Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
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
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_(9),Li_(5)InBr_(9),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)Ig_(9).展开更多
The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and fla...The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.展开更多
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 NH3 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
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.展开更多
With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By int...With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By integrating the high ionic conductivity of liquid electrolytes with the mechanical robustness of solid frameworks,hydrogel electrolytes offer distinct advantages in suppressing zinc dendrite formation,enhancing interfacial stability,and enabling reliable operation under extreme environmental conditions.This review systematically summarizes the fundamental characteristics and design criteria of hydrogel electrolytes,including mechanical flexibility,ionic transport capabilities,and environmental adaptability.It further explores various compositional design strategies involving natural polymers,synthetic polymers,and composite systems,as well as the incorporation of electrolyte salts and functional additives.In addition,recent advances in functional optimization,such as anti-freezing properties,self-healing abilities,thermal responsiveness,and biocompatibility,are comprehensively discussed.Finally,the review outlines the current challenges and proposes potential directions for future research.展开更多
Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimen...Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.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
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
In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of...In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).展开更多
The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24...The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24.3 MPa)bicontinuous porous poly(m-phthaloyl-m-phenylenediamine)(PMIA)membrane integrated into PEO/LiTFSI(PL),thus forming a PMIA/PEO/LiTFSI(PPL)composite electrolyte.Compared to the PL electrolyte,the PPL electrolyte reinforced by a bicontinuous porous PMIA membrane exhibits significantly enhanced mechanical strength,reaching 13.4 MPa.In addition,the amide groups on PMIA strongly coordinate with LiTFSI and form hydrogen bonds with PEO,promoting Li salt dissociation and reducing the Li^(+)migration barrier.This creates efficient,fast Li^(+)transport channels at the PMIA/PL interfaces,effectively promoting the uniform Li^(+)deposition and minimizing lithium dendrite formation.The PPL electrolyte achieves high ionic conductivity(1×10^(−4)S cm^(−1)at 30°C)and Li^(+)transference number(tLi^(+)=0.43).The assembled LiFePO_(4)/Li battery demonstrates excellent cycling stability,retaining 80%capacity after 2000 cycles at 2 C,while the Li/Li symmetric cell operates stably for over 900 h at 0.3 mA cm^(−2).Therefore,the scalable porous PMIA membrane effectively enhances both the mechanical strength and Li^(+)transport in PEO-based electrolytes,offering a viable strategy for their commercial-scale implementation.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.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
Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interf...Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.展开更多
To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate elect...To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).展开更多
Ionic liquids(ILs)have appeared as the most promising electrolytes for lithium-ion batteries,owing to their unique high ionic conductivity,chemical stability and thermal stability properties.Poly(ionic liquid)s(PILs)w...Ionic liquids(ILs)have appeared as the most promising electrolytes for lithium-ion batteries,owing to their unique high ionic conductivity,chemical stability and thermal stability properties.Poly(ionic liquid)s(PILs)with both IL-like characteristic and polymer structure are emerging as an alternative of traditional electrolyte.In this review,recent progresses on the applications of IL/PIL-based semi-solid state electrolytes,including gel electrolytes,ionic plastic crystal electrolytes,hybrid electrolytes and single-ion conducting electrolytes for lithium-ion batteries are discussed.展开更多
To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. Ho...Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.展开更多
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金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 Higher Education and Science Committee of Armenia in the frames of the research projects 20TTSG-2F010,23AA-2F033 and ANSEF(EN-matsc-2660)grantConvex hull calculations were done on the Oracle HPC clouds provided by the Oracle for Research grant(16576595)The USPEX calculations were performed on the Armenian National Supercomputing Center(ANSCC).MLIP training and ionic conductivity calculations were performed with the support of the Russian Science。
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_(9),Li_(5)InBr_(9),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)Ig_(9).
基金supported by the National Natural Science Foundation of China(32501592,32271814,32301530,32471806)Young Elite Scientist Sponsorship Program by Cast(No.YESS20230242)+3 种基金Natural Science Foundation of Tianjin(23JCZDJC00630,24JCZDJC00630)the China Postdoctoral Science Foundation(2023M740563)Tianjin Enterprise Technology Commissioner Project(25YDTPJC00690)China Scholarship Council(202408120091,202408120105).
文摘The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.
