Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separ...Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separators for devices and safety for users. They also allow the assembly of stretchable and bendable supercapacitors. Comparing solid-state to quasi-solid-states, the last provides the most significant energy and power densities due to the better ionic conductivity. Our goal here is to present recent advances on quasisolid-state electrolytes, including gel-polymer electrolytes. We reviewed the most recent literature on quasi-solid-state electrolytes with different solvents for supercapacitors. Organic quasi-solid-state electrolytes need greater attention once they reach an excellent working voltage window greater than 2.5 V.Meanwhile, aqueous-based solid-state electrolytes have a restricted voltage window to less than 2 V. On the other hand, they are easier to handle, provide greater ionic conductivity and capacitance. Recent water-in-salt polymer-electrolytes have shown stability as great as 2 V encouraging further development in aqueous-based quasi-solid-state electrolytes. Moreover, hydrophilic conductive polymers have great commercial appeal for bendable devices. Thus, these electrolytes can be employed in flexible and bendable devices, favoring the improvement of portable electronics and wearable devices(376 references were evaluated and summarized here).展开更多
Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and...Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.展开更多
Hydrogel-based quasi-solid-state electrolytes(Q-SSEs) swollen with electrolyte solutions are important components in stretchable supercapacitors and other wearable devices. This work fabricates a supertough, fatigue-r...Hydrogel-based quasi-solid-state electrolytes(Q-SSEs) swollen with electrolyte solutions are important components in stretchable supercapacitors and other wearable devices. This work fabricates a supertough, fatigue-resistant, and alkali-resistant multi-bond network(MBN) hydrogel aiming to be an alkaline Q-SSE. To synthesize the hydrogel, a 2-ureido-4[1H]-pyrimidone(UPy) motif is introduced into a poly(acrylic acid) polymer chain. The obtained MBN hydrogels with 75 wt% water content exhibit tensile strength as high as 2.47 MPa, which is enabled by the large energy dissipation ability originated from the dissociation of UPy dimers due to their high bond association energy. Owing to the high dimerization constant of UPy motifs, the dissociated UPy motifs are able to partially re-associate soon after being released from external forces, resulting in excellent fatigue-resistance. More importantly, the MBN hydrogels exhibit excellent alkali-resistance ability. The UPy Gel-10 swollen with 1 mol/L KOH display a tensile strength as high as ~1.0 MPa with elongation at break of ~550%. At the same time, they show ionic conductivity of ~17 m S/cm, which do not decline even when the hydrogels are stretched to 500% strain.The excellent mechanical property and ionic conductivity of the present hydrogels demonstrate potential application as a stretchable alkaline Q-SSE.展开更多
The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low ...The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low conductivity,and inadequate self-discharge-suppression capability.This study introduces a novel“water-in-montmorillonite(Mont)”(WiME)electrolyte to address these limitations.WiME leverages the layered struc-ture of the inexpensive Mont to confine water,achieving a high ionic conductivity of 64.82 mS/cm and remark-able self-discharge suppression capability and maintaining 92.7%capacity after 720 h.The WiME architec-ture facilitates uniform Zn deposition and promotes cycling stability at high current densities.WiME-based symmetric cells show excellent long-term cycling,surpassing 1900 h,and full Zn||MnOOH cells display stable cycling for 500 cycles without capacity decay,demonstrating synergy among mitigated parasitic reactions,homogenous zinc deposition,and enhanced interfacial stability enabled by WiMEs.This study presents a low-cost and high-performance strategy for advancing the practical application of AZIBs for various fields.展开更多
The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous st...The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.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
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
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
