For a long period of time, the determination of phase diagrams was only supported by experiments related to thermal effects or thermodynamic measurements: thermal analysis, calorimetric measurements, vapor pressures,...For a long period of time, the determination of phase diagrams was only supported by experiments related to thermal effects or thermodynamic measurements: thermal analysis, calorimetric measurements, vapor pressures, and EMF measurements. As a matter of fact, solid-solid transformations were not so accurately determined and could not be taken into account in the system's analysis. First, X-ray diffraction methods were used as a support for the thermal analysis. Second, the implementation of novel tools in structural analysis (for example, the Rietveld method) has permitted to increase the knowledge of phase stability. Finally, modeling the phases using a Calphad method needed increasingly more structural results to determine and better understand the phase diagrams. On the other hand, the Calphad method has been widely developed for metallic systems, for oxide systems, and in the past 10 years, for some semi-conductor systems, for example, gallium arsenide, cadmium telluride, and lead telluride systems. In such applications, it is very important to bring point defects in the modeling of the phases to map the defects as a function of the chemical composition. Owing to its complexity, this characteristic, the knowledge of which is crucial for the understanding and the control of potential physical applications, was ignored in the previous assessment of semi-conductor systems.展开更多
Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivit...Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivity.However,the typical synthesis of Ga-LLZO is usually accompanied by the formation of undesired LiGaO_(2) impurity phase that causes severe instability of the electrolyte in contact with molten Li metal during half/full cell assembly.In this study,we show that by simply engineering the defect chemistry of Ga-LLZO,namely,the lithium deficiency level,LiGaO_(2) impurity phase is effectively inhibited in the final synthetic product.Consequently,defect chemistry engineered Ga-LLZO exhibits excellent electrochemical stability against lithium metal,while its high room temperature ionic conductivity(~1.9×10^(-3)S·cm^(-1))is well reserved.The assembled Li/Ga-LLZO/Li symmetric cell has a superior critical current density of 0.9 mA·cm^(-2),and cycles stably for 500 hours at a current density of 0.3 mA·cm^(-2).This research facilitates the potential commercial applications of high performance Ga-LLZO solid electrolytes in ASSLBs.展开更多
The power conversion efficiency of organometallic perovskite-based solar cells has skyrocketed in recent years. Intensive efforts have been made to prepare high-quality perovskite films tailored to various device conf...The power conversion efficiency of organometallic perovskite-based solar cells has skyrocketed in recent years. Intensive efforts have been made to prepare high-quality perovskite films tailored to various device configurations. Planar heterojunction devices have achieved record efficiencies; however, the preparation of perovskite films for planar junction devices requires the use of expensive vacuum facilities and/or the fine control of experimental conditions. Here, we demonstrate a facile preparation of perovskite films using solid-state chemistry. Solid-state precursor thin films of CHBNH3I and PbI2 are brought into contact with each other and allowed to react via thermally accelerated diffusion. The resulting perovskite film displays good optical absorption and a smooth morphology. Solar cells based on these films show an average efficiency of 8.7% and a maximum efficiency of 10%. The solid-state synthesis of organometallic perovskite can also be carried out on flexible plastic substrates. Using this method on a PET/ITO substrate produces devices with an efficiency of 3.2%. Unlike existing synthetic methods for organometallic perovskite films, the solid-state reaction method does not require the use of orthogonal solvents or careful adjustment of reaction conditions, and thus shows good potential for mass production in the future.展开更多
Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage ...Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.展开更多
Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward ...Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility.In particular,all-solid-state lithium-sulfur batteries(ASSLSBs)that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system,surpassing conventional lithium-ion batteries.This can be attributed predominantly to their exceptional energy density,extended operational lifespan,and heightened safety attributes.Despite these advantages,the adoption of ASSLSBs in the commercial sector has been sluggish.To expedite research and development in this particular area,this article provides a thorough review of the current state of ASSLSBs.We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs,explore the fundamental scientific principles involved,and provide a comprehensive evaluation of the main challenges faced by ASSLSBs.We suggest that future research in this field should prioritize plummeting the presence of inactive substances,adopting electrodes with optimum performance,minimizing interfacial resistance,and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.展开更多
All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,si...All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.展开更多
Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical applicati...Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.展开更多
All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations ...All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.展开更多
Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues...Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues under extreme conditions are the main challenges for the practical application.With the expansion of human activities,such as space missions,polar exploration,and so on,the investigation of SSC with wide temperature tolerance,high energy density,power density,and sustainability is highly desired.In this review,the effects of temperature on SSC are systematically illustrated and clarified,including the properties of the electrolyte,ion diffusion,and reaction dynamics of the supercapacitor.Subsequently,we summarize the recent advances in wide-temperature-range SSCs from the aspect of electrolyte modification,electrode design,and interface adjustment between electrode and electrolyte,especially with critical concerns on ionic conductivity and cycling stability.In the end,a perspective is presented,expecting to promote the practical application of the SSC in harsh conditions.展开更多
Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay ...Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay in AF-SSLBs,either determined by dead Li or solid electrolyte interface(SEI),limits the proposal of effective strategies to prolong cycling life.To clarify the underlying mechanism,herein,the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance(ss-NMR)technology in a typical LiPF6-based polymer electrolyte.The results show that the initial capacity loss is attributed to the formation of SEI,while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm^(−2)cycle−1.To reduce the active Li loss,the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior,which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds,respectively.As a result,the initial Coulombic efficiency(ICE)and stable CE increase by 15.1%and 15.3%in Li-Cu cells,which guides the rational design of high-performance AF-SSLBs.展开更多
The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high in...The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.展开更多
The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues inc...The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.展开更多
Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction ...Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.展开更多
All-solid-state lithium metal batteries(ASSLMBs)are considered as one of the ultimate goals for the development of energy storage systems due to their high energy density and high safety.However,the mismatching of int...All-solid-state lithium metal batteries(ASSLMBs)are considered as one of the ultimate goals for the development of energy storage systems due to their high energy density and high safety.However,the mismatching of interface transport kinetics as well as interfacial instability induces the growth of lithium dendrite and thus,leads to severe degradation of battery electrochemical performances.Herein,an integrated interface configuration(IIC)consisting of in-situ generated Li I interphase and Li-Ag alloy anode is proposed through in-situ interface chemistry.The IIC is capable of not only regulating charge transport kinetics but also synchronously stabilizing the lithium/electrolyte interface,thereby achieving uniform lithium platting.Therefore,Li||Li symmetric cells with IIC achieve a critical current density of up to 1.6 mA cm^(-2)and achieve stable cycling over 1600 hours at a high current density of 0.5 mA cm^(-2).Moreover,a high discharge capacity of 140.1 mA h g-1at 0.1 C is also obtained for the Li(Ni_(0.6)Co_(0.2)Mn_(0.2))O_(2)(NCM622)full battery with a capacity retention of 65.6%after 300 cycles.This work provides an effective method to synergistically regulate the interface transport kinetics and inhibit lithium dendrite growth for high-performance ASSLMBs.展开更多
Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)co...Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.展开更多
Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric press...Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric pressure.The dragline silk fiber,which is essentially a spider's lifeline,surpasses the strength of a steel wire of equivalent thickness.Regrettably,humans have yet to replicate this process to produce fibers with similar high strength and elasticity in an eco-friendly manner.Therefore,it is of utmost importance to thoroughly comprehend the extraordinary structure and fibrillation mechanism of silk,and leverage this understanding in the manufacturing of high-strength,high-elasticity fibers.This review will delve into the recent progress in comprehending the structure of silks derived from silkworms and spiders,emphasizing the distinctive attributes of solidstate NMR.展开更多
To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study pre...To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study presents a systematic exploration of selenide-based materials as potential SSE candidates.Initially,Li_(8)SeN_(2)and Li_(7)PSe_(6)were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal.Subsequently,their favorable electronic insulation and mechanical properties were verified.Furthermore,extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li-ion migration in Li_(8)SeN_(2),Li_(7)PSe_(6),and derived Li_(6)PSe_(5)X(X=Cl,Br,I).Notably,the highly favorable Li-ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li_(7)PSe_(6),which exhibited remarkably low activation energies of 0.21 and 0.23 eV,and conductivity values of 3.85×10^(-2)and 2.47×10^(-2)S cm^(-1)at 300 K,respectively.In contrast,Li-ion migration in Li_(8)SeN_(2)was found to occur via a substitution mechanism with a significant diffusion energy barrier,resulting in a high activation energy and low Li-ion conductivity of 0.54 eV and 3.6×10^(-6)S cm^(-1),respectively.Throughout this study,it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li-ion conduction mechanisms.Utilizing both methods proved to be efficient,as relying on only one of them would be insufficient.The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.展开更多
