Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth a...Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.展开更多
Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+...Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.展开更多
Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic device...Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic devices,a growing focus on safety and durability becomes increasingly apparent.An effective strategy to address these increased requirements involves employing the quasi-solid gel electrolytes(QSGEs).This review focuses on the application of QSGEs in AMBs,emphasizing four types of gel electrolytes and their influence on battery performance and stability.First,self-healing gels are discussed to prolong battery life and enhance safety through self-repair mechanisms.Then,flexible gels are explored for their mechanical flexibility,making them suitable for wearable devices and flexible electronics.In addition,biomimetic gels inspired by natural designs are introduced for high-performance AMBs.Furthermore,biomass materials gels are presented,derived from natural biomaterials,offering environmental friendliness and biocompatibility.Finally,the perspectives and challenges for future developments are discussed in terms of enhancing the ionic conductivity,mechanical strength,and environmental stability of novel gel materials.The review underscores the significant contributions of these QSGEs in enhancing AMBs performance,including increased lifespan,safety,and adaptability,providing new insights and directions for future research and applications in the field.展开更多
Lithium metal batteries face serious safety challenges caused by flammable organic electrolytes and the growth of lithium dendrite.Trimethyl phosphate(TMP)is a promising alternative for flammable carbonate electrolyte...Lithium metal batteries face serious safety challenges caused by flammable organic electrolytes and the growth of lithium dendrite.Trimethyl phosphate(TMP)is a promising alternative for flammable carbonate electrolyte solvents owing to its nonflammable nature.But the low-concentration TMP-based electrolyte is unstable with the lithium metal anode.Here,a TMP-contained quasisolid electrolyte(PIQSE)with porous polyimide(PI)as supporting skeleton is designed.The cross-linking structure generated by UV curing in PIQSE can lock the reactive TMP solvent to reduce its contact with Li metal.Besides,the PI supporting skeleton with high-temperature resistance can significantly enhance the thermal stability of PIQSE.The combination of PI and TMP prompts the high ionic conductivity and excellent nonflammability of PIQSE.The LiFePO_(4)/Li cell using PIQSE shows superior electrochemical performance in a wide temperature range from-10 to 60°C.Furthermore,the cells with highvoltage cathode of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)were matched with PIQSE exhibit good cyclic and rate performance.The NCM622/PIQSE/Li pouch cell was also fabricated.It exhibits a high discharge capacity of 182.9mAh.g^(-1),and can stably light up LEDs after folding and shearing tests,demonstrating broad prospects for highly safe energy storage applications.展开更多
Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a s...Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.展开更多
Solid-state lithium(Li) metal batteries overwhelm the lithium-ion batteries by harvesting high energy from Li metal anode with ultrahigh capacities and gaining excellent safety from solid electrolytes.However,the unco...Solid-state lithium(Li) metal batteries overwhelm the lithium-ion batteries by harvesting high energy from Li metal anode with ultrahigh capacities and gaining excellent safety from solid electrolytes.However,the uncontrollable solvents in solid electrolytes usually aggravate poor interfacial contact with lithium metal anode and deteriorate Li^(+) pathways.Here a copolymeric network-structured ion conductor by rationally integrating cellulose nanofibril as a two-in-one functional material is employed to anchor the solvent.Taking advantages of tightly anchoring of cellulose nanofibril to solvent,the asconstructed quasi-solid polymer-based electrolyte offers rapid Li^(+) transport channels and realizes effective Li-dendrite suppression,which enables high ionic conductivity of 1.93 × 10^(-3)S cm^(-1) at room temperature,long-term Li plating/stripping over 1900 h,and high capacity retention of 99%.This work provides a fresh strategy for creating solid electrolytes that meet both high ionic conductivity and interfacial stability requirements for practical solid-state lithium metal battery.展开更多
Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has no...Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has not been studied extensively and the underlying mechanism and theoretical basis of this type of batteries are not well understood.Herein,a highly active cobalt-doped Ni_(3)S_(2) porous nanocone framework(C12NS)is designed and demonstrated as a zinc-ion battery electrode.First-principles calculation and experiments reveal that the cobalt dopant improves the battery properties greatly.The assembled flexible zinc-ion battery exhibits a high specific capacity of 453.3 mAh g^(−1)at a current density of 0.4 A g^(−1)in as well as excellent cycling stability as manifested by a capacity retention ratio of 89.5%at a current density of 4 A g^(−1)after 5000 cycles.The peak energy density of 553.9 Wh kg^(−1)is also superior to those of most recently reported NiCo-based zinc-ion batteries.More importantly,the flexible battery can be operated under severe mechanical bending and even continues to work after physical puncturing without showing leakage.These exciting results not only reveal a novel design of cathode materials for zinc-based batteries,but also suggest their immense commercial potential in portable and wearable electronics.展开更多
