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
The olivine-type lithium iron phosphate(LiFePO_(4))cathode material is promising and widely used as a high-performance lithium-ion battery cathode material in commercial batteries due to its low cost,environmental fri...The olivine-type lithium iron phosphate(LiFePO_(4))cathode material is promising and widely used as a high-performance lithium-ion battery cathode material in commercial batteries due to its low cost,environmental friendliness,and high safety.At present,LiFePO_(4)/C sec-ondary batteries are widely used for electronic products,automotive power batteries,and other occasion-related applications with good thermal stability,stable cycle performance,and low room-temperature self-discharge rate.However,LiFePO_(4)-based battery applications are seriously limited when they are operated in a cold climate.This outcome is due to a considerable decrease in Li+transport capabilities within the elec-trode,particularly leading to a dramatic decrease in the electrochemical capacity and power performance of the electrolyte.Therefore,the design of low-temperature electrolytes is important for the further commercial application of LiFePO_(4) batteries.This paper reviews the key factors for the poor low-temperature performance of LiFePO_(4)-based batteries and the research progress of low-temperature electrolytes.Spe-cial attention is paid to electrolyte components,including lithium salts,cosolvents,additives,and the development of new electrolytes.The factors affecting the anode are also analyzed.Finally,according to the current research progress,some viewpoints are summarized to provide suitable modification methods and research suggestions for improving the practicability of LiFePO_(4)/C commercial batteries at low temperat-ures in the future.展开更多
Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent ...Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.展开更多
Aqueous Zn-metal batteries(AZMBs)performance is hampered by freezing water at low temperatures,which hampers their multi-scenario application.Hydrogen bonds(HBs)play a pivotal role in water freezing,and proton transpo...Aqueous Zn-metal batteries(AZMBs)performance is hampered by freezing water at low temperatures,which hampers their multi-scenario application.Hydrogen bonds(HBs)play a pivotal role in water freezing,and proton transport is indispensable for the establishment of HBs.Here,the accelerated proton transport modulates the dynamic hydrogen bonding network of a Zn(BF4)2/EMIMBF4impregnated polyacrylamide/poly(vinyl alcohol)/xanthan gum dual network eutectic gel electrolyte(PPX-ILZSE)for lowtemperature AZMBs.The PPX-ILZSE forms more HBs,shorter HBs lifetimes,higher tetrahedral entropy,and faster desolvation processes,as demonstrated by experimental and theoretical calculations.This enhanced dynamic proton transport promotes rapid cycling of HBs formation-failure,and for polyaniline cathode(PANI)abundant redox sites of proton,confers excellent low temperature electrochemical performance to the Zn//PANI full cell.Specific capacities for 1000 and 5000 cycles at 1 and 5 A g^(-1)were149.8 and 128.4 m A h g^(-1)at room temperature,respectively.Furthermore,specific capacities of 131.1 mA hg^(-1)(92.4%capacity retention)and 0.0066%capacity decay per lap were achieved for 3000and 3500 laps at-30 and 40℃,respectively,at 0.5 A g^(-1).Furthermore,in-situ protective layer of ZnOHF nano-arrays on the Zn anode surface to eliminate dendrite growth and accelerate Zn-ions adsorption and charge transfer.展开更多
Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-form...Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.展开更多
The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solv...The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solvent-resistant Nitrate-coordinated electrolyte.The practical Ah-level graphite LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) pouch cell with the newly developed electrolyte demonstrates a significant breakthrough in cycling stability,exhibiting negligible capacity fade after 250 cycles at-30℃ and 0.1 C.NO_(3)^(-),as the functional additive,compresses the electric field around Li^(+)through electrostatic interactions,mimicking the Debye-screening effect and inducing the coordinative exclusion of free ethyl acetate molecules at low temperatures.The transformation from contact ion pairs(CIPs)formed by Pto solventseparated ion pairs is significantly restrained,which mitigates the continuous reactions between the electrolyte and inevitable lithium deposition at low temperature.Additionally,this customized inert CIPs form a solid electrolyte interphase on graphite that exhibits remarkable ionic conductivity and rigidity,preventing excessive Li dendrite growth.This finding offers new insights into the relationship of microstructure-performance for low-temperature electrolytes,demonstrating that relying solely on inert CIPs can also inhibit the decomposition of the interfacial electrolyte,and inspires a unique design concept for high-performance,commercially viable LIBs that operate reliably in sub-zero environments.展开更多
Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature c...Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.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
Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electro...Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.展开更多
The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-...The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-step method to model the paleo-geothermal gradient using low-temperature thermochronology.(1)It uses the Monte Carlo approach to generate thermal histories in a vertical section randomly and calculates the entire thermal history within the goodnessof-fit thresholds based on different paleo-geothermal gradients.(2)It selects the optimum paleogeothermal gradient by comparing the entire thermal history within different goodness-of-fit thresholds.We validated the method with apatite(U-Th)/He and fission track data collected from two drill cores in the Haiyuan-Liupanshan region.The result revealed that the best-fit paleo-geothermal gradient was~42℃/km during the Early Cretaceous–Miocene and has decreased rapidly to 20℃/km since~10 Ma.The crust thickening in the study area may explain the rapid reduction in the paleogeothermal gradient since~10 Ma.Our results are consistent with earlier studies in the region,suggesting that our simple and more intuitive approach provides an alternative method for paleogeothermal gradient modeling.展开更多
In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study invest...In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study investigates the specific surface area,pore volume,structure complexity/connectivity,heterogeneity/local features of pore size distribution,and oxygen consumption dynamics of igneous metamorphic coal through N_(2)/CO_(2) isothermal adsorption tests and low-temperature oxidation experiments,and elucidates the influence mechanisms of pore structure evolution on oxygen consumption dynamics during low-temperature oxidation.With increasing metamorphic degree,igneous metamorphic coal exhibits a more pronounced reduction in specific surface area during oxidation,while the increase in structure complexity due to coal-oxygen reactions is suppressed.Thermally metamorphic coal demonstrates accelerated oxygen consumption,with oxidation amplifying the difference in reaction rates compared to raw coal.Key mechanisms include oxidation-induced reduction in mesopore complexity and micropore volume,decreased dominance of small-pore-volume apertures,and increased heterogeneity,collectively leading to a lower half-oxygen-consuming temperature and steeper oxygen consumption curves.Simultaneously,increased pore volume/complexity and reduced uniformity/connectivity act synergistically to enhance oxygen consumption capacity,highlighting the coupling between pore structure evolution and oxidation behavior in igneous metamorphic coal.This study provides theoretical insights into the pore-oxygen coupling mechanisms governing coal spontaneous combustion in igneous intrusion areas.展开更多
Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identifi...Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identified numerous crystal structures with the Li_(3)MX_(6)composition,although many remain unexplored across various chemical systems.In this research,we developed a comprehensive method to examine all conceivable space groups and structures within theLi-M-X system,where M includes In,Ga,and La,and X includes F,Cl,Br,and 1.Our findings revealed two metastable structures:Li_(3)InF_(6)with P3c1 symmetry and Li_(3)InI_(6)with C2/c symmetry,exhibiting ionic conductivities of 0.55 and 2.18mS/cm at 300K,respectively.Notably,the trigonal symmetry of Li3InF6 demonstrates that high ionic conductivities are not limited to monoclinic structures but can also be achieved with trigonal symmetries.The electrochemical stability windows,mechanical properties,and reaction energies of these materials with known cathodes suggest their potential for use in all-solid-state batteries.Additionally,we predicted the stability of novel materials,including Li_(5)InCl_(8),Li_(5)InBr_(8),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)I_(9).展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and fla...The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.展开更多
Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.H...Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.展开更多
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.展开更多