The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder...The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder their practical implementation.Polymer has been used extensively to improve the cathode-electrolyte interface in garnet-based all-solid-state LIBs(ASSLBs),while it introduces new concerns about thermal stability.In this study,we propose the incorporation of a multi-functional flame-retardant triphenyl phos-phate additive into poly(ethylene oxide),acting as a thin buffer layer between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and garnet electro-lyte.Through electrochemical stability tests,cycling performance evaluations,interfacial thermal stability analysis and flammability tests,improved thermal stability(capacity retention of 98.5%after 100 cycles at 60℃,and 89.6%after 50 cycles at 80℃)and safety characteristics(safe and stable cycling up to 100℃)are demonstrated.Based on various materials characterizations,the mechanism for the improved thermal stability of the interface is proposed.The results highlight the potential of multi-functional flame-retardant additives to address the challenges associated with the electrode-electrolyte interface in ASSLBs at high temperature.Efficient thermal modification in ASSLBs operating at elevated temperatures is also essential for enabling large-scale energy storage with safety being the primary concern.展开更多
Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more com...Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more complex,high-order structures.The molecular properties of chromatin are dynamically regulated by several factors,such as post-translational modifications and effector proteins,to maintain genome stability.In the past two decades,high-resolution techniques have led to many breakthroughs in understanding the molecular mechanisms that govern chromatin regulation.Nuclear magnetic resonance(NMR)has emerged as one of the major techniques in this field,providing new insights into the nucleosomes and nucleosome-protein complexes in different states ranging from soluble form to condensed states.Solution-state NMR has proven valuable in elucidating the conformational dynamics and molecular interactions for histone N-terminal tails,histone core regions and DNA with the combination of specific isotopic labeling.Solid-state NMR,which is not constrained by the high molecular weights of complexes like nucleosomes,has been applied to capture the structural and dynamical characteristics of both flexible tails and rigid histone core regions in nucleosomes and their complexes with effector proteins.Furthermore,the combination of the two techniques allows tracking molecular properties of nucleosomes during phase separation processes,which potentially play essential roles in chromatin regulation.This review summarizes recent advances in NMR studies of chromatin structure and dynamics.It highlighted that NMR revealed unique molecular characteristics for nucleosomes that are often invisible experimentally by other techniques like cryogenic electron microscopy(cryo-EM)and X-ray diffraction(XRD).I envision that,with future ef-forts such as the development of NMR methods and optimization of sample production protocols,solution-state NMR and solid-state NMR will provide invaluable information to expand our understanding of chromatin activity and its regulatory processes.展开更多
文摘For a long period of time, the determination of phase diagrams was only supported by experiments related to thermal effects or thermodynamic measurements: thermal analysis, calorimetric measurements, vapor pressures, and EMF measurements. As a matter of fact, solid-solid transformations were not so accurately determined and could not be taken into account in the system's analysis. First, X-ray diffraction methods were used as a support for the thermal analysis. Second, the implementation of novel tools in structural analysis (for example, the Rietveld method) has permitted to increase the knowledge of phase stability. Finally, modeling the phases using a Calphad method needed increasingly more structural results to determine and better understand the phase diagrams. On the other hand, the Calphad method has been widely developed for metallic systems, for oxide systems, and in the past 10 years, for some semi-conductor systems, for example, gallium arsenide, cadmium telluride, and lead telluride systems. In such applications, it is very important to bring point defects in the modeling of the phases to map the defects as a function of the chemical composition. Owing to its complexity, this characteristic, the knowledge of which is crucial for the understanding and the control of potential physical applications, was ignored in the previous assessment of semi-conductor systems.
基金financially supported by the National Natural Science Foundation of China (Grant No.52171221)the National Key Research and Development Program of China (Grant No.2019YFA0704900)。
文摘Ga-doped Li_(7)La_(3)Zr_(2)O_(12)(Ga-LLZO)has long been considered as a promising garnet-type electrolyte candidate for all-solid-state lithium metal batteries(ASSLBs)due to its high room temperature ionic conductivity.However,the typical synthesis of Ga-LLZO is usually accompanied by the formation of undesired LiGaO_(2) impurity phase that causes severe instability of the electrolyte in contact with molten Li metal during half/full cell assembly.In this study,we show that by simply engineering the defect chemistry of Ga-LLZO,namely,the lithium deficiency level,LiGaO_(2) impurity phase is effectively inhibited in the final synthetic product.Consequently,defect chemistry engineered Ga-LLZO exhibits excellent electrochemical stability against lithium metal,while its high room temperature ionic conductivity(~1.9×10^(-3)S·cm^(-1))is well reserved.The assembled Li/Ga-LLZO/Li symmetric cell has a superior critical current density of 0.9 mA·cm^(-2),and cycles stably for 500 hours at a current density of 0.3 mA·cm^(-2).This research facilitates the potential commercial applications of high performance Ga-LLZO solid electrolytes in ASSLBs.
