Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,saf...Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.展开更多
Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effe...Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.展开更多
The uncontrolled growth of lithium dendrites and accumulation of"dead lithium"upon cycling are among the main obstacles that hinder the widespread application of lithium metal anodes.Herein,an ionic liquid(I...The uncontrolled growth of lithium dendrites and accumulation of"dead lithium"upon cycling are among the main obstacles that hinder the widespread application of lithium metal anodes.Herein,an ionic liquid(IL)consisting of 1-methyl-1-propylpiperidinium cation(Pp_(13)^+) and bis(fluorosulfonyl)imide anion(FSI^(-)),was chosen as the additive in propylene carbonate(PC)-based liquid electrolytes to circumvent the shortcoming of lithium metal anodes.The optimal 1%Pp_(13) FSI acts as the role of electrostatic shielding,lithiophobic effect and participating in the formation of solid electrolyte interface(SEI)layer with enhanced properties.The in-situ optical microscopy records that the addition of IL can effectively inhibit the growth of lithium dendrites and the corrosion of lithium anode.This study delivers an effective modification to optimize electrolytes for stable lithium metal batteries.展开更多
The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additiv...The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.展开更多
The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-ri...The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.展开更多
Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges ...Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.展开更多
The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic framework...The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic frameworks(MOF)is incorporated into a polyethylene oxide(PEO)-based polymer solid electrolyte,leading to the insitu formation of LiF and other compounds at the electrolyte interface.This modification significantly improves lithium-ion transport capabilities and regulates lithium deposition behavior,suppressing the formation of lithium dendrites.展开更多
Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li den...Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application.One efficient strategy is to construct a superior solid electrolyte interface.Herein,a stable interface enriched with Li3N and LiF is in-situ formed between Li anode and a terna ry salt electrolyte.This terna ry salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide(LiTFSI),lithium bis(fluorosulfonyl)imide(LiFSI),and LiNO_(3)to poly(ethylene oxide)matrix.Surface characterization indicates that LiNO3and LiFSI contribute to forming a Li3N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity.Theoretically,among various Li compound components,Li3N has high ionic conductivity,which is beneficial for reducing overpotential,while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites.The experimental results show that ASSLBs coupled with LiFePO4cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C,with a final and corresponding discharge specific capacity of 96.7 mA h g^(-1).Additionally,a schematic illustration of the working mechanism for the Li_(3)N-LiF interface is proposed.展开更多
Lithium(Li)metal is considered the most promising anode material for the next generation of secondary batteries due to its high theoretical specific capacity and low potential.However,the application of Li anode in re...Lithium(Li)metal is considered the most promising anode material for the next generation of secondary batteries due to its high theoretical specific capacity and low potential.However,the application of Li anode in rechargeable Li metal batteries(LMBs)is hindered due to the short cycle life caused by uncontrolled dendrite growth.In this work,a dendrite-free anode(Li–Sn/Cu)is reinforced synergistically by lithophilic alloy,and a 3D grid structure is designed.Li^(+)diffusion and uniform nucleation are effectively induced by the lithophilic alloy Li_(22)Sn_(5).Moreover,homogeneous deposition of Li^(+)is caused by the reversible gridded Li plating/stripping effect of Cu mesh.Furthermore,the local space electric field is redistributed throughout the 3D conductive network,whereby the tip effect is suppressed,thus inhibiting the growth of Li dendrites.Also,the volume expansion of the anode during cycling is eased by the 3D grid structure.The results show that the Li–Sn/Cu symmetric battery can stably cycle for more than 10,000 h at 2 mA.cm^(-2)and 1 mAh.cm^(-2)with a low overpotential.The capacity retention of the LiFePO_(4)full battery remains above 90.7%after 1,000 cycles at 1C.This work provides a facile,low-cost,and effective strategy for obtaining Li metal batteries with ultra-long cycle life.展开更多
