Spent Lithium Ion Batteries Research Articles

Material and Waste Flow Analysis for Environmental and Economic Impact Assessment of Inorganic Acid Leaching Routes for Spent Lithium Batteries’ Cathode Scraps

With the development trend and technological progress of lithium batteries, the battery market is booming. This means that the demand for lithium batteries has increased significantly, resulting in a large number of discarded lithium batteries. The consumption of plenty of lithium batteries may lead to the scarcity and expending of relevant raw material metal resources, as well as serious heavy metal environmental pollution. Therefore, it is of great significance to recycle valuable metal resources from discarded lithium batteries. The proper recycling of these valuable metals can reduce the shortage of mineral resources and environmental hazards caused by a large number of scrapped vehicle batteries. Recently, different systematic approaches have been developed for spent lithium battery recovery. However, most of these approaches do not account for the hidden costs incurred from various processing steps. This work is determined by the concept of material flow cost accounting (MFCA). Hence, in this research, a MFCA-based approach is developed for the leaching process of spent lithium batteries recovery, taking into consideration the hidden costs embedded in process streams. In this study, hydrochloric acid had the worst leaching efficiency due to its high solid-to-liquid ratio and the lowest acid concentration, so it was excluded in the first stage selection. It takes TWD 16.03 and TWD 24.10 to leach 10 g of lithium battery powder with sulfuric acid and nitric acid, respectively. The final sulfuric acid was the acid solution with the highest leaching efficiency and relatively low cost among inorganic acids.

Optimization of the Electrochemical Discharge of Spent Li-Ion Batteries from Electric Vehicles for Direct Recycling

Numerous studies have been conducted on spent lithium-ion batteries (LIBs) recycled from electric vehicles. Research on pre-processing techniques to safely disassemble spent LIB packs has mainly focused on water-based discharge methods, such as salt-water discharge. However, salt-water discharge corrodes the electrodes and case, causing internal contamination. Therefore, we propose an electrical discharge process that is suitable for the direct recycling and safe disassembly of spent Li-ion batteries. Spent LIBs from electric vehicles (EV) that were scrapped after EV operation were recovered and electrochemically discharged to voltages of 0, 1, 2, and 2.5 V. These discharged spent LIBs were analyzed through X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy. The spent LIB with a state-of-health (SoH) of 66.8% exhibited significantly increased swelling and bulging when over-discharged. Notably, the discharging of the spent battery to 0 V increased the thickness of the cell by 115%, which could result in a fire and/or explosion. After being discharged to 0 V, the voltage was able to recover to 2.689 V. The appropriate voltage for the discharge process was estimated to be 2.5 V. The proposed electrical discharge process will be suitable for the direct recycling of spent LIBs in the form of pouch cells.

Direct Electrochemical Leaching Method for High-Purity Lithium Recovery from Spent Lithium Batteries.

Recovering lithium from lithium batteries (LIBs) is a promising approach for sustainable ternary lithium battery (T-LIB) development. Current lithium recovery methods from spent T-LIBs mainly concentrated on chemical leaching methods. However, chemical leaching relying on the additional acid seriously threatens the global environment and nonselective leaching also leads to low Li recovery purity. Here, we first reported a direct electro-oxidation method for lithium leaching from spent T-LIBs (Li0.8Ni0.6Co0.2Mn0.2O2); 95.02% of Li in the spent T-LIBs was leached under 2.5 V in 3 h. Meanwhile, nearly 100% Li recovery purity was also achieved, attributed to no other metal leaching and additional agents. We also clarified the relationship between lithium leaching and other metals during the electro-oxidation of spent T-LIBs. Under the optimized voltage, Ni and O maintain the electroneutrality in the structure assisting Li leaching, while Co and Mn maintain their valence states. A direct electro-oxidation Li leaching approach achieves high Li recovery purity and meanwhile overcomes the secondary pollution problem.

Recycling Valuable Metals from Spent Lithium-Ion Batteries Using Carbothermal Shock Method.

Pyrometallurgy technique is usually applied as a pretreatment to enhance the leaching efficiencies in the hydrometallurgy process for recovering valuable metals from spent lithium-ion batteries. However, traditional pyrometallurgy processes are energy and time consuming. Here, we report a carbothermal shock (CTS) method for reducing LiNi0.3 Co0.2 Mn0.5 O2 (NCM325) cathode materials with uniform temperature distribution, high heating and cooling rates, high temperatures, and ultrafast reaction times. Li can be selectively leached through water leaching after CTS process with an efficiency of >90 %. Ni, Co, and Mn are recovered by dilute acid leaching with efficiencies >98 %. The CTS reduction strategy is feasible for various spent cathode materials, including NCM111, NCM523, NCM622, NCM811, LiCoO2 , and LiMn2 O4 . The CTS process, with its low energy consumption and potential scale application, provides an efficient and environmentally friendly way for recovering spent lithium-ion batteries.