文摘The power conversion efficiency of organometallic perovskite-based solar cells has skyrocketed in recent years. Intensive efforts have been made to prepare high-quality perovskite films tailored to various device configurations. Planar heterojunction devices have achieved record efficiencies; however, the preparation of perovskite films for planar junction devices requires the use of expensive vacuum facilities and/or the fine control of experimental conditions. Here, we demonstrate a facile preparation of perovskite films using solid-state chemistry. Solid-state precursor thin films of CHBNH3I and PbI2 are brought into contact with each other and allowed to react via thermally accelerated diffusion. The resulting perovskite film displays good optical absorption and a smooth morphology. Solar cells based on these films show an average efficiency of 8.7% and a maximum efficiency of 10%. The solid-state synthesis of organometallic perovskite can also be carried out on flexible plastic substrates. Using this method on a PET/ITO substrate produces devices with an efficiency of 3.2%. Unlike existing synthetic methods for organometallic perovskite films, the solid-state reaction method does not require the use of orthogonal solvents or careful adjustment of reaction conditions, and thus shows good potential for mass production in the future.
基金the National Natural Science Foundation of China(22178120)the China Postdoctoral Science Foundation(2022TQ0173,2023M731922,2022M720076,BX20220182,2023M731921,2023M731919,2023M741919).
文摘Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.
基金funded by the Ministry of Science and ICT through the National Research Foundation of Korea(202300262366)the Basic Research Lab(RS-2023-00219710)the Ministry of Commerce,Industry,and Energy(20025720)of Korea.
文摘Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility.In particular,all-solid-state lithium-sulfur batteries(ASSLSBs)that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system,surpassing conventional lithium-ion batteries.This can be attributed predominantly to their exceptional energy density,extended operational lifespan,and heightened safety attributes.Despite these advantages,the adoption of ASSLSBs in the commercial sector has been sluggish.To expedite research and development in this particular area,this article provides a thorough review of the current state of ASSLSBs.We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs,explore the fundamental scientific principles involved,and provide a comprehensive evaluation of the main challenges faced by ASSLSBs.We suggest that future research in this field should prioritize plummeting the presence of inactive substances,adopting electrodes with optimum performance,minimizing interfacial resistance,and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.
基金supported by National Key Research and Development Program of China(No.2021YFF0500600)Key R&D Projects in Henan Province(221111240100)China Postdoctoral Science Foundation(2022TQ0291 and 2022M712869)
文摘All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.
基金support from the National Natural Science Foundation of China (No.51806072)。
文摘Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
基金supported by the Ensemble Grant for Early Career Researchers 2022 and the 2023 Ensemble Continuation Grant of Tohoku University,the Hirose Foundation,the Iwatani Naoji Foundation,and the AIMR Fusion Research Grantsupported by JSPS KAKENHI Nos.JP23K13599,JP23K13703,JP22H01803,and JP18H05513+2 种基金the Center for Computational Materials Science,Institute for Materials Research,Tohoku University for the use of MASAMUNEIMR(Nos.202212-SCKXX0204 and 202208-SCKXX-0212)the Institute for Solid State Physics(ISSP)at the University of Tokyo for the use of their supercomputersthe China Scholarship Council(CSC)fund to pursue studies in Japan.
文摘All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.