The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuri...The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuring a trilayer architecture is developed by incorporating a thin polyethylene(PE)separator into a blending polymer matrix of poly(ethylene oxide)and poly(vinylidene fluoride)(PEO-PVDF)through a hot pressing technique.This structural design provides complementary functions:the flexible outer layers confine lithium deposition within a restricted area,while the robust interlayer prevents lithium dendrite penetration.Additionally,the incorporation of LiNO_(3) significantly enhances the stability of the CSE/Li interface by gradually forming a Li_(3)N-rich interfacial film,which promotes uniform lithium deposition.Consequently,the assembled Li||Li symmetrical cell demonstrates stable cycling for over 6000 h at a current density of 0.2 mA cm^(–2)with an areal capacity of 1.2 mAh cm^(–2).More attractively,ASSLBs constructed with the designed CSEs,high mass loading LFP/NCM811(LFP:LiFePO_(4);NCM811:LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2))cathodes(≥12 mg cm^(–2)),and lithium metal anodes deliver superior cycling performance without short-circuiting at current densities of 0.3/0.2 mA cm^(–2),respectively.This work offers critical insights for the design of high-performance ASSLBs with improved durability at high areal capacities.展开更多
Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemica...Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.展开更多
Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion...Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion conducting polymer electrolytes(SICPEs)are less affected by lithium dendrites growth and thus are particularly interesting for application in lithium metal batteries.In this work,novel SIC-PEs are developed,based on an ionomer having poly(ethylene-alt-maleimide)backbone and lithium phenylsulfonyl(trifluoromethanesulfonyl)imide pendant moieties,further blended with poly(ethylene oxide)(PEO)and poly(ethylene glycol)dimethyl ether(PEGDME).These SIC-PEs exhibit ionic conductivity around~7×10^(−6)S·cm^(−1) at 70℃,lithium transference number close to unity,and excellent mechanical properties,with fracture toughness over 30 J·cm^(−3).Additionally,the electrolytes show very high resistance against lithium dendrites growth,by cycling for more than 1200 h in Li°symmetric cells at a current density of 0.1 mA·cm^(−2).LiFePO4||Li°cells with these SIC-PEs were cycled at 70℃ and C/10,showing initial capacity of almost 160 mAh·g^(−1)and residual capacity of 45%after 100 cycles.This work shows that single-ion conducting polymer electrolytes based on poly(ethylene-alt-maleimide)backbone are promising materials for application as electrolytes or catholytes in lithium metal polymer batteries.展开更多
High energy density lithium(Li)metal batteries have attracted great attention,but they are faced with challenges of cycling instability and safety hazards.Due to high activity and drastic volume changes of metallic Li...High energy density lithium(Li)metal batteries have attracted great attention,but they are faced with challenges of cycling instability and safety hazards.Due to high activity and drastic volume changes of metallic Li,potential dendritic risks cannot be fully eliminated.Therefore,suppressing already existing Li dendrites must be evaluated.In addition,Li-active solids alloying with Li always face mechanical instability and fractures with cycling.Herein,we present touch ablation of dendrites by liquid metal,namely forming a defense layer on the electrode to directly react with the dendrites.Embrittlement,supercooling,and other liquid characteristics make the liquid gallium(Ga)exhibit continuous and reversible reactions with Li.The unique layout with a hierarchical porous structure inhibits upward growth of the dendrites.The protected Li||Li cells achieve stable cyclic performance even at 10 mA cm^(–2)and a large capacity of 5 mA h cm^(-2).展开更多
Poor cycling stability in lithium–sulfur(Li–S)batteries necessitates advanced electrode/electrolyte design and innovative interlayer architectures.Heterogeneous catalysis has emerged as a promising approach,leveragi...Poor cycling stability in lithium–sulfur(Li–S)batteries necessitates advanced electrode/electrolyte design and innovative interlayer architectures.Heterogeneous catalysis has emerged as a promising approach,leveraging the adsorption and catalytic performance on lithium polysulfides(LiPSs)to inhibit LiPSs shuttling and improve redox kinetics.In this study,we report an ultrathin and laminar SnO_(2)@MXene heterostructure interlayer(SnO_(2)@MX),where SnO_(2) quantum dots(QDs)are uniformly distributed across the MXene layer.The combined structure of SnO_(2) QDs and MXene,along with the creation of numerous active boundary sites with coordination electron environments,plays a critical role in manipulating the catalytic kinetics of sulfur species.The Li–S cell with the SnO_(2)@MX-modified separator not only demonstrates superior electrochemical performance compared to cells with a bare separator but also induces homogeneous Li deposition during cycling.As a result,an areal capacity of 7.6 mAh cm^(-2) under a sulfur loading of 7.5 mg cm^(-2) and a high stability over 500 cycles are achieved.Our work demonstrates a feasible strategy of utilizing a laminar separator interlayer for advanced Li–S batteries awaiting commercialization and may shed light on the understanding of heterostructure catalysis with enhanced reaction kinetics.展开更多
Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-...Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.展开更多
