Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conv...Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synth...Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.展开更多
Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the de...Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.展开更多
Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid e...Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.展开更多
Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stabil...Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.展开更多
Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is s...Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is still a limitation for ion adsorption of internal voids and dopants in the bulk phase of carbon materials due to the sluggish intercalation kinetics of large-size sodium ions.In this work,the highly sulfur-doped carbon nanosheets are synthesized and investigated as the anode of SIBs.It shows that the electrochemical performance in ether-based electrolytes significantly outperforms that in ester-based electrolytes.The carbon anodes exhibit a specific capacity of 617 mAh·g^(-1) at 100 mA·g^(-1) after 300 cycles,especially an outstanding rate performance of delivering specific capacities of 305 and 191 mAh·g^(-1) at current densities of 10 and 50 A·g^(-1),respectively.It is speculated that the ion-storage kinetics was greatly enhanced in ether-based electrolytes owing to the better accessibility of sodium-ion diffusion from electrode interfaces to internal hosts.As a result,the carbon nanovoids and sulfur dopants in the bulk phase are efficiently activated for ion storage.This work provides a new insight into the ion-storage mechanism optimization of carbon materials for SIBs.展开更多
The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electr...The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li+.As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.展开更多
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
Driven by the increasing demand for high-energy-density batteries in electric vehicles and portable electronics,lithium metal batteries have made significant breakthroughs[1–3].While critical challenges associated wi...Driven by the increasing demand for high-energy-density batteries in electric vehicles and portable electronics,lithium metal batteries have made significant breakthroughs[1–3].While critical challenges associated with lithium metal anodes in liquid electrolytes(e.g.,dendrite growth,interface instability)have hindered commercialization[4–6],solid electrolyte systems have shown promise in mitigating these issues.Among these,solid polymer electrolytes(SPEs)have emerged as a viable solution for enabling stable quasisolid-state lithium metal batteries[7–9].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
The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theo...The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theory and density functional theory calculations.The material features a wide band gap of 4.0 eV and a considerable reduced Na^(+)migration barrier of 0.44 eV,a 1.26-eV decrease compared to pristine Na MgPO_(4)(~1.70 eV).Ab initio molecular dynamics simulations further reveal significantly enhanced ionic conductivity in the oxysulfide-based system compared to the pristine oxide structure.In addition,the calculated decomposition energy indicates that the modified material exhibits good moisture stability.Our findings suggest that sulfur-doping strategy can simultaneously achieve improved ionic conductivity and high moisture stability in oxide solid electrolytes,which could pave the way for designing high-performance solid electrolytes.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
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 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
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
Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion ele...Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation.Herein,we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer.Robust hydrogen bonding of hydroxyl groups in SiO_(2)with fluorinated moieties in PVDF-hfp regulates Zn^(2+)solvation and suppresses H_(2)O activity,while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field,jointly enabling a durable Zn plating/stripping.Effective confinement of intermediates also ensures the high reversibility across single-(I^(-)/I0),double-(I^(-)/I0/I^(-)),and triple-(I^(-)/I0/I^(-),Cl-/Cl0)electron transfer mechanisms at cathode,as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰over 4500 cycles at 10 mA cm^(-2)and a high areal capacity of 11.9 mAh cm^(-2)at 2 mA cm^(-2).This work presents a novel“container engineering”approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金supported by the National Natural Science Foundation of China(No.21972049)。
文摘Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金supported by funding from the National Key Technologies R&D Program (2016YFB0901500)the NSFC (11234013 and 51421002)the One Hundred Talent Project of the Chinese Academy of Sciences
文摘Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.
基金the National Natural Science Foundation of China (21773055, U1604122, 22005085)。
文摘Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.
基金support from the National Key Research and Development Program of China(No.2022YFB2402200)National Natural Science Foundation of China(No.22109028)+1 种基金Natural Science Foundation of Shanghai(No.22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.19CG01).
文摘Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
基金financial support from the Natural Science Foundation of Hunan Province,China (No.2023JJ40759)the State Key Laboratory of Powder Metallurgy in Central South University,China。
文摘Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.
