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
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
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
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
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
The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batterie...The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.展开更多
Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage c...Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.展开更多
In the pursuit of safer and more energy-dense all-solid-state Li-ion batteries,solid-state electrolytes(SSEs)have emerged as pivotal components,with halide SSEs distinguished by their excellent electrochemical stabili...In the pursuit of safer and more energy-dense all-solid-state Li-ion batteries,solid-state electrolytes(SSEs)have emerged as pivotal components,with halide SSEs distinguished by their excellent electrochemical stability,enhanced Li-ion diffusion,and potential cost-efficiency.These properties depend on the anion elements and the structure of closely packed anion sublattices,such as cubic close-packed(ccp)and hexagonal close-packed(hcp)frameworks.Hence,understanding these key differences is essential because they influence the ion diffusion kinetic properties of various halide SSEs.However,research has predominantly shown that ccp anion sublattices generally exhibit higher ionic conductivities than their hcp counterparts,often overlooking the importance of the structural frameworks.To address this issue,we re-evaluated the assumption that a ccp framework is necessary for high electrochemical performance.Specifically,we utilized the three previously synthesized hcp and a ccp frameworks,all with an identical composition of Li_(3)YCl_(6),to assess their thermodynamic stability,synthesizability,and ionic conductivity through ab initio molecular dynamics simulations.The results revealed that hcp frameworks could be promising candidates for SSEs,challenging the conventional preference for the ccp framework.With this structural insight,we designed a novel hcp framework to predict a new Li_(3)YCl_(6) crystal structure with the highest ionic conductivity(38 mS·cm^(−1))among the halide frameworks and a superior 2D Li-ion diffusion pathway.This breakthrough underscores the significance of the anion framework geometry in Li-ion diffusion and highlights the importance of precise crystallographic predictions in developing more efficient and cost-effective battery technologies.展开更多
In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an ...In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.展开更多
Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a...Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a dual-functional Ti_(3)(PO_(4))_(4)coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs.The electrochemically stabilized Ti_(3)(PO_(4))_(4)coating prevents direct contact between the SSEs and NCM811,thereby inhibiting interfacial side reactions.In addition,the internal structure of NCM811 can be stabilized by Ti doping,which inhibits the oxygen release behavior of NCM811 at high charge state,preventing further electrochemical oxidation of the SSEs.The modified NCM811@TiP cathode exhibits excellent long cycle stability,with 74.4%capacity retention after 100 cycles at a cut-off voltage of 4.2 V.This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.展开更多
Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_...Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).展开更多
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
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
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
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
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
Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the as...Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the assembly of the zeolite structure.In this study,we inves-tigate the complex interplay between boron species and TPA cations during the crystallization of[B,Al]-ZSM-5 zeolites.Two-dimensional(2D)11B-{1H}cross-polarization heteronuclear correlation(CP-HECTOR)NMRexperiments elucidate distinct interactions between two boron species,B(IV)-1 and B(IV)-2,and the propyl chain of the TPAs.Amorphous B(IV)-1 species exhibit a strong preference for proximity to the nitrogen cation center of the OSDAs,while framework B(IV)-2 species engage with components situated at greater distances from the cation center.Moreover,13C-{11B}symmetry-based resonance-echo saturation-pulse double-resonance(S-RESPDOR)experiments revealed that framework boron species preferentially occupy the straight channels of the MFI structure,as evidenced by their interaction with specificmethyl groups on the TPAmolecules.This observation provides valuable insights into the crystallization mechanism of boron-based zeolites,suggesting that the conformation and orientation of the OSDA molecules play a critical role in determining the location of boron atoms within the zeolite framework.展开更多
