Spent Lithium Ion Batteries Research Articles

Study of reaction characteristics and controlling mechanism of chlorinating conversion of cathode materials from spent lithium-ion batteries

Spent lithium-ion batteries (LIBs) recycling has attracted much attention because it is highly favorable to environment protection and sustainable development. Developing a cleaner method for metals extraction can greatly reduce risk of secondary pollution. Chlorinating technology has been proved as an efficient method for metals extraction instead of traditional hydrometallurgy. In this paper, cathode materials from spent LIBs could be rapidly converted into metal chlorides by NH4Cl roasting at 623 K for 20 min. The results indicated nearly 100% metal leaching rates were achieved. Further, in-depth study is performed to obtain the mechanism function of chlorinating conversion based on roasting and TGA experiments. The apparent activation energy as 73.40 kJ/mol was firstly obtained, and then the reaction model of chlorination reaction was determined by model fitting and verifying. Herein, sub-reactions of chlorination reaction were figured out and their contributions were used to determinate reaction controlling mechanisms of chlorination reaction. The results indicated that nucleation reaction played a leading role in the initial stage (0.05 <α < 0.43) while phase boundary reaction took the control in next stage (0.43 <α < 0.95), which gave a good explanation to activation energy change. Finally, our findings provided inspirations for studying the controlling mechanism of gas-solid reaction.

Recovery of Nickel and Cobalt By Electrowinning from Spent Lithium-Ion Batteries Using Molten Salt Electrolytes

Electrodeposition of metals is of wide interest with application in several fields such as electroplating, electrorefining and electrowinning (EW). Particularly, electrowinning is used in the fabrication of commercially pure copper and zinc, with approximately 20% of the world refined copper (Cu) produced by this process. One of the main advantages of EW is the high purity achieved of the final product. Electrowinning has been implemented recently as one of the final steps in the hydrometallurgical recycling process of lithium-ion batteries (LIBs) to recover some of the valuable metals present in the battery such as cobalt and nickel.This work describes advances in the recovery of metals from spent LIBs, by using a two-phase molten salt of sodium borate/sodium chloride at high temperature. The study takes advantage of the versatility of the molten salts used as electrolytes - sodium borate’s easiness for dissolving metal oxides, and sodium chloride as the chosen electrolysis media. For the study, two different cathode chemistries were used, NMC 111 and NCA. The electrolytic cell comprises of a gas-tight vertical tube furnace under argon atmosphere, possible in a single-vessel configuration by utilizing the immiscibility of the two liquid phases used (see Figure 1). The experiments are conducted in a three-electrode setup, using graphite (C) as counter electrode, and tungsten (W) as pseudo-reference and working electrodes. The process operates within the temperature range of 800-900℃, where both salts are in liquid state. The reduction potentials were applied stepwise using chronoamperometry to record the current output. Cyclic voltammetry was used beforehand to corroborate the reduction potential for each metal, and to compare it to the reported ones by Amietszajew et. al. The plating potentials and recovered metals quality are reported (see Figures 2-3), indicating successful process proof-of-concept.Evaluation of the energy efficiency of the process and purity of the deposited metals is compared with the current commercial processes for metal recovery employed to recycle batteries from portable devices. The system demonstrates stability, and gives the possibility to be used in joint with other metal recycling sources and process. It has the possibility to solve some of the issues related to the hydrometallurgical methods including significant amounts of water waste, sulphates by-products presence and toxic acids resulting in highly detrimental effects on the environment. The reduction in energy consumption and hazardous gases generation that the common pyrometallurgical process adds to the advantages. Furthermore, the method developed is inclusive of a range of metals, which is of high importance considering the growing and future complexity of the battery waste stream. Figure 1

A Combined Pyro- and Hydrometallurgical Approach to Recycle Pyrolyzed Lithium-Ion Battery Black Mass Part 2: Lithium Recovery from Li Enriched Slag—Thermodynamic Study, Kinetic Study, and Dry Digestion

