Managing the surge:A comprehensive review of the entire disposal framework for retired lithium-ion batteries from electric vehicles

Anticipating the imminent surge of retired lithium-ion batteries(R-LIBs)from electric vehicles,the need for safe,cost-effective and environmentally friendly disposal technologies has escalated.This paper seeks to offer a comprehensive overview of the entire disposal framework for R-LIBs,encompassing a broad spectrum of activities,including screening,repurposing and recycling.Firstly,we delve deeply into a thorough examination of current screening technologies,shifting the focus from a mere enumeration of screening methods to the exploration of the strategies for enhancing screening efficiency.Secondly,we outline battery repurposing with associated key factors,summarizing stationary applications and sizing methods for R-LIBs in their second life.A particular light is shed on available reconditioning solutions,demonstrating their great potential in facilitating battery safety and lifetime in repurposing scenarios and identifying their techno-economic issues.In the realm of battery recycling,we present an extensive survey of pre-treatment options and subsequent material recovery technologies.Particularly,we introduce several global leading recyclers to illustrate their industrial processes and technical intricacies.Furthermore,relevant challenges and evolving trends are investigated in pursuit of a sustainable end-of-life management and disposal framework.We hope that this study can serve as a valuable resource for researchers,industry professionals and policymakers in this field,ultimately facilitating the adoption of proper disposal practices.

Thermal safety boundary of lithium-ion battery at different state of charge

Thermal runaway(TR)is a critical issue hindering the large-scale application of lithium-ion batteries(LIBs).Understanding the thermal safety behavior of LIBs at the cell and module level under different state of charges(SOCs)has significant implications for reinforcing the thermal safety design of the lithium-ion battery module.This study first investigates the thermal safety boundary(TSB)correspondence at the cells and modules level under the guidance of a newly proposed concept,safe electric quantity boundary(SEQB).A reasonable thermal runaway propagation(TRP)judgment indicator,peak heat transfer power(PHTP),is proposed to predict whether TRP occurs.Moreover,a validated 3D model is used to quantitatively clarify the TSB at different SOCs from the perspective of PHTP,TR trigger temperature,SOC,and the full cycle life.Besides,three different TRP transfer modes are discovered.The interconversion relationship of three different TRP modes is investigated from the perspective of PHTP.This paper explores the TSB of LIBs under different SOCs at both cell and module levels for the first time,which has great significance in guiding the thermal safety design of battery systems.

Exploring impedance spectrum for lithium-ion batteries diagnosis and prognosis:A comprehensive review

Lithium-ion batteries have extensive usage in various energy storage needs,owing to their notable benefits of high energy density and long lifespan.The monitoring of battery states and failure identification are indispensable for guaranteeing the secure and optimal functionality of the batteries.The impedance spectrum has garnered growing interest due to its ability to provide a valuable understanding of material characteristics and electrochemical processes.To inspire further progress in the investigation and application of the battery impedance spectrum,this paper provides a comprehensive review of the determination and utilization of the impedance spectrum.The sources of impedance inaccuracies are systematically analyzed in terms of frequency response characteristics.The applicability of utilizing diverse impedance features for the diagnosis and prognosis of batteries is further elaborated.Finally,challenges and prospects for future research are discussed.

Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism

The proper recycling of spent lithium-ion batteries(LIBs)can promote the recovery and utilization of valuable resources,while also negative environmental effects resulting from the presence of toxic and hazardous substances.In this study,a new environmentally friendly hydro-metallurgical process was proposed for leaching lithium(Li),nickel(Ni),cobalt(Co),and manganese(Mn)from spent LIBs using sulfuric acid with citric acid as a reductant.The effects of the concentration of sulfuric acid,the leaching temperature,the leaching time,the solid-liquid ratio,and the reducing agent dosage on the leaching behavior of the above elements were investigated.Key parameters were optimized using response surface methodology(RSM)to maximize the recovery of metals from spent LIBs.The maxim-um recovery efficiencies of Li,Ni,Co,and Mn can reach 99.08%,98.76%,98.33%,and 97.63%.under the optimized conditions(the sulfuric acid concentration was 1.16 mol/L,the citric acid dosage was 15wt%,the solid-liquid ratio was 40 g/L,and the temperature was 83℃ for 120 min),respectively.It was found that in the collaborative leaching process of sulfuric acid and citric acid,the citric acid initially provided strong reducing CO_(2)^(-),and the transition metal ions in the high state underwent a reduction reaction to produce transition metal ions in the low state.Additionally,citric acid can also act as a proton donor and chelate with lower-priced transition metal ions,thus speeding up the dissolution process.