Quasi-solid-state electrolytes(QSSEs)have gar-nered significant attention due to combining the dynamic properties of liquid electrolytes and the high safety of solid-state electrolytes.However,the limited electrochemi...Quasi-solid-state electrolytes(QSSEs)have gar-nered significant attention due to combining the dynamic properties of liquid electrolytes and the high safety of solid-state electrolytes.However,the limited electrochemical stability window(ESW)of liquid electrolytes and the low conductivity of the polymer matrix seriously constrain practical applica-tion.Herein,an ant-nest electrospun amphiphilic polyurethane-based gel electrolyte(eAPG)with hy-drophilic ion channels in an organic polyurethane matrix was synthesized by swelling electrospun amphiphilic polyurethane(eAP)membrane in NaClO_(4)-based trimethyl phosphate aqueous solu-tion.The dynamically reconstructed hydrophilic ion channels enhance the Na^(+)transport rate five times compared to that in the polymer hydrophobic regions,which leads to a remarkable ion conductivity of 23.6 mS cm^(−1).The transport of free water in QSSEs via the Grotthuss mechanism is intimately associated with the ESW,where the eAP cross-linked network diminished the activity of free water,resulting in an increased ESW of 2.3 V.Additionally,symmetric supercapacitors assembled by eAPG and activated carbon electrode exhibit 45.32 Wh kg^(−1)at a power density of 0.933 kW kg^(−1)with stable and long-term cycling.This rational electrolyte design strategy and remarkable electrochemical performance pave the way for the next generation of energy storage devices.展开更多
Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electro...Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electrode compatibility.However,their practical use in high-temperature LMBs suffers from the softened polymer chains of gelator at high temperatures,leading to liquid leakage and severe growth of Li dendrite.Here,a novel inorganic ionogel(PCNIL)combining lithium salt-containing IL with porous graphitic carbon nitride nanosheets(PCN)is developed through direct physical mixing.PCNIL exhibits a superior ionic conductivity(0.75 mS cm^(-1))at room temperature similar to that of neat IL electrolyte(LiIL)and a Li^(+)transference number(0.56)greatly higher than that of Li-IL(0.20).Furthermore,PCNIL maintains a temperature-independent shear storage modulus of up to 5 MPa from room temperature to 150℃.Consequently,the Li|PCNIL|Li symmetrical cell demonstrates extended reversible lithium plating/stripping over 1200 h without dendritic growth.The robust mechanical strength,excellent thermal stability,and electrochemical stability of PCNIL allow Li|PCNIL|LiFePO_(4)cells to operate stably in a wide temperature range of 25–150℃.展开更多
One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible p...One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.展开更多
Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive ...Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.展开更多
Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode...Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.展开更多
Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their...Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their applicability has been hindered by low output discharge potential,high discharge polarizations,and singular aqueous configuration.To address these,the catalyst with faster oxygen reduction reaction(ORR)kinetic rate,nitrogen-doped carbon materials functionalized with FeMo metal clusters(FeMo-NC),was designed in acid electrolyte and thus high output voltage and energy density SABs with asymmetric-electrolytes have been developed.This innovative design aligns the reaction rates of the cathode and anode in SABs,achieving stable discharge around 1.7 V for 188 h.Furthermore,an all-in-one quasisolid-state SAB(QSSSAB)was first developed using a suitable acid-base gel electrolyte.This all-in-one QSSSAB showcases good safety,low cost,and portability,with open-circuit voltage of 1.6 V and energy density of 300.2 Wh kg^(-1),surpassing the energy density of most previously reported aqueous SABs.In terms of application,these compact all-in-one QSSSABs can provide stable and reliable power support for portable small electronic devices(such as electronic players,diodes,and electronic watches).展开更多
Quasi solid-state lithium-metal batteries(QSSLMBs)hold significant promise for enhanced energy density when compared to conventional battery systems.Nevertheless,current QSSLMBs face challenges in lithium dendrites an...Quasi solid-state lithium-metal batteries(QSSLMBs)hold significant promise for enhanced energy density when compared to conventional battery systems.Nevertheless,current QSSLMBs face challenges in lithium dendrites and electrode-electrolyte interfacial side reactions driven by excessive active free solvent molecules.Herein,a metal–organic framework(MOF)with chemically grafted soft multiether molecules(D-Gluconic acid,2,4:3,5-di-O-methylene-,denoted as G)has been proposed to serve as a solid-state electrolyte(SSE).The as-obtained M-G based electrolyte(MGE)comprises structured MOF channels with semi-immobilized solvent-like sites(G molecules),which replace liquid molecules to coordinate with Li+ions.The MGE reduces the demand for solvents compared with traditional quasi-solid-state electrolytes,thus suppressing interface side reactions.This arrangement also facilitates achieving an elevated Li+transference number(0.64)and a broad electrochemical stability window(5.4 V).Ultimately,the solid-state Li//Li symmetrical battery displays an extended lifetime surpassing 1500 h under 1mA cm^(−2).The solid-state LiFePO4//Li battery utilizing the flame-retarded MGE attains an impressive capacity retention of 95.75%over 600 cycles.The MOF-based functionalization strategy introduces an innovative approach to designing a high-performance SSE for advanced solid-state lithium metal batteries.展开更多