基金supported by the National Natural Science Foundation of China(Nos.52307243 and 52272213)the Natural Science Foundation of Jiangsu Province(No.BK20230537)+2 种基金the China Postdoctoral Science Foundation(No.2023M741451)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.23KJB140003)the Jiangsu University Advanced Talent Research Startup Fund(No.22JDG052).
文摘Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is still a limitation for ion adsorption of internal voids and dopants in the bulk phase of carbon materials due to the sluggish intercalation kinetics of large-size sodium ions.In this work,the highly sulfur-doped carbon nanosheets are synthesized and investigated as the anode of SIBs.It shows that the electrochemical performance in ether-based electrolytes significantly outperforms that in ester-based electrolytes.The carbon anodes exhibit a specific capacity of 617 mAh·g^(-1) at 100 mA·g^(-1) after 300 cycles,especially an outstanding rate performance of delivering specific capacities of 305 and 191 mAh·g^(-1) at current densities of 10 and 50 A·g^(-1),respectively.It is speculated that the ion-storage kinetics was greatly enhanced in ether-based electrolytes owing to the better accessibility of sodium-ion diffusion from electrode interfaces to internal hosts.As a result,the carbon nanovoids and sulfur dopants in the bulk phase are efficiently activated for ion storage.This work provides a new insight into the ion-storage mechanism optimization of carbon materials for SIBs.
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supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金supported by the National Natural Science Foundation of China(22279028,21975063,22421001)the Natural Science Foundation of Hebei Province(B2021205019)the 333 Project of Hebei Province(C20231106)。
文摘Driven by the increasing demand for high-energy-density batteries in electric vehicles and portable electronics,lithium metal batteries have made significant breakthroughs[1–3].While critical challenges associated with lithium metal anodes in liquid electrolytes(e.g.,dendrite growth,interface instability)have hindered commercialization[4–6],solid electrolyte systems have shown promise in mitigating these issues.Among these,solid polymer electrolytes(SPEs)have emerged as a viable solution for enabling stable quasisolid-state lithium metal batteries[7–9].
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Project supported by the National Natural Science Foundation of China(Grant Nos.22473010,22303114,and 12474372)the Fundamental Research Funds for the Central Universities,Jilin University,the National Key Research and Development Program of China(Grant No.SQ2023YFB2805600)+4 种基金the Natural Science Foundation of Beijing Municipality(Grant No.Z210004)the Fund from the State Key Laboratory of Information Photonics and Optical Communications(Grant No.IPOC2021ZT01)Beijing Nova Program from Beijing Municipal Science and Technology Commission(Grant No.20230484433)Beijing University of Posts and Telecommunications Excellent Ph.D.Students Foundation(Grant No.CX20241078)Beijing Natural Science Foundation(Undergraduate Program)(Grant No.QY24218)。
文摘The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theory and density functional theory calculations.The material features a wide band gap of 4.0 eV and a considerable reduced Na^(+)migration barrier of 0.44 eV,a 1.26-eV decrease compared to pristine Na MgPO_(4)(~1.70 eV).Ab initio molecular dynamics simulations further reveal significantly enhanced ionic conductivity in the oxysulfide-based system compared to the pristine oxide structure.In addition,the calculated decomposition energy indicates that the modified material exhibits good moisture stability.Our findings suggest that sulfur-doping strategy can simultaneously achieve improved ionic conductivity and high moisture stability in oxide solid electrolytes,which could pave the way for designing high-performance solid electrolytes.
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)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 Science Fund for Distinguished Young Scholars of Hunan Province(2023JJ10060)the National Natural Science Foundation of China(22575269)Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)。
文摘Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation.Herein,we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer.Robust hydrogen bonding of hydroxyl groups in SiO_(2)with fluorinated moieties in PVDF-hfp regulates Zn^(2+)solvation and suppresses H_(2)O activity,while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field,jointly enabling a durable Zn plating/stripping.Effective confinement of intermediates also ensures the high reversibility across single-(I^(-)/I0),double-(I^(-)/I0/I^(-)),and triple-(I^(-)/I0/I^(-),Cl-/Cl0)electron transfer mechanisms at cathode,as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰over 4500 cycles at 10 mA cm^(-2)and a high areal capacity of 11.9 mAh cm^(-2)at 2 mA cm^(-2).This work presents a novel“container engineering”approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.
