Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this ...Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.展开更多
Due to its high theoretical capacity(820 mAh g^(−1)),low standard electrode potential(−0.76 V vs.SHE),excellent stability in aqueous solutions,low cost,environmental friendliness and intrinsically high safety,zinc(Zn)...Due to its high theoretical capacity(820 mAh g^(−1)),low standard electrode potential(−0.76 V vs.SHE),excellent stability in aqueous solutions,low cost,environmental friendliness and intrinsically high safety,zinc(Zn)-based batteries have attracted much attention in developing new energy storage devices.In Zn battery system,the battery performance is significantly affected by the solid electrolyte interface(SEI),which is controlled by electrode and electrolyte,and attracts dendrite growth,electrochemical stability window range,metallic Zn anode corrosion and passivation,and electrolyte mutations.Therefore,the design of SEI is decisive for the overall performance of Zn battery systems.This paper summarizes the formation mechanism,the types and characteristics,and the characterization techniques associated with SEI.Meanwhile,we analyze the influence of SEI on battery performance,and put forward the design strategies of SEI.Finally,the future research of SEI in Zn battery system is prospected to seize the nature of SEI,improve the battery performance and promote the large-scale application.展开更多
Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochem...Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.展开更多
Owing to its low potential, crustal abundances and environmental friendliness, calcium metal anode(CMA) is emerging as a powerful contender in post-lithium era. However, the passivation of CMA fatally hinders its deve...Owing to its low potential, crustal abundances and environmental friendliness, calcium metal anode(CMA) is emerging as a powerful contender in post-lithium era. However, the passivation of CMA fatally hinders its development. Recently, several feasible electrolytes have been developed. Nevertheless, as a pivotal part, the solid electrolyte interface(SEI) formed on CMA has not been paid enough attention to. In this review, based on the passivation mechanism of CMA, the favorable composition of SEI is emphasized with the corresponding electrolytes. It is considered that boron-containing and organic–inorganic hybrid SEI might be preferred. By comparing electrolytes and SEI on CMA with lithium and magnesium metal anodes, the root causes of CMA passivation are further elaborated, enlightening rational design rules of suitable SEI. Furthermore, some noteworthy details when assembling secondary calcium metal batteries(CMBs) are put forward. It is expected that deeper understanding of SEI on CMA will promote the development of CMBs.展开更多
The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid elect...The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.展开更多
electrolyte. The properties of lithium-ion (Li-ion) battery, such as cycle life, irreversible capacity loss, self-discharge rate, electrode corrosion and safety are usually ascribed to the quality of the SEI, which ar...electrolyte. The properties of lithium-ion (Li-ion) battery, such as cycle life, irreversible capacity loss, self-discharge rate, electrode corrosion and safety are usually ascribed to the quality of the SEI, which are highly dependent on the thickness. Thus, understanding the formation mechanism and the SEI thickness is of prime interest. First, we apply dimensional analysis to obtain an explicit relation between the thickness and the number density in this study. Then the SEI thickness in the initial charge-discharge cycle is analyzed and estimated for the first time using the Cahn-Hilliard phase-field model. In addition, the SEI thickness by molecular dynamics simulation validates the theoretical results. It has been shown that the established model and the simulation in this paper estimate the SEI thickness concisely within order-of-magnitude of nanometers. Our results may help in evaluating the performance of SEI and assist the future design of Li-ion battery.展开更多
Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the p...Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the possible maximum apparent current density that a given ASSLSC system can endure and how to reveal this potential still require study.Herein,a capacity perturbation strategy aiming to better measure the possible maximum j_(Ac)^(a)is proposed for the first time.With garnet-based plane-surface structure ASSLSCs as an exemplification,the j_(Ac)^(a)is quite small when the capacity is dramatically large.Under a perturbed capacity of 0.001 mA h cm^(-2),the j_(Ac)^(a)is determined to be as high as 2.35 mA cm^(-2)at room temperature.This investigation demonstrates that the capacity perturbation strategy is a feasible strategy for measuring the possible maximum j_(Ac)^(a)of Li/solid electrolyte interface,and hopefully provides good references to explore the critical current density of other types of electrochemical systems.展开更多