With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By int...With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By integrating the high ionic conductivity of liquid electrolytes with the mechanical robustness of solid frameworks,hydrogel electrolytes offer distinct advantages in suppressing zinc dendrite formation,enhancing interfacial stability,and enabling reliable operation under extreme environmental conditions.This review systematically summarizes the fundamental characteristics and design criteria of hydrogel electrolytes,including mechanical flexibility,ionic transport capabilities,and environmental adaptability.It further explores various compositional design strategies involving natural polymers,synthetic polymers,and composite systems,as well as the incorporation of electrolyte salts and functional additives.In addition,recent advances in functional optimization,such as anti-freezing properties,self-healing abilities,thermal responsiveness,and biocompatibility,are comprehensively discussed.Finally,the review outlines the current challenges and proposes potential directions for future research.展开更多
Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.H...Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.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
The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it t...The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it to polymer segmental motion.In this study,a low-content ionic plasticizer additive1-butyl-3-dimethylimidazolium bromide(BMImBr)was introduced into the PVDF-HFP/LiTFSI/DMF matrix to modulate the Li^(+)solvation environment.Unlike conventional dual-salt systems,the introduced Br-anions dynamically compete for Li^(+)coordination,disrupting the rigid Li^(+)-TFSI^(-)/DMF solvation shell and constructing a"statistically labile and diffuse ionic cloud"characterized by reduced coordination numbers,weakened binding energies,and a more diffuse electrostatic potential landscape.This restructured solvation environment facilitates partially decoupled Li^(+)transport,as evidenced by dielectric spectroscopy and molecular dynamics simulations.Furthermore,the in situ formation of a LiBr-rich solid electrolyte interphase(SEI)effectively stabilizes the Li-metal interface and significantly reduces interfacial resistance.As a result,the optimized polymer electrolyte delivers outstanding electrochemical performance,achieving a high ionic conductivity of 0.8×10^(-4) S/cm,ultra-stable symmetric cell cycling over 500 h,and superior capacity retention exceeding 94%after 150 cycles at 0.5 C.This study elucidates a dynamic ion transport mechanism driven by competitive anion coordination and provides a viable strategy for simultaneously addressing the conductivity-stability trade-off in solid-state lithium metal batteries.展开更多
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supported by the National Natural Science Foundation of China (No. 52102470)Guangxi Innovation Driven Development Project (No. AA17204100)
文摘The olivine-type lithium iron phosphate(LiFePO_(4))cathode material is promising and widely used as a high-performance lithium-ion battery cathode material in commercial batteries due to its low cost,environmental friendliness,and high safety.At present,LiFePO_(4)/C sec-ondary batteries are widely used for electronic products,automotive power batteries,and other occasion-related applications with good thermal stability,stable cycle performance,and low room-temperature self-discharge rate.However,LiFePO_(4)-based battery applications are seriously limited when they are operated in a cold climate.This outcome is due to a considerable decrease in Li+transport capabilities within the elec-trode,particularly leading to a dramatic decrease in the electrochemical capacity and power performance of the electrolyte.Therefore,the design of low-temperature electrolytes is important for the further commercial application of LiFePO_(4) batteries.This paper reviews the key factors for the poor low-temperature performance of LiFePO_(4)-based batteries and the research progress of low-temperature electrolytes.Spe-cial attention is paid to electrolyte components,including lithium salts,cosolvents,additives,and the development of new electrolytes.The factors affecting the anode are also analyzed.Finally,according to the current research progress,some viewpoints are summarized to provide suitable modification methods and research suggestions for improving the practicability of LiFePO_(4)/C commercial batteries at low temperat-ures in the future.
基金supported by the National Natural Science Foundation of China(22409071)Natural Foundation of Shandong Province(ZR2024QB120)+2 种基金Youth Innovation Group Plan of Shandong Province(2024KJG046)Higher-Level Talent Initial Scientific Research and Discipline Construction Fund(511/1009530)Joint Funds of the National Natural Science Foundation of China(No.U22A20140)。
文摘Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.