Quasi-solid electrolytes promote the development of safe and flexible energy storage devices.In this work,a chitosan and citric acid crosslinked membrane is prepared by a freeze-thaw cross-linking method,in which the ...Quasi-solid electrolytes promote the development of safe and flexible energy storage devices.In this work,a chitosan and citric acid crosslinked membrane is prepared by a freeze-thaw cross-linking method,in which the chemical crosslinking of chitosan and citric acid increase the viscoelastic behavior of the polymer membrane,and the freeze-thaw assist freeze drying process to create abundant interconnected open-pores and three-dimensional(3D)network.Due to the good viscoelasticity,excellent electrolyte loading capacity(596%)and high ion conductivity(7.7×10^(-3)S·cm^(-)1),as quasi-solid electrolyte,our proposed chitosan and citric acid crosslinked membrane helps ZnICCFT-ZnSO4lAC hybrid supercapacitor to delivers wide operating voltage,high specific capacity of 100.5 F·g^(-1)and stable cycle life(93%after1000 cycles),which suggests that our proposed freezethaw assisted freeze drying method has great potential in designing quasi-solid state electrolyte for energy storage device.展开更多
To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the perform...To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the performance of the battery,a sulfonated covalent organic framework(SCOF),TpPa-SO3H,was synthesized and the quasi-solid polymer electrolyte SCOF-PVDF/Zn(CF3SO3)2 was successfully prepared with a polymer matrix of PVDF and an ion-transporting backbone of SCOF.Both of Zn//Zn symmetric batteries and Zn//NH4V4O10 full batteries assembled using SCOF-PVDF/Zn(CF3SO3)2 electrolyte exhibited excellent battery cycling stability.The high ionic conductivity of 3×10^(-4)S·cm^(-1)could be achieved.The assembled symmetric batteries demonstrated a cycle life of 980 h at a current density of 2 mA·cm^(-2).The Zn//NH4V4O10 full battery can provide a specific capacity of 196 mAh·g^(-1)at a high current density of 10 A·g^(-1).展开更多
Dye-sensitized solar cells （DSSCs） are the most promising, low cost and most extensively investigated solar cells. They are famous for their clean and efficient solar energy conversion. Nevertheless this, long-time ...Dye-sensitized solar cells （DSSCs） are the most promising, low cost and most extensively investigated solar cells. They are famous for their clean and efficient solar energy conversion. Nevertheless this, long-time sta- bility is still to be acquired. In recent years research on solid and quasi-solid state electrolytes is extensively in- creased. Various quasi-solid electrolytes, including composites polymer electrolytes, ionic liquid electrolytes, thermoplastic polymer electrolytes and thermosetting polymer electrolytes have been used. Performance and stability of a quasi-solid state electrolyte are between liquid and solid electrolytes. High photovoltaic performances of QS-DSSCs along better long-term stability can be obtained by designing and optimizing quasi-solid electrolytes. It is a prospective candidate for highly efficient and stable DSSCs.展开更多
Scale-up synthesis of sub-micron ZSM-5 molecular sieve in a quasi-solid system was investigated. Compared with traditional hydrothermal synthesis, the synthesis in a quasi-solid system has the advantages of high yield...Scale-up synthesis of sub-micron ZSM-5 molecular sieve in a quasi-solid system was investigated. Compared with traditional hydrothermal synthesis, the synthesis in a quasi-solid system has the advantages of high yield, short crystallization time, low energy consumption as well as low emissions. However, the high solid content in the quasi-solid system can cause the mass and heat transfer problems and make scalable production difficult. In order to solve the problem, we have developed a method for the optimization of the mass and heat transfer. By this method one can vary the flow field in the reactor by changing the stirrer speed. Scale-up synthesis of the sub-micron ZSM-5 molecular sieve in a quasi-solid system was carried out in a 5 L reactor with double propeller-type agitators. The process was investigated with product characterization using X-ray diffraction （XRD） and scanning electron microscopy （SEM） and the flow field information was collected using laser Doppler velocimetry （LDV）. The results showed that the flow field patterns can be tuned by using different stirrer speeds, the morphology and size of assynthesized of ZSM-5 can be effectively controlled.展开更多
Rechargeable room-temperature(RT)sodium–sulfur(Na–S)batteries hold great potential for large-scale energy storage owing to their high energy density and low cost.However,their practical application is hindered by ch...Rechargeable room-temperature(RT)sodium–sulfur(Na–S)batteries hold great potential for large-scale energy storage owing to their high energy density and low cost.However,their practical application is hindered by challenges such as polysulfide shuttling and Na dendrite formation.In this study,a dual salt-based quasi-solid polymer electrolyte(DS–QSPE)was developed via in situ polymerization,achieving high ionic conductivity(4.8×10^(-4) S·cm^(-1) at 25°C),a high sodium-ion transference number(0.73),and effective polysulfide confinement.Theoretical calculations and experimental results indicate that the enhanced Na-ion transport is attributed to the strengthened coordination of anions with the polydioxolane chain and the increased dissociation of sodium salts.Importantly,the DS–QSPE forms an interconnected network structure in the sulfurized polyacrylonitrile(SPAN)cathode.This provides abundant and seamless electrochemical reaction interfaces that facilitate efficient and uniform ion transport pathways.As a result,the Na||SPAN battery with DS–QSPE delivers a high capacity of approximately 327.4 mAh·g^(-1)(based on the mass of SPAN)after 200 cycles at 0.2 A·g^(-1),retaining 81.4%of its initial capacity.This performance considerably surpasses that of batteries using liquid electrolytes.This study offers a straightforward approach to addressing the inter-facial challenges in solid-state Na–S batteries.展开更多
