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
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
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
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
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
Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial inst...The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial instability,elucidating the synergistic effect of macroscopic ineffective regions and microscopic passivation.Based on the analysis,we develop an electrolyte-triggered interphase construction strategy to resolve the interfacial failure.This strategy couples the in situ formation of hydrogel interphase on both the anode and cathode with the electrolyte filling process,thereby(1)facilitating contact between electrodes and the separator;(2)promoting anode reversibility through inducing a bilayer SEI that enhances Zn^(2+)desolvation kinetics and blocks electron tunneling;(3)ensuring long-term cathode cycling stability via restricting the irreversible dissolution of MnO_(2)and side-reactions.The resultant Zn metal anode exhibited a near-unity Coulombic efficiency(99.5%)for Zn plating/stripping at an extremely low current density of 0.1 mA cm^(-2)and the Zn/MnO_(2)full cell sustained 2000 full-duty-cycles with an exceptionally low decay rate of 0.0051%per-cycle.This work unlocks an alternative angle for promoting practical ZMB s toward more sustainable energy storage systems.展开更多
Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wi...Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.展开更多
Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy densit...Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.展开更多
Zinc-iodine batteries have received significant attention due to their high theoretical capacity and environmental friendliness,but their performance is restricted by the growth of zinc dendrites,the hydrogen evolutio...Zinc-iodine batteries have received significant attention due to their high theoretical capacity and environmental friendliness,but their performance is restricted by the growth of zinc dendrites,the hydrogen evolution reaction,and the shuttling effect of polyiodide ions.In this study,an amidoximefunctionalized hydrogel electrolyte,created by amidoximated porous polymer of intrinsic microporosity(AO-PIM-1)and sodium alginate(Alg),is designed to address the aforementioned problems through synergistically optimizing the interfaces of the zinc anode and iodine cathode.The rigid microporous framework and amidoxime groups of AO-PIM-1 can repel polyiodides and inhibit their shuttle effect.Meanwhile,the polyanionic properties of Alg guide the uniform deposition of Zn^(2+)along the(002)crystal plane through the“egg-box”structure,thus suppressing the formation of dendrites.The AO-PIM-1/Alg electrolyte has a high ionic conductivity(18.6 mS cm^(-1)).The assembled symmetric battery can achieve highly reversible dendrite-free zinc plating/stripping(stably cycling for 2550 h at 1 mA cm^(-2)).The Zn-I_(2) full battery with the AO-PIM-1/Alg electrolyte has a long lifespan of 8700 cycles at 0.5 A g^(-1).The working mechanism of the electrolyte was elucidated through density functional theoretical calculations and molecular dynamics simulations.This study provides a new strategy for the hydrogel electrolyte of ZnI_(2) batteries.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
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
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
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
Aqueous zinc-ion batteries(AZIBs)hold great promise for next-generation energy storage but face challenges such as Zn dendrite growth,side reactions,and limited performance at low temperatures.Here,we propose an elect...Aqueous zinc-ion batteries(AZIBs)hold great promise for next-generation energy storage but face challenges such as Zn dendrite growth,side reactions,and limited performance at low temperatures.Here,we propose an electrolyte design strategy that reconstructs the hydrogenbond network through the synergistic effect of glycerol(GL)and methylsulfonamide(MSA),enabling the formation of a(100)-oriented Zn anode.This design significantly broadens the operating current and temperature windows of AZIBs.As a result,Zn||Zn symmetric cells exhibit remarkable cycling stability,achieving 4,000 h at 1 mA cm^(-2)and 600 h at 40 mA cm^(-2)(both at 1 mAh cm^(-2)capacity);even at-20℃,Zn||Zn symmetric cells deliver ultra-stable cycling for over 5,400 h.Furthermore,Zn||VO_(2)full cells retain 77.3%of their capacity after 2,000 cycles at 30°C with a current density of 0.5 A g^(-1)and 85.4%capacity retention after 2,000 cycles at-20°C and 0.25 A g^(-1).These results demonstrate a robust pathway for enhancing the practicality and low-temperature adaptability of AZIBs.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