Aluminum-ion batteries(AIBs)with Al metal anode are attracting increasing research interest on account of their high safety,low cost,large volumetric energy density(≈8046 mA h cm−3),and environmental friendliness.Spe...Aluminum-ion batteries(AIBs)with Al metal anode are attracting increasing research interest on account of their high safety,low cost,large volumetric energy density(≈8046 mA h cm−3),and environmental friendliness.Specifically,the reversible Al electrostripping/deposition is achieved with the rapid development of room temperature ionic liquids,and rapid progress has been made in fabricating high-performance and durable AIBs during the past decade.This review provides an integrated comprehension of the evolution of AIBs and highlights the development of various non-aqueous and aqueous electrolytes including high-temperature molten salts,room temperature ionic liquids,and gel–polymer electrolytes.The critical issues on the interplay of electrolytes are outlined in terms of the voltage window span,the effective ion species during charge storage(Al 3+or Al x Cl?y)and their underlying charge transfer(e.g.,interfacial transfer and diffusion),and the solid electrolyte interface formation and its role.Following the critical insight,future perspectives on how to practically design feasible AIBs are given.展开更多
Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,...Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.展开更多
Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a h...Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.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
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
With the increasing demand for high energy-density batteries for portable electronics and large-scale energy storage systems,the lithium metal anode(LMA)has received tremendous attention because of its high theoretica...With the increasing demand for high energy-density batteries for portable electronics and large-scale energy storage systems,the lithium metal anode(LMA)has received tremendous attention because of its high theoretical capacity and low redox potential.However,the commercial application of LMAs is impeded by the uncontrolled growth of lithium dendrites.Such dendrite growth may result in internal short circuits,detrimental side reactions,and the formation of dead lithium.Therefore,the growth of lithium metal must be controlled.This article summarizes our recent efforts in inhibiting such dendrite growth,decreasing the detrimental side reactions,and elongating the LMA lifespan by optimizing the electrolyte structure and by designing appropriate current collectors.After identifying that the unstable solid electrolyte inter-face(SEI)film is responsible for the potential dropping in carbonate electrolytes,we developed LiPF_(6)-LiNO_(3) dual-salt electrolyte and lithium bis(fluorosulfonyl)imide(LiFSI)-carbonate electrolyte to stabilize the SEI film of LMAs.In addition,we achieved controlled lithium depos-ition by designing the structure and material of the current collectors,including selective lithium deposition in porous current collectors,lithio-philic metal guided lithium deposition,and iron carbide induced underpotential lithium deposition in nano-cavities.The limitations of the cur-rent strategies and prospects for future research are also presented.展开更多
Hard carbon(HC)is a promising anode material for sodium ion batteries(SIBs),whereas inferior initial coulombic efficiency(ICE)severely limits its practical application.In the present work,we propose an in situ electro...Hard carbon(HC)is a promising anode material for sodium ion batteries(SIBs),whereas inferior initial coulombic efficiency(ICE)severely limits its practical application.In the present work,we propose an in situ electrochemical presodiation approach to improve ICE by mixing sodium biphenyl(Na-Bp)dimethoxyethane(DME)solution with DME-based ether electrolyte.A solid electrolyte interface(SEI)could be formed beforehand on the HC electrode and Na^(+)was absorbed to nanopores and graphene stacks,compensating for the sodium loss and preventing electrolyte decomposition during the initial charge and discharge cycle.By this way,the ICE of half-cells was increased to nearly 100%and that of full-cells from 45%to 96%with energy density from 132.9 to 230.5 W h kg^(-1).Our work provides an efficient and facile method for improving ICE,which can potentially promote the practical application of HCbased materials.展开更多