The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate ba...The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte(ETPTAQSSE)with a three-dimensional(3D)network is prepared by a one-step in-situ photopolymerization method.The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes.The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10^(−3)S cm^(−1),a high lithium ion transference number of 0.57,along with a wide electrochemical window of 5.3 V(vs.Li+/Li),which outperforms most ever of the reported solid-state electrolytes.Owing to the robust network structure and the cathodeelectrolyte integrated electrode design,Li metal symmetrical cells show reduced interface resistance and reinforced electrode/electrolyte interface stability.When applying the ETPTA-QSSE in LiFePO_(4)||Li cells,the quasi-solid-state cell demonstrates an enhanced initial discharge capacity(155.5 mAh g^(−1)at 0.2 C)accompanied by a high average Coulombic efficiency of greater than 99.3%,offering capacity retention of 92%after 200 cycles.Accordingly,this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes,which is promising for high-voltage LIBs.展开更多
Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interf...Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interfacial properties.However,PVDF has a series of inherent drawbacks such as low ionic conductivity,ease of crystallization,and hydrophobic character that leading to poor cell properties.To tackle these issues,a lignin-reinforced PVDF electrolyte is proposed in this work to solve these drawbacks of PVDF and enhance the comprehensive performance of QSSBs.The lithophilic polar groups of lignin can promote uniform deposition of Li on the electrodes.Cooperating with the improved mechanical properties can efficiently prevent Li dendrites penetration through the separator.In addition,more active sites provided by lignin can also enhance Li^(+)transport and lead to a faster electrochemical reaction kinetic.Benefitting from the ingenious design,Li symmetric cells with 5%lignin-PVDF quasi-solid-state electrolyte can operate for 900 h at a high current density/capacity of 5 mA·cm^(-2)/5 mAh·cm^(-2),while shortcircuiting occurs after 56 h for the counterpart(pure PVDF).Moreover,a full cell of Li/5%lignin-PVDF/LFP cell demonstrates a high capacity of 96.2 mAh·g^(-1)after 2000 cycles at 10 C.This work is expected to open up promising opportunities to develop other high-energy/power-density QSSLMBs.展开更多
Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.L...Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.展开更多
基金the funding agencies FAPESP(2014/02163-7,2017/11958-1,2020/14968-0)and CNPq(PQ-2 grant:Process 131234/2020-0&310544/2019-0)the funding from Shell and the importance of the support provided by the ANP(Brazil’s National Oil,Natural Gas,and Biofuels Agency)by the R&D levy regulation。
文摘Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separators for devices and safety for users. They also allow the assembly of stretchable and bendable supercapacitors. Comparing solid-state to quasi-solid-states, the last provides the most significant energy and power densities due to the better ionic conductivity. Our goal here is to present recent advances on quasisolid-state electrolytes, including gel-polymer electrolytes. We reviewed the most recent literature on quasi-solid-state electrolytes with different solvents for supercapacitors. Organic quasi-solid-state electrolytes need greater attention once they reach an excellent working voltage window greater than 2.5 V.Meanwhile, aqueous-based solid-state electrolytes have a restricted voltage window to less than 2 V. On the other hand, they are easier to handle, provide greater ionic conductivity and capacitance. Recent water-in-salt polymer-electrolytes have shown stability as great as 2 V encouraging further development in aqueous-based quasi-solid-state electrolytes. Moreover, hydrophilic conductive polymers have great commercial appeal for bendable devices. Thus, these electrolytes can be employed in flexible and bendable devices, favoring the improvement of portable electronics and wearable devices(376 references were evaluated and summarized here).