Flexible bidirectional pulse charging regulation achieving long-life lithium-ion batteries

Typical application scenarios,such as vehicle to grid(V2G)and frequency regulation,have imposed significant long-life demands on lithium-ion batteries.Herein,we propose an advanced battery life-extension method employing bidirectional pulse charging(BPC)strategy.Unlike traditional constant current charging methods,BPC strategy not only achieves comparable charging speeds but also facilitates V2G frequency regulation simultaneously.It significantly enhances battery cycle ampere-hour throughput and demonstrates remarkable life extension capabilities.For this interesting conclusion,adopting model identification and postmortem characterization to reveal the life regulation mechanism of BPC:it mitigates battery capacity loss attributed to loss of lithium-ion inventory(LLI)in graphite anodes by intermittently regulating the overall battery voltage and anode potential using a negative charging current.Then,from the perspective of internal side reaction,the life extension mechanism is further revealed as inhibition of solid electrolyte interphase(SEI)and lithium dendrite growth by regulating voltage with a bidirectional pulse current,and a semi-empirical life degradation model combining SEI and lithium dendrite growth is developed for BPC scenarios health management,the model parameters are identified by genetic algorithm with the life simulation exhibiting an accuracy exceeding 99%.This finding indicates that under typical rate conditions,adaptable BPC strategies can extend the service life of LFP battery by approximately 123%.Consequently,the developed advanced BPC strategy offers innovative perspectives and insights for the development of long-life battery applications in the future.

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Mathematical modeling and simulations of stress mitigation by coating polycrystalline particles in lithium-ion batteries

A chemo-mechanical model is developed to investigate the effects on the stress development of the coating of polycrystalline Ni-rich LiNixMnyCo_(z)O_(2)(x≥0.8)(NMC)particles with poly(3,4-ethylenedioxythiophene)(PEDOT).The simulation results show that the coating of primary NMC particles significantly reduces the stress generation by efficiently accommodating the volume change associated with the lithium diffusion,and the coating layer plays roles both as a cushion against the volume change and a channel for the lithium transport,promoting the lithium distribution across the secondary particles more homogeneously.Besides,the lower stiffness,higher ionic conductivity,and larger thickness of the coating layer improve the stress mitigation.This paper provides a mathematical framework for calculating the chemo-mechanical responses of anisotropic electrode materials and fundamental insights into how the coating of NMC active particles mitigates stress levels.

Unveiling the tailorable electrochemical properties of zeolitic imidazolate framework-derived Ni-doped LiCoO_(2) for lithium-ion batteries in half/full cells

As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.

Thermodynamic equilibrium theory-guided design and synthesis of Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4)/C cathode for lithium-ion batteries

Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.

Reviewing electrochemical stability of ionic liquids-/deep eutectic solvents-based electrolytes in lithium-ion,lithium-metal and post-lithium-ion batteries for green and safe energy

Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.

Nano-alumina@cellulose-coated separators with the reinforcedconcrete-like structure for high-safety lithium-ion batteries

Separators play a critical role in the safety and performance of lithium-ion batteries.However,commercial polyolefin separators are limited by their poor affinity with electrolytes and low melting points.In this work,we constructed a reinforced-concrete-like structure by homogeneously dispersing nano-Al_(2)O_(3) and cellulose on the separators to improve their stability and performance.In this reinforcedconcrete-like structure,the cellulose is a reinforcing mesh,and the nano-Al_(2)O_(3) acts as concrete to support the separator.After constructing the reinforced-concrete-like structure,the separators exhibit good stability even at 200℃(thermal shrinkage of 0.3%),enhanced tensile strain(tensile stress of 133.4 MPa and tensile strains of 62%),and better electrolyte wettability(a contact angle of 6.5°).Combining these advantages,the cells with nano-Al_(2)O_(3)@cellulose-coated separators exhibit stable cycling performance and good rate performance.Therefore,the construction of the reinforced-concretelike structure is a promising technology to promote the application of lithium-ion batteries in extreme environments.

