Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selectiv...Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.展开更多
Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous ...Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.展开更多
Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition be...Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.展开更多
In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost ef...In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.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
Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological...Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.展开更多
Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic t...Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li<sup> </sup>. Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO<sub>4</sub>, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.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
Scientific research is one of the primary ways to drive human civilization forward.Countless research institutions and researchers worldwide are dedicated to exploring the unknown,resulting in a flood of research find...Scientific research is one of the primary ways to drive human civilization forward.Countless research institutions and researchers worldwide are dedicated to exploring the unknown,resulting in a flood of research findings[1].For instance,Web of Science alone collects over 10,000 academic papers on a daily basis.While each research field typically has around 10%of review articles,these mainly focus on a limited portion of the subject,failing to provide a comprehensive and real-time updated overview.As a result,researchers or students in a particular field may spend several months,or even longer,comprehending the state of research that has developed over just a few years.The lack of systematic background often leads to redundant or similar studies,which is highly detrimental to the progress of science and technology.展开更多
Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines gi...Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.展开更多
The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical ...The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical specific capacity of about 3860 mA h g^(-1) and very low redox potential(-3.04 V vs.the standard hydrogen electrode)promise substantially higher energy densities compared to current lithium-ion batteries(LIBs)[1].However,lithium metal electrodes face severe challenges associated with the risk of dendritic lithium deposition and the high reactivity with traditional organic liquid electrolytes,resulting in a continuous loss of electrochemically active lithium and a relatively low Coulombic efficiency[2].To address these challenges,solid inorganic and polymer electrolytes have emerged as a potentially saferalternative.展开更多
As a key material for lithium metal batteries(LMBs),lithium metal is one of the most promising anode materials to break the bottleneck of battery energy density and a commonly used active material for reference electr...As a key material for lithium metal batteries(LMBs),lithium metal is one of the most promising anode materials to break the bottleneck of battery energy density and a commonly used active material for reference electrodes.Although lithium anodes are regarded as the holy grail of lithium batteries,decades of exploration have not led to the successful commercialization of LMBs,due mainly to the challenges related to the inherent properties of lithium metal.To pave the way for further investigation,herein,a comprehensive review focusing on the fundamental science of lithium are provided.Firstly,the natures of lithium atoms and their isotopes,lithium clusters and lithium crystals are revisited,especially their structural and energetic properties.Subsequently,the electrochemical properties of lithium metal are reviewed.Numerous important concepts and scientific questions,including the electronic structure of lithium,influence of high pressure and low temperature on the properties of lithium,factors influencing lithium deposition,generation of lithium dendrites,and electrode potential of lithium in different electrolytes,are explained and analyzed in detail.Approaches to improve the performance of lithium anodes and thoughtfulness about the electrode potential in lithium battery research are proposed.展开更多
The global importance of lithium-ion batteries(LIBs)has been increasingly underscored with the advancement of high-performance energy storage technologies.However,the end-of-life of these batteries poses significant c...The global importance of lithium-ion batteries(LIBs)has been increasingly underscored with the advancement of high-performance energy storage technologies.However,the end-of-life of these batteries poses significant challenges from environmental,economic,and resource management perspectives.This review paper focuses on the pyrometallurgy-based recycling process of lithium-ion batteries,exploring the fundamental understanding of this process and the importance of its optimization.Centering on the high energy consumption and emission gas issues of the pyrometallurgical recycling process,we systematically analyzed the capital-intensive nature of this process and the resulting technological characteristics.Furthermore,we conducted an in-depth discussion on the future research directions to overcome the existing technological barriers and limitations.This review will provide valuable insights for researchers and industry stakeholders in the battery recycling field.展开更多
