This paper presents a study on CO<sub>2</sub> atmospheric transformation which was reacted directly with lithium hydroxide solution and metallic lithium. This solution was obtained through the reaction bet...This paper presents a study on CO<sub>2</sub> atmospheric transformation which was reacted directly with lithium hydroxide solution and metallic lithium. This solution was obtained through the reaction between metallic lithium and deionized water where hydrogen is produced and by exposing the metal at ambient conditions. In the transformation process, atmospheric CO<sub>2</sub> gas reacts directly with LiOH solution, in both cases, the CO<sub>2</sub> transformation kinetics was different. For this purpose, reactions between CO<sub>2</sub> and LiOH solution were carried out under controlled temperature and the second process only with metallic lithium, which was exposed at room temperature, however, in these two processes lithium carbonate oxide was formed and identified. According to the results, the efficiency in CO<sub>2</sub> transformation is a function of temperature value which was variable until completely obtaining the by-product, its XRD characterization indicated the formation only of Li<sub>2</sub>CO<sub>3</sub> in both procedures. Under laboratory conditions lithium compounds selectively reacted with CO<sub>2</sub>. In the same way, there is an alternative procedure to obtain LiOH and Li<sub>2</sub>CO<sub>3</sub> for different applications in various areas.展开更多
Ionic selectivity is of significant importance in both fundamental science and practical applications.For instance,an ion-selective material allows the passage of a particular kind of ions while blocking the others,wh...Ionic selectivity is of significant importance in both fundamental science and practical applications.For instance,an ion-selective material allows the passage of a particular kind of ions while blocking the others,which could be used for purification of materials.Herein,the Li-ion-selectivity of a garnet-type solid electrolyte is discussed by comparing the difference of activation energy between different ions migrating in solids.The high ion-selectivity is confirmed by harvesting high-purity metallic lithium(99.98 wt%)from low-lithium-purity sources(80 wt%)at a moderate temperature(190℃).This gives it huge potential in separating lithium with impurities especially alkali and alkali-earth elements.The cost of metallic lithium production is only 25%of the international lithium price.The proposed electrochemical metallic lithium separating method is advantageous compared with the traditional process in terms of efficiency,safety,and cost.展开更多
The effects of different coating layers on lithium metal anode formed by reacting with different controlled atmospheres(argon,CO_2–O_2(2:1),N_2,and CO_2–O_2–N_2(2:1:3))have been investigated.The obtained X...The effects of different coating layers on lithium metal anode formed by reacting with different controlled atmospheres(argon,CO_2–O_2(2:1),N_2,and CO_2–O_2–N_2(2:1:3))have been investigated.The obtained XRD,second ion mass spectroscopy(SIMS),and scanning probe microscope(SPM)results demonstrate the formation of coating layers composed of Li_2CO_3,Li_3N,and the mixture of them on lithium tablets,respectively.The Li/Li symmetrical cell and Li/S cell are assembled to prove the advantages of the protected lithium tablet on electrochemical performance.The comparison of SEM and SIMS characterizations before/after cycles clarifies that an SEI-like composition formed on the lithium tablets could modulate the interfacial stabilization between the lithium foil and the ether electrolyte.展开更多
Lithium-ion batteries(LIBs)with fast-charging capability are essential for enhancing consumer experience and accelerating the global market adoption of electric vehicles.However,achieving fast-charging capability with...Lithium-ion batteries(LIBs)with fast-charging capability are essential for enhancing consumer experience and accelerating the global market adoption of electric vehicles.However,achieving fast-charging capability without compromising energy density,cycling lifespan,and safety of LIBs remains a significant challenge due to the formation of dendritic Li metal on graphite anode under fast charging condition.In view of this,the fundamentals for the dendritic metallic Li formation and the strategies for suppressing metallic Li plating based on analyzing the entire Li^(+)transport pathway at the anode including electrolyte,pore structure of electrode,and surface and bulk of materials are summarized and discussed in this review.Besides,we highlight the importance of designing thick electrodes with fast Li^(+)transport kinetics and comprehensively understanding the interaction between solid electrolyte interphase(SEI)and Li^(+)migration in order to avoid the formation of dendritic Li metal in practical fast-charging batteries.Finally,the regulation of Li metal plating with plane morphology,instead of dendritic structure,on the surface of graphite electrode under fast-charging condition is analyzed as a future direction to achieve higher energy density of batteries without safety concerns.展开更多
Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact l...Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium brom...An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.展开更多
Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(L...Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.展开更多
Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li util...Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.展开更多
The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal ba...The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.展开更多
The lithium metal anode is hailed as the desired "holy grail" for the forthcoming generation of highenergy-density batteries,given its astounding theoretical capacity and low potential.Nonetheless,the format...The lithium metal anode is hailed as the desired "holy grail" for the forthcoming generation of highenergy-density batteries,given its astounding theoretical capacity and low potential.Nonetheless,the formation and growth of dendrites seriously compromise battery life and safety.Herein,an yttriastabilized bismuth oxide(YSB) layer is fabricated on the polypropylene(PP) separator,where YSB reacts with Li anode in-situ in the cell to form a multi-component composite interlayer consisting of Li_(3)Bi,Li_(2)O,and Y_(2)O_(3).The interlayer can function not only as a redistributor to regulate Li^(+) distribution but also as an anion adsorber to increase the Li^(+) transference number from 0.37 to 0.79 for suppressing dendrite nucleation and growth.Consequently,compared with the cell with a baseline separator,those with modified separators exhibit prolonged lifespan in both Li/Li symmetrical cells and Li/Cu half-cells.Notably,the full cells coupled with ultrahigh-loading LiFePO_(4) display an excellent cycling performance of 1700 cycles with a high capacity retention of ~80% at 1 C,exhibiting great potential for practical applications.This work provides a feasible and effective new strategy for separator modification towards building a much-anticipated dendrite-free Li anode and realizing long-lifespan lithium metal batteries.展开更多
In lithium-sulfur batteries,cell design,specifically electrolyte design,has a key impact on the battery performance.The effect of lithium salt anion donor number(DN)(DN[PF_(6)]^(-)=2.5,DN[N(SO_(2)CF_(3))_(2)]^(-)=5.4,...In lithium-sulfur batteries,cell design,specifically electrolyte design,has a key impact on the battery performance.The effect of lithium salt anion donor number(DN)(DN[PF_(6)]^(-)=2.5,DN[N(SO_(2)CF_(3))_(2)]^(-)=5.4,DN[ClO_(4)]^(-)=8.4,DN[SO_(3)CF_(3)]^(-)=16.9,and DN[NO_(3)]^(-)=21.1)on the patterns of lithium-sulfur batteries and lithium metal electrode performances with sulfola ne-based electrolytes is investigated.An increase in DN of lithium salt anions leads to an increase in the depth and rate of electrochemical reduction of sulfur and long-chain lithium polysulfides and to a decrease in those for medium-and short-chain lithium polysulfides.DN of lithium salt anions has weak effect on the discharge capacity of lithium-sulfur batteries and the Coulomb efficiency during cycling,with the exception of LiSO_(3)CF_(3)and LiNO_(3).An increase in DN of lithium salt anions leads to an increase in the cycling duration of lithium metal anodes and to a decrease in the presence of lithium polysulfides.In sulfolane solutions of LiNO_(3)and LiSO_(3)CF_(3),lithium polysulfides do not affect the cycling duration of lithium metal anodes.展开更多
The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically r...The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate(CA) matrix with rigid graphene oxide(GO) and Li F fillers(termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium(Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups(C=O) enriched in GCL foster a strengthened correlation with Li^(+), which availably aids the Li^(+)desolvation process and expedites facile Li^(+)mobility, yielding exceptional Li^(+) transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO_(4) full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.展开更多
Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriou...Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriously limit the practical application of LM.Herein,with the aid of a hard template approach,a novel lithiophilic CoF_(2)-carbon hollow sphere(CoF_(2)@C-HS)composite material is successfully prepared via a facile in-situ fluorination and etching strategy.The lithiophilic CoF_(2) acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiFrich solid electrolyte interphase(SEI),and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition.Theoretical simulations reveal that the synergistic effect of lithiophilic CoF_(2) and hollow carbon matrix homogenizes the electric field distribution and Li~+flux.Benefiting from these advantages,the CoF_(2)@C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency(CE)of 93.7%for 280 cycles at 1 mA cm^(-2)and 1 mA h cm^(-2).The symmetrical cell using CoF_(2)@C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 MA cm^(-2)and an areal capacity of 0.5 mA h cm^(-2).Moreover,the Li@CoF_(2)@C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95%in LiFePO_(4)-based full cell and 110 stable cycles at 1 C in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based highvoltage full cell.This work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition,realizing dendrite-free LM anodes and the practical applications of LM batteries.展开更多