Solid-state lithium metal batteries(SSLMBs)have attracted considerable attention as one of the most promising energy storage systems owing to their high safety and energy density.Solid electrolytes,particularly polyme...Solid-state lithium metal batteries(SSLMBs)have attracted considerable attention as one of the most promising energy storage systems owing to their high safety and energy density.Solid electrolytes,particularly polymer-based composite solid electrolytes(CSEs),are considered promising electrolyte candidates for SSLMBs.However,theirwide application is inhibited by various electrochemical issues,such as low ionic conductivity,the growth of lithium dendrites,and poor cycling stability,which are related to interface issues within SSLMBs.In this review,the parameters related to various interfaces in the CSE of SSLMBs,including the interfaces between the polymer matrix and inorganic fillers,between the CSEs and the cathode,and between the CSEs and the lithium metal anode,are examined.Relevant issues and corresponding remediation strategies are proposed.Finally,future perspectives based on interfacial engineering and the characterization of polymer/inorganic filler interactions are proposed for building high-performance CSEs for use in SSLMBs.展开更多
The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries(LIBs).However,it is difficult for the silicon-based anode...The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries(LIBs).However,it is difficult for the silicon-based anode to form a stable solid-state interphase(SEI)during Li alloy/de-alloy process due to the large volume change(up to 300%)between silicon and Li4.4Si,which seriously limits the cycle life of the LIBs.Herein,we use strontium fluoride(SrF_(2))particle to coat the silicon-carbon(Si/C)electrode(SrF_(2)@Si/C)to help forming a stable and high mechanical strength SEI by spontaneously embedding the SrF_(2) particle into SEI.Meanwhile the formed SEI can inhibit the volume expansion of the silicon-carbon anode during the cycle.The electrochemical test results show that the cycle performance and the ionic conductivity of the SrF_(2)@Si/C anode has been significantly improved.The X-ray photoelectron spectroscopy(XPS)analysis reveals that there are fewer electrolyte decomposition products formed on the surface of the SrF_(2)@Si/C anode.This study provides a facile approach to overcome the problems of Si/C electrode during the electrochemical cycling,which will be beneficial to the industrial application of silicon-based anode materials.展开更多
Severe performance drop and fire risk due to the uneven lithium(Li) dendrite formation and growth during charge/discharge process has been considered as the major obstacle to the practical application of Li metal batt...Severe performance drop and fire risk due to the uneven lithium(Li) dendrite formation and growth during charge/discharge process has been considered as the major obstacle to the practical application of Li metal batteries.So inhibiting dendrite growth and producing a stable and robust solid electrolyte interface(SEI) layer are essential to enable the use of Li metal anodes.In this work,a functional lithiophilic polymer composed of chitosan(CTS),polyethylene oxide(PEO),and poly(triethylene glycol dimethacrylate)(PTEGDMA),was homogeneously deposited on a commercial Celgard separator by combining electrospraying and polymer photopolymerization techniques.The lithiophilic environment offered by the CTS-PEO-PTEGDMA layer enables uniform Li deposition and facilitates the formation of a robust homogeneous SEI layer,thus prevent the formation and growth of Li dendrites.As a result,both Li/Li symmetric cells and LiFePO4/Li full cells deliver significantly enhanced electrochemical performance and cycle life.Even after 1000 cycles,the specific capacity of the modified full cell could be maintained at65.8 mAh g^(-1), twice which of the unmodified cell(32.8 mAh g^(-1)).The long-term cycling stability in Li/Li symmetric cells,dendrite-free anodes in SEM images and XPS analysis suggest that the pulverization of the Li anode was effectively suppressed by the lithiophilic polymer layer.展开更多
Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batt...Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batteries(LIBs)is limited at low temperatures due to several critical challenges,such as the decreased ionic conductivity of liquid electrolyte,sluggish Li+desolvation process,poor Li+diffusivity across the interphase layer and bulk graphite materials.Various approaches have therefore been explored to address these challenges.On the basis of graphite anode and corresponding LIBs,this review herein offers a comprehensive analysis of the latest advances in electrolyte engineering and electrode modification.First,electrolyte engineering is discussed in detail,highlighting the design of new electrolyte formula with broad liquid temperature range,optimized solvation structure,and well-performed inorganic-rich solid electrolyte interface.The advances in material modification have been then depicted with the view of improving the solid bulk diffusion rate to show general strategies with excellent performance at low temperatures.Finally,the corresponding challenges and opportunities have also been outlined to shed light on viable strategies for developing efficient and reliable graphite anode and graphite-based LIBs under low-temperature scenarios.展开更多
Lithium metal batteries(LMBs)with extremely high energy densities have several advantages among energy storage equipment.However,the uncontrolled growth of dendrites and the flammable liquid electrolytes(LEs)often cau...Lithium metal batteries(LMBs)with extremely high energy densities have several advantages among energy storage equipment.However,the uncontrolled growth of dendrites and the flammable liquid electrolytes(LEs)often cause safety accidents.All solid-state batteries seem to be the ultimate choice,but solvent-free electrolytes usually fail in terms of conductivity at room temperature.Therefore,gel polymer electrolytes(GPEs)with a simple manufacturing process and high ionic conductivity are considered as the most competitive candidates to resolve the present difficulties.Herein,we design a polymeric network structure via esterification and amidation reactions between polyethylene glycol(PEG)and carbon dots(CDs).After incorporation with polyvinylidene fluoride and some LEs,the as-prepared PEG-CDs composite electrolytes(PCCEs)show a high ionic conductivity of 5.5 mS/cm and an ion transference number of 0.71 at room temperature,as well as good flexibility and thermostability.When the PCCEs are assembled with lithium metal anodes and LiFePO4 or LiCoO2 cathodes,both the cycling stability and the retention rate of these LMBs show excellent performance at room temperature.展开更多
Hydrous electrolytes with high electrochemical potentials were obtained by hydrating water molecules into solutes to form high Li:water molar ratio electrolytes(HMRE).Solid polyethylene glycol(PEG) were e mployed to e...Hydrous electrolytes with high electrochemical potentials were obtained by hydrating water molecules into solutes to form high Li:water molar ratio electrolytes(HMRE).Solid polyethylene glycol(PEG) were e mployed to enha nce the molar ratio of Li^(+) to water in the electrolytes while reducing the consumption of Li-salt.The obtained mole ratio of Li^(+) to wa ter molecules in the hydrous electrolytes was greater than 1:1;however,the mass fraction of Li-salt was reduced to 61%(approximately 5.5 mol/kg,based on water and PEG).Compared with that of water-in-salt electrolytes,the mass fraction of Li-salt could be remarkably reduced by adding solid PEG.The electrochemical stability of the electrolytes improved considerably because of the strong hydration of Li^(+) by the water molecules.A beneficial passivation effect,arising from the decomposition of the electrolyte,at a wide potential window was observed.展开更多
基金supported by the National Natural Science Foundation of China(grant nos.21975026 and 22005033)the National Postdoctoral Program of China(no.BX20180037)+1 种基金China Postdoctoral Science Foundation(no.2018M640077)the Beijing Institute of Technology Research Fund Program for Young Scholars(no.XSQD-202108005).
文摘Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.
基金This research was supported by the Fundamental Research Funds for the Central Universities(0515022GH0202253 and 0515022SH0201253).
文摘Due to its high theoretical capacity(820 mAh g^(−1)),low standard electrode potential(−0.76 V vs.SHE),excellent stability in aqueous solutions,low cost,environmental friendliness and intrinsically high safety,zinc(Zn)-based batteries have attracted much attention in developing new energy storage devices.In Zn battery system,the battery performance is significantly affected by the solid electrolyte interface(SEI),which is controlled by electrode and electrolyte,and attracts dendrite growth,electrochemical stability window range,metallic Zn anode corrosion and passivation,and electrolyte mutations.Therefore,the design of SEI is decisive for the overall performance of Zn battery systems.This paper summarizes the formation mechanism,the types and characteristics,and the characterization techniques associated with SEI.Meanwhile,we analyze the influence of SEI on battery performance,and put forward the design strategies of SEI.Finally,the future research of SEI in Zn battery system is prospected to seize the nature of SEI,improve the battery performance and promote the large-scale application.