Due to the increasing demand for battery raw materials, such as cobalt, nickel, manganese, and lithium, the extraction of these metals, not only from primary, but also from secondary sources, is becoming increasingly important. Spent lithium-ion batteries (LIBs) represent a potential source of raw materials. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. The generation of mixed cobalt, nickel, and copper alloy and lithium slag as intermediate products in an electric arc furnace is investigated in part 1. Hydrometallurgical recovery of lithium from the Li slag is investigated in part 2 of this article. Kinetic study has shown that the leaching of slag in H2SO4 takes place according to the 3-dimensional diffusion model and the activation energy is 22–24 kJ/mol. Leaching of the silicon from slag is causing formation of gels, which complicates filtration and further recovery of lithium from solutions. The thermodynamic study presented in the work describes the reasons for the formation of gels and the possibilities of their prevention by SiO2 precipitation. Based on these findings, the Li slag was treated by the dry digestion (DD) method followed by dissolution in water. The silicon leaching efficiency was significantly reduced from 50% in the direct leaching experiment to 5% in the DD experiment followed by dissolution, while the high leaching efficiency of lithium was maintained. The study takes into account the preparation of solutions for the future trouble-free acquisition of marketable products from solutions.

A green, efficient, closed-loop direct regeneration technology for reconstructing of the LiNi0.5Co0.2Mn0.3O2 cathode material from spent lithium-ion batteries

Lithium nickel manganese cobalt oxide in the spent lithium ion batteries (LIBs) contains a lot of lithium, nickel, cobalt and manganese. However, how to effectively recover these valuable metals under the premise of reducing environmental pollution is still a challenge. In this work, a green, efficient, closed-loop direct regeneration technology is proposed to reconstruct LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode materials from spent LIBs. Firstly, the failure mechanism of NCM523 cathode materials in the spent LIBs is analyzed deeply. It is found that the spent NCM523 material has problems such as the dissolution of lithium and transition metals, surface interface failure and structural transformation, resulting in serious deterioration of electrochemical performance. Then NCM523 material was directly regenerated by supplementing metal ions, granulation, ion doping and heat treatment. Meanwhile, PO43− polyanions were doped into the regenerated NCM material in the recovery process, showing excellent electrochemical performance with discharge capacity of 189.8 mAh g−1 at 0.1 C. The recovery process proposed in this study puts forward a new strategy for the recovery various lithium nickel cobalt manganese oxide (e.g., LiNi1/3Co1/3Mn1/3O2, LiNi0.5Co0.2Mn0.3O2, LiNi0.6Co0.2Mn0.2O2 and LiNi0.8Co0.1Mn0.1O2) and accelerates the industrialization of spent lithium ion battery recycling.

Full recycling of spent lithium ion batteries with production of core-shell nanowires//exfoliated graphite asymmetric supercapacitor

Electrodic powder coming from real waste spent lithium ion batteries was employed as raw material for the production of asymmetric supercapacitor allowing the full recycling of the electrodic powder components. A novel process is reported which produces an asymmetric supercapacitor through the complete recycling of end-of-life lithium ion batteries. The electrodic powder recovered by industrial scale mechanical treatment of spent batteries was leached and the dissolved metals were precipitated as mixed metals carbonates. Nanowires battery-type positive electrodes were produced by electrodeposition into nanoporous alumina templates from the electrolytic baths prepared by dissolution of the precipitated carbonates. The impact of the different metals contained in the electrodic powder was evaluated by benchmarking the electrochemical performances of the recovered nanowires-based electrodes against electrodes produced by using high-purity salts. Presence of inactive Cu in the nanowires lowered the final capacitance of the electrodes while Ni showed a synergistic effect with cobalt providing a higher capacitance with respect to synthetic Co electrodes. The carbonaceous solid recovered after leaching was in-depth characterized and tested as negative electrode. Both the chemical and electrochemical characterization indicate that the recovered graphite is characterized by the presence of oxygen functionalities introduced by the leaching treatment. This has led to the obtainment of a recovered graphite characterized by an XPS C/O ratio, Raman spectrum and morphology close to literature reports for reduced graphene oxide. The asymmetric supercapacitor assembled using the recovered nanowires-based positive electrodes and graphite as negative electrodes has shown a specific capacitance of 42 F g −1 , computed including the whole weight of the positive electrode and recovered graphite, providing a maximum energy density of ~9 Wh kg −1 and a power density of 416 W kg −1 at 2.5 mA cm −2 .

Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method

Applying spent lithium iron phosphate battery as raw material, valuable metals in spent lithium ion battery were effectively recovered through separation of active material, selective leaching, and stepwise chemical precipitation. Using stoichiometric Na2S2O8 as an oxidant and adding low-concentration H2SO4 as a leaching agent was proposed. This route was totally different from the conventional methods of dissolving all of the elements into solution by using excess mineral acid. When experiments were done under optimal conditions (Na2S2O8-to-Li molar ratio 0.45, 0.30 mol/L H2SO4, 60 °C, 1.5 h), leaching efficiencies of 97.53% for Li+, 1.39% for Fe3+, and 2.58% for PO43− were recorded. FePO4 was then recovered by a precipitation method from the leachate while maintaining the pH at 2.0. The mother liquor was concentrated and maintained at a temperature of approximately 100 °C, and then a saturated sodium carbonate solution was added to precipitate Li2CO3. The lithium recovery yield was close to 80%.

Bioprocessing of spent lithium ion batteries for critical metals recovery – A review

The increasing demand for metals and the concomitant depletion of the primary metallic resources is one of the most important environmental and societal challenges nowadays. Critical metals, rare earth elements, base and precious metals demand is growing day-by-day and driving many metals towards the edge of supply risk. On the other hand, the problems linked to waste generation (especially waste electrical and electronic equipment (WEEE)) are also increasing globally. These end-of-life electronic wastes contain significant concentration of critical raw materials accompanied by harmful substances. Spent Li ion batteries is a kind of WEEE stream, bearing considerable concentrations of valuable metals (like Co, Li, Mn and Ni). If the end-of-life Li ion batteries are not managed properly, there is a high risk that these valuable metals and toxic substances could end into the environment. In order to address the environmental complications, sustainable resource management and boost circular economy, it is important to properly manage and recycle these spent Li ionbatteries. Conventional methods based on high-temperature pyro-metallurgical routes together with hydro-metallurgical processing have been widely studied for the recovery of metals from spent LiBs. However, bio-metallurgical approaches have an edge over their counter parts because of their environmentally friendly nature. Microbe-metal interactions have received special attention both in terms of leaching metals from WEEE and also in recovering metal ions from aqueous streams. Microbial technologies are promising for removing metal ions because of less cost, technical feasibility for large scale applications and no need for addition of toxic chemicals thereby avoiding generation of toxic or hazardous byproducts. In this study, particular emphasis is placed on reviewing the progress made in biohydrometallurgy (i.e. bacterial and fungal leaching practices as one and two-step mode) for the leaching of critical metals from waste lithium ion batteries. Biotechnological methods (e.g. biosorption, bioprecipitation and bioelectrochemical treatment) for the recovery of critical metals from pregnant leachates and aqueous streams are also discussed.

Electric field driven de-lithiation: A strategy towards comprehensive and efficient recycling of electrode materials from spent lithium ion batteries

Along with the rapidly growing market of lithium-ion batteries, exploration of efficient strategies to recycle the retired lithium-ion batteries has become an imminent issue. Herein, a green and comprehensive recycling method based on the direct current (DC) electric field driven de-lithiation is developed and the feasibility of the strategy is systematically investigated. The results demonstrate that during the recycling process, the lithium ions can be effectively recovered with simultaneous H2 production. Meanwhile, the de-lithiated electrode materials exhibit a remarkable electrocatalytic activity, which is proved to be related to their high specific surface area as well as their large amount of lattice oxygen. Based on the Daedalian combination of efficient lithium recycling and applications of the de-lithiated cathode materials for oxygen evolution reaction, this study provides an effective strategy for recycling and making maximum use of the spent lithium-ion battery electrode materials based on the DC electric field driven de-lithiation process.