基金supported by the National Natural Science Foundation of China(51874019 and 51725401)the China Postdoctoral Science Foundation(2020M680347 and 2021T140051)the Fundamental Research Funds for the Central Universities(FRFTP-20-045A1)。
文摘Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.
基金the National Natural Science Foundation of China (Nos. 21774069, 51633003 and 21474058) for financial support。
文摘Hydrogel-based quasi-solid-state electrolytes(Q-SSEs) swollen with electrolyte solutions are important components in stretchable supercapacitors and other wearable devices. This work fabricates a supertough, fatigue-resistant, and alkali-resistant multi-bond network(MBN) hydrogel aiming to be an alkaline Q-SSE. To synthesize the hydrogel, a 2-ureido-4[1H]-pyrimidone(UPy) motif is introduced into a poly(acrylic acid) polymer chain. The obtained MBN hydrogels with 75 wt% water content exhibit tensile strength as high as 2.47 MPa, which is enabled by the large energy dissipation ability originated from the dissociation of UPy dimers due to their high bond association energy. Owing to the high dimerization constant of UPy motifs, the dissociated UPy motifs are able to partially re-associate soon after being released from external forces, resulting in excellent fatigue-resistance. More importantly, the MBN hydrogels exhibit excellent alkali-resistance ability. The UPy Gel-10 swollen with 1 mol/L KOH display a tensile strength as high as ~1.0 MPa with elongation at break of ~550%. At the same time, they show ionic conductivity of ~17 m S/cm, which do not decline even when the hydrogels are stretched to 500% strain.The excellent mechanical property and ionic conductivity of the present hydrogels demonstrate potential application as a stretchable alkaline Q-SSE.
基金supported by National Key Research and Development Program of China(Grant No.2022YFB2404500)Shenzhen Outstanding Talents Training Fund(Grant No.01090100002)+1 种基金National Natural Science Foundation of China(Grant No.52201280)Natural Science Foundation of Shandong Province(Grant No.ZR2021QB200).
文摘The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low conductivity,and inadequate self-discharge-suppression capability.This study introduces a novel“water-in-montmorillonite(Mont)”(WiME)electrolyte to address these limitations.WiME leverages the layered struc-ture of the inexpensive Mont to confine water,achieving a high ionic conductivity of 64.82 mS/cm and remark-able self-discharge suppression capability and maintaining 92.7%capacity after 720 h.The WiME architec-ture facilitates uniform Zn deposition and promotes cycling stability at high current densities.WiME-based symmetric cells show excellent long-term cycling,surpassing 1900 h,and full Zn||MnOOH cells display stable cycling for 500 cycles without capacity decay,demonstrating synergy among mitigated parasitic reactions,homogenous zinc deposition,and enhanced interfacial stability enabled by WiMEs.This study presents a low-cost and high-performance strategy for advancing the practical application of AZIBs for various fields.
基金financially supported by the Scientific Research Startup Funds from Tsinghua Shenzhen International Graduate School。
文摘The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.
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.
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.
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 National Key R&D Program of China(2022YFA1503501)Shanghai Pilot Program for Basic Research(22T01400100-18)+1 种基金the National Natural Science Foundation of China(no.22278127,22078088)the Fundamental Research Funds for the Central Universities(no.2022ZFJH004).