The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits.Three‐dimensional hollow carbon is receiving incr...The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits.Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity;however,uncontrollable and nonuniform deposition of Li remains a challenge.In this study,we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters(Zn and Ag)on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host.Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag^(+) and metallic Zn.Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating.Through combined electrochemical,microstructural,and computational studies,we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and,in turn,enhancing electrochemical performance.This study provides new insights into the design of reversible host materials for practical Li metal batteries.展开更多
Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume ch...Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume changes during lithium deposition/stripping processes lead to sustained accumulation of inactive lithium and poor cycling reversibility.Quantifying the formation and evolution of inactive lithium under different conditions and fully evaluating the complex failure modes are the key issues in this challenging field.This article comprehensively reviews recent research progress on the quantification of formation and evolution of inactive lithium detected by different quantitative techniques in rechargeable lithium metal batteries.The key research challenges such as failure mechanism,modification strategies and operando characterization of lithium metal anodes are systematically summarized and prospected.This review provides a new angle of view to understand failure mechanism of lithium metal anodes and inspiration and guidance for the future development of rechargeable lithium metal batteries.展开更多
Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,i...Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,inherent challenges of deleterious lithium dendrite growth and poor interfacial stability hinder their commercial application.Herein,we report a liquid metal-coated lithium metal(LM@Li)anode strategy to improve the contact between lithium metal and a Li6PS5Cl inorganic electrolyte.The LM@Li symmetric cell shows over 1000 h of stable lithium plating/stripping cycles at 2mA cm^(-2) and a significantly higher critical current density of 9.8 mAcm^(-2) at 25°C.In addition,a full battery assembled with a high-capacity composite LiNbO3@-LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)(LNO@NCM721)cathode shows stable cycling performance.Experimental and computational results have demonstrated that dendrite growth tolerance and physical contact in solid-state batteries can be reinforced by using LM interlayers for interfacial modification.展开更多
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv...Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.展开更多
Solid-state polymer electrolytes(SPEs)are candidate schemes for meeting the safety and energy density needs of advanced lithium-based battery because of their improved mechanical and electrochemical stability compared...Solid-state polymer electrolytes(SPEs)are candidate schemes for meeting the safety and energy density needs of advanced lithium-based battery because of their improved mechanical and electrochemical stability compared to traditional liquid electrolytes.However,low ionic conductivity and side reactions occurring in traditional high-voltage lithium metal batteries(LMBs)hinder their practical applications.Here,amino-modified metal-organic frameworks(UiO-66-NH_(2))with abundant defects as multifunctional fillers in the polyurethane based SPEs achieve the collaborative promotion of the mechanical strength and room temperature ionic conductivity.The surface modified amino groups serve as anchoring points for oxygen atoms of polymer chains,forming a firmly hydrogen-bond interface with polycarbonate-based polyurethane frameworks.The rich interfaces between UiO-66-NH_(2) and polymers dramatically decrease the crystallization of polymer chains and reduce ion transport impedance,which markedly boosted the ionic conductivity to 2.1×10^(−4) S·cm^(−1) with a high Li+transference numbers of 0.71.As a result,LiFePO4∣SPEs∣Li cells exhibit prominent cyclability for 700 cycles under 0.5 C with 96.5%capacity retention.The LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)∣SPEs∣Li cells deliver excellent long-term lifespan for 260 cycles with a high capacity retention of 91.9%and high average Coulombic efficiency(98.5%)under ambient conditions.This simple and effective hybrid SPE design strategy sheds a milestone significance light for high-voltage Li-metal batteries.展开更多
Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed...Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed solid-state electrolytes(SSEs)are still difficult to meet the practical application requirements of SSLMBs.In this review,based on the analysis of main problems and challenges faced by the development of SSEs,the ingenious application and latest progresses including specific suggestions of various polymer fibers and their membrane products in solving these issues are emphatically reviewed.Firstly,the inherent defects of inorganic and organic electrolytes are pointed out.Then,the application strategies of polymer fibers/fiber membranes in strengthening strength,reducing thickness,enhancing thermal stability,increasing the film formability,improving ion conductivity and optimizing interface stability are discussed in detail from two aspects of improving physical structure properties and electrochemical performances.Finally,the researches and development trends of the intelligent applications of high-performance polymer fibers in SSEs is prospected.This review intends to provide timely and important guidance for the design and development of polymer fiber composite SSEs for SSLMBs.展开更多
文摘This paper presents a study on CO<sub>2</sub> atmospheric transformation which was reacted directly with lithium hydroxide solution and metallic lithium. This solution was obtained through the reaction between metallic lithium and deionized water where hydrogen is produced and by exposing the metal at ambient conditions. In the transformation process, atmospheric CO<sub>2</sub> gas reacts directly with LiOH solution, in both cases, the CO<sub>2</sub> transformation kinetics was different. For this purpose, reactions between CO<sub>2</sub> and LiOH solution were carried out under controlled temperature and the second process only with metallic lithium, which was exposed at room temperature, however, in these two processes lithium carbonate oxide was formed and identified. According to the results, the efficiency in CO<sub>2</sub> transformation is a function of temperature value which was variable until completely obtaining the by-product, its XRD characterization indicated the formation only of Li<sub>2</sub>CO<sub>3</sub> in both procedures. Under laboratory conditions lithium compounds selectively reacted with CO<sub>2</sub>. In the same way, there is an alternative procedure to obtain LiOH and Li<sub>2</sub>CO<sub>3</sub> for different applications in various areas.
基金supported by the Basic Science Center Program of the National Natural Science Foundation of China(NSFC)under Grant No.51788104Beijing Natural Science Foundation under Grant No.JQ19005.
文摘Ionic selectivity is of significant importance in both fundamental science and practical applications.For instance,an ion-selective material allows the passage of a particular kind of ions while blocking the others,which could be used for purification of materials.Herein,the Li-ion-selectivity of a garnet-type solid electrolyte is discussed by comparing the difference of activation energy between different ions migrating in solids.The high ion-selectivity is confirmed by harvesting high-purity metallic lithium(99.98 wt%)from low-lithium-purity sources(80 wt%)at a moderate temperature(190℃).This gives it huge potential in separating lithium with impurities especially alkali and alkali-earth elements.The cost of metallic lithium production is only 25%of the international lithium price.The proposed electrochemical metallic lithium separating method is advantageous compared with the traditional process in terms of efficiency,safety,and cost.
基金supported by the National Key Research and Development Program of China(Grant No.2016YFB0100100)the National Natural Science Foundation of China(Grants Nos.52315206 and 51502334)the Fund from Beijing Municipal Science&Technology Commission,China(Grants No.D171100005517001)
文摘The effects of different coating layers on lithium metal anode formed by reacting with different controlled atmospheres(argon,CO_2–O_2(2:1),N_2,and CO_2–O_2–N_2(2:1:3))have been investigated.The obtained XRD,second ion mass spectroscopy(SIMS),and scanning probe microscope(SPM)results demonstrate the formation of coating layers composed of Li_2CO_3,Li_3N,and the mixture of them on lithium tablets,respectively.The Li/Li symmetrical cell and Li/S cell are assembled to prove the advantages of the protected lithium tablet on electrochemical performance.The comparison of SEM and SIMS characterizations before/after cycles clarifies that an SEI-like composition formed on the lithium tablets could modulate the interfacial stabilization between the lithium foil and the ether electrolyte.
