The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity...The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.展开更多
Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electro...Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.展开更多
Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is l...Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.展开更多
With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety a...With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li^(+)ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.展开更多
Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to add...Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to address these issues.However,the high interfacial resistance of rigid ceramic electrolytes and the limited ionic conductivity of polymer electrolytes remain significant challenges,further complicated by the substantial volume expansion of Si.In this work,we chemically grafted a flame-retardant,self-healing polyurethane-thiourea polymer onto Li_(7)P_(3)S_(11)(SHPUSB-40%LPS)via nucleophilic addition,creating an electrolyte with exceptional ionic conductivity,high elasticity,and strong compatibility with Si anodes.We observed that FSI^(-)was strongly adsorbed onto the LPS surface through electrostatic interactions with sulfur vacancies,enhancing Li^(+)transport.Furthermore,SHPUSB-40%LPS exhibits dynamic covalent disulfide bonds and hydrogen bonds,enabling self-assembly of the electrolyte at the interface.This dynamic bonding provides a self-healing mechanism that mitigates structural changes during Si expansion and contraction cycles.As a result,the Si anode with SHPUSB-40%LPS presents excellent cycling stability,retaining nearly 53.5%of its capacity after 300 cycles.The practical applicability of this design was validated in a 2 Ah all-solid-state Si‖LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)pouch cell,which maintained a stable Li-ion storage capacity retention of 76.3%after 350cycles at 0.5C.This novel solid-state electrolyte with selfhealing properties offers a promising strategy to address fundamental interfacial and performance challenges associated with Si anodes.展开更多
Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challe...Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.展开更多
Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electroc...Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature.Herein,a dual-salt electrolyte consisting of(lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)and lithium difluoro(oxalato)borate(Li ODFB))is proposed to regulate the solvation structure of Li^(+) ions and improve the reaction kinetics under low temperature.Based on the comprehensive electrochemical tests and theoretical computations,the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface(CEI)layer on the surface of LiFePO_(4) electrode,but also inhibits the chemical corrosion effect of Li TFSIcontaining electrolytes on Al foil.As expected,the optimized Li||LiFePO_(4) cells can display high reversible capacity of 117.0 m Ah/g after 100 cycles at-20℃.This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.展开更多
Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is ...Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.展开更多
High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address thes...High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.展开更多
Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc....Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc.However,achieving high Li+conductivity remains a major challenge,particularly at low temperatures.A key obstacle lies in the limited understanding of the complex interplay among amorphous components,including fillers,plasticizers,and residual solvents,which significantly hampers the rational design of high-performing CPEs.In this contribution,a polyvinylidene fluoride(PVDF)-based composite electrolyte has been developed,exhibiting high room-temperature ionic conductivity/mobility(>1 mS cm^(-1)/0.95×10^(-11)m^(2)s^(-1)),along with excellent electrochemical performances,including a wide stability window(4.8 V vs.Li/Li^(+)),superior charge/discharge capacity,and reversibility.By performing advanced solid-state nuclear magnetic resonance(ssNMR)techniques,in combination with systematic investigations into solid polymer electrolytes(SPEs),gel polymer electrolytes(GPEs),and CPEs,we establish an efficient NMR-based strategy for deconvoluting the structural and dynamic features of complex electrolyte systems.Notably,the simple1H magic-angle spinning(MAS)NMR spectroscopy enables the identification and monitoring of nearly all components in the composite matrix.Motion-sensitive1H-13C and1H-7Li correlation experiments further reveal that the rigidity of PVDF polymer chain segments and the presence of residual solvents are two critical factors governing Li+mobility.Moreover,we demonstrate that the order of the filler and plasticizer addition during the CPE fabrication significantly influences the performance of the electrolyte by regulating the retention of residual solvents.This work not only provides molecular-level insights into the structure-ion mobility relationships in the PVDF-based CPEs but also establishes a general NMR-based characterization approach for investigating other complex composite electrolyte materials.展开更多