基金Special Fund for Carbon Peak and Carbon Neutralization Scientific and Technological Innovation Project of Jiangsu Province,Grant/Award Number:BE2022042National Natural Science Foundation of China,Grant/Award Numbers:22201275,51873086,51673096,51873086,51673096+2 种基金the Project on the Enterprises-Universities-Research Cooperation of Kucap Smart Technology(Nanjing)Co.,Ltd.,Grant/Award Number:202240607Postgraduate Research&Practice Innovation Program of Jiangsu Province,Grant/Award Number:KYCX23-1407Anhui Provincial Natural Science Foundation,Grant/Award Number:2208085QB32。
文摘Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues under extreme conditions are the main challenges for the practical application.With the expansion of human activities,such as space missions,polar exploration,and so on,the investigation of SSC with wide temperature tolerance,high energy density,power density,and sustainability is highly desired.In this review,the effects of temperature on SSC are systematically illustrated and clarified,including the properties of the electrolyte,ion diffusion,and reaction dynamics of the supercapacitor.Subsequently,we summarize the recent advances in wide-temperature-range SSCs from the aspect of electrolyte modification,electrode design,and interface adjustment between electrode and electrolyte,especially with critical concerns on ionic conductivity and cycling stability.In the end,a perspective is presented,expecting to promote the practical application of the SSC in harsh conditions.
基金supported by the CAS Project of Young Scientists in Basic Research(YSBR-058)the National Natural Science Foundation of China(22279135)+2 种基金the Outstanding Youth Foundation of Liaoning Province(2023JH3/10200019)the Dalian Science and Technology Innovation Fund(2023JJ11CG004)the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(YIICE E411010316)。
文摘Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay in AF-SSLBs,either determined by dead Li or solid electrolyte interface(SEI),limits the proposal of effective strategies to prolong cycling life.To clarify the underlying mechanism,herein,the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance(ss-NMR)technology in a typical LiPF6-based polymer electrolyte.The results show that the initial capacity loss is attributed to the formation of SEI,while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm^(−2)cycle−1.To reduce the active Li loss,the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior,which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds,respectively.As a result,the initial Coulombic efficiency(ICE)and stable CE increase by 15.1%and 15.3%in Li-Cu cells,which guides the rational design of high-performance AF-SSLBs.
基金the funding support from the National Natural Science Foundation of China(22222902,22209062)the Natural Science Foundation of Jiangsu Province(BK20200047)+2 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB150004)the Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China(JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program(202310320066Z)。
文摘The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.
基金National Natural Science Foundation of China (Grant Nos. 22379077 and 22005163)。
文摘The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.
基金the support from the National Natural Science Foundation of China(Grant No.22179006)supported by the Beijing Natural Science Foundation(2244101)+1 种基金the National Natural Science Foundation of China(Grant No.52072036)the SINOPEC project(223128)。
文摘Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.
基金supported by the Beijing Natural Science Foundation(L223009)the National Natural Science Foundation of China(22075029)+1 种基金the National Key Research and Development Program of China(2021YFB2500300)the Key Research and Development(R&D)Projects of Shanxi Province(2021020660301013)。
文摘All-solid-state lithium metal batteries(ASSLMBs)are considered as one of the ultimate goals for the development of energy storage systems due to their high energy density and high safety.However,the mismatching of interface transport kinetics as well as interfacial instability induces the growth of lithium dendrite and thus,leads to severe degradation of battery electrochemical performances.Herein,an integrated interface configuration(IIC)consisting of in-situ generated Li I interphase and Li-Ag alloy anode is proposed through in-situ interface chemistry.The IIC is capable of not only regulating charge transport kinetics but also synchronously stabilizing the lithium/electrolyte interface,thereby achieving uniform lithium platting.Therefore,Li||Li symmetric cells with IIC achieve a critical current density of up to 1.6 mA cm^(-2)and achieve stable cycling over 1600 hours at a high current density of 0.5 mA cm^(-2).Moreover,a high discharge capacity of 140.1 mA h g-1at 0.1 C is also obtained for the Li(Ni_(0.6)Co_(0.2)Mn_(0.2))O_(2)(NCM622)full battery with a capacity retention of 65.6%after 300 cycles.This work provides an effective method to synergistically regulate the interface transport kinetics and inhibit lithium dendrite growth for high-performance ASSLMBs.
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.
基金support by a JSPS KAKENHI,Grant-in-Aid for Scientific Research(C),Grant Number JP19K05609.
文摘Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric pressure.The dragline silk fiber,which is essentially a spider's lifeline,surpasses the strength of a steel wire of equivalent thickness.Regrettably,humans have yet to replicate this process to produce fibers with similar high strength and elasticity in an eco-friendly manner.Therefore,it is of utmost importance to thoroughly comprehend the extraordinary structure and fibrillation mechanism of silk,and leverage this understanding in the manufacturing of high-strength,high-elasticity fibers.This review will delve into the recent progress in comprehending the structure of silks derived from silkworms and spiders,emphasizing the distinctive attributes of solidstate NMR.