In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications...In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications due to the risks associated with organic liquid electrolytes,among which their low flash points are one of the major safety concerns.The adoption of high flash point quasi-solid polymer electrolytes(QSPE) that is compatible with the lithium metal anode and high-voltage cathode is therefore a promising strategy for exploring high-performance and high-safety LMBs.Herein,we employed the in-situ polymerization of poly (epoxidized soya fatty acid Bu esters-isooctyl acrylate-ditrimethylolpropane tetraacrylate)(PEID) to gel the liquid electrolyte that formed a PEID-based QSPE (PEID-QSPE).The flash point of PEID-QSPE rises from 25 to 82℃ after gelation,contributing to enhanced safety of the battery at elevated temperatures,whereas the electrochemical window increases to 4.9 V.Moreover,the three-dimensional polymer framework of PEID-QSPE is validated to facilitate the uniform growth of the solid electrolyte interphase on the anode,thereby improving the cycling stability of the battery.By employing PEID-QSPE,the Li|LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cell achieved long-term cycling stability (Coulombic efficiency,99.8%;>200 cycles at 0.1 C) even with a high cathode loading (~5 mg cm^(-2)) and an ultrathin Li(~50μm).This electrolyte is expected to afford inspiring insights for the development of safe and long-term cyclability LMBs.展开更多
The influencing mechanisms of elements Ti and Ce and their interactions on fracture behaviors of casting alloys AI-4.5Cu-0.6Mn were studied by observing tensile fracture behavior in quasi-solid zone under SEM and EDX ...The influencing mechanisms of elements Ti and Ce and their interactions on fracture behaviors of casting alloys AI-4.5Cu-0.6Mn were studied by observing tensile fracture behavior in quasi-solid zone under SEM and EDX instruments.The results indicate that the resistance stress against hot cracking can be improved obviously by addition of Ti,because of its grain refining function.It is also found that,when Ce is added into the alloys,besides its effect in refining crystalline,the mechanical behavior of lower melting point eutectic phase in quasi-solid zone can be improved efficiently by some compounds with Ce formed and deposited between dendrites.Therefore,a colligating effect of Ti and Ce on improving resistance stress against hot cracking is more efficient than that only single alloy element is applied.When hot cracking occurs,grains yield at first,and then crack spreads.Both inter-grain and trans-grain fractures are observed,but the major fracture manner is brittleness.展开更多
A novel transparent and soft quasi-solid-state electrolyte （QSSE） was proposed and fabricated, which consists of ionic liquid （PYR14TFSI） and nano-fumed silica. The QSSE demonstrates high ionic conductivity of 4.6...A novel transparent and soft quasi-solid-state electrolyte （QSSE） was proposed and fabricated, which consists of ionic liquid （PYR14TFSI） and nano-fumed silica. The QSSE demonstrates high ionic conductivity of 4.6× 10-4 S/cm at room temperature and wide electrochemical stability window of over 5 V. The Li-O2 battery using such quasi-solidstate electrolyte exhibits a low charge-discharge overpotential at the first cycle and excellent long-term cyclability over 500 cycles.展开更多
The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4...The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10^-4S/cm at 20℃. Linear sweep voltammetry（LSV） is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li^＋1. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn2O4 and Li/CQSE/Li Mn2O4 batteries is evaluated and shows good electrochemical characteristics at 60℃.展开更多
Solid-statelithium batteries are promising next-generation energystorage systems due to their high safety and energy density.However,the poor low-temperature performance of solid-state electrolytes remains a critical ...Solid-statelithium batteries are promising next-generation energystorage systems due to their high safety and energy density.However,the poor low-temperature performance of solid-state electrolytes remains a critical challenge.Herein,we present a facile and scalable approach for synthesizing a low-temperature-resilient polymer electro-lyte based on ethylene-vinyl acetate,leveraging its unique molecular structure for enhanced lithium-ion transport.The ethylene-vinyl acetate polymer electrolyte(EPE)demonstrates a high ionic conductivity of 5.13×10^(-4) S cm^(-1) at room tem-perature and retains a remarkable conductivity of 2.72×10^(-5) S cm^(-1) at-40℃.This superior performance is at-tributed to the synergistic interaction between the ester functional groups of ethylene-vinyl acetate and lithium salts,which reduces the ion dissociation energy barrierand facil-itates efficient ion migration.The EPE enables stable lithium plating/stripping cycling for over 3000 h at-40℃ and sup-ports the long-term cycling of LiFePO¡-based full cells at-40℃ for over 900 cycles.This work highlights the potential of cost-effective,scalable EPEs for next-generation solid-state lithium batteries,particularly in extreme environmental con-ditions.展开更多
