across a wide range of defect scenarios.This model allows us to efficiently obtain the electro-chemo-mechanical failure of solid-state electrolyte,thereby guiding micro structural modifications and facilitating the design of SSLMB for practical applications.展开更多
Solid-state lithium batteries(SSLBs)are regarded as an essential growth path in energy storage systems due to their excellent safety and high energy density.In particular,SSLBs using conversion-type cathode materials ...Solid-state lithium batteries(SSLBs)are regarded as an essential growth path in energy storage systems due to their excellent safety and high energy density.In particular,SSLBs using conversion-type cathode materials have received widespread attention because of their high theoretical energy densities,low cost,and sustainability.Despite the great progress in research and development of SSLBs based on conversiontype cathodes,their practical applications still face challenges such as blocked ionic-electronic migration pathways,huge volume change,interfacial incompatibility,and expensive processing costs.This review focuses on the advantages and critical issues of coupling conversion-type cathodes with solid-state electrolytes(SSEs),as well as state-of-the-art progress in various promising cathodes(e.g.,FeS_(2),CuS,FeF_(3),FeF_(2),and S)in SSLBs.Furthermore,representative research on conversion-type solid-state full cells is discussed to offer enlightenment for their practical application.Significantly,the energy density exhibited by the S cathode stands out impressively,while sulfide SSEs and halide SSEs have demonstrated immense potential for coupling with conversion-type cathodes.Finally,perspectives on conversion-type cathodes are provided at the material,interface,composite electrode,and battery levels,with a view to accelerating the development of conversion-type cathodes for high-energy–density SSLBs.展开更多
Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical dur...Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical durability and humidity stability,hindering their large-scale applications.Here,we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene(PTFE)binder to encapsulate Li_(3)InCl_(6)(LIC)particles(the most representative HSSE).By manipulating the fibrillating process,only 0.5 wt%PTFE is sufficient to prepare free-standing LIC-PTFE(LIC-P)HSSEs.Additionally,LIC-P demonstrates excellent mechanical durability and humidity resistance.They can maintain their shapes after being exposed to humid atmosphere for 30 min,meanwhile still exhibit high ionic conductivity of>0.2m S/cm at 25℃.Consequently,the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 m Ah/g at0.1 C and long cyclability of 200 cycles at 0.2 C.More importantly,the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7%after 100 cycles under0.2 C.Furthermore,for the first time,we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.展开更多
基金financially supported by the National Key Research and Development Program(2022YFE0127400)the National Natural Science Foundation of China(52172040,52202041,and U23B2077)+1 种基金Taishan Scholar Project of Shandong Province(tsqn202211086,ts202208832,tsqnz20221118)the Fundamental Research Funds for the Central Universities(23CX06055A).
文摘Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.
基金supported by the National Natural Science Foundation of China(No.42272044)the High-performance Computing Platform of China University of Geosciences Beijing。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
文摘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the National Natural Science Foundation of China (52076076, 52006065)Fundamental Research Funds for Central Universities (2025JC003)Beijing Municipal Natural Science Foundation (3242022)
文摘In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).
基金financially supported by the National Natural Science Foundation of China(Nos.52263010 and 52372188)2023 Introduction of studying abroad talent program,Henan Provincial Key Scientific Research Project of Collegesand Universities(No.23A150038)+1 种基金Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National students'platform for innovation and entrepreneurship training program(No.201910476010).
文摘Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt.Thus,TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries.However,the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains,which greatly reduces the dissociation of lithium salts.Herein,a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate)(PEGDA)in fully dispersed TPU.Hence a stretchable solid-state electrolyte(denoted as TELL and the contrast sample was denoted as TLL)with high ionic conductivity of 7.18×10^(-4) S/cm was obtained at room temperature.The Li^(+)transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of O.1 mA/cm^(2),while the contrast sample is short-circuited after 634 h of cycling.The LiFePO_(4)|TELL|Li cell achieves a capacity retention of 78.93%after 200 cycles at 2 C.The LiFePO_(4) TLL Li cellonly gains the capacity retention of 51.9%after 50 cyclesat the same current density.So,the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.