Recycling of LiCoO2 cathode material from spent lithium ion batteries by ultrasonic enhanced leaching and one-step regeneration

A novel process for recycling of spent LiCoO2 cathode materials has been developed. The novel process comprises an ultrasonic enhanced leaching and one-step regeneration of LiCoO2 materials with spray drying method. The ultrasonic is novelly applied for effectively improving leaching process of spent LiCoO2 materials in the system of DL-malic acid and H2O2. The leaching efficiencies of 98.13% for Li and 98.86% for Co were presented under the optimal condition of 1.5 mol/L DL-malic acid with 3 vol% H2O2, the solid/liquid ratio of 4 g/L, ultrasonic power of 95 W, temperature of 80 °C and leaching time of 25 min. Based on kinetic analysis, the ultrasonic enhanced leaching process is mainly controlled by the diffusion control model. Meanwhile, the product of Co(C4O5O5)2 formed on particles surface of spent LiCoO2 materials during ultrasonic enhanced leaching process, which is provided from reaction mechanism analysis of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). Finally, the regenerated LiCoO2 materials are regenerated in one step by spray drying from leaching solution, which present good electrochemical performance.

Metal extraction from spent lithium-ion batteries (LIBs) at high pulp density by environmentally friendly bioleaching process

Spent lithium-ion batteries (LIBs) are more hazardous due to the presence of several toxic metals such as cobalt, lithium, nickel, manganese, etc. as well as electrolytes such as LiPF6, LiBF4, or LiClO4. However, these spent LIBs are the secondary source of metals that can be extracted and reused in many ways to decrease their potential environmental risks. Metal extraction from the mixture of LiCoO2-based spent LIBs at a high pulp density by bioleaching is challenging because of microbial inhibition due to high metal toxicity and substrate (iron) limitation. In the present study, we have investigated the bioleaching of a mixture of LiCoO2-based LIBs at high pulp density (100 g/L) using cost-efficient autotrophic bacteria Acidithiobacillus ferrooxidans. By increasing the biogenic H2SO4 production in the culture media, as well as replenishing the bacterial culture for three cycles, we could recover 94% cobalt and 60% lithium in 72 h at 100 g/L pulp density. The X-ray diffraction (XRD), Scanning electron microscope (SEM), and Inductively coupled plasma - optical emission spectrometry (ICP-OES) analysis of LIB powder before and after bioleaching confirmed that more than 90% cobalt leached out from the LIB powder. This bioleaching process is an environmentally friendly way of extracting metals from the mixture of LIBs in gadgets and can be used for all types of spent LIBs.

Novel targetedly extracting lithium: An environmental-friendly controlled chlorinating technology and mechanism of spent lithium ion batteries recovery

A targeted extraction technology for recycling lithium from spent lithium transition metal oxides (LTMO) type batteries is developed in this paper. The chlorinating technology with ammonium chloride as the only additive is employed and controlled to selectively extract lithium. High lithium extraction rate with a low selectivity was first obtained at non-controlled chlorinating conditions. During this process, it was found that the reducing driving force (RDF) played a vital role in metals extraction. Once RDF was controlled at a low level, lithium elements could be targetedly extracted out while other metal elements still remained in the residues. The results showed that 91.73% lithium elements were leached out with a selectivity of 90.04% at the optimal conditions. Further, the mechanism was proposed to explain the release behavior of metals from cathode materials from the perspective of extracting driving force. These principles also offer inspiration for metal selective extraction fields such as metallurgy and recovery of complex systems including multiple metals.

Stepwise Recovery of Valuable Metals from Spent Lithium Ion Batteries by Controllable Reduction and Selective Leaching and Precipitation

The remarkably increasing consumption of lithium ion batteries (LIBs) has been an issue worldwide for the contained valuable metals and intrinsic toxicity in spent LIBs. Here, a novel process inclu...