All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-impr...All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.展开更多
Lithium batteries have always played a key role in the field of new energy sources.However,non-controllable lithium dendrites and volume dilatation of metallic lithium in batteries with lithium metal as anodes have li...Lithium batteries have always played a key role in the field of new energy sources.However,non-controllable lithium dendrites and volume dilatation of metallic lithium in batteries with lithium metal as anodes have limited their development.Recently,a large number of studies have shown that the electrochemical performances of lithium batteries can be enhanced through the regulation of external physical fields.Especially,it significantly hinders the growth of lithium dendrites and promoting the reaction kinetics.This review summarizes recent innovations in the investigation of various physical fields of lithium batteries.The application of magnetic field in the synthesis of lithium battery electrode materials is introduced.The influence factors and regulation mechanism of various physical fields on the electrochemical performance of lithium batteries are reviewed emphatically.In addition,the current research status and existing challenges,along with future directions for the evolution of lithium batteries,are minutely discussed and prospected.New strategies for the further evolution of lithium batteries have also been provided.展开更多
The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,...The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,wide electrochemical window,and stability to Li metal anode,are promising solid-state electrolyte(SSEs)materials for SSLMBs.However,Li/LLZTO interface issues including high interface resistance,inhomogeneous Li deposition,and Li dendrite growth have hindered the practical application of SSLMBs.Herein,a multi-functional Li–SnF_(2) composite anode with Li,LiF,and Li-Sn alloy was specifically designed and prepared.The composite anode improves the wettability to LLZTO,constructing an intimate contact interface between it and LLZTO.Meanwhile,ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li dendrite.The solid-state symmetric cell exhibits low interface resistance(11Ω·cm^(2)) and high critical current density(1.3 mA·cm^(−2))at 25℃.The full SSLMB based on LiFePO_(4) or LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode also shows stable cycling performance and high rate capability.This work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.展开更多
Li-B alloy is expected to meet the expanding demands of energy storage,primarily driven by their high energydensity and structural stability.The fibrous porous skeleton can increase the electrochemical active area and...Li-B alloy is expected to meet the expanding demands of energy storage,primarily driven by their high energydensity and structural stability.The fibrous porous skeleton can increase the electrochemical active area and reduce thelocal current density,therefore diminishing the lithium dendrites.In this study,we prepared Li-B alloys with differentlithium contents and examined the impact of lithium content on the structure and electrochemical properties of Li-Balloys.With the increase of lithium content,the spacing between the skeleton of the Li-B alloys increases.The lithiumdeposition on the top of the skeleton decreases,leading to thinner SEI,and lower polarization.The Li-B alloy with thehighest lithium content(64 wt.%lithium content)in the symmetric battery exhibits the longest cycle time,lasting over140 h at 1 mA/cm^(2)and 0.5 mA·h/cm^(2),with a minimal overpotential of 0.08 V.When paired with LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2),thefull battery has the highest specific discharge capacity and the best rate capacity.展开更多
Lithium(Li)dendrite issue,which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase(SEI),impedes the further development of high-energy Li metal batteries.However,the integrated c...Lithium(Li)dendrite issue,which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase(SEI),impedes the further development of high-energy Li metal batteries.However,the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short.Herein,we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix.The generated Co and LiF both enable fast Li-ion diffusion kinetics,meanwhile,the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites,thereby contributing to uniform Li nucleation and non-dendritic growth.As a result,a dendrite-free Li deposition with a low overpotential(16.1 mV)is achieved,which enables an extended lifespan over 750 h under strict conditions.The full cells with high-mass-loading LiFePO_(4)(11.5 mg/cm^(2))as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4%after undergoing 180 cycles.展开更多
基金supported by Yunnan Natural Science Foundation Project(No.202202AG050003)Yunnan Fundamental Research Projects(Nos.202101BE070001-018 and 202201AT070070)+1 种基金the National Youth Talent Support Program of Yunnan Province China(No.YNQR-QNRC-2020-011)Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(No.2023-XMDJ-00617107)。
文摘Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565).