A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm ...A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.展开更多
Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was de...Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.展开更多
Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at ro...Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.展开更多
One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible p...One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.展开更多
Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers f...Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.展开更多
Polyvinylidene fluoride(PVDF)/garnet composite polymer electrolytes(CPEs) have shown great potential in the development of solid-state lithium metal batteries(SSLMBs) due to their excellent flexibility, high ionic con...Polyvinylidene fluoride(PVDF)/garnet composite polymer electrolytes(CPEs) have shown great potential in the development of solid-state lithium metal batteries(SSLMBs) due to their excellent flexibility, high ionic conductivity and superior mechanical strength.However, uneven dispersion of garnet fillers in CPEs would lead to deterioration of lithium metal batteries(LMBs) performance and severely limit their widespread application. Considering the rapidly growing research of addressing above-mentioned issue, herein, recent progress in the design and fabrication of uniformly dispersed fillers in PVDF/garnet CPEs for high-performance SSLMBs is summarized. We firstly analyze the mechanism for the aggregation of inorganic fillers, and provide a detailed introduction to the strategies for solving the uneven dispersion of nanoparticles in solid electrolytes. Moreover, we also comprehensively summarize their applications in PVDF/garnet electrolytes and their impact on the electrochemical performance of SSLMBs. Finally, the application challenges and future prospects of PVDF/garnet CPEs in SSLMBs were also proposed to promote their further development. It is anticipated that this review could inspire ongoing research interest in rational designing and fabricating novel CPEs for high-performance SSLMBs.展开更多
Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode...Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.展开更多
The development of high-performance solid-state electrolytes(SSEs)capable of reconciling high ionic conductivity with robust mechanical strength is crucial for advancing safe lithium-metal batteries(LMBs).In this stud...The development of high-performance solid-state electrolytes(SSEs)capable of reconciling high ionic conductivity with robust mechanical strength is crucial for advancing safe lithium-metal batteries(LMBs).In this study,we synthesized a novel BAB-type triblock copolymer PuPyMA-b-PEO-b-PuPyMA and used it to prepare SSEs.The copolymer design incorporates polyethylene oxide(PEO)segments to achieve ionic conduction,while uracil ketone(uPy)groups are introduced to provide quadruple hydrogen bonding.This molecular architecture leverages microphase separation and supramolecular interactions to optimize performance.The optimized electrolyte,PPMP-30 with w(uPyMA)=30%,n(EO)/n(Li^(+))=25/1,exhibits outstanding comprehensive properties at room temperature:an ionic conductivity of 4.0×10^(-4)S·cm^(-1),a high Li^(+)transference number of 0.41,and an extended electrochemical stability window up to 5.6 V(vs.Li^(+)/Li).Li//Li symmetric cells demonstrate exceptional interfacial stability and lithium dendrite suppression,cycling stably for over 650 h at 0.05 mA·cm^(-2).When assembled into LiFePO_(4)//Li cells,the electrolyte enables a high initial discharge capacity(about 160 mAh·g^(-1)at 0.1 C),excellent cycling stability(85.0%capacity retention after 120 cycles),and good rate capability with significant capacity recovery upon returning to low rates.These results highlight the significant potential of this tetrahedral hydrogen-bonded block copolymer electrolyte in overcoming the ionic conductivity-mechanical strength trade-off for practical solid-state LMBs.展开更多
Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread appli...Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.展开更多
基金supported by the National Natural Science Foundation of China(51973236,51573213)Zhuhai Industry University-Research Cooperation Program(2320004002721)。
文摘The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.
基金supported by the National Natural Science Foundation of China(No.52472219,62133007)the project ZR2024ME073 supported by Shandong Provincial Natural Science Foundationthe Shenzhen Fundamental Research Program(No.JCYJ20220530141017039)。
文摘Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.
基金the Natural Sci-ence Foundation of Shandong Province(Nos.ZR2022QE014,ZR2021QH237)the Guangdong Provincial Key Laboratory of Elec-tronic Functional Materials and Devices(No.EFMD2022017M)+1 种基金the National Natural Science Foundation of China(Grant Nos.52401221,51971120,U1902221)the Medical StaffScience and Technology Plan of Shandong Province(No.SDYWZGKCJH2022073).