基金supported by the National Natural Science Foundation of China(NSFC 52432002,52372041,and 52302087)China Postdoctoral Science Foundation(Grant No.2023 M740895)+1 种基金Heilongjiang Touyan Team Programthe Fundamental Research Funds for the Central Universities(Grant No.HIT.OCEF.2021003 and HIT.DZJJ.2025002)。
文摘Aqueous Zn-metal batteries(AZMBs)performance is hampered by freezing water at low temperatures,which hampers their multi-scenario application.Hydrogen bonds(HBs)play a pivotal role in water freezing,and proton transport is indispensable for the establishment of HBs.Here,the accelerated proton transport modulates the dynamic hydrogen bonding network of a Zn(BF4)2/EMIMBF4impregnated polyacrylamide/poly(vinyl alcohol)/xanthan gum dual network eutectic gel electrolyte(PPX-ILZSE)for lowtemperature AZMBs.The PPX-ILZSE forms more HBs,shorter HBs lifetimes,higher tetrahedral entropy,and faster desolvation processes,as demonstrated by experimental and theoretical calculations.This enhanced dynamic proton transport promotes rapid cycling of HBs formation-failure,and for polyaniline cathode(PANI)abundant redox sites of proton,confers excellent low temperature electrochemical performance to the Zn//PANI full cell.Specific capacities for 1000 and 5000 cycles at 1 and 5 A g^(-1)were149.8 and 128.4 m A h g^(-1)at room temperature,respectively.Furthermore,specific capacities of 131.1 mA hg^(-1)(92.4%capacity retention)and 0.0066%capacity decay per lap were achieved for 3000and 3500 laps at-30 and 40℃,respectively,at 0.5 A g^(-1).Furthermore,in-situ protective layer of ZnOHF nano-arrays on the Zn anode surface to eliminate dendrite growth and accelerate Zn-ions adsorption and charge transfer.
基金financial support from the Department of Science and Technology of Jilin Province(20240304104SF,20240304103SF)the Research and Innovation Fund of the Beihua University for the Graduate Student(Major Project 2023012)。
文摘Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.
基金support from the Heilongjiang Touyan Innovation Team Program(HITTY-20190033)National Natural Science Foundation of China(22278096)Innovation Special Project on Science and Technology for Carbon Peaking and Carbon Neutrality in Jiangsu Province(WSSJH20230015)。
文摘The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solvent-resistant Nitrate-coordinated electrolyte.The practical Ah-level graphite LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) pouch cell with the newly developed electrolyte demonstrates a significant breakthrough in cycling stability,exhibiting negligible capacity fade after 250 cycles at-30℃ and 0.1 C.NO_(3)^(-),as the functional additive,compresses the electric field around Li^(+)through electrostatic interactions,mimicking the Debye-screening effect and inducing the coordinative exclusion of free ethyl acetate molecules at low temperatures.The transformation from contact ion pairs(CIPs)formed by Pto solventseparated ion pairs is significantly restrained,which mitigates the continuous reactions between the electrolyte and inevitable lithium deposition at low temperature.Additionally,this customized inert CIPs form a solid electrolyte interphase on graphite that exhibits remarkable ionic conductivity and rigidity,preventing excessive Li dendrite growth.This finding offers new insights into the relationship of microstructure-performance for low-temperature electrolytes,demonstrating that relying solely on inert CIPs can also inhibit the decomposition of the interfacial electrolyte,and inspires a unique design concept for high-performance,commercially viable LIBs that operate reliably in sub-zero environments.
基金Supported by National Key Research and Development Program of China(2020YFD1100302)。
文摘Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.
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supported by the National Natural Science Foundation of China(No.52472219,62133007)the project ZR2024ME073 supported by Shandong Provincial Natural Science Foundationthe Shenzhen Fundamental Research Program(No.JCYJ20220530141017039)。
文摘Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.