Ribonucleic acid(RNA)structures and dynamics play a crucial role in elucidating RNA functions and facilitating the design of drugs targeting RNA and RNA-protein complexes.However,obtaining RNA structures using convent...Ribonucleic acid(RNA)structures and dynamics play a crucial role in elucidating RNA functions and facilitating the design of drugs targeting RNA and RNA-protein complexes.However,obtaining RNA structures using conventional biophysical techniques,such as Xray crystallography and solution nuclear magnetic resonance(NMR),presents challenges due to the inherent flexibility and susceptibility to degradation of RNA.In recent years,solid-state NMR(SSNMR)has rapidly emerged as a promising alternative technique for characterizing RNA structure and dynamics.SSNMR has several distinct advantages,including flexibility in sample states,the ability to capture dynamic features of RNA in solid form,and suitability to character RNAs in various sizes.Recent decade witnessed the growth of ^(1)H-detected SSNMR methods on RNA,which targeted elucidating RNA topology and base pair dynamics in solid state.They have been applied to determine the topology of RNA segment in human immunodeficiency virus(HIV)genome and the base pair dynamics of riboswitch RNA.These advancements have expanded the utility of SSNMR techniques within the RNA research field.This review provides a comprehensive discussion of recent progress in ^(1)H-detected SSNMR investigations into RNA structure and dynamics.We focus on the established ^(1)H-detected SSNMR methods,sample preparation protocols,and the implementation of rapid data acquisition approaches.展开更多
All-solid-state batteries(ASSBs)with Li or Si anodes promise enhanced safety and high energy densities but face challenges with complex fabrication,stringent storage requirements,and pressure-dependent operation.Polye...All-solid-state batteries(ASSBs)with Li or Si anodes promise enhanced safety and high energy densities but face challenges with complex fabrication,stringent storage requirements,and pressure-dependent operation.Polyethylene oxide(PEO)-based composite solid electrolytes(CSEs)enable easy processing and flexible interfaces,supporting pressure-free operation and reducing costs.However,their low ionic conductivity remains a key limitation.Here,we present a rapid(~5 min)and eco-friendly laser modification strategy for post-synthesized PEO CSEs,achieving enhanced ionic conductivity while retaining the attributes of simple fabrication and compatibility with Li and Si anodes under pressure-free operation.Laser engineering reduces PEO crystallinity,introduces additional Li^(+)coordination sites,and improves interfacial stability through tailored solid electrolyte interphases.The laser-modified electrolyte enables LiFePO_(4)//Li cells to retain 142.4 mAh g^(-1)after 800 cycles with 99.8%Coulombic efficiency at 1 C and 60℃.Moreover,without stack pressure,a Si anode paired with the laser-modified electrolyte delivers a high capacity of 1710.3 mAh g^(-1)with 56%retention at 0.5 A g^(-1)after 50 cycles at 60℃.Beyond performance enhancements,this work establishes a link between fluorescence emission and Li^(+)transport in CSEs.Specifically,fluorescence shifts to shorter wavelengths correspond to shorter molecular chain lengths and lower coordination bonds,supported by time-dependent density functional theory calculations.These factors give rise to improved Li^(+)transport.This optical probe offers a non-destructive approach for rapidly assessing electrolyte properties and enriching electrolyte design.Overall,this work demonstrates laser engineering as a practical post-synthetic strategy and highlights fluorescence as a practical indicator for advancing next-generation ASSBs.展开更多
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.
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.
基金Financial support from National Key R&D Program(2022YFB2404600)Natural Science Foundation of China(Key Project of 52131306)+1 种基金Project on Carbon Emission Peak and Neutrality of Jiangsu Province(BE2022031-4)the Big Data Computing Center of Southeast University are greatly appreciated.
文摘The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.
基金financially supported by Natural Science Foundation of Hebei Province(Nos.B2020203037,F2021203097)Science Research Project of Hebei Education Department(No.JZX2024022)National Natural Science Foundation of China(Nos.52022088,51971245)。
文摘Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.
基金supported by the Ministry of Trade,Industry and Energy(MOTIE)of Korea(Nos.P0022336 and RS-2024-00437260)Hyundai Motor Company.
