With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candida...With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.展开更多
Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmemb...Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.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
The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interfa...The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interface with a dendrite-free zinc anode is developed by adding acetone into the aqueous electrolyte.The as-formed water/acetone hybrid solvent effectively optimizes the Zn^(2+)solvation structure(coordinated water changes from 6 to 4)and induces the uniform zinc ion deposition through the high adsorption energy with the Zn(002)surface.It also stabilizes the zinc metal by reducing the corrosion reaction(hydrogen evolution)with water and the formation of a basic zinc salt by-product.As a result,the symmetrical cell with the acetone/water electrolyte exhibits a superior stability of 3700 h(154 days)at 1 mA cm^(-2).The battery with the Na_(2)V_(6)O_(16)·3H_(2)O cathode delivers an 84.1%capacity retention after 1000 cycles at 1.0 A g^(-1).The organic/aqueous electrolyte provides a new insight into understanding the relationship between solvation structure,electrode/electrolyte interface,and the performance of the zinc ion battery.展开更多
Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle ...Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.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
High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery p...High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery performance is still a challenge.Herein,we propose a non-coordinating solvent anchoring strategy to regulate fluorinated amide electrolyte to enhance the stability and ionic conductivity of the interfaces.Specifically,hexafluorobenzene is employed to anchor fluorinated amide solvent by the robust dipole–dipole interactions,which weaken the coordination between fluorinated amide and Li^(+),facilitate more anions coordinating with Li^(+),and form more ion aggregates.Consequently,stable and highly conductive electrode/electrolyte interfaces enriched with LiF and Li_(3)N are constructed,drastically improving the interfacial stability and reducing interface impedance of Li metal anodes and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes.Such a rationally designed electrolyte demonstrates excellent flame retardancy,high oxidation stability(5.1 V vs.Li^(+)/Li),and enhanced low-temperature ionic conductivity.As a result,this electrolyte substantially enhances the high-voltage cycle stability(-4.8 V),rate capability(-50 C)and low-temperature cycle performance(-20℃)of Li||NCM811 cells,which retain 80.0%of the initial capacity over 600 cycles at 4.7 V.This research offers a promising strategy to design ideal electrolytes for highperformance Li metal batteries.展开更多
Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditio...Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.展开更多
Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish...Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish Mg^(2+)transport kinetics at the electrode/electrolyte interface.Herein,we propose an electrolyte design strategy that modulates the Mg^(2+)solvation structure by introducing tetrahydrofuran(THF)as a co-solvent into a borate-based electrolyte,Mg[B(hfip)_(4)](MBF)in dimethoxyethane(DME).THF,selected from a series of linear and cyclic ethers,has a comparable dielectric constant and donor number to DME,but its cyclic structure introduces steric hindrance that induces competitive coordination with Mg^(2+).This competition weakens Mg^(2+)-solvent interactions,yielding a more labile solvation structure and enhanced desolvation kinetics.As a result,Mg||Mg cells employing the optimized MBF/1D1T electrolyte(DME:THF=1:1,v:v)exhibit a significantly reduced Mg plating/stripping overpotential of 120 mV at 10 mA cm^(-2),compared with 316 mV at 8 mA cm^(-2)with MBF/DME,along with exceptional cycling stability exceeding 1200 h.Furthermore,representative sulfide cathodes such as CuS and VS_(4)demonstrate faster activation and improved high-rate performance in the presence of MBF/1D1T.展开更多
The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electr...The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.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
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
Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reac...Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.展开更多
Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region inter...Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.展开更多
Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion...Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.展开更多
The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by ca...The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.展开更多
Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(...Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.展开更多
The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit e...The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.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
Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.展开更多
基金the financial support provided by the National Natural Science Foundation of China(grant no.22373032)the open research fund of Songshan Lake Materials Laboratory(grant no.2023SLABFK06)。
文摘With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.
基金the financial support from the National Natural Science Foundation of China(22408182)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT24024)the Natural Science Foundation of Inner Mongolia Autonomous Region(2023QN02007 and 2025QN02009)。
文摘Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.
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supported by the National Natural Science Foundation of China(52202118)the Henan Provincial Department of Education(232301420050)+1 种基金the China Postdoctoral Science Foundation(2020TQ0275)the Postdoctoral Science Foundation of Zhengzhou University(22120027).
文摘The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interface with a dendrite-free zinc anode is developed by adding acetone into the aqueous electrolyte.The as-formed water/acetone hybrid solvent effectively optimizes the Zn^(2+)solvation structure(coordinated water changes from 6 to 4)and induces the uniform zinc ion deposition through the high adsorption energy with the Zn(002)surface.It also stabilizes the zinc metal by reducing the corrosion reaction(hydrogen evolution)with water and the formation of a basic zinc salt by-product.As a result,the symmetrical cell with the acetone/water electrolyte exhibits a superior stability of 3700 h(154 days)at 1 mA cm^(-2).The battery with the Na_(2)V_(6)O_(16)·3H_(2)O cathode delivers an 84.1%capacity retention after 1000 cycles at 1.0 A g^(-1).The organic/aqueous electrolyte provides a new insight into understanding the relationship between solvation structure,electrode/electrolyte interface,and the performance of the zinc ion battery.