Phase matching or quasi-phase matching(QPM)is of significant importance to the conversion efficiency of second harmonic generation(SHG)in artificial nonlinear crystals like lithium niobate(LN)crystal or microstructure...Phase matching or quasi-phase matching(QPM)is of significant importance to the conversion efficiency of second harmonic generation(SHG)in artificial nonlinear crystals like lithium niobate(LN)crystal or microstructured nonlinear crystals like periodic-poled lithium niobate(PPLN)crystals.In this paper,we propose and show that the incident angle of pump laser light can be harnessed as an alternative versatile tool to engineer QPM for high-efficiency SHG in a PPLN crystal,in addition to conventional means of period adjusting or temperature tuning.A rigorous model is established and analytical solution of the nonlinear conversion efficiency under the small and large signal approximation theory is obtained at different incident angles.The variation of phase mismatching and walk-off length with incident angle or incident wavelength are also explored.Numerical simulations for a PPLN crystal with first order QPM structure are used to confirm our theoretical predictions based on the exact analytical solution of the general large-signal theory.The results show that the narrow-band tunable SHG output covers a range of 532 nm–552.8 nm at the ideal incident angle from 0°to 90°.This theoretical scheme,fully considering the reflection and transmission at the air-crystal interface,would offer an efficient theoretical system to evaluate the nonlinear frequency conversion and help to obtain the maximum SHG conversion efficiency by selecting an optimum incident wavelength and incident angle in a specially designed PPLN crystal,which would be very helpful for the design of tunable narrow-band pulse nanosecond,picosecond,and femtosecond laser devices via PPLN and other microstructured LN crystals.展开更多
Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted...Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.展开更多
In this study,we have explored the use of water as a non-solvent for tuning the microstructure of poly-benzimidazole(PBI)membranes,which are potential separators for lithium metal batteries(LMBs).The traditional metho...In this study,we have explored the use of water as a non-solvent for tuning the microstructure of poly-benzimidazole(PBI)membranes,which are potential separators for lithium metal batteries(LMBs).The traditional method for membrane synthesis called nonsolvent-induced phase separation(NIPS),usually relies on hazardous and costly organic non-solvents.By dissolving sodium chloride(Nacl)in water,we could adjust the water ionic potency and the exchange speed of the non-solvent with the DMAC solution to change the micropore structure of the PBI membrane.With increasing Nacl concentration,the micro-pores in the PBI membrane transitioned from finger-like to sponge-like morphology.Compared to com-mercial separators like the Celgard separator,the PBI membrane with sponge-like micropores exhibited better regulation of lithium deposition and improved Li^(+) transportation capability due to its good wetta-bility with the electrolyte.Consequently,the PBI membrane-based Li/Li symmetric cell and Li/LiFePO_(4) full cell demonstrated superior performance compared to the Celgard-based ones.This research proposes an eco-friendly and scalable synthetic approach for fabricating commercial separators for LMBs,addressing the issue of lithium dendrite growth and improving overall battery safety and performance.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
This work is a simulation modelling with the LAMMPS calculation code of an electrode based on alkali metals (lithium, sodium and potassium) using the MEAM potential. For different multiplicities, two models were studi...This work is a simulation modelling with the LAMMPS calculation code of an electrode based on alkali metals (lithium, sodium and potassium) using the MEAM potential. For different multiplicities, two models were studied;with and without gap. In this work, we present the structural, physical and chemical properties of the lithium, sodium and potassium electrodes. For the structural properties, the cohesive energy and the mesh parameters were calculated, revealing that, whatever the chemical element selected, the compact hexagonal hcp structure is the most stable, followed by the face-centred cubic CFC structure, and finally the BCC structure. The most stable structure is lithium, with a cohesion energy of -6570 eV, and the lowest bcc-hcp transition energy of -0.553 eV/atom, followed by sodium. For physical properties, kinetic and potential energies were calculated for each of the sectioned chemical elements, with lithium achieving the highest value. Finally, for the chemical properties, we studied the diffusion coefficient and the activation energy. Only potassium followed an opposite order to the other two, with the quantities with lacunae being greater than those without lacunae, whatever the multiplicity. The order of magnitude of the diffusion coefficients is given by the relationship D<sub>Li</sub> > D<sub>Na</sub> > D<sub>k</sub> for the multiplicity 6*6*6, while for the activation energy the order is reversed.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.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
基金the Science and Technology Key Project of Anhui Province,China(No.2022e03020004).
文摘Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.
基金This work was supported by the Fundamental Research Funds for the Central Universities(DUT20LAB123 and DUT20LAB307)the Natural Science Foundation of Jiangsu Province(BK20191167).
文摘Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.
基金supported by the National Natural Science Foundation of China (52302292, 52302058, 52302085)the China Postdoctoral Science Foundation (2021M702225)+1 种基金the Anhui Province University Natural Science Research Project (2023AH030093, 2023AH040301)the Startup Research Fund of Chaohu University (KYQD-2023005, KYQD-2023051)。
文摘Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.
基金support by,National Key Research and Development Program(2023YFB2503700 and 2023YFC3008804)the Beijing Municipal Science&Technology Commission No.Z231100006123003+1 种基金the National Science Foundation of China(22071133)the Beijing Natural Science Foundation(No.Z220020).
文摘In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.
