Aqueous electrochemical delithiation of cathode materials as a strategy to selectively recover lithium from waste lithium-ion batteries

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.

Targeted regeneration and upcycling of spent graphite by defect‐driven tin nucleation

The recycling of spent batteries has become increasingly important owing to their wide applications,abundant raw material supply,and sustainable development.Compared with the degraded cathode,spent anode graphite often has a relatively intact structure with few defects after long cycling.Yet,most spent graphite is simply burned or discarded due to its limited value and inferior performance on using conventional recycling methods that are complex,have low efficiency,and fail in performance restoration.Herein,we propose a fast,efficient,and“intelligent”strategy to regenerate and upcycle spent graphite based on defect‐driven targeted remediation.Using Sn as a nanoscale healant,we used rapid heating(~50 ms)to enable dynamic Sn droplets to automatically nucleate around the surface defects on the graphite upon cooling owing to strong binding to the defects(~5.84 eV/atom),thus simultaneously achieving Sn dispersion and graphite remediation.As a result,the regenerated graphite showed enhanced capacity and cycle stability(458.9 mAh g^(−1) at 0.2 A g^(−1) after 100 cycles),superior to those of commercial graphite.Benefiting from the self‐adaption of Sn dispersion,spent graphite with different degrees of defects can be regenerated to similar structures and performance.EverBatt analysis indicates that targeted regeneration and upcycling have significantly lower energy consumption(~99%reduction)and near‐zero CO2 emission,and yield much higher profit than hydrometallurgy,which opens a new avenue for direct upcycling of spend graphite in an efficient,green,and profitable manner for sustainable battery manufacture.

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.

Analysis of cooperation equilibrium of participants in power battery recycling chains considering information barrier

In the era of large-scale retirement of power batteries,there are information barriers and high recovery costs in their recycling.In view of this,in this study we constructed a tripartite evolutionary game model of the cooperation between power battery production and recycling enterprises and government participation.We analyzed the strategic choice of the three parties in the process of power battery recycling and simulated the influence of participants'willingness and information barriers on the strategic choices of the parties.The results showed that power battery production and recycling enterprises,and the government are affected by each other's willingness to participate at different degrees.The willingness of power battery manufacturers and recycling enterprises to cooperate with each other decreased with increases in information barriers.By analyzing the impact of information barrier on power battery recycling,some suggestions are put forward to provide decision-making reference for promoting the sustainable development of power battery industry.

Application of a Sulfur Removal Hydrometallurgical Process in a Lead-Acid Battery Recycling Plant in Costa Rica

This study presents the implementation of a desulphurization process for lead recycling under different chemical and physical conditions using pyro-metallurgical processes. Desulphurization was done using a hydrometallurgical process using sodium carbonate as a desulphurization agent and different lead-bearing loads compositions. Waste characterization included: SO2 concentrations in the stack emissions, total lead content in the furnace ash, the total lead content in the slag, and the toxicity characteristic leaching procedure (TCLP). A significant reduction in SO2 emissions was achieved (~55% reduction) where mean SO2 concentrations changed from 2193 ± 135 ppm to 1006 ± 62 ppm after the implementation of the modified processes. The desulfurized lead paste (i.e. the metallic fraction lead of the battery) of the modified process exhibited an improvement in the concentration of the lead in the TCLP test, with an average value of 1.5 ppm which is below US EPA limit of 5 ppm. The traditional process TCLP mean value for the TCLP was 54.2 ppm. The total lead content in the bag house ashes shows not significant variations, when comparing the desulphurization (67.6% m/m) and non-desulphurization process (64.9% m/m). The total lead mean content in the slag was higher in the desulphurization process (2.49% m/m) than the traditional process (1.91% m/m). Overall, the implementation of a new desulphurization method would potentially increase the operation costs in 10.3%. At the light of these results, a combination of hydrometallurgical and pyro-metallurgical processes in the recycling of lead-acid batteries can be used to reduce the environmental impact of these industries but would increase the operational costs of small lead recyclers.