基金supported by the Fundamental Research Funds for Central Universities(SCUT Grant No.2019ZD22)the Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N569)。
文摘Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.
基金supported by the National Natural Science Foundation of China(51872196)the Natural Science Foundation of Tianjin,China(17JCJQJC44100)。
文摘Owing to its low potential, crustal abundances and environmental friendliness, calcium metal anode(CMA) is emerging as a powerful contender in post-lithium era. However, the passivation of CMA fatally hinders its development. Recently, several feasible electrolytes have been developed. Nevertheless, as a pivotal part, the solid electrolyte interface(SEI) formed on CMA has not been paid enough attention to. In this review, based on the passivation mechanism of CMA, the favorable composition of SEI is emphasized with the corresponding electrolytes. It is considered that boron-containing and organic–inorganic hybrid SEI might be preferred. By comparing electrolytes and SEI on CMA with lithium and magnesium metal anodes, the root causes of CMA passivation are further elaborated, enlightening rational design rules of suitable SEI. Furthermore, some noteworthy details when assembling secondary calcium metal batteries(CMBs) are put forward. It is expected that deeper understanding of SEI on CMA will promote the development of CMBs.
基金supported by the National Natural Science Foundation of China (51773134)the Sichuan Science and Technology Program (2019YFH0112)+2 种基金the Fundamental Research Funds for the Central UniversitiesInstitutional Research Fund from Sichuan University (2021SCUNL201)the 111 Project (B20001)。
文摘The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.
基金supported by the National Natural Science Foundation of China (Grant Nos. 11372313, U1562105, and 11611130019)the Chinese Academy of Sciences (CAS) through CAS Interdisciplinary Innovation Team Project, the CAS Key Research Program of Frontier Sciences (Grant No. QYZDJ-SSW-JSC019)the CAS Strategic Priority Research Program (Grant No. XDB22040401)
文摘electrolyte. The properties of lithium-ion (Li-ion) battery, such as cycle life, irreversible capacity loss, self-discharge rate, electrode corrosion and safety are usually ascribed to the quality of the SEI, which are highly dependent on the thickness. Thus, understanding the formation mechanism and the SEI thickness is of prime interest. First, we apply dimensional analysis to obtain an explicit relation between the thickness and the number density in this study. Then the SEI thickness in the initial charge-discharge cycle is analyzed and estimated for the first time using the Cahn-Hilliard phase-field model. In addition, the SEI thickness by molecular dynamics simulation validates the theoretical results. It has been shown that the established model and the simulation in this paper estimate the SEI thickness concisely within order-of-magnitude of nanometers. Our results may help in evaluating the performance of SEI and assist the future design of Li-ion battery.
基金the financial support from the Natural Science Foundation for Distinguished Young Scholars of Hunan Province(2020JJ2047)the science and technology innovation Program of Hunan Province(2022RC3048)+2 种基金the Program of Huxiang Young Talents(2019RS2002)the Innovation-Driven Project of Central South University(2020CX027)the Fundamental Research Funds for the Central Universities of Central South University(2021zzts0125)。
文摘Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the possible maximum apparent current density that a given ASSLSC system can endure and how to reveal this potential still require study.Herein,a capacity perturbation strategy aiming to better measure the possible maximum j_(Ac)^(a)is proposed for the first time.With garnet-based plane-surface structure ASSLSCs as an exemplification,the j_(Ac)^(a)is quite small when the capacity is dramatically large.Under a perturbed capacity of 0.001 mA h cm^(-2),the j_(Ac)^(a)is determined to be as high as 2.35 mA cm^(-2)at room temperature.This investigation demonstrates that the capacity perturbation strategy is a feasible strategy for measuring the possible maximum j_(Ac)^(a)of Li/solid electrolyte interface,and hopefully provides good references to explore the critical current density of other types of electrochemical systems.