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
Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The ch...Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).展开更多
Micro-sized silicon(mSi)anodes offer high capacity for next-generation lithium-ion batteries but suffer from severe volume changes,causing unstable interphases and poor cycling.Traditional electrolytes derive unstable...Micro-sized silicon(mSi)anodes offer high capacity for next-generation lithium-ion batteries but suffer from severe volume changes,causing unstable interphases and poor cycling.Traditional electrolytes derive unstable electrolyte/electrolyte interphases,and flammable solvents pose safety risks.Here,we introduce a non-flammable molten salt electrolyte,which consists of lithium bis(fluorosulfonyl)imide,potassium bis(fluorosulfonyl)amide,and cesium bis(fluorosulfonyl)imide in a mole ratio of 0.3:0.35:0.35(noted as Li_(0.3)K_(0.35)Cs_(0.35)FSA),that forms an inorganic interphase on mSi,stabilizing the electrode/electrolyte interface.Computational and experimental insights elucidate the FSA-anion decomposition-derived SEI predominantly of LiF,Li_(3)N,Li_(2)O,and Li_(2)S,which exhibits mechanical resilience and low interfacial resistance,effectively accommodating the significant volume expansion of silicon during lithiation/delithiation.As a result,the Li||mSi half-cell achieves 60.7%capacity retention after 100 cycles with 99.5%average Coulombic efficiency.Overall,the Li_(0.3)K_(0.35)Cs_(0.35)FSA electrolyte eliminates flammability concerns while enabling robust cycling performance.This work demonstrates a safe,high-energy battery system by coupling mSi anodes with stable molten salt electrolytes,addressing both interfacial instability and safety challenges in mSi-based lithium-ion batteries.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
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 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.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 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 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 Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金supported by the National Natural Science Foundation of China(62201369,52203142)Natural Science Foundation of Sichuan Province(2024NSFSC0226)the Open Fund of Key Laboratory of Green Chemical Technology of Fujian Province University(WYKF-EIGT2023-1)。
文摘The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial instability,elucidating the synergistic effect of macroscopic ineffective regions and microscopic passivation.Based on the analysis,we develop an electrolyte-triggered interphase construction strategy to resolve the interfacial failure.This strategy couples the in situ formation of hydrogel interphase on both the anode and cathode with the electrolyte filling process,thereby(1)facilitating contact between electrodes and the separator;(2)promoting anode reversibility through inducing a bilayer SEI that enhances Zn^(2+)desolvation kinetics and blocks electron tunneling;(3)ensuring long-term cathode cycling stability via restricting the irreversible dissolution of MnO_(2)and side-reactions.The resultant Zn metal anode exhibited a near-unity Coulombic efficiency(99.5%)for Zn plating/stripping at an extremely low current density of 0.1 mA cm^(-2)and the Zn/MnO_(2)full cell sustained 2000 full-duty-cycles with an exceptionally low decay rate of 0.0051%per-cycle.This work unlocks an alternative angle for promoting practical ZMB s toward more sustainable energy storage systems.
基金supported by the Science Foundation of High-Level Talents of Wuyi University(Nos.2019AL017,2021AL002).
文摘Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities.However,operating in wide temperature range and at high voltage is a tough challenge for them.Herein,F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)batteries with excellent performance in wide temperature range is developed.F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity(1.52 mS/cm at 30℃),enhance oxidation stability(5.0 V vs.Li^(+)/Li)and fabricate robust LiF/Li_(3)N-rich electrode-electrolyte interphases,which significantly improve the interface stability of Li metal anode and NCM811 cathode.The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200℃.Capitalizing on these advantageous attributes,the Li||NCM811 cells show excellent cycle stability and rate capability from−20℃ to 60℃ at high voltages(∼4.6 V),and under high-loading full cell condition,which display impressive capacity retention of 84.4%after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C.This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.
基金supported by the University of Wollongong,Wollongong,Australiafinancial support from the National Natural Science Foundation of China(22272086)Natural Science Foundation of Sichuan Province(2023NSFSC0009).
文摘Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.