基金the support by the National Natural Science Foundation of China(52072137 and 52272207)。
文摘Lithium-ion batteries(LIBs)with fast-charging capability are essential for enhancing consumer experience and accelerating the global market adoption of electric vehicles.However,achieving fast-charging capability without compromising energy density,cycling lifespan,and safety of LIBs remains a significant challenge due to the formation of dendritic Li metal on graphite anode under fast charging condition.In view of this,the fundamentals for the dendritic metallic Li formation and the strategies for suppressing metallic Li plating based on analyzing the entire Li^(+)transport pathway at the anode including electrolyte,pore structure of electrode,and surface and bulk of materials are summarized and discussed in this review.Besides,we highlight the importance of designing thick electrodes with fast Li^(+)transport kinetics and comprehensively understanding the interaction between solid electrolyte interphase(SEI)and Li^(+)migration in order to avoid the formation of dendritic Li metal in practical fast-charging batteries.Finally,the regulation of Li metal plating with plane morphology,instead of dendritic structure,on the surface of graphite electrode under fast-charging condition is analyzed as a future direction to achieve higher energy density of batteries without safety concerns.
基金This work was financially supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)+1 种基金This work was also financially supported by the Shenzhen Science and Technology Innovation Commission(GJHZ20200731095606021,20200925155544005)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083)。
文摘Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金financial support from Singapore Ministry of Education under its AcRF Tier 2 Grant No MOE-T2EP10123-0001Singapore National Research Foundation Investigatorship under Grant No NRF-NRFI08-2022-0009Academic Excellence Foundation of BUAA for PhD Students(applicant:Hongfei Xu).
文摘An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.
基金supported by the National Natural Science Foundation of China(52122702,52277215)the Natural Science Foundation of Heilongjiang Province of China(JQ2021E005)。
文摘Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.
基金supported by the National Natural Science Foundation of China(31870570)the Science and Technology Plan of Fujian Provincial,China(2020H4026,2022G02020 and 2022H6002)+1 种基金the Science and Technology Plan of Xiamen(3502Z20203005)the Scientific Research Start-up Funding for Special Professor of Minjiang Scholars。
文摘Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.
基金This work is supported by the Technologies R&D Program of Huzhou City(No.2022JB01)the Key Research and Development Program of Zhejiang Province(No.2023C01127)the Highstar Corporation HSD20210118.
文摘The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.
基金supported by the National Nature Science Foundation of China [52172247, 21875237]the National Key R&D Program of China [2018YFB0905400]。
文摘The lithium metal anode is hailed as the desired "holy grail" for the forthcoming generation of highenergy-density batteries,given its astounding theoretical capacity and low potential.Nonetheless,the formation and growth of dendrites seriously compromise battery life and safety.Herein,an yttriastabilized bismuth oxide(YSB) layer is fabricated on the polypropylene(PP) separator,where YSB reacts with Li anode in-situ in the cell to form a multi-component composite interlayer consisting of Li_(3)Bi,Li_(2)O,and Y_(2)O_(3).The interlayer can function not only as a redistributor to regulate Li^(+) distribution but also as an anion adsorber to increase the Li^(+) transference number from 0.37 to 0.79 for suppressing dendrite nucleation and growth.Consequently,compared with the cell with a baseline separator,those with modified separators exhibit prolonged lifespan in both Li/Li symmetrical cells and Li/Cu half-cells.Notably,the full cells coupled with ultrahigh-loading LiFePO_(4) display an excellent cycling performance of 1700 cycles with a high capacity retention of ~80% at 1 C,exhibiting great potential for practical applications.This work provides a feasible and effective new strategy for separator modification towards building a much-anticipated dendrite-free Li anode and realizing long-lifespan lithium metal batteries.