Tin-air batteries(TABs) exhibit high safety and low cost,and are expected to be used in electric vehicles and portable electronic devices.However,challenges such as the irregular deposition of tin(Sn) particles on Sn ...Tin-air batteries(TABs) exhibit high safety and low cost,and are expected to be used in electric vehicles and portable electronic devices.However,challenges such as the irregular deposition of tin(Sn) particles on Sn anodes,surface passivation,and significant hydrogen evolution have hindered the development of high-performance TABs.To address these challenges,this study introduces quasi-solid TABs(QSTABs) with satisfactory high-temperature resistance.A conductive metal-organic framework(c-MOF),particularly Ni_(3)(HITP)_(2),was synthesized and deposited onto the Sn anode surface.The porous structure of c-MOF increased the specific surface area of the Sn anode,improved electronic conductivity and facilitated the absorption and release of ions during charge and discharge cycling.Theoretical calculations revealed that Ni3(HITP)_(2) provided more electron donor sites to coordinate with Sn^(2+) and inhibited hydrogen release.Additionally,carboxymethyl cellulose(CMC) was incorporated into the organic gel polymer electrolytes(OGPEs)to significantly enhance their water retention,ensuring stable operation of QSTABs between 25 and 50℃.Notably,QSTABs assembled with CMC-OGPE/Sn@Ni_(3)(HITP)_(2) exhibited a fine cycle life of over 200 cycles at 50℃.The electronic c-MOF material effectively inhibited metal shedding and side reactions on the Sn anode.These findings provide valuable guidance for developing QSTABs with high-temperature resistance.展开更多
Con ventio nal liquid electrolytes based sodium metal batteries suffer from severe safety hazards owing to electrolyte leakage,in flammability and dendritic sodium deposit!on.Herein,we report a flame-retardant quasi-s...Con ventio nal liquid electrolytes based sodium metal batteries suffer from severe safety hazards owing to electrolyte leakage,in flammability and dendritic sodium deposit!on.Herein,we report a flame-retardant quasi-solid polymer electrolyte with poly(methyl vinyl ether-alt-maleic an hydride)(P(MVE-alt-MA))as host,bacterial cellulose(BC)as reinforceme nt,and triethyl phosphate/vinyle ne carb on ate/sodium perchlorate(TEP/VC/NaClO4)as plasticizer for highly safe sodium metal batteries.The as-obtained quasi-solid polymer electrolyte exhibits superior flame retardancy(self-extinguish within 1 s),complete non-leakage property and wide electrochemical windows(4.4 V).More importantly,Na3V2(PO4)3/Na metal batteries using such polymer electrolyte delivers superior I on g-term cycli ng stability(84.4%capacity rete ntion after 1000 cycles)which is significantly better than that(only 2%after 240 cycles)of liquid electrolyte.In addition,this flame-retardant quasi-solid polymer electrolyte provides favorable cycle performance(80.2%capacity retention after 70 cycles at 50°C and 84.8%capacity retention after 50 cycles at-10°C)for Na3V2(PO4)3/Na metal batteries.And this battery also displayed a normal charge/discharge property even at-15°C.These fascinating cycle properties are mainly ascribed to the effective pro怕ctive layers formed on Na3V2(PC>4)3 cathode and sodium metal ano de.More thorough in vestigati on elucidates that such flame-retardant quasi-solid polymer electrolyte plays a multif unctional role in the adva need sodium metal batteries:(1)being in volved in the formatio n of a favorable cathode electrolyte in terface(CEI)to inhibit the dissolutio n of van adium and maintai n the structure integrity of the Na3V2(PO4)3;(2)participati ng in building a stable solid electrolyte in terface(SEI)to suppress the growth of Na dendrites;(3)integrating flame-retardanee into polymer sodium batteries to enhance flame-resistanee,eliminate electrolyte leakage,and thus improve safety of sodium batteries.Based on these results,we further assembled Na3V2(PO4)3/MoS2 pouch cell which can withsta nd harsh conditions(be nded or cut off a corn er),confirming the obtai ned polymer electrolyte with superior non-leakage property.In all,these outstanding characteristics would endow this flame-retardant quasi-solid polymer electrolyte a very promising can didate for highly-safe sodium metal batteries.展开更多
基金a seed grant from IIT Delhi(SGNF148)supported by the JST-ERATO Yamauchi Materials SpaceTectonics Project(JPMJER2003)+2 种基金the ARC Australian Laureate Fellowship(FL230100095)the UQ-Yonsei International Joint Research Projectthe support from JSPS Postdoctoral Fellowships for Research in Japan。
文摘Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.
基金supported by the National Natural Science Foundation of China(22078228)。
文摘Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.
基金support from the Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University)(KYCX23_3508)the Yangzhou University International Academic Exchange Fund.Prof.Guoxiu Wang acknowledges the Australian Research Council(ARC)Linkage project(LP200200926).
文摘Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic devices,a growing focus on safety and durability becomes increasingly apparent.An effective strategy to address these increased requirements involves employing the quasi-solid gel electrolytes(QSGEs).This review focuses on the application of QSGEs in AMBs,emphasizing four types of gel electrolytes and their influence on battery performance and stability.First,self-healing gels are discussed to prolong battery life and enhance safety through self-repair mechanisms.Then,flexible gels are explored for their mechanical flexibility,making them suitable for wearable devices and flexible electronics.In addition,biomimetic gels inspired by natural designs are introduced for high-performance AMBs.Furthermore,biomass materials gels are presented,derived from natural biomaterials,offering environmental friendliness and biocompatibility.Finally,the perspectives and challenges for future developments are discussed in terms of enhancing the ionic conductivity,mechanical strength,and environmental stability of novel gel materials.The review underscores the significant contributions of these QSGEs in enhancing AMBs performance,including increased lifespan,safety,and adaptability,providing new insights and directions for future research and applications in the field.