基金D.M.and D.Y.contributed equally to this work.This research was financially supported by the National Natural Science Foundation of China(No.51772094).
文摘Aluminum-ion batteries(AIBs)with Al metal anode are attracting increasing research interest on account of their high safety,low cost,large volumetric energy density(≈8046 mA h cm−3),and environmental friendliness.Specifically,the reversible Al electrostripping/deposition is achieved with the rapid development of room temperature ionic liquids,and rapid progress has been made in fabricating high-performance and durable AIBs during the past decade.This review provides an integrated comprehension of the evolution of AIBs and highlights the development of various non-aqueous and aqueous electrolytes including high-temperature molten salts,room temperature ionic liquids,and gel–polymer electrolytes.The critical issues on the interplay of electrolytes are outlined in terms of the voltage window span,the effective ion species during charge storage(Al 3+or Al x Cl?y)and their underlying charge transfer(e.g.,interfacial transfer and diffusion),and the solid electrolyte interface formation and its role.Following the critical insight,future perspectives on how to practically design feasible AIBs are given.
基金the Basic Research Project(C123000,C210200,C310200,&C421000)of the Korea Basic Science Institute(KBSI)funded by the Korea Ministry of Science and ICT(MSIT)the Technology Development Program to Solve Climate Changes through the National Research Foundation of Korea(NRF)funded by MSIT(NRF-2021M1A2A2038141).O.H.Han thanks to Prof.I.S.Yang at Ewha Womans University for insightful discussion.
文摘Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.
基金Department of Education of Gansu Province: Industrial Support Plan Project (2022CYZC-23)National Natural Science Foundation of China (22269012)Gansu Key Research and Development Program (23YFGA0053)。
文摘Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.
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.
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financially supported by the National Natural Science Foundation of China(No.21773301)。
文摘With the increasing demand for high energy-density batteries for portable electronics and large-scale energy storage systems,the lithium metal anode(LMA)has received tremendous attention because of its high theoretical capacity and low redox potential.However,the commercial application of LMAs is impeded by the uncontrolled growth of lithium dendrites.Such dendrite growth may result in internal short circuits,detrimental side reactions,and the formation of dead lithium.Therefore,the growth of lithium metal must be controlled.This article summarizes our recent efforts in inhibiting such dendrite growth,decreasing the detrimental side reactions,and elongating the LMA lifespan by optimizing the electrolyte structure and by designing appropriate current collectors.After identifying that the unstable solid electrolyte inter-face(SEI)film is responsible for the potential dropping in carbonate electrolytes,we developed LiPF_(6)-LiNO_(3) dual-salt electrolyte and lithium bis(fluorosulfonyl)imide(LiFSI)-carbonate electrolyte to stabilize the SEI film of LMAs.In addition,we achieved controlled lithium depos-ition by designing the structure and material of the current collectors,including selective lithium deposition in porous current collectors,lithio-philic metal guided lithium deposition,and iron carbide induced underpotential lithium deposition in nano-cavities.The limitations of the cur-rent strategies and prospects for future research are also presented.
基金supported by the National Natural Science Foundation of China,China(51932011,52072411,52104285)the Natural Science Foundation of Hunan Province,China(2021JJ20060)+1 种基金the Science and Technology Innovation Program of Hunan Province,China(2021RC3001)the Fundamental Research Funds for the Central Universities,China(202044011)。
文摘Hard carbon(HC)is a promising anode material for sodium ion batteries(SIBs),whereas inferior initial coulombic efficiency(ICE)severely limits its practical application.In the present work,we propose an in situ electrochemical presodiation approach to improve ICE by mixing sodium biphenyl(Na-Bp)dimethoxyethane(DME)solution with DME-based ether electrolyte.A solid electrolyte interface(SEI)could be formed beforehand on the HC electrode and Na^(+)was absorbed to nanopores and graphene stacks,compensating for the sodium loss and preventing electrolyte decomposition during the initial charge and discharge cycle.By this way,the ICE of half-cells was increased to nearly 100%and that of full-cells from 45%to 96%with energy density from 132.9 to 230.5 W h kg^(-1).Our work provides an efficient and facile method for improving ICE,which can potentially promote the practical application of HCbased materials.