基金supported by grants from the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant Nos.XDB1040100 and XDB1040300)the National Natural Science Foundation of China(Grant Nos.22379108,52202279,52225105,22279127,22425403,92372125,22421001,22205241,22425403,92372125,22421001,22205241,92472207,52472223,52102280,22393900 and 22209010)+1 种基金the National Key Research and Development Program of China(Grant Nos.2021YFF0500600 and 2021YFB2500300)the Fundamental Research Funds for the Central Univer-sities(Grant No.WK9990000170)。
文摘Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their practical applications,includ-ing dendrite formation,unstable solid electrolyte interphase(SEI),side reactions with electrolytes,and associated safety risks.This review systematically explores the mechanisms of lithium nucleation,growth,and stripping in both liquid and solid-state battery systems,analyzing critical theoretical concepts like heterogeneous nucleation thermodynamics,surface diffusion kinetics,space charge effects,and SEI-induced nucleation,which are crucial for understanding the genesis of dendrite growth.Additionally,the review discusses the electrochemical-mechanical coupling failures that lead to SEI degra-dation and the formation of dead lithium.For liquid systems,the review proposes strategies to mitigate dendrite formation and SEI instability,which include electrolyte optimization,artificial SEI design,and electrode framework design.In solid-state batteries,the review offers a granular analysis of the interface challenges associated with polymer,sulfide,and halide electrolytes and summarizes different solutions for different solid-state electrolytes.Meanwhile,the review emphasizes the importance of advanced characterization techniques and computational modeling in understanding and regulating the interface between lithium metal and electrolytes.Looking ahead,the review highlights future research directions that emp-hasize the integration of cross-disciplinary approaches to tackle these interconnected challenges.By addressing these issues,the path will be clear for the rapid commercialization and widespread application of lithium metal batteries,bringing us closer to realizing stable,high-energy-density batteries that can satisfy the escalating demands of modern energy storage applications across various industries.
文摘This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,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 O_(2)-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 O_(2)source 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(Nos.22102212 and 22479067).
文摘High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions with the solid-state electrolytes.To circumvent these issues,a continuous uniform layer polyacrylonitrile(PAN)was introduced on the surface of LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) via in situ polymerization of acrylonitrile(AN).Furthermore,the partial-cyclized treatment of PAN(cPAN)coating layer presents high ionic and electron conductivity,which can accelerate interfacial Li+and electron diffusion simultaneously.And the thermodynamically stabilized cPAN coating layer cannot only effectively inhibit detrimental side reactions between cathode and solid-state electrolytes but also provide a homogeneous stress to simultaneously address the problems of bulk structural degradation,which contributes to the exceptional mechanical and electrochemical stabilities of the modified electrode.Besides,the coordination bond interaction between the cPAN and NCM811 can suppress the migration of Ni to elevate the stability of the crystal structure.Benefited from these,the In-cPAN-260@NCM811 shows excellent cycling performance with a retention of 86.8%after 300 cycles and superior rate capability.And endow the solid-state battery with thermal safety stability even at hightemperature extreme environment.This facile and scalable surface engineering represents significant progress in developing high-performance solid-state lithium metal batteries.
基金the financial support from the National Key R&D Program of China (Grant No. 2021YFB3800300)the supports from National Key R&D Program of China (Grant No. 2022YFB3807700)+6 种基金the National Natural Science Foundation of China (Grant No. U20A20248)the supports from the National Natural Science Foundation of China (Grant Nos. W2441017, 22409103)the “Innovation Yongjiang 2035” Key R&D Program (Grant Nos. 2024Z040, 2025Z063)the National Key R&D Program of China (Grant No. 2023YFC2812700)the Natural Science Foundation of Shandong Province (Grant No. ZR2024YQ008)funding supports from the National Key R&D Program of China (Grant No. 2021YFB3800300)science and technology innovation fund for emission peak and carbon neutrality of Jiangsu province (Grant Nos. BK20220034, BK20231512)。
文摘With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li^(+)ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.