基金supported by the National Natural Science Foundation of China (Grant No. U21A20332)support from the Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.
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 Science Foundation of High-Level Talents of Wuyi University(2019AL017,2021AL002)。
文摘High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery performance is still a challenge.Herein,we propose a non-coordinating solvent anchoring strategy to regulate fluorinated amide electrolyte to enhance the stability and ionic conductivity of the interfaces.Specifically,hexafluorobenzene is employed to anchor fluorinated amide solvent by the robust dipole–dipole interactions,which weaken the coordination between fluorinated amide and Li^(+),facilitate more anions coordinating with Li^(+),and form more ion aggregates.Consequently,stable and highly conductive electrode/electrolyte interfaces enriched with LiF and Li_(3)N are constructed,drastically improving the interfacial stability and reducing interface impedance of Li metal anodes and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes.Such a rationally designed electrolyte demonstrates excellent flame retardancy,high oxidation stability(5.1 V vs.Li^(+)/Li),and enhanced low-temperature ionic conductivity.As a result,this electrolyte substantially enhances the high-voltage cycle stability(-4.8 V),rate capability(-50 C)and low-temperature cycle performance(-20℃)of Li||NCM811 cells,which retain 80.0%of the initial capacity over 600 cycles at 4.7 V.This research offers a promising strategy to design ideal electrolytes for highperformance Li metal batteries.
基金supported by the Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology(LRMKF202405)the National Natural Science Foundation of China(52402226)the Sichuan Provincial Natural Science Foundation (2024NSFSC1016)
文摘Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.
基金supported by the National Natural Science Foundation of China(NSFC,Grant Nos.52222211 and 52472209)the State Key Laboratory of Materials-Oriented Chemical Engineering(Grant No.SKL-MCE-23A05)+1 种基金“333”Project of Jiangsu Provincethe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish Mg^(2+)transport kinetics at the electrode/electrolyte interface.Herein,we propose an electrolyte design strategy that modulates the Mg^(2+)solvation structure by introducing tetrahydrofuran(THF)as a co-solvent into a borate-based electrolyte,Mg[B(hfip)_(4)](MBF)in dimethoxyethane(DME).THF,selected from a series of linear and cyclic ethers,has a comparable dielectric constant and donor number to DME,but its cyclic structure introduces steric hindrance that induces competitive coordination with Mg^(2+).This competition weakens Mg^(2+)-solvent interactions,yielding a more labile solvation structure and enhanced desolvation kinetics.As a result,Mg||Mg cells employing the optimized MBF/1D1T electrolyte(DME:THF=1:1,v:v)exhibit a significantly reduced Mg plating/stripping overpotential of 120 mV at 10 mA cm^(-2),compared with 316 mV at 8 mA cm^(-2)with MBF/DME,along with exceptional cycling stability exceeding 1200 h.Furthermore,representative sulfide cathodes such as CuS and VS_(4)demonstrate faster activation and improved high-rate performance in the presence of MBF/1D1T.
基金supported by the National Natural Science Foundation of China(Nos.U21A20311 and 52400163).
文摘The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
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.
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the financial support by the National Natural Science Foundation of China(No.52573221,U2330124,U20A2072,52072352,21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)+1 种基金the Scientific Research Funds for Central Universities(ZYGX2025XJ016)the Sichuan Science and Technology Program(2023ZYD0026)。
文摘Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.52125405 and U22A20108)Thailand Science Research and Innovation Fund Chulalongkorn University,National Research Council of Thailand(NRCT)and Chulalongkorn University(N42A660383).D.D.Zhang would like to thank the financial support from the Scientific Research Fund of Liaoning Provincial Education Department of China(No.JYTQN2023289)+3 种基金Liaoning Provincial Science and Technology Joint Plan(Fund)Project(No.2023-BSBA-259)and the opening project of State Key Laboratory of Metastable Materials Science and Technology,Yanshan University(No.202404).J.Cao would like to acknowledge the support from National Natural Science Foundation of China(Grant No.52402279)China Postdoctoral Science Foundation Special Funding(Grant Nos.2025T180002,2024M751753)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(No.202401).
文摘Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.
基金the National Natural Science Foundation of China(No.22379047)Yinzhou R&D Team(X.W.)+2 种基金Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)the Project Funded by the China Scholarship Council(No.202108320278)the support from the Vacuum Interconnected Nanotech Workstation(Nano-X)from Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO)。
文摘Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00217581)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2024-00406724)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2025-25430676)。
文摘The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.
基金supported by the National Natural Science Foundation of China(22269020,42167068,U23A20582)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17,2023CYZC-68)+1 种基金the Key Project of Natural Science Foundation of Gansu Province(25JRRA004)2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10).
文摘Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.
基金supported by the National Key R&D Program of China(Grant No.2022YFE0207300)the National Natural Science Foundation of China(Grant Nos.22179142 and 22075314)+1 种基金Jiangsu Provincial Science and Technology Program(Grant No.BG 2024020).XPSWAXS and TOF-SIMS characterizations were supported by Nano-X(Vacuum Interconnected Nanotech Workstation,Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO),Suzhou 215123,China)。
文摘The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.
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 the Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