基金financially supported by the Natural Science Basic Research Program of Shaanxi Province(No.2024JC-YBQN-0582)the Natural Science Foundation of Shaanxi Provincial Department of Education(No.23JK0702)+1 种基金Scientific Research fund of Xijing University(No.XJ23B05)the Fundamental Research Funds for the Central Universities(No.xzy012024005)。
文摘Lithium metal batteries face serious safety challenges caused by flammable organic electrolytes and the growth of lithium dendrite.Trimethyl phosphate(TMP)is a promising alternative for flammable carbonate electrolyte solvents owing to its nonflammable nature.But the low-concentration TMP-based electrolyte is unstable with the lithium metal anode.Here,a TMP-contained quasisolid electrolyte(PIQSE)with porous polyimide(PI)as supporting skeleton is designed.The cross-linking structure generated by UV curing in PIQSE can lock the reactive TMP solvent to reduce its contact with Li metal.Besides,the PI supporting skeleton with high-temperature resistance can significantly enhance the thermal stability of PIQSE.The combination of PI and TMP prompts the high ionic conductivity and excellent nonflammability of PIQSE.The LiFePO_(4)/Li cell using PIQSE shows superior electrochemical performance in a wide temperature range from-10 to 60°C.Furthermore,the cells with highvoltage cathode of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)were matched with PIQSE exhibit good cyclic and rate performance.The NCM622/PIQSE/Li pouch cell was also fabricated.It exhibits a high discharge capacity of 182.9mAh.g^(-1),and can stably light up LEDs after folding and shearing tests,demonstrating broad prospects for highly safe energy storage applications.
基金supported by the Natural Science Foundation of China(22379073,52373275)the Natural Science Foundation of Tianjin,China(18JCZDJC31400)the Ministry of Education Innovation Team(IRT13022).
文摘Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.
基金financial support from the projects of the National Natural Science Foundation of China (52373074 and 51972121)the Independent Research Project of Maoming Laboratory (2022ZD002)。
文摘Solid-state lithium(Li) metal batteries overwhelm the lithium-ion batteries by harvesting high energy from Li metal anode with ultrahigh capacities and gaining excellent safety from solid electrolytes.However,the uncontrollable solvents in solid electrolytes usually aggravate poor interfacial contact with lithium metal anode and deteriorate Li^(+) pathways.Here a copolymeric network-structured ion conductor by rationally integrating cellulose nanofibril as a two-in-one functional material is employed to anchor the solvent.Taking advantages of tightly anchoring of cellulose nanofibril to solvent,the asconstructed quasi-solid polymer-based electrolyte offers rapid Li^(+) transport channels and realizes effective Li-dendrite suppression,which enables high ionic conductivity of 1.93 × 10^(-3)S cm^(-1) at room temperature,long-term Li plating/stripping over 1900 h,and high capacity retention of 99%.This work provides a fresh strategy for creating solid electrolytes that meet both high ionic conductivity and interfacial stability requirements for practical solid-state lithium metal battery.
基金jointly supported by the National Natural Science Foundation of China(Grant Nos.61176108 and 61774060)the Science and Technology Commission of Shanghai Municipality(Grant No.18DZ2270800)+1 种基金the City University of Hong Kong Strategic Research Grant(SRG)(Grant No.7005505)the support of the Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry(Grant No.[2015]-1098)。
文摘Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has not been studied extensively and the underlying mechanism and theoretical basis of this type of batteries are not well understood.Herein,a highly active cobalt-doped Ni_(3)S_(2) porous nanocone framework(C12NS)is designed and demonstrated as a zinc-ion battery electrode.First-principles calculation and experiments reveal that the cobalt dopant improves the battery properties greatly.The assembled flexible zinc-ion battery exhibits a high specific capacity of 453.3 mAh g^(−1)at a current density of 0.4 A g^(−1)in as well as excellent cycling stability as manifested by a capacity retention ratio of 89.5%at a current density of 4 A g^(−1)after 5000 cycles.The peak energy density of 553.9 Wh kg^(−1)is also superior to those of most recently reported NiCo-based zinc-ion batteries.More importantly,the flexible battery can be operated under severe mechanical bending and even continues to work after physical puncturing without showing leakage.These exciting results not only reveal a novel design of cathode materials for zinc-based batteries,but also suggest their immense commercial potential in portable and wearable electronics.