文摘Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.
基金the financial support from the National Key R&D Program of China (Grant No. 2021YFB3800300)the supports from National Key R&D Program of China (Grant No. 2022YFB3807700)+6 种基金the National Natural Science Foundation of China (Grant No. U20A20248)the supports from the National Natural Science Foundation of China (Grant Nos. W2441017, 22409103)the “Innovation Yongjiang 2035” Key R&D Program (Grant Nos. 2024Z040, 2025Z063)the National Key R&D Program of China (Grant No. 2023YFC2812700)the Natural Science Foundation of Shandong Province (Grant No. ZR2024YQ008)funding supports from the National Key R&D Program of China (Grant No. 2021YFB3800300)science and technology innovation fund for emission peak and carbon neutrality of Jiangsu province (Grant Nos. BK20220034, BK20231512)。
文摘With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li^(+)ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.
基金supported financially by the National Natural Science Foundation of China(No.52172202)Science and Technology Program of Guangzhou,China(No.SL2024A03J00326)+1 种基金Key Research and Development project of High-Level Scientific and Technological Talent Introduction for Luliang City(No.2023RC27)the Basic Research Program(Free Exploration Category)Project for Shanxi Province(No.202303021222251)
文摘Severe structural fractures and persistent side reactions at the interface with liquid electrolytes have hindered the commercialization of silicon(Si)anodes.Solid-state electrolytes present a promising solution to address these issues.However,the high interfacial resistance of rigid ceramic electrolytes and the limited ionic conductivity of polymer electrolytes remain significant challenges,further complicated by the substantial volume expansion of Si.In this work,we chemically grafted a flame-retardant,self-healing polyurethane-thiourea polymer onto Li_(7)P_(3)S_(11)(SHPUSB-40%LPS)via nucleophilic addition,creating an electrolyte with exceptional ionic conductivity,high elasticity,and strong compatibility with Si anodes.We observed that FSI^(-)was strongly adsorbed onto the LPS surface through electrostatic interactions with sulfur vacancies,enhancing Li^(+)transport.Furthermore,SHPUSB-40%LPS exhibits dynamic covalent disulfide bonds and hydrogen bonds,enabling self-assembly of the electrolyte at the interface.This dynamic bonding provides a self-healing mechanism that mitigates structural changes during Si expansion and contraction cycles.As a result,the Si anode with SHPUSB-40%LPS presents excellent cycling stability,retaining nearly 53.5%of its capacity after 300 cycles.The practical applicability of this design was validated in a 2 Ah all-solid-state Si‖LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)pouch cell,which maintained a stable Li-ion storage capacity retention of 76.3%after 350cycles at 0.5C.This novel solid-state electrolyte with selfhealing properties offers a promising strategy to address fundamental interfacial and performance challenges associated with Si anodes.
基金supported by the Natural Science Foundation of Henan Province(No.242300420021)the Major Science and Technology Projects of Henan Province(No.221100230200)+4 种基金the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Key Science and Technology Program of Henan Province(No.232102241020)the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province(No.S202310464012)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001).
文摘Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.
基金the financial support from the S&T program of Hebei(Nos.215A4401D and 225A4404D)the Collaborative Innovation Center of Marine Science and Technology of Hainan University(No.XTCX2022HYC14)+3 种基金the Fundamental Research Funds for the Hebei University(No.2021YWF11)the Science Research Project of Hebei Education Department(No.QN2024087)the Xingtai City Natural Science Foundation(No.2023ZZ027)partially supported by the Pico Election Microscopy Center of Hainan University。
文摘Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature.Herein,a dual-salt electrolyte consisting of(lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)and lithium difluoro(oxalato)borate(Li ODFB))is proposed to regulate the solvation structure of Li^(+) ions and improve the reaction kinetics under low temperature.Based on the comprehensive electrochemical tests and theoretical computations,the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface(CEI)layer on the surface of LiFePO_(4) electrode,but also inhibits the chemical corrosion effect of Li TFSIcontaining electrolytes on Al foil.As expected,the optimized Li||LiFePO_(4) cells can display high reversible capacity of 117.0 m Ah/g after 100 cycles at-20℃.This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.