文摘Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.
基金supported by the Key Research and Development Program of Guangdong Province(No.2020B090919005)the National Natural Science Foundation of China(Nos.21975056,52002079 and U1801257)Pearl River Science and Technology New Star Project(No.201806010039)。
文摘The uncontrolled growth of lithium dendrites and accumulation of"dead lithium"upon cycling are among the main obstacles that hinder the widespread application of lithium metal anodes.Herein,an ionic liquid(IL)consisting of 1-methyl-1-propylpiperidinium cation(Pp_(13)^+) and bis(fluorosulfonyl)imide anion(FSI^(-)),was chosen as the additive in propylene carbonate(PC)-based liquid electrolytes to circumvent the shortcoming of lithium metal anodes.The optimal 1%Pp_(13) FSI acts as the role of electrostatic shielding,lithiophobic effect and participating in the formation of solid electrolyte interface(SEI)layer with enhanced properties.The in-situ optical microscopy records that the addition of IL can effectively inhibit the growth of lithium dendrites and the corrosion of lithium anode.This study delivers an effective modification to optimize electrolytes for stable lithium metal batteries.
基金supported by the National Natural Science Foundation of China(U21A20311)Researchers Supporting Project Number(RSP2025R304),King Saud University,Riyadh,Saudi Arabia。
文摘The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.
基金supported by the National Natural Science Foundation of China(No.51972066)the Natural Science Foundation of Guangdong Province of China(No.2024A1515012499)。
文摘The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.
基金support from The Hong Kong Polytechnic University(U-CDCA)and Innovation and Technology Fund(ITS-322-23FP)。
文摘Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.
基金supported by the National Natural Science Foundation of China(Nos.52374302 and 51874099)the Natural Science Foundation of Fujian Province’s Key Project(No.2021J02031)+1 种基金support from the open fund from Academy of Carbon Neutrality of Fujian Normal University(No.TZH_(2)022-06)We also thank the Undergraduate Training Programs for Innovation and Entrepreneurship(No.cxx1-2024363)。
文摘The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic frameworks(MOF)is incorporated into a polyethylene oxide(PEO)-based polymer solid electrolyte,leading to the insitu formation of LiF and other compounds at the electrolyte interface.This modification significantly improves lithium-ion transport capabilities and regulates lithium deposition behavior,suppressing the formation of lithium dendrites.
基金supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Natural Science Foundation of Hebei Province(no.E2022501014)+3 种基金the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)the Fundamental Research Funds for the Central Universities(no.N2423054)the 2023 Hebei Provincial Doctoral Candidate Innovation Ability Training Funding Project(no.CXZZBS2023159)the Performance Subsidy Fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H).
文摘Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application.One efficient strategy is to construct a superior solid electrolyte interface.Herein,a stable interface enriched with Li3N and LiF is in-situ formed between Li anode and a terna ry salt electrolyte.This terna ry salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide(LiTFSI),lithium bis(fluorosulfonyl)imide(LiFSI),and LiNO_(3)to poly(ethylene oxide)matrix.Surface characterization indicates that LiNO3and LiFSI contribute to forming a Li3N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity.Theoretically,among various Li compound components,Li3N has high ionic conductivity,which is beneficial for reducing overpotential,while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites.The experimental results show that ASSLBs coupled with LiFePO4cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C,with a final and corresponding discharge specific capacity of 96.7 mA h g^(-1).Additionally,a schematic illustration of the working mechanism for the Li_(3)N-LiF interface is proposed.