基金supported by the National Natural Science Foundation of China(Nos.22171102 and 22090044)the National Key R&D Program of China(Nos.2021YFF0500502 and 2023YFA1506304)+2 种基金the Jilin Province Science and Technology Development Plan(No.20230101024JC)the"Medicine+X"crossinnovation team of Bethune Medical Department of Jilin University"Leading the Charge with Open Competition"construction project(No.2022JBGS04)the Jilin University Graduate Training Office(Nos.2021JGZ08 and 2022YJSJIP20).
文摘Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.
基金supported financially by the National Natural Science Foundation of China(No.52172202)Science and Technology Program of Guangzhou,China(No.SL2024A03J00326)+1 种基金Key Research and Development project of High-Level Scientific and Technological Talent Introduction for Luliang City(No.2023RC27)the Basic Research Program(Free Exploration Category)Project for Shanxi Province(No.202303021222251)
文摘Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to address these issues.However,the high interfacial resistance of rigid ceramic electrolytes and the limited ionic conductivity of polymer electrolytes remain significant challenges,further complicated by the substantial volume expansion of Si.In this work,we chemically grafted a flame-retardant,self-healing polyurethane-thiourea polymer onto Li_(7)P_(3)S_(11)(SHPUSB-40%LPS)via nucleophilic addition,creating an electrolyte with exceptional ionic conductivity,high elasticity,and strong compatibility with Si anodes.We observed that FSI^(-)was strongly adsorbed onto the LPS surface through electrostatic interactions with sulfur vacancies,enhancing Li^(+)transport.Furthermore,SHPUSB-40%LPS exhibits dynamic covalent disulfide bonds and hydrogen bonds,enabling self-assembly of the electrolyte at the interface.This dynamic bonding provides a self-healing mechanism that mitigates structural changes during Si expansion and contraction cycles.As a result,the Si anode with SHPUSB-40%LPS presents excellent cycling stability,retaining nearly 53.5%of its capacity after 300 cycles.The practical applicability of this design was validated in a 2 Ah all-solid-state Si‖LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)pouch cell,which maintained a stable Li-ion storage capacity retention of 76.3%after 350cycles at 0.5C.This novel solid-state electrolyte with selfhealing properties offers a promising strategy to address fundamental interfacial and performance challenges associated with Si anodes.
基金supported by National Science Fund for Distinguished Young Scholars(Grant No.52325206)National Key Research and Development Program of China(Grant No.2021YFF0500600)+3 种基金National Natural Science Foundation of China(Grant Nos.U2001220 and 52203298)Shenzhen Technical Plan Project(Grant Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008,and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(Grant No.SZPR2023006)Shenzhen Science and Technology Program(Grant No.WDZC20231126160733001).
文摘Composite solid electrolytes(CSEs)are considered among the most promising candidates for solid-state batteries.However,their practical application is hindered by low ionic conductivity and a limited lithium-ion transference number,primarily owing to the insufficient mobility of Li+.In this work,we design a heterojunc-tion nanoparticle composed of bimetallic zeolitic imidazolate frameworks(ZIFs)coupled with amorphous tita-nium oxide(TiO_(2)@Zn/Co–ZIF)as a filler to fabricate a composite solid-state electrolyte(PVZT).The amor-phous TiO_(2) coating facilitates salt dissociation through Lewis acid–base interactions with the anions of the lithium salt.Meanwhile,the Zn/Co–ZIF framework not only provides additional selective pathways for Li+transport but also effectively restricts anion migration through its confined pore size.The synergistic effect results in a high room-temperature ionic conductivity(8.8×10^(-4) S·cm^(-1))and a lithium-ion transference number of 0.47 for PVZT.A symmetrical cell using PVZT demonstrates stable Li+deposition/stripping for over 1100 h at a current density of 0.1 mA·cm^(-2).Additionally,a LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li full cell using PVZT retains 75.0%of its capacity after 1200 cycles at a 2 C rate.This work offers valuable insights into the design of func-tional fillers for CSEs with highly efficient ion transport.