基金supported by the Russian Science Foundation as part of joint project of RSF-NSFC no.21-43-00006“Polysulfide IonSolvent Complexes and Their Electrochemical Behavior in Lithium-Sulfur Batteries”with the National Natural Science Foundation of China(22061132002)。
文摘In lithium-sulfur batteries,cell design,specifically electrolyte design,has a key impact on the battery performance.The effect of lithium salt anion donor number(DN)(DN[PF_(6)]^(-)=2.5,DN[N(SO_(2)CF_(3))_(2)]^(-)=5.4,DN[ClO_(4)]^(-)=8.4,DN[SO_(3)CF_(3)]^(-)=16.9,and DN[NO_(3)]^(-)=21.1)on the patterns of lithium-sulfur batteries and lithium metal electrode performances with sulfola ne-based electrolytes is investigated.An increase in DN of lithium salt anions leads to an increase in the depth and rate of electrochemical reduction of sulfur and long-chain lithium polysulfides and to a decrease in those for medium-and short-chain lithium polysulfides.DN of lithium salt anions has weak effect on the discharge capacity of lithium-sulfur batteries and the Coulomb efficiency during cycling,with the exception of LiSO_(3)CF_(3)and LiNO_(3).An increase in DN of lithium salt anions leads to an increase in the cycling duration of lithium metal anodes and to a decrease in the presence of lithium polysulfides.In sulfolane solutions of LiNO_(3)and LiSO_(3)CF_(3),lithium polysulfides do not affect the cycling duration of lithium metal anodes.
基金National Natural Science Foundation of China (No. 22209014)5.5 Engineering Research & Innovation Team Project of Beijing Forestry University (No.BLRC 2023B05)。
文摘The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate(CA) matrix with rigid graphene oxide(GO) and Li F fillers(termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium(Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups(C=O) enriched in GCL foster a strengthened correlation with Li^(+), which availably aids the Li^(+)desolvation process and expedites facile Li^(+)mobility, yielding exceptional Li^(+) transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO_(4) full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.
基金supported by the Natural Science Foundation of China (52277218)the Hubei Provincial Natural Science Foundation of China (2024AFA094)+1 种基金the Excellent Discipline Cultivation Project by JHUN (2023XKZ009)supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,Materials Sciences and Engineering Division under contract number DE-AC05-00OR22725。
文摘Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriously limit the practical application of LM.Herein,with the aid of a hard template approach,a novel lithiophilic CoF_(2)-carbon hollow sphere(CoF_(2)@C-HS)composite material is successfully prepared via a facile in-situ fluorination and etching strategy.The lithiophilic CoF_(2) acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiFrich solid electrolyte interphase(SEI),and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition.Theoretical simulations reveal that the synergistic effect of lithiophilic CoF_(2) and hollow carbon matrix homogenizes the electric field distribution and Li~+flux.Benefiting from these advantages,the CoF_(2)@C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency(CE)of 93.7%for 280 cycles at 1 mA cm^(-2)and 1 mA h cm^(-2).The symmetrical cell using CoF_(2)@C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 MA cm^(-2)and an areal capacity of 0.5 mA h cm^(-2).Moreover,the Li@CoF_(2)@C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95%in LiFePO_(4)-based full cell and 110 stable cycles at 1 C in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based highvoltage full cell.This work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition,realizing dendrite-free LM anodes and the practical applications of LM batteries.
基金National Research Foundation,Grant/Award Numbers:NRF‐2018R1A5A1025594,NRF‐2022M3J1A1062644。
文摘The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits.Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity;however,uncontrollable and nonuniform deposition of Li remains a challenge.In this study,we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters(Zn and Ag)on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host.Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag^(+) and metallic Zn.Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating.Through combined electrochemical,microstructural,and computational studies,we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and,in turn,enhancing electrochemical performance.This study provides new insights into the design of reversible host materials for practical Li metal batteries.
基金financially supported by the National Key R&D Program of China, Grant No. 2021YFB2401800
文摘Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume changes during lithium deposition/stripping processes lead to sustained accumulation of inactive lithium and poor cycling reversibility.Quantifying the formation and evolution of inactive lithium under different conditions and fully evaluating the complex failure modes are the key issues in this challenging field.This article comprehensively reviews recent research progress on the quantification of formation and evolution of inactive lithium detected by different quantitative techniques in rechargeable lithium metal batteries.The key research challenges such as failure mechanism,modification strategies and operando characterization of lithium metal anodes are systematically summarized and prospected.This review provides a new angle of view to understand failure mechanism of lithium metal anodes and inspiration and guidance for the future development of rechargeable lithium metal batteries.
