Spent Lithium Ion Batteries Research Articles

Selective Leaching of Lithium and Beyond: Sustainable Eggshell-Mediated Recovery from Spent Li-Ion Batteries

This study introduces an innovative strategy for the selective leaching of lithium from spent Li-ion batteries. Based on thermodynamic assessments and exploiting waste eggshells as a source of calcium carbonate, an impressive 38% of lithium was dissolved selectively through mechanical milling and water leaching, outperforming conventional thermochemical methods. Afterwards, a hydrogen peroxide-assisted sulfuric acid leaching was also implemented to solubilize targeted elements (Mn, Co, Ni, and Li), with an exceptional 99% efficiency in Mn removal from the leachate using potassium permanganate and a pH range of 1.5 to 3.5. Selective separations of Co and Ni were then facilitated utilizing CYANEX 272 and n-heptane. This comprehensive study presents a promising and sustainable avenue for the effective recovery of Li and associated co-elements from spent lithium batteries.

Short process for Li2CO3 synthesis and spent LiCoO2 remediation via Glycine-LiOH slurry electrolysis

Effectively recycling spent lithium-ion batteries (S-LIBs) has considerable economic and environmental benefits. In this study, a novel approach for simultaneously synthesizing Li2CO3 and remediating LiCoO2 from S-LIBs via slurry electrolysis is proposed, employing glycine-LiOH as the electrolyte. The operating conditions were optimized to a solid-to-liquid ratio of 20 g/L, slurry electrolysis time of 8 h, current density of 50 mA/cm2, reaction temperature of 80 °C, and glycine concentration of 1.0 mol/L. Li2CO3 was directly synthesized in the anode region, with a purity of up to 99.52 %. Additionally, LiCoO2 was partially remediated in the cathode, increasing Li-Co molar ratio from 0.659 to 0.93. The obtained Li2CO3 and the electrolysis residue LiCoO2 then underwent additional calcination, yielding a layered LiCoO2. At a Li-Co molar ratio of 1.1, the initial specific capacity of the calcined LiCoO2 material was 129.9 mAh/g, exhibiting a capacity retention rate of 50.48 % over 100 cycles. Therefore, a novel, cost-effective, and energy-saving strategy for recycling S-LIBs is proposed.

Fabrication of High-performance LiCoO2 Cathode Materials by Regulated Resource Regeneration from Spent Lithium-Ion Batteries

Fabrication of High-performance LiCoO2 Cathode Materials by Regulated Resource Regeneration from Spent Lithium-Ion Batteries

Flotation separation of lithium–ion battery electrodes predicted by a long short-term memory network using data from physicochemical kinetic simulations and experiments

Anode and cathode active materials from spent lithium–ion batteries may be recovered and potentially used in new batteries to promote recycling and resource circulation. Froth flotation was applied to pristine active materials and the black mass obtained from pretreated spent batteries. Flotation kinetics was simulated with the use of computational fluid dynamics and surface chemistry. Bubble surface coverage and entrainment in the flotation kinetics model were selected and optimized by systematic fitting to experimental data. Entrainment influences the recovery and grade of the active materials. The optimized flotation kinetics model was used for generating additional data that, along with the fitted data, were used to train a deep learning neural network. The trained network was validated using anode–cathode and black mass flotation experiments, and its predictions showed a maximum residual error of 0.18 ± 0.11 recovery. The simulation framework was developed into a desktop application that predicts the flotation behavior of active materials. It provides information for estimating results following operational and physicochemical changes and for optimizing flotation processes. Finally, recovered anode active materials from black mass were selected for coin cell tests. The coulombic efficiency of these coin cells was initially lower (86.8 %) than that of cells made with pristine graphite particles (98.4 %).

A Combined Physical-Mechanical and Hydrometallurgical Approach for Recovering Valuable Metals from Spent Lithium-ion Batteries

In this work, the chemical composition of electrode materials from two samples of lithium-ion batteries (LiB) is comprehensively investigated. The material balance of the physical and mechanical processing of the LiBs mixture is determined. The developed dry process scheme made it possible to extract the following components (wt.%): 15.6 plastic (ABS), 1.89 electronic materials (PP), 59.1 black mass (three types), 6.43 plastic (PVC), 2.97 Al, 6.31 Cu and 7.1 magnetic fraction (Fe). The thermodynamics of reductive leaching of LiCoO<sub>2</sub> in the H<sub>2</sub>SO<sub>4</sub>-HCOOH system was studied. It was calculated that the Gibbs energy of the leaching reaction at 363 K is -327.4 kJ/mol, the equilibrium constant is 2.02×10<sup>44</sup>. All these factors showed the potential of using formic acid as a reducing agent instead of the commonly used hydrogen peroxide solution. It is known to be unstable, since when the solution is heated from 20 to 50<sup>0</sup> C, the decomposition of H<sub>2</sub>O<sub>2</sub> increases 20 times, and the presence of copper sulfate, which usually accompanies the decomposition of the black mass in a sulfuric acid medium, leads to the destruction of 76% of hydrogen peroxide. Therefore, from a practical point of view, it was of interest to study the kinetics of cobalt dissolution from the cathode material in the H<sub>2</sub>SO<sub>4</sub>-HCOOH system. It was shown that the Crank-Ginstling-Braunstein equation agrees satisfactorily with the experimental data, which indicates intra-diffusion limitation of dissolution. The activation energy was determined. The optimal composition and conditions of the leaching solution for dissolving cobalt, lithium and associated transition metals from the black mass were determined. The thermodynamics and kinetics of dissolution of Ag, Au and Pd from electrode materials in a bromide-bromine solution were also studied.