基金financial support from National Natural Science Foundation of China(22271178,U2032131,21972103)International Cooperation Key Project of Science and Technology Department of Shaanxi,China(2022KWZ-06)+3 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(20210602)Research Project of Xi’an Science and Technology Bureau(2022GXFW0011)Science and Technology New Star in Shaanxi Province(2023KJXX-045)Shaanxi Provincial Department of Education Service Local Special Project,Industrialization Cultivation Project(23JC007)。
文摘Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.
基金supported by the National Natural Science Foundation of China(22379074)Young Science and Technology Talent Program of Inner Mongolia Province(NJYT24001)+4 种基金Natural Sciences and Engineering Research Council of Canada(NSERC)GLABAT Solid-State Battery Inc.,China Automotive Battery Research Institute Co.Ltd,Canada Research Chair Program(CRC)Canada Foundation for Innovation(CFI)Ontario Research Fundsupported by the Chinese Scholarship Council.
文摘High-energy-density lithium(Li)–air cells have been considered a promising energy-storage system,but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development.To address these above issues,solid-state Li–air batteries have been widely developed.However,many commonly-used solid electrolytes generally face huge interface impedance inLi–air cells and also showpoor stability towards ambient air/Li electrodes.Herein,we fabricate a differentiating surface-regulated ceramic-based composite electrolyte(DSCCE)by constructing disparately LiI-containing polymethyl methacrylate(PMMA)coating and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)layer on both sides of Li_(1.5)Al_(0.5)Ge_(1.5)(PO_(4))_(3)(LAGP).The cathode-friendly LiI/PMMA layer displays excellent stability towards superoxide intermediates and also greatly reduces the decomposition voltage of discharge products in Li–air system.Additionally,the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes.Moreover,Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniformand compact composite framework.As a result,the DSCCE-based Li–air batteries possess high capacity/low voltage polarization(11,836mAh g^(-1)/1.45Vunder 500mAg^(-1)),good rate performance(capacity ratio under 1000mAg^(-1)/250mAg^(-1) is 68.2%)and longterm stable cell operation(~300 cycles at 750 mA g^(-1) with 750 mAh g^(-1))in ambient air.
基金financially supported by the National Natural Science Foundation of China(Grant No.22325405,22432005,22321002,and 22404159)the Dalian Science and Technology Talent Innovation Program(Grant No.2024RG009)+2 种基金the China Postdoctoral Science Foundation(Grant Number 2024M753120)the LiaoNing Revitalization Talents Program(XLYC2203134)the ANSO Scholarship for Young Talents for financial support。
文摘Composite polymer electrolytes(CPEs)are considered as promising electrolytes for next-generation lithium batteries due to their superior advantages in safety,mechanical stability/flexibility,cathode compatibility,etc.However,achieving high Li+conductivity remains a major challenge,particularly at low temperatures.A key obstacle lies in the limited understanding of the complex interplay among amorphous components,including fillers,plasticizers,and residual solvents,which significantly hampers the rational design of high-performing CPEs.In this contribution,a polyvinylidene fluoride(PVDF)-based composite electrolyte has been developed,exhibiting high room-temperature ionic conductivity/mobility(>1 mS cm^(-1)/0.95×10^(-11)m^(2)s^(-1)),along with excellent electrochemical performances,including a wide stability window(4.8 V vs.Li/Li^(+)),superior charge/discharge capacity,and reversibility.By performing advanced solid-state nuclear magnetic resonance(ssNMR)techniques,in combination with systematic investigations into solid polymer electrolytes(SPEs),gel polymer electrolytes(GPEs),and CPEs,we establish an efficient NMR-based strategy for deconvoluting the structural and dynamic features of complex electrolyte systems.Notably,the simple1H magic-angle spinning(MAS)NMR spectroscopy enables the identification and monitoring of nearly all components in the composite matrix.Motion-sensitive1H-13C and1H-7Li correlation experiments further reveal that the rigidity of PVDF polymer chain segments and the presence of residual solvents are two critical factors governing Li+mobility.Moreover,we demonstrate that the order of the filler and plasticizer addition during the CPE fabrication significantly influences the performance of the electrolyte by regulating the retention of residual solvents.This work not only provides molecular-level insights into the structure-ion mobility relationships in the PVDF-based CPEs but also establishes a general NMR-based characterization approach for investigating other complex composite electrolyte materials.