基金supported by the National Key R&D Program of China(2024YFA1211100)the National Natural Science Foundation of China(52301278,22479080,52202254,92372001,22393900,and 92372203)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20230937,BK20220966)the Science and Technology Plans of Tianjin(23JCYBJC00170,24JCJQJC00220,and 24ZXZSSS00390)the Fundamental Research Funds for the Central Universities(02063253167,30922010708)。
文摘Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.
基金supported by the National Research Foundation of Korea(NRF 2018M3D1A1058624)funded by the Ministry of Science and ICT。
文摘Poly(vinyl alcohol)(PVA)/1-butyl-3-methylimidazolium trifluoromethanesulfonate(BMIMOTf)/Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)solid-state composite electrolyte(SSCE)membranes were synthesized for solid-state lithium metal battery application.The garnet-type LLZTO nanoparticles were surface-coated with the polydopamine layer of 8-10 nm thickness to enhance the dispersion status of LLZTO particles in the PVA matrix.The hydrophilic BMIMOTf ionic liquid(IL)was added along with LLZTO nanoparticles to enhance the ionic conductivity and electrochemical stability of the SSCE membranes.The synthesized composite electrolyte membrane containing 7 wt%of LLZTO and 60 wt%of BMIMOTf showed the outstanding Li+conductivity of 2×10^(-3)S cm^(-1)and the lithium transference number of 0.76 at room temperature in the firm and flexible solid state with the tensile strength of 8 MPa.Such a high single ion conduction characteristic led to the quite low interfacial resistance of 39Ωbetween the composite electrolyte and the lithium anode.Owing to these superior properties of composite membranes,the LiFePO_(4)|SSCE|Li cell exhibited an excellent discharge capacity of 165 mAh g^(-1)at 0.2 C,maintaining the coulombic efficiency of 98%after 100 cycles at room temperature.
文摘Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular structure and luminescence properties,TADF molecules are far from meeting the needs of practical applications in terms of variety and number.In this paper,three twisted TADF molecules are studied and their photophysical properties are theoretically predicted based on the thermal vibrational correlation function method combined with multiscale calculations.The results show that all the molecules exhibit fast reverse intersystem crossing(RISC)rates(kRISC),predicting their TADF luminescence properties.In addition,the binding of DHPAzSi as the donor unit with different acceptors can change the dihedral angle between the ground and excited states,and the planarity of the acceptors is positively correlated with the reorganization energy,a property that has a strong influence on the non-radiative process.Furthermore,a decrease in the energy of the molecular charge transfer state and an increase in the kRISC were observed in the films.This study not only provides a reliable explanation for the observed experimental results,but also offers valuable insights that can guide the design of future TADF molecules.
基金This work was supported by the National Key R&D Program of China(2022YFB4102000 and 2022YFA1505100)the NSFC(22472038)the Shanghai Science and Technology Innovation Action Plan(22dz1205500).
