Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesteri...Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry （DSC）, Ubbelohde viscosity method and gel permeation chromatography （GPC）. The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles （2 mm） increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.展开更多
Microwave irradiation was employed to assist the synthesis of poly（amino-quinone） （PAQ） from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern （continuously or intermittently） o...Microwave irradiation was employed to assist the synthesis of poly（amino-quinone） （PAQ） from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern （continuously or intermittently） of microwave irradiation on yield and intrinsic viscosity of PAQs were studied. It is shown that the continuous microwave irradiation at a high power leads to rapid increase of yield and a sudden halt in polymerization afterwards, due to the subsequent loss of volatile reactants at a high reaction temperature. Alternatively, the high-power microwave irradiation is applicable to raising the yield if used intermittently. In contras4 the low-power microwave irradiation favours the way of continuous exposure to ensure sufficient heat for polymerization. In both cases of high and low power, the yield and intrinsic viscosity can be further promoted by prolonging the exposure time. It is found that under a preliminarily optimized condition of intermittent irradiation at 490 W with six sequences of 5 min irradiation followed by 5 rain interval, the yield and intrinsic viscosity of PAQ from p-benzoquinone and p-phenylene diamine can reach as high as 83% and 41.9 mL/g, respectively.展开更多
Solid-state lithium batteries are considered one of the most promising next-generation energy storage technologies owing to their safety and high energy density.The key to solid-state lithium battery advancement lies ...Solid-state lithium batteries are considered one of the most promising next-generation energy storage technologies owing to their safety and high energy density.The key to solid-state lithium battery advancement lies in the design and optimization of suitable solid-state electrolytes.Among various solid-state electrolytes,solid-state composite polymer electrolytes offer the combined benefits of solid inorganic electrolytes and solid polymer electrolytes.In particular,Li1_(+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)/polymer composite polymer electrolytes exhibit high ionic conductivity due to LATP and improved flexibility from the polymer matrix.These systems also demonstrate robust mechanical properties and excellent electrode contact.While recent reviews have primarily focused on the performance of LATP/polymer composite polymer electrolytes and the general effects of composite polymer electrolyte modifications for solid-state lithium battery applications,this review provides a concise overview of the Li^(+)transport mechanisms in LATP/polymer composite polymer electrolytes and strategies to enhance ionic conductivity.It highlights several modification approaches,including the use of fillers,additives,and LATP coatings,which markedly influence the performance of composite polymer electrolytes across different polymer matrices.Finally,the review addresses the challenges of LATP/polymer composite polymer electrolytes and outlines key research directions for developing advanced composite polymer electrolytes for high-performance solid-state lithium batteries.展开更多
Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wi...Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
[Background]Surfactin is a biosurfactant with remarkable surface/interfacial activity.Surfactin production suffers from high costs of carbon sources and severe foaming problem during fermentation.Unreasonable utilizat...[Background]Surfactin is a biosurfactant with remarkable surface/interfacial activity.Surfactin production suffers from high costs of carbon sources and severe foaming problem during fermentation.Unreasonable utilization of soybean residue(okara)can cause resource waste and environmental pollution.[Objective]To achieve sustainable production of surfactin and valueadded conversion of okara,we explored foam-free production of surfactin by Bacillus subtilis using okara as a low-cost substrate and evaluated its application prospects.[Methods]We evaluated and compared the feasibility of B.subtilis utilizing okara to synthesize surfactin through liquid and solid-state fermentation methods.Biosurfactants were extracted from solid-state culture via a weak alkaline water extraction method.The products were identified by HPLC-MS,and the physicochemical properties of the produced surfactin were analyzed.The solid-state medium for fermentation of okara was optimized by the response surface method.The viable count of B.subtilis in solid-state fermentation residue was determined by the plate colony counting method.