Review of preferentially selective lithium extraction from spent lithium batteries: Principle and performance

Lithium, as the lightest and lowest potential metal, is an ideal “battery metal” and the core strategic metal of the new energy industry revolution. Recovering lithium from spent lithium batteries (LIBs) has become one of the significant approaches to obtaining lithium resources. At present, the lithium extraction being generally placed at the last step of the spent LIBs recovery process has puzzles such as high acid consumption, low Li recovery purity and low recovery efficiency. Selective lithium extraction at the first step of the recovery process can effectively solve those puzzles. Since lithium leaching is a non-spontaneous reaction requiring additional energy to achieve, it is found that these methods can be divided into five ways according to the different types of energy driving the reaction occurring: (i) electric energy driving lithium extraction; (ii) chemical energy driving lithium extraction; (iii) mechanical energy driving lithium extraction; (iv) thermal energy driving lithium extraction; (v) other energy driving lithium extraction. Through the analysis of the principle, reaction process and results of recovering lithium methods can provide a few directions for scholars' subsequent research. It is necessary to speed up the exploration of the principle of these methods. It is expected that this study could provide a reference for the research on the selective lithium extraction.

Green and Low-Cost Approach for Recovering Valuable Metals from Spent Lithium-Ion Batteries

Spent lithium-ion batteries (LIBs) are increasingly produced as the consumption of LIBs for electric vehicles and 3C products is increasing. Herein, a process to recycle valuable metals from the cathodes of LIBs is proposed, in which the separation of aluminum foil and cathode material is realized by calcining the spent cathode sheet in CO2. The spent aluminum foil separated from cathode sheet is used as a reducing agent to displace Ni2+, Co2+, and Mn2+ in the leachate to generate high-purity Ni–Co–Mn nanopowders. In addition, the recovery efficiencies of Li, Ni, Co, and Mn are 95.04, 97.5, 99.3, and 4%, respectively. Ternary cathode materials are synthesized by the solid-phase method using the reduction products as the precursors. The initial discharge capacity of the synthetic material at 0.2 C reaches 165 mA h g–1. The use of the spent aluminum current collector reduces the consumption of auxiliary materials, and the aluminum current collector is transformed from waste into a high-value-added reductant, greatly lowering the process costs and also making the process green. Finally, an economic and energy consumption analysis of the entire process is performed. This green and low-cost process achieves a closed loop of LIBs, which is critical to support sustainable expansion of the LIB production.

Separation of Valuable Metals in The Recycling of Lithium Batteries via Solvent Extraction

With the development trend and technological progress of lithium batteries, the battery market is booming, which means that the consumption demand for lithium batteries has increased significantly, and, therefore, a large number of discarded lithium batteries will be generated accordingly. Solvent extraction is a promising approach because it is simple. Solvent extraction is low in time consumption and is easy to industrialize. This paper is focused on the selective recovery of cobalt (Co), nickel (Ni), and manganese (Mn) contained in leachate obtained by digesting a cathodic material from spent lithium batteries with hydrochloric acid. After leaching the cathodic material, Mn was selectively extracted from leachate by using solvent extraction with D2EHPA diluted in kerosene in an optimized condition. Afterward, Co was extracted from the Mn-depleted aqueous phase using Cyanex272 diluted in kerosene. Finally, the raffinate obtained via a stripping reaction with H2SO4 was used in the Ni extraction experiments. Cyanex272 extractant was employed to separate Ni and Li. The process can recover more than 93% of Mn, 90% of Co, and 90% of Ni. The crucial material recovered in the form of sulfuric acid solutions can be purified and returned to the manufacturer for use. This process proposes a complete recycling method by effectively recovering Mn, Co, and Ni with solvent extraction, to contribute to the supply of raw materials and to reduce tensions related to mineral resources for the production of lithium batteries.

Selective Extraction of Critical Metals from Spent Lithium-Ion Batteries.

Selective and highly efficient extraction technologies for the recovery of critical metals including lithium, nickel, cobalt, and manganese from spent lithium-ion battery (LIB) cathode materials are essential in driving circularity. The tailored deep eutectic solvent (DES) choline chloride-formic acid (ChCl-FA) demonstrated a high selectivity and efficiency in extracting critical metals from mixed cathode materials (LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1) under mild conditions (80 °C, 120 min) with a solid-liquid mass ratio of 1:200. The leaching performance of critical metals could be further enhanced by mechanochemical processing because of particle size reduction, grain refinement, and internal energy storage. Furthermore, mechanochemical reactions effectively inhibited undesirable leaching of nontarget elements (iron and phosphorus), thus promoting the selectivity and leaching efficiency of critical metals. This was achieved through the preoxidation of Fe and the enhanced stability of iron phosphate framework, which significantly increased the separation factor of critical metals to nontarget elements from 56.9 to 1475. The proposed combination of ChCl-FA extraction and the mechanochemical reaction can achieve a highly selective extraction of critical metals from multisource spent LIBs under mild conditions.