Separation of Co(II), Mn(II), and Ni(II) by solvent extraction with Cyanex 272 and D2EHPA from the sulfuric acid leaching solution of spent lithium-ion batteries

Spent lithium-ion batteries contain valuable metals such as cobalt, lithium, manganese and nickel. Smelting reduction of spent LIBs at high temperature results in metallic alloys. Therefore, it is necessary to recover the valuable metal ions present in the sulfuric acid leaching solutions of the metallic alloys. In this work, solvent extraction experiments were performed to separate the three metal ions, Co(II), Mn(II) and Ni(II) present in the leaching solutions of the metallic alloys. Synthetic sulfate solutions were prepared and commercial organophosphorous extractants were employed. First, both Co(II) and Mn(II) were completely extracted in one stage by using 40% saponified 0.3 M Cyanex 272, leaving Ni(II) in the raffinate. The small amount of Ni(II) co-extracted into Cyanex 272 was removed by two stages of cross-current scrubbing using pure CoSO4 solution. The effect of pH and CoSO4 concentration of the scrubbing solution on the scrubbing of Ni(II) was investigated. The Co(II) and Mn(II) present in the scrubbed Cyanex 272 were completely stripped by 0.05 M H2SO4 solution. Batch simulation experiments for the three stage of counter-current extraction with 1 M D2EHPA verified that Mn(II) and Co(II) were completely separated by selective extraction of Mn(II) into D2EHPA, leaving Co(II) in the raffinate. By consecutive extraction with Cyanex 272 and D2EHPA, pure solutions of Co(II), Mn(II) and Ni(II) with purity higher than 99.9% can be recovered from the starting solutions. A process was proposed for the treatment of sulfuric acid leaching solutions of spent LIBs containing Co(II), Mn(II) and Ni(II) by solvent extraction.

Enhanced Recovery of Lithium and Cobalt from Spent Lithium-Ion Batteries Using Ultrasound-Assisted Deep Eutectic Solvent Leaching

This study investigates the ultrasound-assisted leaching of Li and Co from spent batteries using a deep eutectic solvent (DES) composed of polyethylene glycol and thiourea. The synergistic effect of ultrasound and DESs was explored to enhance the efficiency of Li and Co recovery. The experimental results demonstrated that ultrasound significantly accelerates the leaching process, achieving up to four times higher recovery rates compared to traditional methods. Optimal leaching conditions were identified at a solid-to-liquid ratio of 0.02 g/g, a temperature of 160 °C, and periodic ultrasound exposure. Under these conditions, the leaching efficiency reached 74% for Li and 71% for Co within 24 h. A kinetic analysis revealed that the ultrasound application shifts the rate-limiting step from a mixed control of mass transfer and chemical reactions to predominantly chemical reaction control, reducing the activation energy by approximately 27%.

Selective recovery of lithium from used lithium-ion batteries spent via grain boundary reconstruction reaction

The demand for lithium resources on the market has increased significantly as a result of the emergence and advancement of the new energy industry. However, improper handling leads to the generation of large amounts of hazardous waste, including spent lithium batteries. The recovery of lithium from these batteries has dual importance in protecting the environment and effectively recycling secondary resources. Herein, a green process for selective extraction of lithium from discarded lithium batteries was proposed. Sodium thiosulfate mixed with waste lithium battery powder was calcined at 600 °C for 90 min, when the molar ratio of sodium thiosulfate to lithium in the raw material was 0.5, and over 99 % lithium can be selectively preferentially extracted. During the roasting process, lithium in the raw materials was converted into water-soluble LiNaSO4, and transition metal oxides after calcination existed as water-insoluble oxides or sulfides, and the goal of preferential lithium extraction can be achieved by simple immersion in water. Lithium-containing leachate was purified by cerium carbonate and NaOH. After removing a small amount of Ni, Co, Mn, Al, Ca, and F impurities, the prepared lithium carbonate had a purity greater than 99.50 %, which met the standard of battery-grade lithium carbonate. This study introduces an approach to the selective extraction of lithium from lithium-containing solid waste, which effectively simplifies the recycling separation procedure and provides support for resource utilization of lithium-containing solid waste.