[Results]The conversion rates of okara to surfactin were 0.6%−0.8%and 1.2%−1.5%in liquid and solid-state fermentation,respectively.Interestingly,solid-state fermentation of okara by B.subtilis achieved both high-yield and foam-free production of surfactin.Five surfactin homologues were produced from okara,mainly including surfactin-C13(34.16%),surfactin-C_(14)(23.95%),and surfactin-C_(15)(35.14%).The produced surfactin,with a critical micelle concentration of 35.0 mg/L,decreased water surface tension to(26.0±0.1)mN/m and emulsified crude oil with emulsifying activity index(EI24)(73.1±3.2)%.It was stable at 4−121℃,pH 5.0−11.0,and NaCl<150 g/L.Okara,NH_(4)Cl,and CaCl_(2)·2H_(2)O were significant components in the solid-state medium.The surfactin yield was increased by 52.1%through solid-state medium optimization.Adding wheat straw further enhanced surfactin production by improving aeration in the solid-state medium.B.subtilis AnPL-1 produced(263.2±7.8)mg surfactin in the optimized solid-state medium containing 14.8 g okara and 1.5 g wheat straw.The conversion rate of okara to surfactin was enhanced to 1.8%.In addition,the residue of solid-state fermentation was expected to be microbial fertilizer since it contained 4.27×10^(10)CFU/g of B.subtilis.[Conclusion]This study established a promising way for foam-free production of surfactin and value-added conversion of okara.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
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
The application of polymer electrolytes is expected to revitalize solidstate lithium metal batteries(SSLMBs)with high energy density and enhanced safety.However,practical deployment faces challenges from inadequate me...The application of polymer electrolytes is expected to revitalize solidstate lithium metal batteries(SSLMBs)with high energy density and enhanced safety.However,practical deployment faces challenges from inadequate mechanical properties of electrolyte and unstable interfaces in high-voltage SSLMB s.Herein,we design an asymmetric composite solid-state electrolyte(ACSE)composed of a cellulose framework in situ self-assembled with zeolitic imidazolate framework nanosheets(CP@MOF)embedded in a polymer matrix.The CP@MOF network provides the electrolyte with an elastic modulus of 1.19 GPa,effectively resisting Li dendrite penetration.Furthermore,theoretical calculations guided the compositional design of ACSE to address asynchronous interfacial requirements at cathode/electrolyte and anode/electrolyte interfaces,facilitating stable interphase formation and thus ensuring prolonged cycling of SSLMBs.Consequently,Li symmetric cells achieve extended cycling stability(>5000 h)with minimal polarization.The NCM811|Li full cell maintains 84.9%capacity retention after 350 cycles.Notably,assembled NCM811 pouch cells deliver practical energy densities of 337.9 Wh kg^(-1)and 711.7 Wh L^(-1),demonstrating exceptional application potential.This work provides novel insights into the application of ACSEs for high-energy-density SSLMBs.展开更多
The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segme...The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
2D MXenes,particularly Ti_(3)C_(2)T_(x),have emerged as promising multifu nctional materials for advancing solidstate batteries(SSBs).While SSBs offer superior safety and energy density over liquid-electrolyte systems...2D MXenes,particularly Ti_(3)C_(2)T_(x),have emerged as promising multifu nctional materials for advancing solidstate batteries(SSBs).While SSBs offer superior safety and energy density over liquid-electrolyte systems,critical challenges such as interfacial resistance,limited ion transport,dendrite growth,and mechanical degradation hinder their widespread adoption.This review aims to provide a comprehensive analysis of the roles and fu nctions of Ti_(3)C_(2)T_(x) MXenes in SSBs,emphasizing their application as interlayers,anode/cathode additives,and current collectors,and highlighting their impact on interracial stability,ionic/electro nic transport,electrochemical performance,and cycling durability in SSB architectures.Unlike other 2D materials,Ti_(3)C_(2)T_(x) exhibits outsta nding metallic conductivity,tu nable surface terminations,hydrophilicity,and excellent mechanical flexibility,making it ideal for multifu nctional integration in SSBs,As a component in solid-state electrolytes(SSEs),Ti_(3)C_(2)T_(x) improves ionic conductivity and mecha nical strength.When used in electrodes,it serves as a conductive scaffold that enhances charge transport and structural durability.Additionally,its role as an interfacial interlayer effectively reduces interfacial impedance,accommodates volume changes,and suppresses dendrite formation.Its lightweight and high conductivity enable its use as a current collector.This review highlights recent advances in Ti_(3)C_(2)T_(x)-based components for SSBs like Li-,Na-,Zn,Li-S,etc.,emphasizing enha ncements in ion/electron transport,interfacial stability,and structural robustness.Finally,the review outlines challenges and opportunities along with a future outlook focused on improving the MXene oxidation,tailoring surface terminations,improving long-term stability,and exploring scalable fabrication strategies for MXene-based SSB components.展开更多