基金partially supported by the National Natural Science Foundation of China(22475035 and 22071021)the Natural Science Foundation of Jilin Province(20240101170JC)。
文摘Zinc-iodine batteries have received significant attention due to their high theoretical capacity and environmental friendliness,but their performance is restricted by the growth of zinc dendrites,the hydrogen evolution reaction,and the shuttling effect of polyiodide ions.In this study,an amidoximefunctionalized hydrogel electrolyte,created by amidoximated porous polymer of intrinsic microporosity(AO-PIM-1)and sodium alginate(Alg),is designed to address the aforementioned problems through synergistically optimizing the interfaces of the zinc anode and iodine cathode.The rigid microporous framework and amidoxime groups of AO-PIM-1 can repel polyiodides and inhibit their shuttle effect.Meanwhile,the polyanionic properties of Alg guide the uniform deposition of Zn^(2+)along the(002)crystal plane through the“egg-box”structure,thus suppressing the formation of dendrites.The AO-PIM-1/Alg electrolyte has a high ionic conductivity(18.6 mS cm^(-1)).The assembled symmetric battery can achieve highly reversible dendrite-free zinc plating/stripping(stably cycling for 2550 h at 1 mA cm^(-2)).The Zn-I_(2) full battery with the AO-PIM-1/Alg electrolyte has a long lifespan of 8700 cycles at 0.5 A g^(-1).The working mechanism of the electrolyte was elucidated through density functional theoretical calculations and molecular dynamics simulations.This study provides a new strategy for the hydrogel electrolyte of ZnI_(2) batteries.
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 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financially supported by Guangdong Major Project of Basic Research(No.2023B0303000002)Shenzhen Fundamental Research Programs(No.JCYJ20241202125404007)+1 种基金Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001)National Natural Science Foundation of China(No.52263016,22265007)。
文摘Aqueous zinc-ion batteries(AZIBs)hold great promise for next-generation energy storage but face challenges such as Zn dendrite growth,side reactions,and limited performance at low temperatures.Here,we propose an electrolyte design strategy that reconstructs the hydrogenbond network through the synergistic effect of glycerol(GL)and methylsulfonamide(MSA),enabling the formation of a(100)-oriented Zn anode.This design significantly broadens the operating current and temperature windows of AZIBs.As a result,Zn||Zn symmetric cells exhibit remarkable cycling stability,achieving 4,000 h at 1 mA cm^(-2)and 600 h at 40 mA cm^(-2)(both at 1 mAh cm^(-2)capacity);even at-20℃,Zn||Zn symmetric cells deliver ultra-stable cycling for over 5,400 h.Furthermore,Zn||VO_(2)full cells retain 77.3%of their capacity after 2,000 cycles at 30°C with a current density of 0.5 A g^(-1)and 85.4%capacity retention after 2,000 cycles at-20°C and 0.25 A g^(-1).These results demonstrate a robust pathway for enhancing the practicality and low-temperature adaptability of AZIBs.
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 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support from the Heilongjiang Province"Double First Class"Discipline Collaborative Innovation Project(No.LJGXCG2023-061).
文摘Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA0400000)the One Hundred Person Project of the Chinese Academy of Sciences,the Shanghai Magnolia Talent Plan Pujiang Project(Grant No.23PJ1415600)the Shanghai International S&T Cooperation Program(Grant No.23160711700).
文摘Micro-sized silicon(mSi)anodes offer high capacity for next-generation lithium-ion batteries but suffer from severe volume changes,causing unstable interphases and poor cycling.Traditional electrolytes derive unstable electrolyte/electrolyte interphases,and flammable solvents pose safety risks.Here,we introduce a non-flammable molten salt electrolyte,which consists of lithium bis(fluorosulfonyl)imide,potassium bis(fluorosulfonyl)amide,and cesium bis(fluorosulfonyl)imide in a mole ratio of 0.3:0.35:0.35(noted as Li_(0.3)K_(0.35)Cs_(0.35)FSA),that forms an inorganic interphase on mSi,stabilizing the electrode/electrolyte interface.Computational and experimental insights elucidate the FSA-anion decomposition-derived SEI predominantly of LiF,Li_(3)N,Li_(2)O,and Li_(2)S,which exhibits mechanical resilience and low interfacial resistance,effectively accommodating the significant volume expansion of silicon during lithiation/delithiation.As a result,the Li||mSi half-cell achieves 60.7%capacity retention after 100 cycles with 99.5%average Coulombic efficiency.Overall,the Li_(0.3)K_(0.35)Cs_(0.35)FSA electrolyte eliminates flammability concerns while enabling robust cycling performance.This work demonstrates a safe,high-energy battery system by coupling mSi anodes with stable molten salt electrolytes,addressing both interfacial instability and safety challenges in mSi-based lithium-ion batteries.
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.