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the Horizon Europe Project“Batteries reuse and direct production of high performances cathodic and anodic materials and other raw materials from batteries recycling using low cost and environmentally friendly technologies” (RHINOCEROS project,grant no.101069685)。
文摘Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.
文摘Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li<sup> </sup>. Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO<sub>4</sub>, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.
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support from the Shenzhen Science and Technology Program(KCXST20221021111201003).
文摘Scientific research is one of the primary ways to drive human civilization forward.Countless research institutions and researchers worldwide are dedicated to exploring the unknown,resulting in a flood of research findings[1].For instance,Web of Science alone collects over 10,000 academic papers on a daily basis.While each research field typically has around 10%of review articles,these mainly focus on a limited portion of the subject,failing to provide a comprehensive and real-time updated overview.As a result,researchers or students in a particular field may spend several months,or even longer,comprehending the state of research that has developed over just a few years.The lack of systematic background often leads to redundant or similar studies,which is highly detrimental to the progress of science and technology.
基金financially supported by the National Natural Science Foundation of China(No.52072322)the Department of Science and Technology of Sichuan Province,China(Nos.23GJHZ0147,23ZDYF0262,2022YFG0294,and 2019-GH02-00052-HZ)。
文摘Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.
基金financial support from the Federal Ministry of Education and Research (BMBF) within the FestBatt project (03XP0175B)the FB2-Poly project(03XP0429B)the Helmholtz Association
文摘The continuously growing importance of batteries for powering(hybrid)electric vehicles and storing renewable energy has prompted a renewed focus on lithium-metal batteries(LMBs)in recent years,as its high theoretical specific capacity of about 3860 mA h g^(-1) and very low redox potential(-3.04 V vs.the standard hydrogen electrode)promise substantially higher energy densities compared to current lithium-ion batteries(LIBs)[1].However,lithium metal electrodes face severe challenges associated with the risk of dendritic lithium deposition and the high reactivity with traditional organic liquid electrolytes,resulting in a continuous loss of electrochemically active lithium and a relatively low Coulombic efficiency[2].To address these challenges,solid inorganic and polymer electrolytes have emerged as a potentially saferalternative.
基金gratitude to the National Natural Science Foundation of China(No.22279070,U21A20170,22279071 and 52206263)the Ministry of Science and Technology of China(No.2019YFA0705703 and 2019YFE0100200)The authors thank Joint Work Plan for Research Projects under the Clean Vehicles Consortium at U.S.and China-Clean Energy Research Center(CERCCVC2.0,2016-2020)。
文摘As a key material for lithium metal batteries(LMBs),lithium metal is one of the most promising anode materials to break the bottleneck of battery energy density and a commonly used active material for reference electrodes.Although lithium anodes are regarded as the holy grail of lithium batteries,decades of exploration have not led to the successful commercialization of LMBs,due mainly to the challenges related to the inherent properties of lithium metal.To pave the way for further investigation,herein,a comprehensive review focusing on the fundamental science of lithium are provided.Firstly,the natures of lithium atoms and their isotopes,lithium clusters and lithium crystals are revisited,especially their structural and energetic properties.Subsequently,the electrochemical properties of lithium metal are reviewed.Numerous important concepts and scientific questions,including the electronic structure of lithium,influence of high pressure and low temperature on the properties of lithium,factors influencing lithium deposition,generation of lithium dendrites,and electrode potential of lithium in different electrolytes,are explained and analyzed in detail.Approaches to improve the performance of lithium anodes and thoughtfulness about the electrode potential in lithium battery research are proposed.
基金the Technology Innovation Program(or Industrial Strategic Technology Development Program)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.20022950)。
文摘The global importance of lithium-ion batteries(LIBs)has been increasingly underscored with the advancement of high-performance energy storage technologies.However,the end-of-life of these batteries poses significant challenges from environmental,economic,and resource management perspectives.This review paper focuses on the pyrometallurgy-based recycling process of lithium-ion batteries,exploring the fundamental understanding of this process and the importance of its optimization.Centering on the high energy consumption and emission gas issues of the pyrometallurgical recycling process,we systematically analyzed the capital-intensive nature of this process and the resulting technological characteristics.Furthermore,we conducted an in-depth discussion on the future research directions to overcome the existing technological barriers and limitations.This review will provide valuable insights for researchers and industry stakeholders in the battery recycling field.