文摘Electrocatalytic carbon dioxide reduction is a promising technology for addressing global energy and environmental crises. However, its practical application faces two critical challenges: the complex and energy-intensive process of separat-ing mixed reduction products and the economic viability of the carbon sources (reactants) used. To tackle these challenges simultaneously, solid-state electrolyte (SSE) reactors are emerging as a promising solution. In this review, we focus on the feasibility of applying SSE for tandem electrochemical CO_(2) capture and conversion. The configurations and fundamental principles of SSE reactors are first discussed, followed by an introduction to its applications in these two specific areas, along with case studies on the implementation of tandem electrolysis. In comparison to conventional H-type cell, flow cell and membrane electrode assembly cell reactors, SSE reactors incorporate gas diffusion electrodes and utilize a solid electro-lyte layer positioned between an anion exchange membrane (AEM) and a cation exchange membrane (CEM). A key inno-vation of this design is the sandwiched SSE layer, which enhances efficient ion transport and facilitates continuous product extraction through a stream of deionized water or humidified nitrogen, effectively separating ion conduction from product collection. During electrolysis, driven by an electric field and concentration gradient, electrochemically generated ions (e.g., HCOO- and CH3COO-) migrate through the AEM into the SSE layer, while protons produced from water oxidation at the anode traverse the CEM into the central chamber to maintain charge balance. Targeted products like HCOOH can form in the middle layer through ionic recombination and are efficiently carried away by the flowing medium through the porous SSE layer, in the absence of electrolyte salt impurities. As CO_(2)RR can generate a series of liquid products, advancements in catalyst discovery over the past several years have facilitated the industrial application of SSE for more efficient chemicals production. Also noteworthy, the cathode reduction reaction can readily consume protons from water, creating a highly al-kaline local environment. SSE reactors are thereby employed to capture acidic CO_(2), forming CO_(3)^(2-) from various gas sources including flue gases. Driven by the electric field, the formed CO_(3)^(2-) can traverse through the AEM and react with protons originating from the anode, thereby regenerating CO_(2). This CO_(2) can then be collected and utilized as a low-cost feedstock for downstream CO_(2) electrolysis. Based on this principle, several cell configurations have been proposed to enhance CO_(2) capture from diverse gas sources. Through the collaboration of two SSE units, tandem electrochemical CO_(2) capture and con-version has been successfully implemented. Finally, we offer insights into the future development of SSE reactors for prac-tical applications aimed at achieving carbon neutrality. We recommend that greater attention be focused on specific aspects, including the fundamental physicochemical properties of the SSE layer, the electrochemical engineering perspective related to ion and species fluxes and selectivity, and the systematic pairing of consecutive CO_(2) capture and conversion units. These efforts aim to further enhance the practical application of SSE reactors within the broader electrochemistry community.
基金financially supported by the National Natural Science Foundation of China(Grant No.22325405,22432005,22321002,and 22404159)the Dalian Science and Technology Talent Innovation Program(Grant No.2024RG009)+2 种基金the China Postdoctoral Science Foundation(Grant Number 2024M753120)the LiaoNing Revitalization Talents Program(XLYC2203134)the ANSO Scholarship for Young Talents for financial support。
文摘Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc.However,achieving high Li+conductivity remains a major challenge,particularly at low temperatures.A key obstacle lies in the limited understanding of the complex interplay among amorphous components,including fillers,plasticizers,and residual solvents,which significantly hampers the rational design of high-performing CPEs.In this contribution,a polyvinylidene fluoride(PVDF)-based composite electrolyte has been developed,exhibiting high room-temperature ionic conductivity/mobility(>1 mS cm^(-1)/0.95×10^(-11)m^(2)s^(-1)),along with excellent electrochemical performances,including a wide stability window(4.8 V vs.Li/Li^(+)),superior charge/discharge capacity,and reversibility.By performing advanced solid-state nuclear magnetic resonance(ssNMR)techniques,in combination with systematic investigations into solid polymer electrolytes(SPEs),gel polymer electrolytes(GPEs),and CPEs,we establish an efficient NMR-based strategy for deconvoluting the structural and dynamic features of complex electrolyte systems.Notably,the simple1H magic-angle spinning(MAS)NMR spectroscopy enables the identification and monitoring of nearly all components in the composite matrix.Motion-sensitive1H-13C and1H-7Li correlation experiments further reveal that the rigidity of PVDF polymer chain segments and the presence of residual solvents are two critical factors governing Li+mobility.Moreover,we demonstrate that the order of the filler and plasticizer addition during the CPE fabrication significantly influences the performance of the electrolyte by regulating the retention of residual solvents.This work not only provides molecular-level insights into the structure-ion mobility relationships in the PVDF-based CPEs but also establishes a general NMR-based characterization approach for investigating other complex composite electrolyte materials.