High-efficiency core-shell magnetic heavy-metal absorbents derived from spent-LiFePO4 Battery

Search for simple and efficient recycling methods to utilize spent lithium-ion batteries is crucial for achieving sustainable resource development and reducing the hazardous materials released from the spent batteries. Herein, we have developed a new strategy to utilize the spent LiFePO4 batteries by utilizing the cathode plate as raw material to synthesize mesoporous core-shell adsorbent Mm@SiO2 (Mm denoted as the magnetic material) through a simple alkaline leaching process. The as-converted material exhibits excellent adsorption capacity when it has been used to remove heavy metal ions in heavy metal polluted water. The adsorption capacities for Cu2+, Cd2+, and Mn2+ have been achieved up to 71.23, 80.31 and 68.73 mg g−1, respectively. The detailed adsorption mechanism has been elucidated with comprehensive characterization techniques, including TEM, XPS, NEXAS, and EXAFS, the edge shared [Cu2O8] bipyramids can be fit against the EXAFS data to represent the atomic-scale local structure after Mm@SiO2 adsorbs Cu2+. The present work demonstrates a novel routine to reutilize the spent lithium batteries, which is of great importance to achieve sustainable development based on the “waste-to-treasure” and “waste-to-control-waste” strategy for simultaneously reducing the hazardous release from industrial solid waste and heavy metal polluted water.

Direct Recovery and Efficient Reutilization of Degraded Ternary Cathode Materials from Spent Lithium-Ion Batteries via a Homogeneous Thermochemical Process

Efficient recycling of cathode materials in scrapped lithium-ion batteries is urgent for the sustainable supply of the transition-metal and lithium resources. The conventional processes always extr...

A Comprehensive Review of the Advancement in Recycling the Anode and Electrolyte from Spent Lithium Ion Batteries

Owing to the increasing pressure on the ecological effect of solid waste disposal and developing the need for disposal of the corresponding hazardous metals, recovery of spent lithium ion batteries (LIBs) has gain worldwide attention in recent years. Much work has been done in this regard in the past few decades, and several new, interesting, and unique methods have been developed to recycle the cathode, anode, and electrolyte. Therefore, time has come to summarize the highlights in this emerging area to facilitate young researchers. In this review, starting from the current market demand and commercial value of lithium ion batteries, we have summarized the most recent progress in the direction of recycling the cathode and anode materials and electrolyte. At the beginning, an overview of the recycling techniques is presented to grasp understanding of the topic. Later, laboratory and industrial investigations and implementation are reviewed with emphasis on anode (graphite) and electrolyte recovery. Life cycle assessment of end-of-life LIB recycling, limitations, and future efforts have also mentioned to focus on improving the efficiency of metal extraction and separation with the sustainable and systematic recycling of spent lithium ion batteries.

Energy models and the process of fluid-magnetic separation for recovering cobalt micro-particles from vacuum reduction products of spent lithium ion batteries

Improper treatment of spent lithium ion batteries will cause great damages to environment. Vacuum reduction was advised as a green recovery technology of nickel and cobalt from spent lithium ion batteries. However, the separation of magnetic particles from the vacuum-reduced products of spent lithium-ion batteries has not been studied. After reduction, the particle size was so small that the formation of agglomerates would affect the separation efficiency which was a common problem in fine magnetic particle sorting. In this paper, a fluid-magnetic separation method was developed for micro-separation of cobalt from the vacuum reduction product of electrode materials of spent lithium ion batteries. This method had a high level of clean production and sustainable development at the same time as high separation rate. An energy model was established to analyze the mechanism of breaking agglomerates, and the experimental parameters affecting recovery efficiency were studied according to the energy model. In simulation experiments, under the optimal parameter conditions of 35 °C, solid-liquid ratio of 500 mL/g and collection mat material of plastic, the recovery rate and purity of cobalt micro-particles were both above 99%. After applying the vacuum reduction product to fluid-magnetic separation, the recovery rate of magnetic fine particles was 98.26%, which fully verified the effectiveness. Further, it provides a new idea for separating micro magnetic particles from micro-sized mixed particles and promoted the process of recycling spent lithium ion batteries.