Closed-loop cobalt recycling from spent lithium-ion batteries based on a deep eutectic solvent (DES) with easy solvent recovery

Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to its potential to reduce the consumption of energy and threat to the environment.However,the simultaneous realization of green,efficient and closed-loop recycling is still challenging.Herein,we report a closed-loop and highly efficient approach to recycle lithium cobalt oxide from spent LIBs based on a choline chloride:oxalic acid(ChCl:OA)type deep eutectic solvent(DES).An ultrafast leaching process is observed at 180°C for 10 s with no observable residues.The energy barrier during leaching is calculated to be 113.9 kJ/mol.Noteworthy,the solubility of cobalt ions can be reversibly tuned by simply adding/evaporating deionized water,thus avoiding the addition of precipitant and enabling the easy recovery of the leaching solvent for realizing a closed-loop recycling process.The simultaneous realization of high efficiency,green and closed-loop process is expected to push the DES into practical application for recycling the electrodes of LIBs.

Rejuvenating LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode directly from battery scraps

Battery recycling is indispensable for alleviating critical material shortages and enabling sustainable battery applications.However,current methods mostly focus on spent batteries,which not only require sophisticated disassembly and material extraction but also have unknown chemistries and states of health,resulting in high costs and extreme challenges to achieve regeneration.Here,we propose the direct recycling and effective regeneration of air-degraded LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)cathode directly from battery scraps generated during battery manufacturing.The NCM523 shows surface degradation only a few nanometers deep and accordingly can be regenerated without adding Li,achieving restored properties(170 mAh g^(-1) at 0.1 C,92.7%retention after 1000 cycles)similar to those of fresh commercial materials.EverBatt analysis shows that scrap recycling has a profit of$1.984 kg^(-1),which is~10 times higher than conventional recycling,making it practical and economical to rejuvenate slightly degraded electrode materials for sustainable battery manufacturing.

Mn3O4/carbon nanotube nanocomposites recycled from waste alkaline Zn–MnO2 batteries as high-performance energy materials

Alkaline zinc manganese dioxide（Zn–MnO2）batteries are widely used in everyday life. Recycling of waste alkaline Zn–MnO2 batteries has always been a hot environmental concern. In this study, a simple and costeffective process for synthesizing Mn3O4/carbon nanotube（CNT） nanocomposites from recycled alkaline Zn–MnO2 batteries is presented. Manganese oxide was recovered from spent Zn–MnO2 battery cathodes. The Mn3O4/CNT nanocomposites were produced by ball milling the recovered manganese oxide in a commercial multi-wall carbon nanotubes（MWCNTs） solution. Scanning electron microscopy（SEM） analysis demonstrates that the nanocomposite has a unique three-dimensional（3D） bird nest structure. Mn3O4 nanoparticles are homogeneously distributed on MWCNT framework. Mn3O4/CNT nanocomposites were evaluated as an anode material for lithium-ion batteries, exhibiting a highly reversible specific capacitance of -580 mA h·g^-1 after 100 cycles. Moreover, Mn3O4/CNT nanocomposite also shows a fairly positive onset potential of -0.15 V and quite high oxygen reducibility when considered as an electrocatalyst for oxygen reduction reaction.

Narada Power Formally Enters The Lithium Battery Recycling Industry to Cope with The "Responsibility Extension" Policy

After several years of development,the power battery recycling period has come.Calculated based on the number of power lithium batteries used by commercial vehicles(3-year battery life)and passenger vehicles(5-year battery life),the capacity of scrapped power batteries in China is expected to reach 11.8Gwh by2018.

Steady Growth in New Energy Vehicle Boosts Power Lithium Battery Recycling Market

Benefiting from rapid growth in new energy vehicle industry,China’s population of new energy vehicles soared in rapid succession,percentage of power lithium battery rose from11%to 28%,in the future this trend will continue,it is expected that by 2020,the percentage of power lithium battery will reach47%.

The Worn-out Power Battery Recycling Market About to Explode

Although a number of new energy automobile enterprises promise consumers that the battery’s service life and quality guarantee period may last about 10 years,the average life expectancy of power batteries is in fact more than 5 years if considering the usage environment and other factors.This means that the power battery recycling market is about to explode in 2018.