Highly Efficient Recovery and Recycling of Cobalt from Spent Lithium-Ion Batteries Using an N-Methylurea-Acetamide Nonionic Deep Eutectic Solvent.

The growing demand for lithium-ion batteries (LiBs) for the electronic and automobile industries combined with the limited availability of key metal components, in particular cobalt, drives the need for efficient methods for the recovery and recycling of these materials from battery waste. Herein, we introduce a novel and efficient approach for the extraction of cobalt, and other metal components, from spent LiBs using a nonionic deep eutectic solvent (ni-DES) comprised of N-methylurea and acetamide under relatively mild conditions. Cobalt could be recovered from lithium cobalt oxide-based LiBs with an extraction efficiency of >97% and used to fabricate new batteries. The N-methylurea was found to act as both a solvent component and a reagent, the mechanism of which was elucidated.

Selective Separation of Lithium, Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors.

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li+ from Ca2+ , Mg2+ , Na+ and K+ . The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Selective Separation of Lithium, Magnesium and Calcium using 4‐Phosphoryl Pyrazolones as pH‐Regulated Receptors

AbstractEnsuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid‐liquid extraction) for both primary sources and certain waste streams. In this work, 4‐phosphoryl pyrazolones are used in an efficient pH‐controlled stepwise separation of Li+ from Ca2+, Mg2+, Na+ and K+. The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co‐ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH&lt;5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Recovery and Recycling of Valuable Metals from Spent Lithium-Ion Batteries: A Comprehensive Review and Analysis

The recycling of spent lithium-ion batteries (Li-ion Batteries) has drawn a lot of interest in recent years in response to the rising demand for the corresponding high-value metals and materials and the mounting concern emanating from the detrimental environmental effects imposed by the conventional disposal of solid battery waste. Numerous studies have been conducted on the topic of recycling used Li-ion batteries to produce either battery materials or specific chemical, metal or metal-based compounds. Physical pre-treatment is typically used to separate waste materials into various streams, facilitating the effective recovery of components in subsequent processing. In order to further prepare the recovered materials or compounds by applying the principles of materials chemistry and engineering, a metallurgical process is then utilized to extract and isolate pure metals or separate contaminants from a particular waste stream. In this review, the current state of spent Li-ion battery recycling is outlined, reviewed, and analyzed in the context of the entire recycling process, with a particular emphasis on hydrometallurgy; however, electrometallurgy and pyrometallurgy are also comprehensively reviewed. In addition to the comprehensive review of various hydrometallurgical processes, including alkaline leaching, acidic leaching, solvent (liquid-liquid) extraction, and chemical precipitation, a critical analysis of the current obstacles to process optimization during Li-ion battery recycling is also conducted. Moreover, the energy-intensive nature of discussed recycling process routes is also assessed and addressed. This study is anticipated to offer recommendations for enhancing wasted Li-ion battery recycling, and the field can be further explored for commercialization.

Effect of lithium ion on the separation of electrode materials in spent lithium ion batteries using froth flotation

There is an urgent need to develop a recycling process for spent Lithium-Ion Batteries (LIBs). Amongst the various recycling technologies proposed, froth flotation is considered a cost-effective candidate for the separation of graphite from the lithium metal oxides due to the hydrophobic nature of graphite. However, experimental studies have identified that soluble lithium has a significant impact on the separation efficiency.Two series of experiments were undertaken to understand the influence of lithium ions. The first used a semi-synthetic mixture of spent anode and pure cathode material based on lithium nickel manganese cobalt oxide (LiNi0.33Mn0.33Co0.33O2) or NMC-111 cathode material. The second used mixed samples of spent lithium ion batteries of the same composition. Both the separation efficiency and the flotation kinetics are reported. The soluble lithium concentration is shown to have a significant impact on both. However, if the spent battery material is washed to reduce the lithium ion concentration, the flotation efficiency and kinetics are similar with the graphite recovery exceeding 90% and the graphite grade exceeding 84% in a single flotation stage.

Comminution and Classification as Important Process Steps for the Circular Production of Lithium Batteries

Lithium-ion batteries (LIBs) provide the largest source of electrical energy storage today. This paper covers the use of comminution processes and, thus, crushers and mills for particle breakage and dispersing, as well as classifiers for particle separation within the process chain, from the raw material to the final lithium battery cell and its recycling at end of life. First of all, the raw materials for the active material production have to be produced either by processing primary raw materials, or by recycling the spent lithium batteries. The end-of-life battery cells have to be shredded, the materials separated and then milled in order to achieve the so-called black mass, which provides a secondary material source with very valuable components. Using these materials for the synthesis of the cathode active materials, milling has to be applied in different stages. The natural graphite, increasingly used as anode material, has to be designed in mills and classifiers for achieving targeted properties. Nanosized silicon is produced by nanomilling using stirred media mills as a primary option. Conductive additives for LIBs, like carbon black, have to be dispersed in a solvent with machines like planetary mixers, extruders or stirred media mills. In the future, mechanochemical synthesis of solid electrolytes will especially require additional application of comminution processes.