基金The Youth Beijing Scholars program,Grant/Award Number:PXM2021_014204_000023Beijing Natural Science Foundation,Grant/Award Numbers:KZ201910005002,KZ202010005007,2222001+2 种基金National Natural Science Foundation of China,Grant/Award Numbers:21875007,21975006,U19A2018,22075007,52002007,22002004General Program of Science and Technology Development Project of Beijing Municipal Education Commission,Grant/Award Number:KM202110005009China Postdoctoral Science Foundation,Grant/Award Number:2021M700297。
文摘Solid-state lithium metal batteries(SSLMBs)have attracted considerable attention as one of the most promising energy storage systems owing to their high safety and energy density.Solid electrolytes,particularly polymer-based composite solid electrolytes(CSEs),are considered promising electrolyte candidates for SSLMBs.However,theirwide application is inhibited by various electrochemical issues,such as low ionic conductivity,the growth of lithium dendrites,and poor cycling stability,which are related to interface issues within SSLMBs.In this review,the parameters related to various interfaces in the CSE of SSLMBs,including the interfaces between the polymer matrix and inorganic fillers,between the CSEs and the cathode,and between the CSEs and the lithium metal anode,are examined.Relevant issues and corresponding remediation strategies are proposed.Finally,future perspectives based on interfacial engineering and the characterization of polymer/inorganic filler interactions are proposed for building high-performance CSEs for use in SSLMBs.
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.2019YFG0220 and 2019-GH02-00052-HZ).
文摘The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries(LIBs).However,it is difficult for the silicon-based anode to form a stable solid-state interphase(SEI)during Li alloy/de-alloy process due to the large volume change(up to 300%)between silicon and Li4.4Si,which seriously limits the cycle life of the LIBs.Herein,we use strontium fluoride(SrF_(2))particle to coat the silicon-carbon(Si/C)electrode(SrF_(2)@Si/C)to help forming a stable and high mechanical strength SEI by spontaneously embedding the SrF_(2) particle into SEI.Meanwhile the formed SEI can inhibit the volume expansion of the silicon-carbon anode during the cycle.The electrochemical test results show that the cycle performance and the ionic conductivity of the SrF_(2)@Si/C anode has been significantly improved.The X-ray photoelectron spectroscopy(XPS)analysis reveals that there are fewer electrolyte decomposition products formed on the surface of the SrF_(2)@Si/C anode.This study provides a facile approach to overcome the problems of Si/C electrode during the electrochemical cycling,which will be beneficial to the industrial application of silicon-based anode materials.
基金supported by the Natural Science Foundation of Jiangsu Province (BK20170237)National Natural Science Foundation of China (21808094 and 51871113)+1 种基金Key Research and Development Program of Xuzhou (KC17004)Startup Funding for Introduced Talents of Jiangsu Normal University (16XLR015)。
文摘Severe performance drop and fire risk due to the uneven lithium(Li) dendrite formation and growth during charge/discharge process has been considered as the major obstacle to the practical application of Li metal batteries.So inhibiting dendrite growth and producing a stable and robust solid electrolyte interface(SEI) layer are essential to enable the use of Li metal anodes.In this work,a functional lithiophilic polymer composed of chitosan(CTS),polyethylene oxide(PEO),and poly(triethylene glycol dimethacrylate)(PTEGDMA),was homogeneously deposited on a commercial Celgard separator by combining electrospraying and polymer photopolymerization techniques.The lithiophilic environment offered by the CTS-PEO-PTEGDMA layer enables uniform Li deposition and facilitates the formation of a robust homogeneous SEI layer,thus prevent the formation and growth of Li dendrites.As a result,both Li/Li symmetric cells and LiFePO4/Li full cells deliver significantly enhanced electrochemical performance and cycle life.Even after 1000 cycles,the specific capacity of the modified full cell could be maintained at65.8 mAh g^(-1), twice which of the unmodified cell(32.8 mAh g^(-1)).The long-term cycling stability in Li/Li symmetric cells,dendrite-free anodes in SEM images and XPS analysis suggest that the pulverization of the Li anode was effectively suppressed by the lithiophilic polymer layer.