Molten salt-assisted regeneration and characterization of submicron-sized LiNi0.5Co0.2Mn0.3O2 crystals from spent lithium ion batteries

Nowadays the increasing demand of energy storage devices leads to consumption of a large number of lithium-ion batteries (LIBs), it is an urgent topic about how to deal with the large quantity of discarded LIBs. In this work, the spent-LiNi0.5Co0.2Mn0.3O2 (SNCM) cathode material was directly re-synthesized by one-pot molten salt-assisted regeneration. The effect of various quantity ratios of molten salts and the spent-LiNi0.5Co0.2Mn0.3O2 (SNCM) material on preparation and electrochemical properties of the regenerated submicron-sized LiNi0.5Co0.2Mn0.3O2 crystals has been studied in detailed. The lithium deficiency, degraded crystal structure and impure surface of SNCM are successfully restored in liquid medium of lithium-contained molten salt. The structural restoring, structure stability and capacity recovering of the regenerated samples are determined by the environment of molten salts. The optimized regenerated sample MS1.1 delivers the highest initial capacity of 152.5 mAh g−1 at 0.2 C rate, and it remains 86% capacity after 100 cycles. MS1.1 with the smallest charge transfer resistance delivers the highest capacity of 133.4 mAh g−1 at 5 C rate, and it presents excellent cyclic stability for 500 cycles. After 100 cycles, stable crystal morphology of MS1.1 is still maintained, and MS1.1 induces less side reactions and low quantity of by-products. The restored electrochemical performances of MS1.1 sample prove that the molten salt-assisted regeneration maybe a facial and effective method for other spent cathode materials.

A green and facile approach for regeneration of graphite from spent lithium ion battery

Low-cost regeneration of graphite from spent lithium ion batteries (LIBs) enjoys great significance in solving the problems of utilization and pollution of spent graphite. In this study, a facile approach for recycling graphite from spent LIBs has been developed. Firstly, anode current collector is smelted under nitrogen atmosphere at 1673 K for 4 h. Then, copper and graphite are further separated from each other by simple ultrasonic vibration and sieving. The results show that more than 80% copper above the 200-mesh (0.075 mm) and 77.53% graphite under the 300-mesh (0.048 mm) can be recovered, and the purity of the recovered graphite is higher than 99.5%. The recycled graphite shows high capacity and good cycle performance (specific capacity can be high up to 360.8 mA h g−1 after 100 cycles at 1C and the retention rate is almost 100%).

From spent graphite to recycle graphite anode for high-performance lithium ion batteries and sodium ion batteries

Nowadays, recycling cathode materials form spent lithium ion batteries (LIBs) has attracted widespread attentions in order to recover highly-valuable metal elements. However, recycling graphite materials is usually discarded because of the low added value and rigorous separation steps. In this study, we investigate the possibility of reusing spent graphite as anode material for LIBs and SIBs after reconstruction process. Benefiting form the structural reconstruction process, which can enhance the interlayer force and reduce the interlayer lattice distance of graphite, lead to the reconstructed graphite with improved and stable layered structure. When used as anode materials for LIBs, the reconstructed graphite exhibits outstanding electrochemical performance. As a result, the reconstructed graphite can deliver high capacity of 427.9 mAh g−1 after 200 cycles at 0.5 C, and also display a outstanding rate capability (a capacity of 114.9 mAh g−1 is achieved at 3 C). Furthermore, the acid-treated graphite can be directly used as anode material for SIBs, which exhibit high reversible capacity of 127 mAh g−1 at 50 mA g−1, and also exhibits excellent long cycle life (a reversible capacity of 106.8 mAh g−1 is achieved after 500 cycles at 2000 mA g−1 with high capacity retention of 90.98%).

Leaching Mechanisms of Recycling Valuable Metals from Spent Lithium-Ion Batteries by a Malonic Acid-Based Leaching System

Considering the shortage and toxicity of raw materials, recycling cathode materials from spent lithium-ion batteries is currently the most promising measure to realize the green sustainability of c...