基金supported by the National Natural Science Foundation of China(Nos.42072229,42030301,41102131,41972049,41972302 and 41977231)the Guangdong Basic and Applied Basic Research Foundation(No.2025A1515010724)+3 种基金the Guangdong Natural Science Foundation(No.2021A1515011658)the Science and Technology Program of Guangzhou(No.202002030184)the Special Fund for Basic Scientific Research of Central Colleges,Chang'an University(No.300102260502)the Deep Earth Probe and Mineral Resources Exploration-National Science and Technology Major Project(No.2024ZD1001003)。
文摘The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-step method to model the paleo-geothermal gradient using low-temperature thermochronology.(1)It uses the Monte Carlo approach to generate thermal histories in a vertical section randomly and calculates the entire thermal history within the goodnessof-fit thresholds based on different paleo-geothermal gradients.(2)It selects the optimum paleogeothermal gradient by comparing the entire thermal history within different goodness-of-fit thresholds.We validated the method with apatite(U-Th)/He and fission track data collected from two drill cores in the Haiyuan-Liupanshan region.The result revealed that the best-fit paleo-geothermal gradient was~42℃/km during the Early Cretaceous–Miocene and has decreased rapidly to 20℃/km since~10 Ma.The crust thickening in the study area may explain the rapid reduction in the paleogeothermal gradient since~10 Ma.Our results are consistent with earlier studies in the region,suggesting that our simple and more intuitive approach provides an alternative method for paleogeothermal gradient modeling.
基金supported by the National Natural Science Foundation of China(No.52374247)the Joint Funds of the National Natural Science Foundation of China(No.U24B2042).
文摘In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study investigates the specific surface area,pore volume,structure complexity/connectivity,heterogeneity/local features of pore size distribution,and oxygen consumption dynamics of igneous metamorphic coal through N_(2)/CO_(2) isothermal adsorption tests and low-temperature oxidation experiments,and elucidates the influence mechanisms of pore structure evolution on oxygen consumption dynamics during low-temperature oxidation.With increasing metamorphic degree,igneous metamorphic coal exhibits a more pronounced reduction in specific surface area during oxidation,while the increase in structure complexity due to coal-oxygen reactions is suppressed.Thermally metamorphic coal demonstrates accelerated oxygen consumption,with oxidation amplifying the difference in reaction rates compared to raw coal.Key mechanisms include oxidation-induced reduction in mesopore complexity and micropore volume,decreased dominance of small-pore-volume apertures,and increased heterogeneity,collectively leading to a lower half-oxygen-consuming temperature and steeper oxygen consumption curves.Simultaneously,increased pore volume/complexity and reduced uniformity/connectivity act synergistically to enhance oxygen consumption capacity,highlighting the coupling between pore structure evolution and oxidation behavior in igneous metamorphic coal.This study provides theoretical insights into the pore-oxygen coupling mechanisms governing coal spontaneous combustion in igneous intrusion areas.
基金supported by the Higher Education and Science Committee of Armenia in the frames of the research projects 20TTSG-2F010, 23AA-2F033 and ANSEF (EN-matsc-2660) grant.
文摘Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identified numerous crystal structures with the Li_(3)MX_(6)composition,although many remain unexplored across various chemical systems.In this research,we developed a comprehensive method to examine all conceivable space groups and structures within theLi-M-X system,where M includes In,Ga,and La,and X includes F,Cl,Br,and 1.Our findings revealed two metastable structures:Li_(3)InF_(6)with P3c1 symmetry and Li_(3)InI_(6)with C2/c symmetry,exhibiting ionic conductivities of 0.55 and 2.18mS/cm at 300K,respectively.Notably,the trigonal symmetry of Li3InF6 demonstrates that high ionic conductivities are not limited to monoclinic structures but can also be achieved with trigonal symmetries.The electrochemical stability windows,mechanical properties,and reaction energies of these materials with known cathodes suggest their potential for use in all-solid-state batteries.Additionally,we predicted the stability of novel materials,including Li_(5)InCl_(8),Li_(5)InBr_(8),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)I_(9).