文摘Quasi-solid-state electrolytes(QSSEs)have gar-nered significant attention due to combining the dynamic properties of liquid electrolytes and the high safety of solid-state electrolytes.However,the limited electrochemical stability window(ESW)of liquid electrolytes and the low conductivity of the polymer matrix seriously constrain practical applica-tion.Herein,an ant-nest electrospun amphiphilic polyurethane-based gel electrolyte(eAPG)with hy-drophilic ion channels in an organic polyurethane matrix was synthesized by swelling electrospun amphiphilic polyurethane(eAP)membrane in NaClO_(4)-based trimethyl phosphate aqueous solu-tion.The dynamically reconstructed hydrophilic ion channels enhance the Na^(+)transport rate five times compared to that in the polymer hydrophobic regions,which leads to a remarkable ion conductivity of 23.6 mS cm^(−1).The transport of free water in QSSEs via the Grotthuss mechanism is intimately associated with the ESW,where the eAP cross-linked network diminished the activity of free water,resulting in an increased ESW of 2.3 V.Additionally,symmetric supercapacitors assembled by eAPG and activated carbon electrode exhibit 45.32 Wh kg^(−1)at a power density of 0.933 kW kg^(−1)with stable and long-term cycling.This rational electrolyte design strategy and remarkable electrochemical performance pave the way for the next generation of energy storage devices.
基金support from National Natural Science Foundation of China(52072118 and 52373206)the Open Foundation of State Key Laboratory of Advanced Design and Manufacturing Technology for Vehicle(72275002)+2 种基金Research fund of Yue Lu Mountain Industrial Innovation Center(2023YCII0137)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2024Z04)Natural Science Foundation of Hunan Province(2024JJ5076)。
文摘Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electrode compatibility.However,their practical use in high-temperature LMBs suffers from the softened polymer chains of gelator at high temperatures,leading to liquid leakage and severe growth of Li dendrite.Here,a novel inorganic ionogel(PCNIL)combining lithium salt-containing IL with porous graphitic carbon nitride nanosheets(PCN)is developed through direct physical mixing.PCNIL exhibits a superior ionic conductivity(0.75 mS cm^(-1))at room temperature similar to that of neat IL electrolyte(LiIL)and a Li^(+)transference number(0.56)greatly higher than that of Li-IL(0.20).Furthermore,PCNIL maintains a temperature-independent shear storage modulus of up to 5 MPa from room temperature to 150℃.Consequently,the Li|PCNIL|Li symmetrical cell demonstrates extended reversible lithium plating/stripping over 1200 h without dendritic growth.The robust mechanical strength,excellent thermal stability,and electrochemical stability of PCNIL allow Li|PCNIL|LiFePO_(4)cells to operate stably in a wide temperature range of 25–150℃.
基金supported by the National Key Research and Development Program(2019YFA0705701)National Natural Science Foundation of China(22075329,22008267,21978332 and 22179149)+1 种基金Research and Development Project of Henan Academy Sciences China(232018002)Guangdong Basic and Applied Basic Research Foundation(2021A1515010731)。
文摘One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515011055 and 2022A1515011438)the Key Project of Shenzhen Basic Research(No.JCYJ2022081800003006)the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(No.JCYJ20220531101013028)。
文摘Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.
基金supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.
基金National Natural Science Foundation of China,Grant/Award Number:62264006。
文摘Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their applicability has been hindered by low output discharge potential,high discharge polarizations,and singular aqueous configuration.To address these,the catalyst with faster oxygen reduction reaction(ORR)kinetic rate,nitrogen-doped carbon materials functionalized with FeMo metal clusters(FeMo-NC),was designed in acid electrolyte and thus high output voltage and energy density SABs with asymmetric-electrolytes have been developed.This innovative design aligns the reaction rates of the cathode and anode in SABs,achieving stable discharge around 1.7 V for 188 h.Furthermore,an all-in-one quasisolid-state SAB(QSSSAB)was first developed using a suitable acid-base gel electrolyte.This all-in-one QSSSAB showcases good safety,low cost,and portability,with open-circuit voltage of 1.6 V and energy density of 300.2 Wh kg^(-1),surpassing the energy density of most previously reported aqueous SABs.In terms of application,these compact all-in-one QSSSABs can provide stable and reliable power support for portable small electronic devices(such as electronic players,diodes,and electronic watches).
基金supported by the National Key Research and Development Program of China(grant nos.2022YFB2402200 and 2019YFA0705600)the National Natural Science Foundation of China(grant nos.92372001,92372203,22121005,and 52072186)+1 种基金the Science and Technology Plans of Tianjin(grant no.23JCYBJC00170)the Fundamental Research Funds for the Central Universities(grant nos.63233017,63231002,and 63231198).