基金financially supported by the National Natural Science Foundation of China(Nos.21972111,21773188)the Venture&Innovation Support Program for Chongqing Overseas Returnees(No.cx2019073)+1 种基金Chongqing Engineering Research Center for Micro-Nano Biomedical Materials and DevicesChongqing Key Laboratory for Advanced Materials and Technologies。
文摘Quasi-solid electrolytes promote the development of safe and flexible energy storage devices.In this work,a chitosan and citric acid crosslinked membrane is prepared by a freeze-thaw cross-linking method,in which the chemical crosslinking of chitosan and citric acid increase the viscoelastic behavior of the polymer membrane,and the freeze-thaw assist freeze drying process to create abundant interconnected open-pores and three-dimensional(3D)network.Due to the good viscoelasticity,excellent electrolyte loading capacity(596%)and high ion conductivity(7.7×10^(-3)S·cm^(-)1),as quasi-solid electrolyte,our proposed chitosan and citric acid crosslinked membrane helps ZnICCFT-ZnSO4lAC hybrid supercapacitor to delivers wide operating voltage,high specific capacity of 100.5 F·g^(-1)and stable cycle life(93%after1000 cycles),which suggests that our proposed freezethaw assisted freeze drying method has great potential in designing quasi-solid state electrolyte for energy storage device.
基金supported by the National Natural Science Foundation of China(22071021).
文摘To address the issues in aqueous zinc-ion batteries(ZIBs),including the formation of zinc dendrites and the occurrence of harmful side reactions(e.g.,the hydrogen evolution reaction),which seriously affect the performance of the battery,a sulfonated covalent organic framework(SCOF),TpPa-SO3H,was synthesized and the quasi-solid polymer electrolyte SCOF-PVDF/Zn(CF3SO3)2 was successfully prepared with a polymer matrix of PVDF and an ion-transporting backbone of SCOF.Both of Zn//Zn symmetric batteries and Zn//NH4V4O10 full batteries assembled using SCOF-PVDF/Zn(CF3SO3)2 electrolyte exhibited excellent battery cycling stability.The high ionic conductivity of 3×10^(-4)S·cm^(-1)could be achieved.The assembled symmetric batteries demonstrated a cycle life of 980 h at a current density of 2 mA·cm^(-2).The Zn//NH4V4O10 full battery can provide a specific capacity of 196 mAh·g^(-1)at a high current density of 10 A·g^(-1).
文摘Dye-sensitized solar cells （DSSCs） are the most promising, low cost and most extensively investigated solar cells. They are famous for their clean and efficient solar energy conversion. Nevertheless this, long-time sta- bility is still to be acquired. In recent years research on solid and quasi-solid state electrolytes is extensively in- creased. Various quasi-solid electrolytes, including composites polymer electrolytes, ionic liquid electrolytes, thermoplastic polymer electrolytes and thermosetting polymer electrolytes have been used. Performance and stability of a quasi-solid state electrolyte are between liquid and solid electrolytes. High photovoltaic performances of QS-DSSCs along better long-term stability can be obtained by designing and optimizing quasi-solid electrolytes. It is a prospective candidate for highly efficient and stable DSSCs.
文摘Scale-up synthesis of sub-micron ZSM-5 molecular sieve in a quasi-solid system was investigated. Compared with traditional hydrothermal synthesis, the synthesis in a quasi-solid system has the advantages of high yield, short crystallization time, low energy consumption as well as low emissions. However, the high solid content in the quasi-solid system can cause the mass and heat transfer problems and make scalable production difficult. In order to solve the problem, we have developed a method for the optimization of the mass and heat transfer. By this method one can vary the flow field in the reactor by changing the stirrer speed. Scale-up synthesis of the sub-micron ZSM-5 molecular sieve in a quasi-solid system was carried out in a 5 L reactor with double propeller-type agitators. The process was investigated with product characterization using X-ray diffraction （XRD） and scanning electron microscopy （SEM） and the flow field information was collected using laser Doppler velocimetry （LDV）. The results showed that the flow field patterns can be tuned by using different stirrer speeds, the morphology and size of assynthesized of ZSM-5 can be effectively controlled.
基金the National Natural Science Foundation of China(Grant Nos.22209027,22179022,and 22109023)the FuXiaQuan National Independent Innovation Demonstration Zone Collaborative Innovation Platform(Grant No.2022-P-027)+1 种基金the Hundred Talents Plan of Fujian Province,the Top Young Talents of Young Eagle Program of Fujian Province,the Youth Innovation Fund of Fujian Province(Grant Nos.2022J05046 and 2021J05043)the Award Program for Fujian Minjiang Scholar Professorship,and the Talent Fund Program of Fujian Normal University.
文摘Rechargeable room-temperature(RT)sodium–sulfur(Na–S)batteries hold great potential for large-scale energy storage owing to their high energy density and low cost.However,their practical application is hindered by challenges such as polysulfide shuttling and Na dendrite formation.In this study,a dual salt-based quasi-solid polymer electrolyte(DS–QSPE)was developed via in situ polymerization,achieving high ionic conductivity(4.8×10^(-4) S·cm^(-1) at 25°C),a high sodium-ion transference number(0.73),and effective polysulfide confinement.Theoretical calculations and experimental results indicate that the enhanced Na-ion transport is attributed to the strengthened coordination of anions with the polydioxolane chain and the increased dissociation of sodium salts.Importantly,the DS–QSPE forms an interconnected network structure in the sulfurized polyacrylonitrile(SPAN)cathode.This provides abundant and seamless electrochemical reaction interfaces that facilitate efficient and uniform ion transport pathways.As a result,the Na||SPAN battery with DS–QSPE delivers a high capacity of approximately 327.4 mAh·g^(-1)(based on the mass of SPAN)after 200 cycles at 0.2 A·g^(-1),retaining 81.4%of its initial capacity.This performance considerably surpasses that of batteries using liquid electrolytes.This study offers a straightforward approach to addressing the inter-facial challenges in solid-state Na–S batteries.