Solid-state sodium batteries(SSSBs)have been highly prized as a promising alternative to conventional battery systems using organic liquid electrolytes due to their improved safety,higher energy density,and substantia...Solid-state sodium batteries(SSSBs)have been highly prized as a promising alternative to conventional battery systems using organic liquid electrolytes due to their improved safety,higher energy density,and substantial resources and low cost of sodium.Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)solid electrolyte is attracting considerable interest owing to its excellent thermal and chemical stability and favorable compatibility with Na metal anode and high-voltage cathode.However,two main challenges of poor roomtemperature ionic conductivity and high interfacial resistance limit the application of NZSP electrolyte in SSSBs.So far,intensive efforts have been devoted to developing modification strategies to improve the room-temperature ionic conductivity of NZSP.This review aims to provide a comprehensive summary and discussion of some optimization strategies for enhancing the room-temperature ionic conductivity of the NZSP solid electrolyte.These optimization strategies are categorized into foreignion doping or substitution,sintering behavior modulation,and regulation of chemical composition based on precursors,and their optimization mechanisms are also elaborated.Finally,the prospects of NZSP-based solid electrolytes are presented.This review is expected to offer better guidance for designing and developing high-performance NZSP-based solid electrolytes for accelerating the practical application of SSSBs.展开更多
Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth ...Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth of lithium dendrites at the lithium metal-electrolytes interface remains a major obstacle to their practical application.In this work,we introduced a scalable three-dimensional(3D)Li-B skeleton structure designed to suppress dendrite formation.The alloy anode demonstrates a lower Young's modulus,which helps alleviate the accumulation of localized stresses at the interface.Additionally,the 3D alloy anode provided a uniform potential distribution,which promoted homogeneous lithium deposition.Benefiting from these structural advantages,symmetric cells with the Li-B alloy achieved a high critical current density of 2.8 mA cm^(-2).Notably,Li-B‖LPSCI‖LVO-NCM ASSLBs exhibited long-term cycling stability,retaining 97.8%of their capacity after 1500 cycles at 2 C.Furthermore,ASSLBs incorporating the Li-B alloy showed cycling stability comparable with Li-In-based cells,while delivering a higher energy density.Overall,this work presents a practical strategy that may accelerate the commercialization of sulfide-based ASSLBs.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
Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive ...Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive monomers.Herein,we report a one-pot multicomponent polymerization method that directly produces main-chain charged polyelectrolytes with intrinsic AIE characteristics from non-emissive building blocks.By optimizing the monomer structures and reaction conditions,a series of soluble high-molecular-weight polymers with welldefined backbones were obtained in high yields.The resulting polyelectrolytes displayed robust AIE behavior,exhibiting fluorescence enhancement up to about 60-fold in an aqueous environment,and maintained excellent thermal stability.Owing to their cationic backbones,these polymers interact strongly with microbial surfaces and exhibit remarkable antimicrobial activities.This study establishes a synthetically efficient route to AIE polyelectrolytes and highlights their potential applications as multifunctional materials for bioimaging,antimicrobial therapy,and other applications.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 0.1 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
Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient co...Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient contact and heterogeneous Li deposition severely hinder their practical applications.Here,a flexible ternary polymethacrylate(PMA)matrix is designed to incorporate with Ta-doped Li_(7)La_(3)Zr_(2)O_(12)(LLZTO-PMA).The PMA matrix ensures excellent interfacial contact,while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li^(+)pathways yield a high ionic conductivity of 0.266 mS cm^(-1)at 20℃.Moreover,the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li_(3)N-rich solid electrolyte interphase,which allows a fast Li^(+)interfacial kinetic due to its lowered Li^(+)diffusion barrier.Consequently,the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase,attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96%capacity after 600 cycles in full battery,demonstrating a breakthrough for high-performance solid-state batteries.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51173112)
文摘Poly（bisphenol A carbonate） （BPA-PC） was post-polymerized by solid-state polymerization （SSP） after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry （DSC）, Ubbelohde viscosity method and gel permeation chromatography （GPC）. The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles （2 mm） increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.