基金supported by the National Natural Science Foundation of China(No.52401221)Shandong Provincial Natural Science Foundation,China(No.ZR2022QE014)+1 种基金the Basic Scientific Research Fund for Central Universities(No.202112018)the Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education)。
文摘Lithium(Li)metal is considered the most promising anode material for the next generation of secondary batteries due to its high theoretical specific capacity and low potential.However,the application of Li anode in rechargeable Li metal batteries(LMBs)is hindered due to the short cycle life caused by uncontrolled dendrite growth.In this work,a dendrite-free anode(Li–Sn/Cu)is reinforced synergistically by lithophilic alloy,and a 3D grid structure is designed.Li^(+)diffusion and uniform nucleation are effectively induced by the lithophilic alloy Li_(22)Sn_(5).Moreover,homogeneous deposition of Li^(+)is caused by the reversible gridded Li plating/stripping effect of Cu mesh.Furthermore,the local space electric field is redistributed throughout the 3D conductive network,whereby the tip effect is suppressed,thus inhibiting the growth of Li dendrites.Also,the volume expansion of the anode during cycling is eased by the 3D grid structure.The results show that the Li–Sn/Cu symmetric battery can stably cycle for more than 10,000 h at 2 mA.cm^(-2)and 1 mAh.cm^(-2)with a low overpotential.The capacity retention of the LiFePO_(4)full battery remains above 90.7%after 1,000 cycles at 1C.This work provides a facile,low-cost,and effective strategy for obtaining Li metal batteries with ultra-long cycle life.
基金financially supported by the National Natural Science Foundation of China(Nos.22178125 and 22478130).
文摘The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuring a trilayer architecture is developed by incorporating a thin polyethylene(PE)separator into a blending polymer matrix of poly(ethylene oxide)and poly(vinylidene fluoride)(PEO-PVDF)through a hot pressing technique.This structural design provides complementary functions:the flexible outer layers confine lithium deposition within a restricted area,while the robust interlayer prevents lithium dendrite penetration.Additionally,the incorporation of LiNO_(3) significantly enhances the stability of the CSE/Li interface by gradually forming a Li_(3)N-rich interfacial film,which promotes uniform lithium deposition.Consequently,the assembled Li||Li symmetrical cell demonstrates stable cycling for over 6000 h at a current density of 0.2 mA cm^(–2)with an areal capacity of 1.2 mAh cm^(–2).More attractively,ASSLBs constructed with the designed CSEs,high mass loading LFP/NCM811(LFP:LiFePO_(4);NCM811:LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2))cathodes(≥12 mg cm^(–2)),and lithium metal anodes deliver superior cycling performance without short-circuiting at current densities of 0.3/0.2 mA cm^(–2),respectively.This work offers critical insights for the design of high-performance ASSLBs with improved durability at high areal capacities.
基金supported by the Qingdao Jiuhuanxinyue New Energy Technology Co.,Ltd.the Guangdong Basic and Applied Basic Research Foundation(Grant No.2021B1515120071)+2 种基金the 21C Innovation Laboratory,Contemporary Amperex Technology Ltd.(Grant No.21C-OP-202112)the financial support from the Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515011873)the Shenzhen Science and Technology Program(Grant No.JCYJ20220531095212027).
文摘Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.
文摘Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion conducting polymer electrolytes(SICPEs)are less affected by lithium dendrites growth and thus are particularly interesting for application in lithium metal batteries.In this work,novel SIC-PEs are developed,based on an ionomer having poly(ethylene-alt-maleimide)backbone and lithium phenylsulfonyl(trifluoromethanesulfonyl)imide pendant moieties,further blended with poly(ethylene oxide)(PEO)and poly(ethylene glycol)dimethyl ether(PEGDME).These SIC-PEs exhibit ionic conductivity around~7×10^(−6)S·cm^(−1) at 70℃,lithium transference number close to unity,and excellent mechanical properties,with fracture toughness over 30 J·cm^(−3).Additionally,the electrolytes show very high resistance against lithium dendrites growth,by cycling for more than 1200 h in Li°symmetric cells at a current density of 0.1 mA·cm^(−2).LiFePO4||Li°cells with these SIC-PEs were cycled at 70℃ and C/10,showing initial capacity of almost 160 mAh·g^(−1)and residual capacity of 45%after 100 cycles.This work shows that single-ion conducting polymer electrolytes based on poly(ethylene-alt-maleimide)backbone are promising materials for application as electrolytes or catholytes in lithium metal polymer batteries.
基金support from the National Natural Science Foundation of China(grant no.21673161)the Sino-German Center for Research Promotion(grant no.1400).