基金financially supported by Hunan Provincial Science and Technology Department,China(No.2021JJ10058)Key Research and Development Program of Hunan Province,China(No.2023GK2016)。
文摘A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.
基金conducted in a project within M-ERA.NET 3 with support from the European Union’s Horizon 2020 research,innovation program under grant agreement No.958174,Vinnova(Swedish Governmental Agency for Innovation Systems)the financial support from the LTU CREATERNITY program+1 种基金the J.Gust Richert Foundationthe National Natural Science Foundation of China(No.U23A20122)。
文摘Quasi-solid-state composite electrolytes(QSCEs)show promise for high-performance solid-state batteries,while they still struggle with interfacial stability and cycling performance.Herein,a F-grafted QSCE(F-QSCE)was developed via copolymerizing the F monomers and ionic liquid monomers.The F-QSCE demonstrates better overall performance,such as high ionic conductivity of 1.21 mS cm^(-1)at 25℃,wide electrochemical windows of 5.20 V,and stable cycling stability for Li//Li symmetric cells over 4000 h.This is attributed to the significant electronegativity difference between C and F in the fluorinated chain(-CF_(2)-CF-CF_(3)),which causes the electron cloud to shift toward the F atom,surrounding it with a negative charge and producing the inductive effect.Furthermore,the interactions between Li^(+)and F,TFSI~-,and C are enhanced,reducing ion pair aggregation(Li^(+)-TFSI~--Li^(+))and promoting Li^(+)transport.Besides,-CF_(2)-CF-CF_(3)decomposes to form Li F preferentially over TFSI~-,resulting in better interfacial stability for F-QSCE.This work provides a pathway to enable the development of high-performance Li metal batteries.
基金supported by National Natural Science Foundation of China(No.22209075)。
文摘Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.
基金supported by the National Key Research and Development Program(2019YFA0705701)National Natural Science Foundation of China(22075329,22008267,21978332 and 22179149)+1 种基金Research and Development Project of Henan Academy Sciences China(232018002)Guangdong Basic and Applied Basic Research Foundation(2021A1515010731)。
文摘One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.
基金supported by the National Key Research and Development Program of China(2021YFF0500600)National Natural Science Foundation of China(Nos.U2001220,52203298 and 523B2022)+2 种基金National Science Fund for Distinguished Young Scholars(No.52325206)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008 and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023006).
文摘Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.
基金financially supported by the National Key Research and Development Program of China(No.2020YFB1713500)the Natural Science Foundation of Henan Province(No.242300420021)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)
文摘Polyvinylidene fluoride(PVDF)/garnet composite polymer electrolytes(CPEs) have shown great potential in the development of solid-state lithium metal batteries(SSLMBs) due to their excellent flexibility, high ionic conductivity and superior mechanical strength.However, uneven dispersion of garnet fillers in CPEs would lead to deterioration of lithium metal batteries(LMBs) performance and severely limit their widespread application. Considering the rapidly growing research of addressing above-mentioned issue, herein, recent progress in the design and fabrication of uniformly dispersed fillers in PVDF/garnet CPEs for high-performance SSLMBs is summarized. We firstly analyze the mechanism for the aggregation of inorganic fillers, and provide a detailed introduction to the strategies for solving the uneven dispersion of nanoparticles in solid electrolytes. Moreover, we also comprehensively summarize their applications in PVDF/garnet electrolytes and their impact on the electrochemical performance of SSLMBs. Finally, the application challenges and future prospects of PVDF/garnet CPEs in SSLMBs were also proposed to promote their further development. It is anticipated that this review could inspire ongoing research interest in rational designing and fabricating novel CPEs for high-performance SSLMBs.