基金the S&T Program of Hebei (Grant Nos. 22344402D,22373709D)the National Natural Science Foundation of China(Grant Nos. 22108151, 22108202, 22109084, 22209010,22379014, and 22309101)+3 种基金the Beijing Natural Science Foundation(Grant Nos. Z200011, L233004)the Young Elite Scientists Sponsorship Program by CAST (Grant No. 2021QNRC001)the Seed Fund of Shanxi Research Institute for Clean Energythe support from the Department of Science and Technology of Jilin Province (Grant No. 20210301021GX)。
文摘In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications due to the risks associated with organic liquid electrolytes,among which their low flash points are one of the major safety concerns.The adoption of high flash point quasi-solid polymer electrolytes(QSPE) that is compatible with the lithium metal anode and high-voltage cathode is therefore a promising strategy for exploring high-performance and high-safety LMBs.Herein,we employed the in-situ polymerization of poly (epoxidized soya fatty acid Bu esters-isooctyl acrylate-ditrimethylolpropane tetraacrylate)(PEID) to gel the liquid electrolyte that formed a PEID-based QSPE (PEID-QSPE).The flash point of PEID-QSPE rises from 25 to 82℃ after gelation,contributing to enhanced safety of the battery at elevated temperatures,whereas the electrochemical window increases to 4.9 V.Moreover,the three-dimensional polymer framework of PEID-QSPE is validated to facilitate the uniform growth of the solid electrolyte interphase on the anode,thereby improving the cycling stability of the battery.By employing PEID-QSPE,the Li|LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cell achieved long-term cycling stability (Coulombic efficiency,99.8%;>200 cycles at 0.1 C) even with a high cathode loading (~5 mg cm^(-2)) and an ultrathin Li(~50μm).This electrolyte is expected to afford inspiring insights for the development of safe and long-term cyclability LMBs.
文摘The influencing mechanisms of elements Ti and Ce and their interactions on fracture behaviors of casting alloys AI-4.5Cu-0.6Mn were studied by observing tensile fracture behavior in quasi-solid zone under SEM and EDX instruments.The results indicate that the resistance stress against hot cracking can be improved obviously by addition of Ti,because of its grain refining function.It is also found that,when Ce is added into the alloys,besides its effect in refining crystalline,the mechanical behavior of lower melting point eutectic phase in quasi-solid zone can be improved efficiently by some compounds with Ce formed and deposited between dendrites.Therefore,a colligating effect of Ti and Ce on improving resistance stress against hot cracking is more efficient than that only single alloy element is applied.When hot cracking occurs,grains yield at first,and then crack spreads.Both inter-grain and trans-grain fractures are observed,but the major fracture manner is brittleness.
基金Project supported by the National Key R&D Program of China(Grant Nos.2016YFB0100300 and 2016YFB0100100)the National Basic Research Program of China(Grant No.2014CB932300)+2 种基金the Beijing Municipal Science&Technology Commission,China(Grant No.D171100005517001)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA09010000)the National Natural Science Foundation of China(Grant No.51502334)
文摘A novel transparent and soft quasi-solid-state electrolyte （QSSE） was proposed and fabricated, which consists of ionic liquid （PYR14TFSI） and nano-fumed silica. The QSSE demonstrates high ionic conductivity of 4.6× 10-4 S/cm at room temperature and wide electrochemical stability window of over 5 V. The Li-O2 battery using such quasi-solidstate electrolyte exhibits a low charge-discharge overpotential at the first cycle and excellent long-term cyclability over 500 cycles.
基金supported by the National Natural Science Foundation of China(Grant Nos.52315206 and 51502334)the Funds from the Ministry of Science and Technology of China(Grant No.2016YFB0100100)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA09010000)the Foundation from Beijing Municipal Science&Technology Commission(Grant No.D171100005517001)
文摘The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10^-4S/cm at 20℃. Linear sweep voltammetry（LSV） is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li^＋1. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn2O4 and Li/CQSE/Li Mn2O4 batteries is evaluated and shows good electrochemical characteristics at 60℃.
基金financial support from the National Natural Science Foundation of China (52373074)the Guangdong Basic and Applied Basic Research Foundation (2024B1515020017)the Guangzhou Basic and Applied Basic Research Foundation (2025A04J7131)。
文摘Solid-statelithium batteries are promising next-generation energystorage systems due to their high safety and energy density.However,the poor low-temperature performance of solid-state electrolytes remains a critical challenge.Herein,we present a facile and scalable approach for synthesizing a low-temperature-resilient polymer electro-lyte based on ethylene-vinyl acetate,leveraging its unique molecular structure for enhanced lithium-ion transport.The ethylene-vinyl acetate polymer electrolyte(EPE)demonstrates a high ionic conductivity of 5.13×10^(-4) S cm^(-1) at room tem-perature and retains a remarkable conductivity of 2.72×10^(-5) S cm^(-1) at-40℃.This superior performance is at-tributed to the synergistic interaction between the ester functional groups of ethylene-vinyl acetate and lithium salts,which reduces the ion dissociation energy barrierand facil-itates efficient ion migration.The EPE enables stable lithium plating/stripping cycling for over 3000 h at-40℃ and sup-ports the long-term cycling of LiFePO¡-based full cells at-40℃ for over 900 cycles.This work highlights the potential of cost-effective,scalable EPEs for next-generation solid-state lithium batteries,particularly in extreme environmental con-ditions.