基金Project supported by the National Natural Science Foundation of China(Grant No.11974119)the Science and Technology Project of Guangdong Province,China(Grant No.2020B010190001)+2 种基金the Guangdong Innovative and Entrepreneurial Research Team Program(Grant No.2016ZT06C594)the National Key Research and Development Program of China(Grant Nos.2018YFA,0306200,and 2019YFB2203500)the Science and Technology Program of Guangzhou City(Grant No.2023A04J1309).
文摘Phase matching or quasi-phase matching(QPM)is of significant importance to the conversion efficiency of second harmonic generation(SHG)in artificial nonlinear crystals like lithium niobate(LN)crystal or microstructured nonlinear crystals like periodic-poled lithium niobate(PPLN)crystals.In this paper,we propose and show that the incident angle of pump laser light can be harnessed as an alternative versatile tool to engineer QPM for high-efficiency SHG in a PPLN crystal,in addition to conventional means of period adjusting or temperature tuning.A rigorous model is established and analytical solution of the nonlinear conversion efficiency under the small and large signal approximation theory is obtained at different incident angles.The variation of phase mismatching and walk-off length with incident angle or incident wavelength are also explored.Numerical simulations for a PPLN crystal with first order QPM structure are used to confirm our theoretical predictions based on the exact analytical solution of the general large-signal theory.The results show that the narrow-band tunable SHG output covers a range of 532 nm–552.8 nm at the ideal incident angle from 0°to 90°.This theoretical scheme,fully considering the reflection and transmission at the air-crystal interface,would offer an efficient theoretical system to evaluate the nonlinear frequency conversion and help to obtain the maximum SHG conversion efficiency by selecting an optimum incident wavelength and incident angle in a specially designed PPLN crystal,which would be very helpful for the design of tunable narrow-band pulse nanosecond,picosecond,and femtosecond laser devices via PPLN and other microstructured LN crystals.
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.92162214,41773015,and U1812402)the Key Research and Development Program of Yunnan Province(202103AQ100003).
文摘Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.
基金supported by the funding from the Natural Science Foundation of China (22105129)the Guangdong Basic and Applied Basic Research Foundation (2022A1515011048,2022A1515010670)the Science and Technology Innovation Commission of Shenzhen (JCYJ20200109105618137,20200812112006001)
文摘In this study,we have explored the use of water as a non-solvent for tuning the microstructure of poly-benzimidazole(PBI)membranes,which are potential separators for lithium metal batteries(LMBs).The traditional method for membrane synthesis called nonsolvent-induced phase separation(NIPS),usually relies on hazardous and costly organic non-solvents.By dissolving sodium chloride(Nacl)in water,we could adjust the water ionic potency and the exchange speed of the non-solvent with the DMAC solution to change the micropore structure of the PBI membrane.With increasing Nacl concentration,the micro-pores in the PBI membrane transitioned from finger-like to sponge-like morphology.Compared to com-mercial separators like the Celgard separator,the PBI membrane with sponge-like micropores exhibited better regulation of lithium deposition and improved Li^(+) transportation capability due to its good wetta-bility with the electrolyte.Consequently,the PBI membrane-based Li/Li symmetric cell and Li/LiFePO_(4) full cell demonstrated superior performance compared to the Celgard-based ones.This research proposes an eco-friendly and scalable synthetic approach for fabricating commercial separators for LMBs,addressing the issue of lithium dendrite growth and improving overall battery safety and performance.
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.
文摘This work is a simulation modelling with the LAMMPS calculation code of an electrode based on alkali metals (lithium, sodium and potassium) using the MEAM potential. For different multiplicities, two models were studied;with and without gap. In this work, we present the structural, physical and chemical properties of the lithium, sodium and potassium electrodes. For the structural properties, the cohesive energy and the mesh parameters were calculated, revealing that, whatever the chemical element selected, the compact hexagonal hcp structure is the most stable, followed by the face-centred cubic CFC structure, and finally the BCC structure. The most stable structure is lithium, with a cohesion energy of -6570 eV, and the lowest bcc-hcp transition energy of -0.553 eV/atom, followed by sodium. For physical properties, kinetic and potential energies were calculated for each of the sectioned chemical elements, with lithium achieving the highest value. Finally, for the chemical properties, we studied the diffusion coefficient and the activation energy. Only potassium followed an opposite order to the other two, with the quantities with lacunae being greater than those without lacunae, whatever the multiplicity. The order of magnitude of the diffusion coefficients is given by the relationship D<sub>Li</sub> > D<sub>Na</sub> > D<sub>k</sub> for the multiplicity 6*6*6, while for the activation energy the order is reversed.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
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.