基金supported by the National Natural Science Foundation of China(Grant No.U21A20332).We also acknowledge 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 NH3 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supported by the National Natural Science Foundation of China(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
基金financially supported by the Guangdong Major Project of Basic Research(No.2023B0303000002)Shenzhen Science and Technology Plan Project(No.SGDX20230116091644003)+3 种基金Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001)high-level special funds(No.G03034K001)the Guangxi Key Technologies R&D Program(AB23075171,AB25069180)National Natural Science Foundation of China(22265007,52263016)。
文摘With the escalating demand for safe,sustainable,and high-performance energy storage systems,hydrogel electrolytes have emerged as promising alternatives to conventional liquid electrolytes in zinc-ion batteries.By integrating the high ionic conductivity of liquid electrolytes with the mechanical robustness of solid frameworks,hydrogel electrolytes offer distinct advantages in suppressing zinc dendrite formation,enhancing interfacial stability,and enabling reliable operation under extreme environmental conditions.This review systematically summarizes the fundamental characteristics and design criteria of hydrogel electrolytes,including mechanical flexibility,ionic transport capabilities,and environmental adaptability.It further explores various compositional design strategies involving natural polymers,synthetic polymers,and composite systems,as well as the incorporation of electrolyte salts and functional additives.In addition,recent advances in functional optimization,such as anti-freezing properties,self-healing abilities,thermal responsiveness,and biocompatibility,are comprehensively discussed.Finally,the review outlines the current challenges and proposes potential directions for future research.
基金supported by the National Natural Science Foundation of China(22072048)the Guangdong Provincial Department of Science and Technology(2021A1515010128 and 2022A0505050013).
文摘Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.
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financial support for this research,from the National Natural Science Foundation of China(52076076,52006065)Fundamental Research Funds for Central Universities(2025JC003)Beijing Municipal Natural Science Foundation(3242022)is gratefully acknowledged.
文摘In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).
基金supported by the National Natural Science Foundation of China(52273059,52203066,52403046 and 52473219)the Science and Technology Plans of Tianjin(22JCYBJC01030)+3 种基金the Tianjin Natural Science Foundation(23JCYBJC00660)the Tianjin Enterprise Science and Technology Commissioner Project(23YDTPJC00490)the China Postdoctoral Science Foundation Grant(2023M742135,2024T170525)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University.
文摘The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24.3 MPa)bicontinuous porous poly(m-phthaloyl-m-phenylenediamine)(PMIA)membrane integrated into PEO/LiTFSI(PL),thus forming a PMIA/PEO/LiTFSI(PPL)composite electrolyte.Compared to the PL electrolyte,the PPL electrolyte reinforced by a bicontinuous porous PMIA membrane exhibits significantly enhanced mechanical strength,reaching 13.4 MPa.In addition,the amide groups on PMIA strongly coordinate with LiTFSI and form hydrogen bonds with PEO,promoting Li salt dissociation and reducing the Li^(+)migration barrier.This creates efficient,fast Li^(+)transport channels at the PMIA/PL interfaces,effectively promoting the uniform Li^(+)deposition and minimizing lithium dendrite formation.The PPL electrolyte achieves high ionic conductivity(1×10^(−4)S cm^(−1)at 30°C)and Li^(+)transference number(tLi^(+)=0.43).The assembled LiFePO_(4)/Li battery demonstrates excellent cycling stability,retaining 80%capacity after 2000 cycles at 2 C,while the Li/Li symmetric cell operates stably for over 900 h at 0.3 mA cm^(−2).Therefore,the scalable porous PMIA membrane effectively enhances both the mechanical strength and Li^(+)transport in PEO-based electrolytes,offering a viable strategy for their commercial-scale implementation.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
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National Natural Science Foundation of China (52073253)。
文摘Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.
基金financially supported by the National Natural Science Foundation of China(Grant No.52372191)the National Natural Science Foundation of China(Grant No.22271106)+2 种基金the National Science Foundation of China(Grant Nos.52073286(C.-Z.L.),22275185(C.-Z.L.))the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ115(C.-Z.L.)the XMIREM Autonomously Deployment Project(2023GG01(C.-Z.L.)).We would like to thank the Instrumental Analysis Center of Huaqiao University for physical characterization(XRD and SEM).
文摘To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).
基金supported by the National Science Fund for Distinguished Young Scholars(No.21425417)the National Natural Science Foundation of China(Nos.21835005 and U1862109)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Ionic liquids(ILs)have appeared as the most promising electrolytes for lithium-ion batteries,owing to their unique high ionic conductivity,chemical stability and thermal stability properties.Poly(ionic liquid)s(PILs)with both IL-like characteristic and polymer structure are emerging as an alternative of traditional electrolyte.In this review,recent progresses on the applications of IL/PIL-based semi-solid state electrolytes,including gel electrolytes,ionic plastic crystal electrolytes,hybrid electrolytes and single-ion conducting electrolytes for lithium-ion batteries are discussed.
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金supported by the National Natural Science Foundation of China (Nos. 22379121, 62005216)Basic Public Welfare Research Program of Zhejiang (No. LQ22F050013)+1 种基金Zhejiang Province Key Laboratory of Flexible Electronics Open Fund (2023FE005)Shenzhen Foundation Research Program (No. JCYJ20220530112812028)。
文摘Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.