基金financially supported by the Shenzhen Science and Technology Program (Grant No.KQTD20200820113045083,ZDSYS20190902093220279,and JCYJ20220818102403007)the National Natural Science Foundation of China (52201257)the Shenzhen Research Fund for Returned Scholars (DD11409017).
文摘Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,inherent challenges of deleterious lithium dendrite growth and poor interfacial stability hinder their commercial application.Herein,we report a liquid metal-coated lithium metal(LM@Li)anode strategy to improve the contact between lithium metal and a Li6PS5Cl inorganic electrolyte.The LM@Li symmetric cell shows over 1000 h of stable lithium plating/stripping cycles at 2mA cm^(-2) and a significantly higher critical current density of 9.8 mAcm^(-2) at 25°C.In addition,a full battery assembled with a high-capacity composite LiNbO3@-LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)(LNO@NCM721)cathode shows stable cycling performance.Experimental and computational results have demonstrated that dendrite growth tolerance and physical contact in solid-state batteries can be reinforced by using LM interlayers for interfacial modification.
基金supported by the National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22379013 and 22209010)the Beijing Institute of Technology“Xiaomi Young Scholars”program。
文摘Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.
基金financially supported by the National Natural Science Foundation of China(Nos.52202236 and 5202780089)China Postdoctoral Science Foundation(Nos.2024T170300 and 2022M711232).
文摘Solid-state polymer electrolytes(SPEs)are candidate schemes for meeting the safety and energy density needs of advanced lithium-based battery because of their improved mechanical and electrochemical stability compared to traditional liquid electrolytes.However,low ionic conductivity and side reactions occurring in traditional high-voltage lithium metal batteries(LMBs)hinder their practical applications.Here,amino-modified metal-organic frameworks(UiO-66-NH_(2))with abundant defects as multifunctional fillers in the polyurethane based SPEs achieve the collaborative promotion of the mechanical strength and room temperature ionic conductivity.The surface modified amino groups serve as anchoring points for oxygen atoms of polymer chains,forming a firmly hydrogen-bond interface with polycarbonate-based polyurethane frameworks.The rich interfaces between UiO-66-NH_(2) and polymers dramatically decrease the crystallization of polymer chains and reduce ion transport impedance,which markedly boosted the ionic conductivity to 2.1×10^(−4) S·cm^(−1) with a high Li+transference numbers of 0.71.As a result,LiFePO4∣SPEs∣Li cells exhibit prominent cyclability for 700 cycles under 0.5 C with 96.5%capacity retention.The LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)∣SPEs∣Li cells deliver excellent long-term lifespan for 260 cycles with a high capacity retention of 91.9%and high average Coulombic efficiency(98.5%)under ambient conditions.This simple and effective hybrid SPE design strategy sheds a milestone significance light for high-voltage Li-metal batteries.
基金supported by the National Natural Science Foundation of China(52203066,51973157,61904123)Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金Tianjin Research Innovation Project for Postgraduate Students(2021YJSB234)Science and Technology Plans of Tianjin(19PTSYJC00010)Science&Technology Development Fund of Tianjin Education Commission for Higher Education(Grant No.2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed solid-state electrolytes(SSEs)are still difficult to meet the practical application requirements of SSLMBs.In this review,based on the analysis of main problems and challenges faced by the development of SSEs,the ingenious application and latest progresses including specific suggestions of various polymer fibers and their membrane products in solving these issues are emphatically reviewed.Firstly,the inherent defects of inorganic and organic electrolytes are pointed out.Then,the application strategies of polymer fibers/fiber membranes in strengthening strength,reducing thickness,enhancing thermal stability,increasing the film formability,improving ion conductivity and optimizing interface stability are discussed in detail from two aspects of improving physical structure properties and electrochemical performances.Finally,the researches and development trends of the intelligent applications of high-performance polymer fibers in SSEs is prospected.This review intends to provide timely and important guidance for the design and development of polymer fiber composite SSEs for SSLMBs.