Enhanced leaching of metals from spent lithium-ion batteries by catalytic carbothermic reduction

Spent Li-ion battery(LIB)recycling has become a challenge with the rapidly developing electric vehicle(EV)industry.To address the problems of high cost and low recovery of Li in the recycling of spent LIBs using traditional hydrometallurgical processes,we developed an alkali metal catalytic carbothermic reduction method to recover spent LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM).Using alkali metal catalysts,such as NaOH,significantly reduced the temperature required for carbothermic NCM material reduction and realized targeted control of the phase of the reduction product,where Li was first separated by prior water leaching,followed by Ni,Co,and Mn recycling by acid leaching.The optimized carbothermic reduction conditions were a reaction time of 3 h,temperature of 550℃,NaOH dosage of 15 wt%,and graphite dosage of 15 wt%.The Li leaching efficiency reached 78.5 wt%during water leaching.And during acid leaching,the Ni,Co and Mn leaching efficiencies were 99.8 wt%,99.7 wt%,and 99.5wt%,respectively.This study provides strong technical support for the development of LIB industry.

Room-temperature extraction of individual elements from charged spent LiFePO_(4)batteries

Recycling millions of metric tons of spent LiFePO_(4) batteries would benefit human health while reducing resource depletion and environmental pollution.However,recovering individual elements from the spent batteries without generating waste is challenging.Here,we present a distinctive approach for recycling spent LiFePO_(4) batteries at room temperature,where water is the only leaching agent consumed.FePO_(4) and lithium intercalated graphite act as a precursor material for selectively extracting lithium,iron,and phosphorus through charging the LiFePO_(4) batteries to the delithiated state.NaOH solution extracted Fe from FePO_(4) within 30 min and regenerated without consumption,similar to a catalyst.Under the optimal leaching conditions(1 mol·L^(-1) NaOH,0.5 h,NaOH/Fe molar ratio of 4.5),Fe and P leaching efficiencies achieved 89.1%and 99.2%,respectively.The methodology reflected in this research reduced the material cost per kg cathode material to a fraction of previously published reports,only occupies 6.13%of previous reports.In addition,the method improved the battery recycling revenue calculated by the EverBatt model by 2.31 times and 1.94 times over pyrometallurgical and hydrometallurgical methods.The proposed method allows for the convenient recovery of the elemental components of spent LiFePO_(4) batteries.

A perspective on sustainable energy materials for lithium batteries

Lithium ion battery has achieved great success in portable electronics and even recently electronic vehicles since its commercialization in 1990s.However,lithium-ion batteries are confronted with several issues in terms of the sustainable development such as the high price of raw materials and electronic products,the emerging safety accidents,etc.The recent progresses are herein emphasized on lithium batteries for energy storage to clearly understand the sustainable energy chemistry and emerging energymaterials.The Perspective presents novel lithium-ion batteries developed with the aims of enhancing the electrochemical performance and sustainability of energy storage systems.First,revolutionary material chemistries,including novel low-cobalt cathode,organic electrode,and aqueous electrolyte,are discussed.Then,the characteristics of safety performance are analyzed and strategies to enhance safety are subsequently evaluated.Battery recycling is considered as the key factor for a sustainable society and related technologies are present as well.Finally,conclusion and outlook are drawn to shed lights on the further development of sustainable lithium-ion batteries.

End-of-life batteries management and material flow analysis in South Korea

Consumers increasingly have worn-out batteries as electrical and electronic equipment with new technical developments are introduced into the market and quickly replace older models. As a result, large amounts of end-of-life （EOL） or waste batteries are generated. Such batteries may contain a variety of materials that includes valuable resources as well as toxic elements. Thus, the proper recycling and management of batteries is very important from the perspective of resource conservation and environmental effect. The collection and recycling of EOL batteries is relatively low in South Korea compared to other countries, although an extended producer responsibility （EPR） policy was adopted for battery recycling in 2003. In this study, the management and material flow of EOL batteries is presented to determine potential problems and quantitative flow, based on literature review, site visits to battery recycling facilities, and interviews with experts in the Korea Battery Recycling Association （KBRA）, manufacturers, and regulators in government. The results show that approximately 558 tons of manganese-alkaline batteries, the largest fraction among recycling target items, was disposed in landfills or incinerators in 2015, while approximately 2,000 tons of batteries were recovered at a recycling facility by simple sorting and crushing processes. By raising environmental awareness, more diverse and effective collection systems could be established for consumers to easily dispose of EOL batteries in many places. Producers, retailers and distributors in South Korea should also play an important role in the collection of EOL batteries from consumers. Lithium-ion batteries from many electronic devices must be included in the EPR system for resource recovery.