文摘In the pursuit of safer and more energy-dense all-solid-state Li-ion batteries,solid-state electrolytes(SSEs)have emerged as pivotal components,with halide SSEs distinguished by their excellent electrochemical stability,enhanced Li-ion diffusion,and potential cost-efficiency.These properties depend on the anion elements and the structure of closely packed anion sublattices,such as cubic close-packed(ccp)and hexagonal close-packed(hcp)frameworks.Hence,understanding these key differences is essential because they influence the ion diffusion kinetic properties of various halide SSEs.However,research has predominantly shown that ccp anion sublattices generally exhibit higher ionic conductivities than their hcp counterparts,often overlooking the importance of the structural frameworks.To address this issue,we re-evaluated the assumption that a ccp framework is necessary for high electrochemical performance.Specifically,we utilized the three previously synthesized hcp and a ccp frameworks,all with an identical composition of Li_(3)YCl_(6),to assess their thermodynamic stability,synthesizability,and ionic conductivity through ab initio molecular dynamics simulations.The results revealed that hcp frameworks could be promising candidates for SSEs,challenging the conventional preference for the ccp framework.With this structural insight,we designed a novel hcp framework to predict a new Li_(3)YCl_(6) crystal structure with the highest ionic conductivity(38 mS·cm^(−1))among the halide frameworks and a superior 2D Li-ion diffusion pathway.This breakthrough underscores the significance of the anion framework geometry in Li-ion diffusion and highlights the importance of precise crystallographic predictions in developing more efficient and cost-effective battery technologies.
基金financially supported by the National Natural Science Foundation of China(No.22301151)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(No.2022QN05024)+1 种基金the Science and Technology Projects of Inner Mongolia Autonomous Region(No.2024SKYPT0011)the Science and Technology Planning Project of Hohhot,China(No.2024-JieBangGuaShuai-Gao-4)
文摘In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.
基金supported by the National Natural Science Foundation of China(No.52272258),the Beijing Nova Program(No.20220484214)Key R&D and transformation projects in Qinghai Province(No.2023-HZ-801)the Fundamental Research Funds for the Central Universities(No.2023ZKPYJD07)。
文摘Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a dual-functional Ti_(3)(PO_(4))_(4)coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs.The electrochemically stabilized Ti_(3)(PO_(4))_(4)coating prevents direct contact between the SSEs and NCM811,thereby inhibiting interfacial side reactions.In addition,the internal structure of NCM811 can be stabilized by Ti doping,which inhibits the oxygen release behavior of NCM811 at high charge state,preventing further electrochemical oxidation of the SSEs.The modified NCM811@TiP cathode exhibits excellent long cycle stability,with 74.4%capacity retention after 100 cycles at a cut-off voltage of 4.2 V.This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
基金financial support from the Science and Technology Project of Shenzhen(Nos.JCYJ20210324094206019 and JCYJ20210324094000001).
文摘Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes(SSEs)for all-solid-state lithium metal batteries.Here,we report on nano-sized boron nitride(BN)-coated Li_(5.7)PS_(4.7)Cl_(1.3)(BN@LPSC1.3)sulfide SSE,which exhibits reduced H_(2)S emission and improved ionic conductivity retention after relative humidity 1.2%-1.5%ambient condition exposure.Furthermore,BN can partially react with lithium metal to create stable Li_(3)N,resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2mA/cm^(2).The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for>2000 h at a current density of 0.1mA/cm^(2).Despite the high cathode mass loading of 13.38mg/cm^(2),the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/BN@LPSC1.3/Li all-solidstate lithium metal battery achieves 84.34%capacity retention even after 500 cycles at 0.1 C and room temperature(25℃).
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 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.
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supported by the National Energy R&D Center of Petroleum Refining Technology(RIPP,SINOPEC),the National Natural Science Foundation of China(Grants 22161132028,22172177,22225205,22372191 and 22372178)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0540000)+2 种基金the International Partnership Program of the Chinese Academy of Sciences(314GJH2022022FN)Natural Science Foundation of Hubei Province(2021CFA021)Hubei International Scientific and Technological Cooperation Program(2024EHA043)and Base(SH2303).