基金Project(50804055) supported by the National Natural Science Foundation of China
文摘Microwave irradiation was employed to assist the synthesis of poly（amino-quinone） （PAQ） from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern （continuously or intermittently） of microwave irradiation on yield and intrinsic viscosity of PAQs were studied. It is shown that the continuous microwave irradiation at a high power leads to rapid increase of yield and a sudden halt in polymerization afterwards, due to the subsequent loss of volatile reactants at a high reaction temperature. Alternatively, the high-power microwave irradiation is applicable to raising the yield if used intermittently. In contras4 the low-power microwave irradiation favours the way of continuous exposure to ensure sufficient heat for polymerization. In both cases of high and low power, the yield and intrinsic viscosity can be further promoted by prolonging the exposure time. It is found that under a preliminarily optimized condition of intermittent irradiation at 490 W with six sequences of 5 min irradiation followed by 5 rain interval, the yield and intrinsic viscosity of PAQ from p-benzoquinone and p-phenylene diamine can reach as high as 83% and 41.9 mL/g, respectively.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.52302303,52472247,52172229,52272201,52072136,51972257)the Natural Science Foundation of Hubei Province(JCZRYB202500537).
文摘Solid-state lithium batteries are considered one of the most promising next-generation energy storage technologies owing to their safety and high energy density.The key to solid-state lithium battery advancement lies in the design and optimization of suitable solid-state electrolytes.Among various solid-state electrolytes,solid-state composite polymer electrolytes offer the combined benefits of solid inorganic electrolytes and solid polymer electrolytes.In particular,Li1_(+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)/polymer composite polymer electrolytes exhibit high ionic conductivity due to LATP and improved flexibility from the polymer matrix.These systems also demonstrate robust mechanical properties and excellent electrode contact.While recent reviews have primarily focused on the performance of LATP/polymer composite polymer electrolytes and the general effects of composite polymer electrolyte modifications for solid-state lithium battery applications,this review provides a concise overview of the Li^(+)transport mechanisms in LATP/polymer composite polymer electrolytes and strategies to enhance ionic conductivity.It highlights several modification approaches,including the use of fillers,additives,and LATP coatings,which markedly influence the performance of composite polymer electrolytes across different polymer matrices.Finally,the review addresses the challenges of LATP/polymer composite polymer electrolytes and outlines key research directions for developing advanced composite polymer electrolytes for high-performance solid-state lithium batteries.
基金supported by the Science Foundation of High-Level Talents of Wuyi University(Nos.2019AL017,2021AL002).
文摘Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金supported by the Research Start-up Foundation for Introduced Talent of Qufu Normal University(609601)。
文摘[Background]Surfactin is a biosurfactant with remarkable surface/interfacial activity.Surfactin production suffers from high costs of carbon sources and severe foaming problem during fermentation.Unreasonable utilization of soybean residue(okara)can cause resource waste and environmental pollution.[Objective]To achieve sustainable production of surfactin and valueadded conversion of okara,we explored foam-free production of surfactin by Bacillus subtilis using okara as a low-cost substrate and evaluated its application prospects.[Methods]We evaluated and compared the feasibility of B.subtilis utilizing okara to synthesize surfactin through liquid and solid-state fermentation methods.Biosurfactants were extracted from solid-state culture via a weak alkaline water extraction method.The products were identified by HPLC-MS,and the physicochemical properties of the produced surfactin were analyzed.The solid-state medium for fermentation of okara was optimized by the response surface method.The viable count of B.subtilis in solid-state fermentation residue was determined by the plate colony counting method.[Results]The conversion rates of okara to surfactin were 0.6%−0.8%and 1.2%−1.5%in liquid and solid-state fermentation,respectively.Interestingly,solid-state fermentation of okara by B.subtilis achieved both high-yield and foam-free production of surfactin.Five surfactin homologues were produced from okara,mainly including surfactin-C13(34.16%),surfactin-C_(14)(23.95%),and surfactin-C_(15)(35.14%).The produced surfactin,with a critical micelle concentration of 35.0 mg/L,decreased water surface tension to(26.0±0.1)mN/m and emulsified crude oil with emulsifying activity index(EI24)(73.1±3.2)%.It was stable at 4−121℃,pH 5.0−11.0,and NaCl<150 g/L.Okara,NH_(4)Cl,and CaCl_(2)·2H_(2)O were significant components in the solid-state medium.The surfactin yield was increased by 52.1%through solid-state medium optimization.Adding wheat straw further enhanced surfactin production by improving aeration in the solid-state medium.B.subtilis AnPL-1 produced(263.2±7.8)mg surfactin in the optimized solid-state medium containing 14.8 g okara and 1.5 g wheat straw.The conversion rate of okara to surfactin was enhanced to 1.8%.In addition,the residue of solid-state fermentation was expected to be microbial fertilizer since it contained 4.27×10^(10)CFU/g of B.subtilis.[Conclusion]This study established a promising way for foam-free production of surfactin and value-added conversion of okara.