Revisiting aluminum current collector in lithium-ion batteries:Corrosion and countermeasures

With the large-scale service of lithium-ion batteries(LIBs),their failures have attracted significant attentions.While the decay of active materials is the primary cause for LIB failures,the degradation of auxiliary materials,such as current collector corrosion,should not be disregarded.Therefore,it is necessary to conduct a comprehensive review in this field.In this review,from the perspectives of electrochemistry and materials,we systematically summarize the corrosion behavior of aluminum cathode current collector and propose corresponding countermeasures.Firstly,the corrosion type is clarified based on the properties of passivation layers in different organic electrolyte components.Furthermore,a thoroughgoing analysis is presented to examine the impact of various factors on aluminum corrosion,including lithium salts,organic solvents,water impurities,and operating conditions.Subsequently,strategies for electrolyte and protection layer employed to suppress corrosion are discussed in detail.Lastly and most importantly,we provide insights and recommendations to prevent corrosion of current collectors,facilitate the development of advanced current collectors and the implementation of next-generation high-voltage stable LIBs.

High mechanical strength Si anode synthesis with interlayer bonded expanded graphite structure for lithium-ion batteries

Despite advancements in silicon-based anodes for high-capacity lithium-ion batteries,their widespread commercial adoption is still hindered by significant volume expansion during cycling,especially at high active mass loadings crucial for practical use.The root of these challenges lies in the mechanical instability of the material,which subsequently leads to the structural failure of the electrode.Here,we present a novel synthesis of a composite combining expanded graphite and silicon nanoparticles.This composite features a unique interlayer-bonded graphite structure,achieved through the application of a modified spark plasma sintering method.Notably,this innovative structure not only facilitates efficient ion and electron transport but also provides exceptional mechanical strength(Vickers hardness:up to658 MPa,Young's modulus:11.6 GPa).This strength effectively accommodates silicon expansion,resulting in an impressive areal capacity of 2.9 mA h cm^(-2)(736 mA h g^(-1)) and a steady cycle life(93% after 100cycles).Such outsta nding performance is paired with features appropriate for large-scale industrial production of silicon batteries,such as active mass loading of at least 3.9 mg cm^(-2),a high-tap density electrode material of 1.68 g cm^(-3)(secondary clusters:1.12 g cm^(-3)),and a production yield of up to 1 kg per day.

Recycled graphite for more sustainable lithium-ion batteries

The demand for lithium-ion batteries(LIBs)is driven largely by their use in electric vehicles,which is projected to increase dramatically in the future.This great success,however,urgently calls for the efficient recycling of LIBs at the end of their life.Herein,we describe a froth flotation-based process to recycle graphite—the predominant active material for the negative electrode—from spent LIBs and investigate its reuse in newly assembled LIBs.It has been found that the structure and morphology of the recycled graphite are essentially unchanged compared to pristine commercial anode-grade graphite,and despite some minor impurities from the recycling process,the recycled graphite provides a remarkable reversible specific capacity of more than 350 mAh g^(−1).Even more importantly,newly assembled graphite‖NMC532 cells show excellent cycling stability with a capacity retention of 80%after 1000 cycles,that is,comparable to the performance of reference full cells comprising pristine commercial graphite.

A review of data-driven whole-life state of health prediction for lithium-ion batteries:Data preprocessing,aging characteristics,algorithms,and future challenges

Lithium-ion batteries are the preferred green energy storage method and are equipped with intelligent battery management systems(BMSs)that efficiently manage the batteries.This not only ensures the safety performance of the batteries but also significantly improves their efficiency and reduces their damage rate.Throughout their whole life cycle,lithium-ion batteries undergo aging and performance degradation due to diverse external environments and irregular degradation of internal materials.This degradation is reflected in the state of health(SOH)assessment.Therefore,this review offers the first comprehensive analysis of battery SOH estimation strategies across the entire lifecycle over the past five years,highlighting common research focuses rooted in data-driven methods.It delves into various dimensions such as dataset integration and preprocessing,health feature parameter extraction,and the construction of SOH estimation models.These approaches unearth hidden insights within data,addressing the inherent tension between computational complexity and estimation accuracy.To enha nce support for in-vehicle implementation,cloud computing,and the echelon technologies of battery recycling,remanufacturing,and reuse,as well as to offer insights into these technologies,a segmented management approach will be introduced in the future.This will encompass source domain data processing,multi-feature factor reconfiguration,hybrid drive modeling,parameter correction mechanisms,and fulltime health management.Based on the best SOH estimation outcomes,health strategies tailored to different stages can be devised in the future,leading to the establishment of a comprehensive SOH assessment framework.This will mitigate cross-domain distribution disparities and facilitate adaptation to a broader array of dynamic operation protocols.This article reviews the current research landscape from four perspectives and discusses the challenges that lie ahead.Researchers and practitioners can gain a comprehensive understanding of battery SOH estimation methods,offering valuable insights for the development of advanced battery management systems and embedded application research.

Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.

The principle and amelioration of lithium plating in fast-charging lithium-ion batteries

Fast charging is restricted primarily by the risk of lithium(Li)plating,a side reaction that can lead to the rapid capacity decay and dendrite-induced thermal runaway of lithium-ion batteries(LIBs).Investigation on the intrinsic mechanism and the position of Li plating is crucial to improving the fast rechargeability and safety of LIBs.Herein,we investigate the Li plating behavior in porous electrodes under the restricted transport of Li^(+).Based on the theoretical model,it can be concluded that the Li plating on the anodeseparator interface(ASI)is thermodynamically feasible and kinetically advantageous.Meanwhile,the prior deposition of metal Li on the ASI rather than the anode-current collector interface(ACI)is verified experimentally.In order to facilitate the transfer of Li^(+)among the electrode and improve the utilization of active materials without Li plating,a bilayer asymmetric anode composed of graphite and hard carbon(GH)is proposed.Experimental and simulation results suggest that the GH hybrid electrode homogenizes the lithiated-rate throughout the electrode and outperforms the pure graphite electrode in terms of the rate performance and inhibition of Li plating.This work provides new insights into the behavior of Li plating and the rational design of electrode structure.

Thermal characteristic evolution of lithium-ion batteries during the whole lifecycle

This work extensively investigates the thermal characteristic evolution of lithium-ion batteries under different degradation paths,and the evolution mechanism through multi-angle characterization is revealed.Under different degradation paths,the evolution trend of temperature rise rate remains unchanged with respect to depth of discharge during the adiabatic discharge process,albeit to varying degrees of alteration.The temperature rise rate changes significantly with aging during the adiabatic discharge process under low-temperature cycling and high-rate cycling paths.The total heat generation rate,irreversible heat generation rate,and reversible heat generation rate exhibit similar evolution behavior with aging under different degradation paths.The interval range of endothermic process of reversible electrochemical reactions increases and the contribution of irreversible heat to the total heat increases with aging.To further standardize the assessment of different degradation paths on the thermal characteristics,this work introduces the innovative concept of“Ampere-hour temperature rise”.In low-temperature cycling and high-rate cycling paths,the ampere-hour temperature rise increases significantly with aging,particularly accentuated with higher discharge rates.Conversely,in high-temperature cycling and high-temperature storage paths,the ampere-hour temperature rise remains relatively stable during the initial stages of aging,yet undergoes a notable increase in the later stages of aging.The multi-angle characterization reveals distinct thermal evolution behavior under different degradation paths primarily attributed to different behavior changes of severe side reactions,such as lithium plating.The findings provide crucial insights for the safe utilization and management of lithium–ion batteries throughout the whole lifecycle.

Pyrometallurgical recycling of end-of-life lithium-ion batteries

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.

Constructing Al@C-Sn pellet anode without passivation layer for lithium-ion battery

Al is considered as a promising lithium-ion battery(LIBs)anode materials owing to its high theoretical capacity and appropri-ate lithation/de-lithation potential.Unfortunately,its inevitable volume expansion causes the electrode structure instability,leading to poor cyclic stability.What’s worse,the natural Al2O3 layer on commercial Al pellets is always existed as a robust insulating barrier for elec-trons,which brings the voltage dip and results in low reversible capacity.Herein,this work synthesized core-shell Al@C-Sn pellets for LIBs by a plus-minus strategy.In this proposal,the natural Al2O3 passivation layer is eliminated when annealing the pre-introduced SnCl2,meanwhile,polydopamine-derived carbon is introduced as dual functional shell to liberate the fresh Al core from re-oxidization and alle-viate the volume swellings.Benefiting from the addition of C-Sn shell and the elimination of the Al2O3 passivation layer,the as-prepared Al@C-Sn pellet electrode exhibits little voltage dip and delivers a reversible capacity of 1018.7 mAh·g^(-1) at 0.1 A·g^(-1) and 295.0 mAh·g^(-1) at 2.0 A·g^(-1)(after 1000 cycles),respectively.Moreover,its diffusion-controlled capacity is muchly improved compared to those of its counterparts,confirming the well-designed nanostructure contributes to the rapid Li-ion diffusion and further enhances the lithium storage activity.