基金financially supported by the National Natural Science Foundation of China(22479067)Yunnan Young Talents Program for“Xingdian Talent Support Plan”(KKXX202551007)。
文摘The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defects in the solid-state electrolyte,leading to internal short circuits that hinder practical application of SSLMB.While conventional experimental and finite element methods provide valuable insights,they are often costly,time-consuming,and inefficient for capturing the complicated stress evolution inside solid-state electrolyte.In this study,we propose a novel machine learning strategy that integrates prior knowledge and physics-informed constraints to predict the von Mises stress distribution induced by the internal defects of solid-state electrolyte.High-quality training datasets generated using a multiphysics simulation framework and key findings from previous studies were incorporated as physicsguided constraints to enhance prediction reliability and physical consistency of machine learning models.By employing a modified UNet architecture with squeeze-and-excitation module,it demonstrates remarkably high accuracy in stress prediction and exhibits excellent robustness and generalization across a wide range of defect scenarios.This model allows us to efficiently obtain the electro-chemo-mechanical failure of solid-state electrolyte,thereby guiding micro structural modifications and facilitating the design of SSLMB for practical applications.
基金National Natural Science Foundation of China(22322903,52072061)Natural Science Foundation of Sichuan,China(2023NSFSC1914)Beijing National Laboratory for Condensed Matter Physics(2023BNLCMPKF015)。
文摘Solid-state lithium batteries(SSLBs)are regarded as an essential growth path in energy storage systems due to their excellent safety and high energy density.In particular,SSLBs using conversion-type cathode materials have received widespread attention because of their high theoretical energy densities,low cost,and sustainability.Despite the great progress in research and development of SSLBs based on conversiontype cathodes,their practical applications still face challenges such as blocked ionic-electronic migration pathways,huge volume change,interfacial incompatibility,and expensive processing costs.This review focuses on the advantages and critical issues of coupling conversion-type cathodes with solid-state electrolytes(SSEs),as well as state-of-the-art progress in various promising cathodes(e.g.,FeS_(2),CuS,FeF_(3),FeF_(2),and S)in SSLBs.Furthermore,representative research on conversion-type solid-state full cells is discussed to offer enlightenment for their practical application.Significantly,the energy density exhibited by the S cathode stands out impressively,while sulfide SSEs and halide SSEs have demonstrated immense potential for coupling with conversion-type cathodes.Finally,perspectives on conversion-type cathodes are provided at the material,interface,composite electrode,and battery levels,with a view to accelerating the development of conversion-type cathodes for high-energy–density SSLBs.
基金supported by the 261 Project of MIITthe National Natural Science Foundation of China(Nos.52250010,52201242,U23A20574)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)。
文摘Halide solid-state electrolytes(HSSEs)with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries(ASSLBs).However,they suffer from poor processability,mechanical durability and humidity stability,hindering their large-scale applications.Here,we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene(PTFE)binder to encapsulate Li_(3)InCl_(6)(LIC)particles(the most representative HSSE).By manipulating the fibrillating process,only 0.5 wt%PTFE is sufficient to prepare free-standing LIC-PTFE(LIC-P)HSSEs.Additionally,LIC-P demonstrates excellent mechanical durability and humidity resistance.They can maintain their shapes after being exposed to humid atmosphere for 30 min,meanwhile still exhibit high ionic conductivity of>0.2m S/cm at 25℃.Consequently,the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 m Ah/g at0.1 C and long cyclability of 200 cycles at 0.2 C.More importantly,the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7%after 100 cycles under0.2 C.Furthermore,for the first time,we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.