基金supported by the National Key Research and Development Program of China(2022YFB3803400)National Natural Science Foundation of China(22109028)+1 种基金Natural Science Foundation of Shanghai(22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(19CG01).
文摘Graphite offers several advantages as an anode material,including its low cost,high theoretical capacity,extended lifespan,and low Li+-intercalation potential.However,the performance of graphite-based lithium-ion batteries(LIBs)is limited at low temperatures due to several critical challenges,such as the decreased ionic conductivity of liquid electrolyte,sluggish Li+desolvation process,poor Li+diffusivity across the interphase layer and bulk graphite materials.Various approaches have therefore been explored to address these challenges.On the basis of graphite anode and corresponding LIBs,this review herein offers a comprehensive analysis of the latest advances in electrolyte engineering and electrode modification.First,electrolyte engineering is discussed in detail,highlighting the design of new electrolyte formula with broad liquid temperature range,optimized solvation structure,and well-performed inorganic-rich solid electrolyte interface.The advances in material modification have been then depicted with the view of improving the solid bulk diffusion rate to show general strategies with excellent performance at low temperatures.Finally,the corresponding challenges and opportunities have also been outlined to shed light on viable strategies for developing efficient and reliable graphite anode and graphite-based LIBs under low-temperature scenarios.
基金supported by the National Natural Science Foundation of China(Nos.21975048 and 21771039)the Shanghai Science and Technology Committee(No.19DZ2270100).
文摘Lithium metal batteries(LMBs)with extremely high energy densities have several advantages among energy storage equipment.However,the uncontrolled growth of dendrites and the flammable liquid electrolytes(LEs)often cause safety accidents.All solid-state batteries seem to be the ultimate choice,but solvent-free electrolytes usually fail in terms of conductivity at room temperature.Therefore,gel polymer electrolytes(GPEs)with a simple manufacturing process and high ionic conductivity are considered as the most competitive candidates to resolve the present difficulties.Herein,we design a polymeric network structure via esterification and amidation reactions between polyethylene glycol(PEG)and carbon dots(CDs).After incorporation with polyvinylidene fluoride and some LEs,the as-prepared PEG-CDs composite electrolytes(PCCEs)show a high ionic conductivity of 5.5 mS/cm and an ion transference number of 0.71 at room temperature,as well as good flexibility and thermostability.When the PCCEs are assembled with lithium metal anodes and LiFePO4 or LiCoO2 cathodes,both the cycling stability and the retention rate of these LMBs show excellent performance at room temperature.
基金supported by the National Natural Science Foundation of China (No.11975043)the Natural Science Foundation of Shandong Province (No.ZR2017LEM011)。
文摘Hydrous electrolytes with high electrochemical potentials were obtained by hydrating water molecules into solutes to form high Li:water molar ratio electrolytes(HMRE).Solid polyethylene glycol(PEG) were e mployed to enha nce the molar ratio of Li^(+) to water in the electrolytes while reducing the consumption of Li-salt.The obtained mole ratio of Li^(+) to wa ter molecules in the hydrous electrolytes was greater than 1:1;however,the mass fraction of Li-salt was reduced to 61%(approximately 5.5 mol/kg,based on water and PEG).Compared with that of water-in-salt electrolytes,the mass fraction of Li-salt could be remarkably reduced by adding solid PEG.The electrochemical stability of the electrolytes improved considerably because of the strong hydration of Li^(+) by the water molecules.A beneficial passivation effect,arising from the decomposition of the electrolyte,at a wide potential window was observed.