基金financially supported by the National Natural Science Foundation of China(Grant No.22273096)the Fundamental Research Funds for Central Universities(20826041G4185)
文摘To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study presents a systematic exploration of selenide-based materials as potential SSE candidates.Initially,Li_(8)SeN_(2)and Li_(7)PSe_(6)were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal.Subsequently,their favorable electronic insulation and mechanical properties were verified.Furthermore,extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li-ion migration in Li_(8)SeN_(2),Li_(7)PSe_(6),and derived Li_(6)PSe_(5)X(X=Cl,Br,I).Notably,the highly favorable Li-ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li_(7)PSe_(6),which exhibited remarkably low activation energies of 0.21 and 0.23 eV,and conductivity values of 3.85×10^(-2)and 2.47×10^(-2)S cm^(-1)at 300 K,respectively.In contrast,Li-ion migration in Li_(8)SeN_(2)was found to occur via a substitution mechanism with a significant diffusion energy barrier,resulting in a high activation energy and low Li-ion conductivity of 0.54 eV and 3.6×10^(-6)S cm^(-1),respectively.Throughout this study,it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li-ion conduction mechanisms.Utilizing both methods proved to be efficient,as relying on only one of them would be insufficient.The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.
基金This work was supported by the Australian Research Council via Discovery Projects(Nos.DP200103315,DP200103332 and DP230100685)Linkage Projects(No.LP220200920).The authors acknowledge the Microscopy and Microanalysis Facility—John de Laeter Centre,Curtin University for the scientific and technical assistance of material characterizations.L.Zhao and C.Cao would like to acknowledge the PhD scholarship supported by BLACKSTONE Minerals Ltd.
文摘The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder their practical implementation.Polymer has been used extensively to improve the cathode-electrolyte interface in garnet-based all-solid-state LIBs(ASSLBs),while it introduces new concerns about thermal stability.In this study,we propose the incorporation of a multi-functional flame-retardant triphenyl phos-phate additive into poly(ethylene oxide),acting as a thin buffer layer between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and garnet electro-lyte.Through electrochemical stability tests,cycling performance evaluations,interfacial thermal stability analysis and flammability tests,improved thermal stability(capacity retention of 98.5%after 100 cycles at 60℃,and 89.6%after 50 cycles at 80℃)and safety characteristics(safe and stable cycling up to 100℃)are demonstrated.Based on various materials characterizations,the mechanism for the improved thermal stability of the interface is proposed.The results highlight the potential of multi-functional flame-retardant additives to address the challenges associated with the electrode-electrolyte interface in ASSLBs at high temperature.Efficient thermal modification in ASSLBs operating at elevated temperatures is also essential for enabling large-scale energy storage with safety being the primary concern.
基金supported by funds from the National Natural Science Foundation of China(grant number:32201006)Guangdong Province(grant number:2021QN02Y103,2022ZDZX2061,2022KCXTD034)2023 Stable Support Plan Program of Shenzhen Colleges and Universities Fund.
文摘Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more complex,high-order structures.The molecular properties of chromatin are dynamically regulated by several factors,such as post-translational modifications and effector proteins,to maintain genome stability.In the past two decades,high-resolution techniques have led to many breakthroughs in understanding the molecular mechanisms that govern chromatin regulation.Nuclear magnetic resonance(NMR)has emerged as one of the major techniques in this field,providing new insights into the nucleosomes and nucleosome-protein complexes in different states ranging from soluble form to condensed states.Solution-state NMR has proven valuable in elucidating the conformational dynamics and molecular interactions for histone N-terminal tails,histone core regions and DNA with the combination of specific isotopic labeling.Solid-state NMR,which is not constrained by the high molecular weights of complexes like nucleosomes,has been applied to capture the structural and dynamical characteristics of both flexible tails and rigid histone core regions in nucleosomes and their complexes with effector proteins.Furthermore,the combination of the two techniques allows tracking molecular properties of nucleosomes during phase separation processes,which potentially play essential roles in chromatin regulation.This review summarizes recent advances in NMR studies of chromatin structure and dynamics.It highlighted that NMR revealed unique molecular characteristics for nucleosomes that are often invisible experimentally by other techniques like cryogenic electron microscopy(cryo-EM)and X-ray diffraction(XRD).I envision that,with future ef-forts such as the development of NMR methods and optimization of sample production protocols,solution-state NMR and solid-state NMR will provide invaluable information to expand our understanding of chromatin activity and its regulatory processes.