文摘High energy density lithium(Li)metal batteries have attracted great attention,but they are faced with challenges of cycling instability and safety hazards.Due to high activity and drastic volume changes of metallic Li,potential dendritic risks cannot be fully eliminated.Therefore,suppressing already existing Li dendrites must be evaluated.In addition,Li-active solids alloying with Li always face mechanical instability and fractures with cycling.Herein,we present touch ablation of dendrites by liquid metal,namely forming a defense layer on the electrode to directly react with the dendrites.Embrittlement,supercooling,and other liquid characteristics make the liquid gallium(Ga)exhibit continuous and reversible reactions with Li.The unique layout with a hierarchical porous structure inhibits upward growth of the dendrites.The protected Li||Li cells achieve stable cyclic performance even at 10 mA cm^(–2)and a large capacity of 5 mA h cm^(-2).
基金financial support from the Swiss National Science Foundation via the Southeast Asia–Europe Joint Funding Scheme 2020(Grant No.IZJFZ2_202476)funding from the National Natural Science Foundation of China(Grant Nos.22209118 and 00301054A1073)the Fundamental Research Funds for the Central Universities(Grant Nos.1082204112A26,20826044D3083,and 20822041G4080)。
文摘Poor cycling stability in lithium–sulfur(Li–S)batteries necessitates advanced electrode/electrolyte design and innovative interlayer architectures.Heterogeneous catalysis has emerged as a promising approach,leveraging the adsorption and catalytic performance on lithium polysulfides(LiPSs)to inhibit LiPSs shuttling and improve redox kinetics.In this study,we report an ultrathin and laminar SnO_(2)@MXene heterostructure interlayer(SnO_(2)@MX),where SnO_(2) quantum dots(QDs)are uniformly distributed across the MXene layer.The combined structure of SnO_(2) QDs and MXene,along with the creation of numerous active boundary sites with coordination electron environments,plays a critical role in manipulating the catalytic kinetics of sulfur species.The Li–S cell with the SnO_(2)@MX-modified separator not only demonstrates superior electrochemical performance compared to cells with a bare separator but also induces homogeneous Li deposition during cycling.As a result,an areal capacity of 7.6 mAh cm^(-2) under a sulfur loading of 7.5 mg cm^(-2) and a high stability over 500 cycles are achieved.Our work demonstrates a feasible strategy of utilizing a laminar separator interlayer for advanced Li–S batteries awaiting commercialization and may shed light on the understanding of heterostructure catalysis with enhanced reaction kinetics.
基金Natural Science Foundation of the Jiangsu Higher Education Institutions of China,Grant/Award Number:22KJB150004Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200047+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:22209062,22222902Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China,Grant/Award Number:JSTJ-2022-023。
文摘Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.
基金supported by Beijing Natural Science Foundation(JQ22028)National Natural Science Foundation of China(U21A2080)+1 种基金Jilin Province Science and Technology Major Project(20210301021GX)Ministry of Science and Technology Rare Earth Special(2022YFB3506300).
文摘All-solid-state lithium metal batteries(ASSLMBs)featuring sulfide solid electrolytes(SEs)are recognized as the most promising next-generation energy storage technology because of their exceptional safety and much-improved energy density.However,lithium dendrite growth in sulfide SEs and their poor air stability have posed significant obstacles to the advancement of sulfide-based ASSLMBs.Here,a thin layer(approximately 5 nm)of g-C_(3)N_(4)is coated on the surface of a sulfide SE(Li_(6)PS_(5)Cl),which not only lowers the electronic conductivity of Li_(6)PS_(5)Cl but also achieves remarkable interface stability by facilitating the in situ formation of ion-conductive Li3N at the Li/Li_(6)PS_(5)Cl interface.Additionally,the g-C_(3)N_(4)coating on the surface can substantially reduce the formation of H_(2)S when Li_(6)PS_(5)Cl is exposed to humid air.As a result,Li-Li symmetrical cells using g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl stably cycle for 1000 h with a current density of 0.2 mA cm^(-2).ASSLMBs paired with LiNbO_(3)-coated LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)exhibit a capacity of 132.8 mAh g^(-1)at 0.1 C and a high-capacity retention of 99.1%after 200 cycles.Furthermore,g-C_(3)N_(4)-coated Li_(6)PS_(5)Cl effectively mitigates the self-discharge behavior observed in ASSLMBs.This surface-coating approach for sulfide solid electrolytes opens the door to the practical implementation of sulfide-based ASSLMBs.