基金supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.
基金supported by the 2024 Capital Construction Funds within the Provincial Budget of Jilin Provincial Development and Reform Commission[2024C018-2].
文摘The development of high-performance solid-state electrolytes(SSEs)capable of reconciling high ionic conductivity with robust mechanical strength is crucial for advancing safe lithium-metal batteries(LMBs).In this study,we synthesized a novel BAB-type triblock copolymer PuPyMA-b-PEO-b-PuPyMA and used it to prepare SSEs.The copolymer design incorporates polyethylene oxide(PEO)segments to achieve ionic conduction,while uracil ketone(uPy)groups are introduced to provide quadruple hydrogen bonding.This molecular architecture leverages microphase separation and supramolecular interactions to optimize performance.The optimized electrolyte,PPMP-30 with w(uPyMA)=30%,n(EO)/n(Li^(+))=25/1,exhibits outstanding comprehensive properties at room temperature:an ionic conductivity of 4.0×10^(-4)S·cm^(-1),a high Li^(+)transference number of 0.41,and an extended electrochemical stability window up to 5.6 V(vs.Li^(+)/Li).Li//Li symmetric cells demonstrate exceptional interfacial stability and lithium dendrite suppression,cycling stably for over 650 h at 0.05 mA·cm^(-2).When assembled into LiFePO_(4)//Li cells,the electrolyte enables a high initial discharge capacity(about 160 mAh·g^(-1)at 0.1 C),excellent cycling stability(85.0%capacity retention after 120 cycles),and good rate capability with significant capacity recovery upon returning to low rates.These results highlight the significant potential of this tetrahedral hydrogen-bonded block copolymer electrolyte in overcoming the ionic conductivity-mechanical strength trade-off for practical solid-state LMBs.
基金supported by the National Natural Science Foundation of China(52372099,52202328,22461142135,22479046)the Shanghai Sailing Program(22YF1455500)the Shanghai Magnolia Talent Plan Pujiang Project(24PJD128)。
文摘Solid-state polymer electrolytes are crucial for advancing solid-state lithium-metal batteries owing to their flexibility,excellent manufacturability,and strong interfacial compatibility.However,their widespread applications are hindered by low ionic conductivity at room temperature and lithium dendrite growth.Herein,we report a novel solid-state composite membrane electrolyte design that combines the vertically aligned channel structure and copolymer with a radial gradient composition.Within the vertically aligned channels,the composition of poly(vinyl ethylene carbonate-co-poly(ethylene glycol)diacrylate)(P(VEC-PEGDA)varies in a gradient along the radial direction:from the center to the wall of vertically aligned channels,the proportion of vinyl ethylene carbonate(VEC)in the copolymer decreases,while the proportion of poly(ethylene glycol)diacrylate(PEGDA)increases accordingly.It can be functionally divided into a mechanical-reinforcement layer and a fast-ion-conducting layer.The resulting solid-state composite membrane electrolyte achieves a high critical current density of 1.2 mA cm^(-2)and high ionic conductivity of 2.03 mS cm^(-1)at room temperature.Employing this composite membrane electrolyte,a Li//Li symmetric cell exhibits stable cycling for over 1850 h at 0.2 m A cm^(-2)/0.2 m A h cm^(-2),and a Li//LiFePO4(LFP)battery maintains 77.3% capacity retention at 2 C after 300 cycles.Our work provides insight into the rational design of safer and more efficient solidstate batteries through electrolyte structural engineering.