基金financially supported by the National Natural Science Foundation of China(No.62464010)Spring City Plan-Special Program for Young Talents(No.K202005007)+2 种基金Yunnan Talents Support Plan for Young Talents(No.XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(No.202101BA070001-138)the Frontier Research Team of Kunming University 2023
文摘Tin-air batteries(TABs) exhibit high safety and low cost,and are expected to be used in electric vehicles and portable electronic devices.However,challenges such as the irregular deposition of tin(Sn) particles on Sn anodes,surface passivation,and significant hydrogen evolution have hindered the development of high-performance TABs.To address these challenges,this study introduces quasi-solid TABs(QSTABs) with satisfactory high-temperature resistance.A conductive metal-organic framework(c-MOF),particularly Ni_(3)(HITP)_(2),was synthesized and deposited onto the Sn anode surface.The porous structure of c-MOF increased the specific surface area of the Sn anode,improved electronic conductivity and facilitated the absorption and release of ions during charge and discharge cycling.Theoretical calculations revealed that Ni3(HITP)_(2) provided more electron donor sites to coordinate with Sn^(2+) and inhibited hydrogen release.Additionally,carboxymethyl cellulose(CMC) was incorporated into the organic gel polymer electrolytes(OGPEs)to significantly enhance their water retention,ensuring stable operation of QSTABs between 25 and 50℃.Notably,QSTABs assembled with CMC-OGPE/Sn@Ni_(3)(HITP)_(2) exhibited a fine cycle life of over 200 cycles at 50℃.The electronic c-MOF material effectively inhibited metal shedding and side reactions on the Sn anode.These findings provide valuable guidance for developing QSTABs with high-temperature resistance.
基金This original research was financially supported by the National Natural Science Foundation of China(Nos.51703236 and U1706229)the National Science Fund for Distinguished Young Scholars(No.51625204)+1 种基金the National Key Research and Development Program of China(No.2018YFB0104300)Think-Tank Mutual Fund of Qingdao Energy Storage Industry Scientific Research,Key Scientific and Technological Innovation Project of Shandong(No.2017CXZC0505).
文摘Con ventio nal liquid electrolytes based sodium metal batteries suffer from severe safety hazards owing to electrolyte leakage,in flammability and dendritic sodium deposit!on.Herein,we report a flame-retardant quasi-solid polymer electrolyte with poly(methyl vinyl ether-alt-maleic an hydride)(P(MVE-alt-MA))as host,bacterial cellulose(BC)as reinforceme nt,and triethyl phosphate/vinyle ne carb on ate/sodium perchlorate(TEP/VC/NaClO4)as plasticizer for highly safe sodium metal batteries.The as-obtained quasi-solid polymer electrolyte exhibits superior flame retardancy(self-extinguish within 1 s),complete non-leakage property and wide electrochemical windows(4.4 V).More importantly,Na3V2(PO4)3/Na metal batteries using such polymer electrolyte delivers superior I on g-term cycli ng stability(84.4%capacity rete ntion after 1000 cycles)which is significantly better than that(only 2%after 240 cycles)of liquid electrolyte.In addition,this flame-retardant quasi-solid polymer electrolyte provides favorable cycle performance(80.2%capacity retention after 70 cycles at 50°C and 84.8%capacity retention after 50 cycles at-10°C)for Na3V2(PO4)3/Na metal batteries.And this battery also displayed a normal charge/discharge property even at-15°C.These fascinating cycle properties are mainly ascribed to the effective pro怕ctive layers formed on Na3V2(PC>4)3 cathode and sodium metal ano de.More thorough in vestigati on elucidates that such flame-retardant quasi-solid polymer electrolyte plays a multif unctional role in the adva need sodium metal batteries:(1)being in volved in the formatio n of a favorable cathode electrolyte in terface(CEI)to inhibit the dissolutio n of van adium and maintai n the structure integrity of the Na3V2(PO4)3;(2)participati ng in building a stable solid electrolyte in terface(SEI)to suppress the growth of Na dendrites;(3)integrating flame-retardanee into polymer sodium batteries to enhance flame-resistanee,eliminate electrolyte leakage,and thus improve safety of sodium batteries.Based on these results,we further assembled Na3V2(PO4)3/MoS2 pouch cell which can withsta nd harsh conditions(be nded or cut off a corn er),confirming the obtai ned polymer electrolyte with superior non-leakage property.In all,these outstanding characteristics would endow this flame-retardant quasi-solid polymer electrolyte a very promising can didate for highly-safe sodium metal batteries.