基金financially supported by the National Natural Science Fund of China(Nos.12172118 and 12172205)the Research Program of Local Science Research Development under the Guidance of Central(No.216Z4402G)+1 种基金Science Research Project of Hebei Education Department(No.JZX2023004)support from"Yuanguang"Scholar Program of Hebei University of Technology。
文摘Lithium batteries have always played a key role in the field of new energy sources.However,non-controllable lithium dendrites and volume dilatation of metallic lithium in batteries with lithium metal as anodes have limited their development.Recently,a large number of studies have shown that the electrochemical performances of lithium batteries can be enhanced through the regulation of external physical fields.Especially,it significantly hinders the growth of lithium dendrites and promoting the reaction kinetics.This review summarizes recent innovations in the investigation of various physical fields of lithium batteries.The application of magnetic field in the synthesis of lithium battery electrode materials is introduced.The influence factors and regulation mechanism of various physical fields on the electrochemical performance of lithium batteries are reviewed emphatically.In addition,the current research status and existing challenges,along with future directions for the evolution of lithium batteries,are minutely discussed and prospected.New strategies for the further evolution of lithium batteries have also been provided.
基金This study was financially supported by the National Natural Science Foundation of China(Nos.52177208,52171202,51971055 and 51871046)the National Safety Academic Fund(Nos.U1930208,U2030206 and U1730136).
文摘The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great attention.Garnet-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,wide electrochemical window,and stability to Li metal anode,are promising solid-state electrolyte(SSEs)materials for SSLMBs.However,Li/LLZTO interface issues including high interface resistance,inhomogeneous Li deposition,and Li dendrite growth have hindered the practical application of SSLMBs.Herein,a multi-functional Li–SnF_(2) composite anode with Li,LiF,and Li-Sn alloy was specifically designed and prepared.The composite anode improves the wettability to LLZTO,constructing an intimate contact interface between it and LLZTO.Meanwhile,ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li dendrite.The solid-state symmetric cell exhibits low interface resistance(11Ω·cm^(2)) and high critical current density(1.3 mA·cm^(−2))at 25℃.The full SSLMB based on LiFePO_(4) or LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode also shows stable cycling performance and high rate capability.This work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.
基金Project(2022JJ40591)supported by the Natural Science Foundation of Hunan Province,ChinaProject(kq2202094)supported by the Natural Science Foundation of Changsha,China。
文摘Li-B alloy is expected to meet the expanding demands of energy storage,primarily driven by their high energydensity and structural stability.The fibrous porous skeleton can increase the electrochemical active area and reduce thelocal current density,therefore diminishing the lithium dendrites.In this study,we prepared Li-B alloys with differentlithium contents and examined the impact of lithium content on the structure and electrochemical properties of Li-Balloys.With the increase of lithium content,the spacing between the skeleton of the Li-B alloys increases.The lithiumdeposition on the top of the skeleton decreases,leading to thinner SEI,and lower polarization.The Li-B alloy with thehighest lithium content(64 wt.%lithium content)in the symmetric battery exhibits the longest cycle time,lasting over140 h at 1 mA/cm^(2)and 0.5 mA·h/cm^(2),with a minimal overpotential of 0.08 V.When paired with LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2),thefull battery has the highest specific discharge capacity and the best rate capacity.
基金financially supported by the National Natural Science Foundation of China(Nos.22279097,52172217)Natural Science Foundation of Guangdong Province(No.2021A1515010144)Shenzhen Science and Technology Program(No.JCYJ20210324120400002).
文摘Lithium(Li)dendrite issue,which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase(SEI),impedes the further development of high-energy Li metal batteries.However,the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short.Herein,we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix.The generated Co and LiF both enable fast Li-ion diffusion kinetics,meanwhile,the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites,thereby contributing to uniform Li nucleation and non-dendritic growth.As a result,a dendrite-free Li deposition with a low overpotential(16.1 mV)is achieved,which enables an extended lifespan over 750 h under strict conditions.The full cells with high-mass-loading LiFePO_(4)(11.5 mg/cm^(2))as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4%after undergoing 180 cycles.