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the National Natural Science Foundation of China(32501592,32271814,32301530,32471806)Young Elite Scientist Sponsorship Program by Cast(No.YESS20230242)+3 种基金Natural Science Foundation of Tianjin(23JCZDJC00630,24JCZDJC00630)the China Postdoctoral Science Foundation(2023M740563)Tianjin Enterprise Technology Commissioner Project(25YDTPJC00690)China Scholarship Council(202408120091,202408120105).
文摘The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.
基金financially supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2020R1A3B2079803 and No.RS-2024-00453815),Republic of Korea。
文摘Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.
基金supported by the National Natural Science Foundation of China(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
基金financially supported by the Guangdong Major Project of Basic Research(No.2023B0303000002)Shenzhen Science and Technology Plan Project(No.SGDX20230116091644003)+3 种基金Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001)high-level special funds(No.G03034K001)the Guangxi Key Technologies R&D Program(AB23075171,AB25069180)National Natural Science Foundation of China(22265007,52263016)。
文摘With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By integrating the high ionic conductivity of liquid electrolytes with the mechanical robustness of solid frameworks,hydrogel electrolytes offer distinct advantages in suppressing zinc dendrite formation,enhancing interfacial stability,and enabling reliable operation under extreme environmental conditions.This review systematically summarizes the fundamental characteristics and design criteria of hydrogel electrolytes,including mechanical flexibility,ionic transport capabilities,and environmental adaptability.It further explores various compositional design strategies involving natural polymers,synthetic polymers,and composite systems,as well as the incorporation of electrolyte salts and functional additives.In addition,recent advances in functional optimization,such as anti-freezing properties,self-healing abilities,thermal responsiveness,and biocompatibility,are comprehensively discussed.Finally,the review outlines the current challenges and proposes potential directions for future research.
基金supported by the National Key R&D Program of China(No.2022YFB3803400)National Natural Science Foundation of China(Nos.52102054,52020105010,51927803,52188101 and 52072378)+1 种基金Liaoning Province Science and Technology Planning Project(No.2022-BS-007)Fujian Science and Technology Program(No.2023T3025).
文摘Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
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.
基金the China Scholarship Council(CSC)for a doctoral scholarship(Grant Nos.202006310030,202108530138 and 202108530139)。
文摘The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it to polymer segmental motion.In this study,a low-content ionic plasticizer additive1-butyl-3-dimethylimidazolium bromide(BMImBr)was introduced into the PVDF-HFP/LiTFSI/DMF matrix to modulate the Li^(+)solvation environment.Unlike conventional dual-salt systems,the introduced Br-anions dynamically compete for Li^(+)coordination,disrupting the rigid Li^(+)-TFSI^(-)/DMF solvation shell and constructing a"statistically labile and diffuse ionic cloud"characterized by reduced coordination numbers,weakened binding energies,and a more diffuse electrostatic potential landscape.This restructured solvation environment facilitates partially decoupled Li^(+)transport,as evidenced by dielectric spectroscopy and molecular dynamics simulations.Furthermore,the in situ formation of a LiBr-rich solid electrolyte interphase(SEI)effectively stabilizes the Li-metal interface and significantly reduces interfacial resistance.As a result,the optimized polymer electrolyte delivers outstanding electrochemical performance,achieving a high ionic conductivity of 0.8×10^(-4) S/cm,ultra-stable symmetric cell cycling over 500 h,and superior capacity retention exceeding 94%after 150 cycles at 0.5 C.This study elucidates a dynamic ion transport mechanism driven by competitive anion coordination and provides a viable strategy for simultaneously addressing the conductivity-stability trade-off in solid-state lithium metal batteries.