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.
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the financial support from the National Natural Science Foundation of China(52072307,22408198)the Fundamental Research Funds for the Central Universities(XJJSKYQD202533)。
文摘The application of polymer electrolytes is expected to revitalize solidstate lithium metal batteries(SSLMBs)with high energy density and enhanced safety.However,practical deployment faces challenges from inadequate mechanical properties of electrolyte and unstable interfaces in high-voltage SSLMB s.Herein,we design an asymmetric composite solid-state electrolyte(ACSE)composed of a cellulose framework in situ self-assembled with zeolitic imidazolate framework nanosheets(CP@MOF)embedded in a polymer matrix.The CP@MOF network provides the electrolyte with an elastic modulus of 1.19 GPa,effectively resisting Li dendrite penetration.Furthermore,theoretical calculations guided the compositional design of ACSE to address asynchronous interfacial requirements at cathode/electrolyte and anode/electrolyte interfaces,facilitating stable interphase formation and thus ensuring prolonged cycling of SSLMBs.Consequently,Li symmetric cells achieve extended cycling stability(>5000 h)with minimal polarization.The NCM811|Li full cell maintains 84.9%capacity retention after 350 cycles.Notably,assembled NCM811 pouch cells deliver practical energy densities of 337.9 Wh kg^(-1)and 711.7 Wh L^(-1),demonstrating exceptional application potential.This work provides novel insights into the application of ACSEs for high-energy-density SSLMBs.
基金financially supported by the National Natural Science Foundation of China(No.52573079)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003).
文摘The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金supported by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(NRF-2020R1A6A1A03043435 and 2020R1A2C1099862)supported by the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korean Government(MOTIE)(P0012451,The Competency Development Program for Industry Specialist)。
文摘2D MXenes,particularly Ti_(3)C_(2)T_(x),have emerged as promising multifu nctional materials for advancing solidstate batteries(SSBs).While SSBs offer superior safety and energy density over liquid-electrolyte systems,critical challenges such as interfacial resistance,limited ion transport,dendrite growth,and mechanical degradation hinder their widespread adoption.This review aims to provide a comprehensive analysis of the roles and fu nctions of Ti_(3)C_(2)T_(x) MXenes in SSBs,emphasizing their application as interlayers,anode/cathode additives,and current collectors,and highlighting their impact on interracial stability,ionic/electro nic transport,electrochemical performance,and cycling durability in SSB architectures.Unlike other 2D materials,Ti_(3)C_(2)T_(x) exhibits outsta nding metallic conductivity,tu nable surface terminations,hydrophilicity,and excellent mechanical flexibility,making it ideal for multifu nctional integration in SSBs,As a component in solid-state electrolytes(SSEs),Ti_(3)C_(2)T_(x) improves ionic conductivity and mecha nical strength.When used in electrodes,it serves as a conductive scaffold that enhances charge transport and structural durability.Additionally,its role as an interfacial interlayer effectively reduces interfacial impedance,accommodates volume changes,and suppresses dendrite formation.Its lightweight and high conductivity enable its use as a current collector.This review highlights recent advances in Ti_(3)C_(2)T_(x)-based components for SSBs like Li-,Na-,Zn,Li-S,etc.,emphasizing enha ncements in ion/electron transport,interfacial stability,and structural robustness.Finally,the review outlines challenges and opportunities along with a future outlook focused on improving the MXene oxidation,tailoring surface terminations,improving long-term stability,and exploring scalable fabrication strategies for MXene-based SSB components.