文摘Quasi solid-state lithium-metal batteries(QSSLMBs)hold significant promise for enhanced energy density when compared to conventional battery systems.Nevertheless,current QSSLMBs face challenges in lithium dendrites and electrode-electrolyte interfacial side reactions driven by excessive active free solvent molecules.Herein,a metal–organic framework(MOF)with chemically grafted soft multiether molecules(D-Gluconic acid,2,4:3,5-di-O-methylene-,denoted as G)has been proposed to serve as a solid-state electrolyte(SSE).The as-obtained M-G based electrolyte(MGE)comprises structured MOF channels with semi-immobilized solvent-like sites(G molecules),which replace liquid molecules to coordinate with Li+ions.The MGE reduces the demand for solvents compared with traditional quasi-solid-state electrolytes,thus suppressing interface side reactions.This arrangement also facilitates achieving an elevated Li+transference number(0.64)and a broad electrochemical stability window(5.4 V).Ultimately,the solid-state Li//Li symmetrical battery displays an extended lifetime surpassing 1500 h under 1mA cm^(−2).The solid-state LiFePO4//Li battery utilizing the flame-retarded MGE attains an impressive capacity retention of 95.75%over 600 cycles.The MOF-based functionalization strategy introduces an innovative approach to designing a high-performance SSE for advanced solid-state lithium metal batteries.
基金supported by the Recruitment Program of Global Expertsthe Hundred-Talent Project of FujianFuzhou University
文摘The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte(ETPTAQSSE)with a three-dimensional(3D)network is prepared by a one-step in-situ photopolymerization method.The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes.The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10^(−3)S cm^(−1),a high lithium ion transference number of 0.57,along with a wide electrochemical window of 5.3 V(vs.Li+/Li),which outperforms most ever of the reported solid-state electrolytes.Owing to the robust network structure and the cathodeelectrolyte integrated electrode design,Li metal symmetrical cells show reduced interface resistance and reinforced electrode/electrolyte interface stability.When applying the ETPTA-QSSE in LiFePO_(4)||Li cells,the quasi-solid-state cell demonstrates an enhanced initial discharge capacity(155.5 mAh g^(−1)at 0.2 C)accompanied by a high average Coulombic efficiency of greater than 99.3%,offering capacity retention of 92%after 200 cycles.Accordingly,this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes,which is promising for high-voltage LIBs.
基金financially supported by the National Natural Science Foundation of China(No.22208039)the Basic Scientific Research Project of the Educational Department of Liaoning Province(No.LJKMZ20220878)+1 种基金the Dalian Science and Technology Talent Innovation Support Plan(No.2022RQ036)Dalian Polytechnic University(No.222002023044,No.6102072202)。
文摘Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interfacial properties.However,PVDF has a series of inherent drawbacks such as low ionic conductivity,ease of crystallization,and hydrophobic character that leading to poor cell properties.To tackle these issues,a lignin-reinforced PVDF electrolyte is proposed in this work to solve these drawbacks of PVDF and enhance the comprehensive performance of QSSBs.The lithophilic polar groups of lignin can promote uniform deposition of Li on the electrodes.Cooperating with the improved mechanical properties can efficiently prevent Li dendrites penetration through the separator.In addition,more active sites provided by lignin can also enhance Li^(+)transport and lead to a faster electrochemical reaction kinetic.Benefitting from the ingenious design,Li symmetric cells with 5%lignin-PVDF quasi-solid-state electrolyte can operate for 900 h at a high current density/capacity of 5 mA·cm^(-2)/5 mAh·cm^(-2),while shortcircuiting occurs after 56 h for the counterpart(pure PVDF).Moreover,a full cell of Li/5%lignin-PVDF/LFP cell demonstrates a high capacity of 96.2 mAh·g^(-1)after 2000 cycles at 10 C.This work is expected to open up promising opportunities to develop other high-energy/power-density QSSLMBs.
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金financially supported by Shenzhen Science and Technology Program(JCYJ20240813142900001)Guangdong Provincial Key Laboratory of New Energy Materials Service Safety。
文摘Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.