Amino Acid Leaching of Critical Metals from Spent Lithium-Ion Batteries Followed by Selective Recovery of Cobalt Using Aqueous Biphasic System.

To reduce the exploitation of mine resources and decrease the harm to the environment caused by urban electronic wastes, the recovery of critical metals in secondary resources is crucial. In this study, we have successfully developed an eco-friendly process to integrate the leaching and separation of cobalt (Co) from a spent lithium-ion battery (LIB) cathode using an amino acid-based aqueous biphasic system (ABS). We, for the first time, demonstrated a simple method for leaching a LIB cathode using only amino acids. In addition, we have investigated the leaching mechanism using the typical cathode active material lithium cobalt oxide (LiCoO2). Then, the Co was selectively extracted by a biphasic system (amino acid-PPG400-H2O). This novel process has an excellent prospect in the field of spent-battery recycling because of its eco-friendly and process-simplified advantages.

Worldwide research on extraction and recovery of cobalt through bibliometric analysis: a review.

Cobalt is a strategic and critical mineral whose demand is expected to grow rapidly. This study aims to provide a comprehensive summary of cobalt extraction and recovery research from 2012 to 2021 in the form of bibliometric analysis. The work was based on the Science Citation Index Expanded (Web of Science) and carried out using the InCites of Clarivate for bibliometric data analysis and the software VOSviewer for science mapping. By analyzing a dataset of 4967 publications, the most influential journals, countries, authors, institutions, and publications were identified, and the keyword co-occurrence networks were mapped. The China mainland produced the most publications, while the USA had the highest average number of citations per publication and the UK was the most collaborative with other countries. The keyword analysis shows that the research hotspots gradually shifted over time from early means and methods for determination of cobalt in solution to recovery of cobalt from spent lithium batteries, smelting slag, copper-cobalt ore, etc. The research will be focused on further improvement and optimization of the separation, extraction, and recovery processes of cobalt from spent batteries in recent and future years, and three approaches were promoted to facilitate economization and industrialization of the processes in this field.

Green Phosphate Route of Regeneration of LiFePO4 Composite Materials from Spent Lithium-Ion Batteries

Green Phosphate Route of Regeneration of LiFePO₄ Composite Materials from Spent Lithium-Ion Batteries

Recycling cobalt in spent lithium ion batteries to design CoN/HPCF/CoN electrocatalysts for advanced zinc-air batteries.

Cobalt (Co) in spent lithium ion batteries was recycled to design a hollow and porous CoN/HPCF/CoN bifunctional electrocatalyst. It reveals superior rechargeable zinc-air battery performance (peak power density is 161.6 mW cm-2) with excellent stability.

Industrial Recycling Process of Batteries for EVs

The growing number of decarbonization standards in the transportation sector has resulted in an increase in demand for electric cars. Renewable energy sources have the ability to bring the fossil fuel age to an end. Electrochemical storage devices, particularly lithium-ion batteries, are critical for this transition’s success. This is owing to a combination of favorable characteristics such as high energy density and minimal self-discharge. Given the environmental degradation caused by hazardous wastes and the scarcity of some resources, recycling used lithium-ion batteries has significant economic and practical importance. Many efforts have been undertaken in recent years to recover cathode materials (such as high-value metals like cobalt, nickel, and lithium). Regrettably, the regeneration of lower-value-added anode materials (mostly graphite) has received little attention. However, given the widespread use of carbon-based materials and the higher concentration of lithium in the anode than in the environment, anode recycling has gotten a lot of attention. As a result, this article provides the most recent research progress in the recovery of graphite anode materials from spent lithium ion batteries, analyzing the strengths and weaknesses of various recovery routes such as direct physical recovery, heat treatment recovery, hydrometallurgy recovery, heat treatment-hydrometallurgy recovery, extraction, and electrochemical methods from the perspectives of energy, environment, and economy; additionally, the reuse of recycled anode mats is discussed. Finally, the problems and future possibilities of anode recycling are discussed. To enable the green recycling of wasted lithium ion batteries, a low energy-consuming and ecologically friendly solution should be investigated.

High Performance Lithium Ion Battery Cathode Based a Reduced Holey Graphene Oxides from Spent Lithium Ion Batteries

High Performance Lithium Ion Battery Cathode Based a Reduced Holey Graphene Oxides from Spent Lithium Ion Batteries