基金National Natural Science Foundation of China,Grant/Award Number:52272225。
文摘Solid-state sodium batteries(SSSBs)have been highly prized as a promising alternative to conventional battery systems using organic liquid electrolytes due to their improved safety,higher energy density,and substantial resources and low cost of sodium.Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)solid electrolyte is attracting considerable interest owing to its excellent thermal and chemical stability and favorable compatibility with Na metal anode and high-voltage cathode.However,two main challenges of poor roomtemperature ionic conductivity and high interfacial resistance limit the application of NZSP electrolyte in SSSBs.So far,intensive efforts have been devoted to developing modification strategies to improve the room-temperature ionic conductivity of NZSP.This review aims to provide a comprehensive summary and discussion of some optimization strategies for enhancing the room-temperature ionic conductivity of the NZSP solid electrolyte.These optimization strategies are categorized into foreignion doping or substitution,sintering behavior modulation,and regulation of chemical composition based on precursors,and their optimization mechanisms are also elaborated.Finally,the prospects of NZSP-based solid electrolytes are presented.This review is expected to offer better guidance for designing and developing high-performance NZSP-based solid electrolytes for accelerating the practical application of SSSBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.52002094)the Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2025A1515011995)+3 种基金the Shenzhen Science and Technology Innovation Program(GXWD20221030205923001)the Shandong Provincial Natural Science Foundation of China(Grant Nos.ZR2024QE525)the Shenzhen Key Laboratory of New Materials Technology(Grant Nos.SYSPG20241211173609003)the State Key Laboratory of Precision Welding&Joining of Materials and Structures(Grant Nos.2024-Z-17,2024-T-08)。
文摘Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth of lithium dendrites at the lithium metal-electrolytes interface remains a major obstacle to their practical application.In this work,we introduced a scalable three-dimensional(3D)Li-B skeleton structure designed to suppress dendrite formation.The alloy anode demonstrates a lower Young's modulus,which helps alleviate the accumulation of localized stresses at the interface.Additionally,the 3D alloy anode provided a uniform potential distribution,which promoted homogeneous lithium deposition.Benefiting from these structural advantages,symmetric cells with the Li-B alloy achieved a high critical current density of 2.8 mA cm^(-2).Notably,Li-B‖LPSCI‖LVO-NCM ASSLBs exhibited long-term cycling stability,retaining 97.8%of their capacity after 1500 cycles at 2 C.Furthermore,ASSLBs incorporating the Li-B alloy showed cycling stability comparable with Li-In-based cells,while delivering a higher energy density.Overall,this work presents a practical strategy that may accelerate the commercialization of sulfide-based ASSLBs.
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supported by the National Natural Science Foundation of China(No.22431004)Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2023B1212060003)。
文摘Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive monomers.Herein,we report a one-pot multicomponent polymerization method that directly produces main-chain charged polyelectrolytes with intrinsic AIE characteristics from non-emissive building blocks.By optimizing the monomer structures and reaction conditions,a series of soluble high-molecular-weight polymers with welldefined backbones were obtained in high yields.The resulting polyelectrolytes displayed robust AIE behavior,exhibiting fluorescence enhancement up to about 60-fold in an aqueous environment,and maintained excellent thermal stability.Owing to their cationic backbones,these polymers interact strongly with microbial surfaces and exhibit remarkable antimicrobial activities.This study establishes a synthetically efficient route to AIE polyelectrolytes and highlights their potential applications as multifunctional materials for bioimaging,antimicrobial therapy,and other applications.
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 0.1 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 the National Natural Science Foundation of China(No.22305106)the Postdoctoral Fellowship Program of CPSF(GZC20230682)Beijing Key Laboratory of High-Entropy Energy materials and Devices,Beijing Institute of Nanoenergy and Nanosystems(No.GS 2025ZD005)。
文摘Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient contact and heterogeneous Li deposition severely hinder their practical applications.Here,a flexible ternary polymethacrylate(PMA)matrix is designed to incorporate with Ta-doped Li_(7)La_(3)Zr_(2)O_(12)(LLZTO-PMA).The PMA matrix ensures excellent interfacial contact,while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li^(+)pathways yield a high ionic conductivity of 0.266 mS cm^(-1)at 20℃.Moreover,the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li_(3)N-rich solid electrolyte interphase,which allows a fast Li^(+)interfacial kinetic due to its lowered Li^(+)diffusion barrier.Consequently,the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase,attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96%capacity after 600 cycles in full battery,demonstrating a breakthrough for high-performance solid-state batteries.