文摘Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the assembly of the zeolite structure.In this study,we inves-tigate the complex interplay between boron species and TPA cations during the crystallization of[B,Al]-ZSM-5 zeolites.Two-dimensional(2D)11B-{1H}cross-polarization heteronuclear correlation(CP-HECTOR)NMRexperiments elucidate distinct interactions between two boron species,B(IV)-1 and B(IV)-2,and the propyl chain of the TPAs.Amorphous B(IV)-1 species exhibit a strong preference for proximity to the nitrogen cation center of the OSDAs,while framework B(IV)-2 species engage with components situated at greater distances from the cation center.Moreover,13C-{11B}symmetry-based resonance-echo saturation-pulse double-resonance(S-RESPDOR)experiments revealed that framework boron species preferentially occupy the straight channels of the MFI structure,as evidenced by their interaction with specificmethyl groups on the TPAmolecules.This observation provides valuable insights into the crystallization mechanism of boron-based zeolites,suggesting that the conformation and orientation of the OSDA molecules play a critical role in determining the location of boron atoms within the zeolite framework.
基金supported by the National Natural Science Foundation of China(grant number:22274050)the Shanghai Science and Technology Commission(contract number:23J21900300)the Fundamental Research Funds for the Central Universities.
文摘Ribonucleic acid(RNA)structures and dynamics play a crucial role in elucidating RNA functions and facilitating the design of drugs targeting RNA and RNA-protein complexes.However,obtaining RNA structures using conventional biophysical techniques,such as Xray crystallography and solution nuclear magnetic resonance(NMR),presents challenges due to the inherent flexibility and susceptibility to degradation of RNA.In recent years,solid-state NMR(SSNMR)has rapidly emerged as a promising alternative technique for characterizing RNA structure and dynamics.SSNMR has several distinct advantages,including flexibility in sample states,the ability to capture dynamic features of RNA in solid form,and suitability to character RNAs in various sizes.Recent decade witnessed the growth of ^(1)H-detected SSNMR methods on RNA,which targeted elucidating RNA topology and base pair dynamics in solid state.They have been applied to determine the topology of RNA segment in human immunodeficiency virus(HIV)genome and the base pair dynamics of riboswitch RNA.These advancements have expanded the utility of SSNMR techniques within the RNA research field.This review provides a comprehensive discussion of recent progress in ^(1)H-detected SSNMR investigations into RNA structure and dynamics.We focus on the established ^(1)H-detected SSNMR methods,sample preparation protocols,and the implementation of rapid data acquisition approaches.
基金the generous support from the Singapore MOE-ARC grant(A-8001494-00-00)supported by the Ministry of Education,Singapore,under its Research Centre of Excellence award to the Institute for Functional Intelligent Materials(EDUNC-33-18-279-V12)。
文摘All-solid-state batteries(ASSBs)with Li or Si anodes promise enhanced safety and high energy densities but face challenges with complex fabrication,stringent storage requirements,and pressure-dependent operation.Polyethylene oxide(PEO)-based composite solid electrolytes(CSEs)enable easy processing and flexible interfaces,supporting pressure-free operation and reducing costs.However,their low ionic conductivity remains a key limitation.Here,we present a rapid(~5 min)and eco-friendly laser modification strategy for post-synthesized PEO CSEs,achieving enhanced ionic conductivity while retaining the attributes of simple fabrication and compatibility with Li and Si anodes under pressure-free operation.Laser engineering reduces PEO crystallinity,introduces additional Li^(+)coordination sites,and improves interfacial stability through tailored solid electrolyte interphases.The laser-modified electrolyte enables LiFePO_(4)//Li cells to retain 142.4 mAh g^(-1)after 800 cycles with 99.8%Coulombic efficiency at 1 C and 60℃.Moreover,without stack pressure,a Si anode paired with the laser-modified electrolyte delivers a high capacity of 1710.3 mAh g^(-1)with 56%retention at 0.5 A g^(-1)after 50 cycles at 60℃.Beyond performance enhancements,this work establishes a link between fluorescence emission and Li^(+)transport in CSEs.Specifically,fluorescence shifts to shorter wavelengths correspond to shorter molecular chain lengths and lower coordination bonds,supported by time-dependent density functional theory calculations.These factors give rise to improved Li^(+)transport.This optical probe offers a non-destructive approach for rapidly assessing electrolyte properties and enriching electrolyte design.Overall,this work demonstrates laser engineering as a practical post-synthetic strategy and highlights fluorescence as a practical indicator for advancing next-generation ASSBs.