Selective Recycling of Spent Lithium‐Ion Batteries Enables Toward Aqueous Zn‐Ion Batteries Cathode

AbstractEffective selective recycling of spent lithium‐ion batteries (S‐LIBs) and giving recycled products a “second life” are crucial for advancing energy supply circularity, environmental and economic sustainability development. However, separating metal compounds with similar charge differences requires substantial energy, water, and chemical inputs. Herein, an innovative strategy is present for selective recycling S‐LIBs by photoexcitation inspired by the Hard Soft Acid Base (HSAB) principle. Theoretical calculations and experimental results show that photoexcitation drives charge transfer and modulates subtle charge density differences among metal components, thereby enhancing their solubility disparity and facilitating metal separation. Remarkably, the photoexcitation‐induced metal separation factor reaches 46900 and the metal recovery efficiency approaches 100%, representing a significant improvement over non‐photoexcitation separation with a separation factor of non‐photoexcitation of merely 2.7. Through techno‐economic analysis, the viability of photoexcitation selective recycling technology has been confirmed as an eco‐friendly and economical approach for battery recycling. Furthermore, high‐value reuse of recovered Mn components is implemented. The Recycled Mn components are treated by calcination to obtain porous, defect‐rich Mn2O3, which showed a specific capacity of 613 mAh g−1 at 0.1 A g−1) in aqueous Zn‐ion batteries (AZIBs). This work provides fresh insight into recycling S‐LIBs and moving toward more sustainable storage technologies.

Selective extraction of Li and Mn from spent lithium-ion battery smelting slag: Insights from isomorphous replacement in minerals

Recycling the high content of valuable metal elements contained in spent lithium-ion batteries (SLIBs) has attracted significant interest. By leveraging the concept of substitution of isomorphous replacement in earth minerals, this study proposes a novel approach for the selective extraction of Li and Mn from the artificial spodumene-type lithium-rich slag comprising LiAlSi2O6 and Mn2SiO4 through two-step selective roasting process with Na2SO4 and CaCl2, respectively. The thermodynamic calculations confirmed the feasibility of selective Li extraction by Na2SO4 roasting, with the experimental results showing that over 99 % Li was preferentially extracted as LiNaSO4. In the subsequent CaCl2 roasting step for Mn recovery, the Mn2SiO4 was effectively transformed into soluble Na2MnCl4, achieving a maximum Mn extraction efficiency of 86.5 %. The leaching kinetics of the Na2SO4 roasting products were investigated, revealing that the leaching of Li was governed by diffusion and chemical reactions in line with the shrinking core model. Characterization methods such as XRD, SEM, XPS, and TG-DSC were employed to reveal the phase transformation mechanisms of Li and Mn during Na2SO4 and CaCl2 roasting, respectively. The proposed process introduces a novel paradigm for its remarkable selective recovery of Li and Mn from SLIBs smelting slag.

High-Performance Pomegranate-Like CuF2 Cathode Derived from Spent Lithium-Ion Batteries.

With the large-scale application of lithium-ion batteries (LIBs), a huge amount of spent LIBs will be generated each year and how to realize their recycling and reuse in a clean and effective way poses a challenge to the society. In this work, using the electrolyte of spent LIBs as solvent, we in situ fluorinate the conductive three-dimensional porous copper foam by a facile solvent-thermal method and then coating it with a cross-linked sodium alginate (SA) layer. Benefiting from the solid-electrolyte interphase (SEI) that accommodating the volume change of internal CuF2 core and SA layer that inhibiting the dissolution of CuF2, the synthesized CuF2@void@SEI@SA cathode with a pomegranate-like structure (yolk-shell) exhibits a large reversible capacity of ~535 mAh g-1 at 0.05 A g-1 and superb cycling stability. This work conforms to the development concept of green environmental protection and comprehensively realizes the unity of environmental, social and economic benefits.

A low-cost salt-tolerant solar evaporator prepared from graphite in spent LIBs for high efficiency seawater desalination

Interfacial photothermal evaporation technology has been greatly promoted due to the increasing demand for sustainable energy around the world. but the development of low cost and durable efficient evaporators remained challenging. In this paper, a polyurethane sponge-loaded chitosan/reconstructed graphite-based evaporator (PCRE) was successfully designed by freeze-drying technique using recycled graphite from spent lithium batteries. The PCRE demonstrated strong hydrophilic properties and exhibited a light absorption rate of 96.06 %. Under the irradiation of 1 light intensity, the photothermal conversion efficiency of PCRE can reach 91.9 %, and the evaporation rate reaches 3.85 kg m-2h−1. Thanks to the large number of hydrophilic groups in PCRE and its excellent pore structure, the enthalpy of evaporation of water inside PCRE (1.2970 kJ g−1) is much lower than that of pure water (2.4417 kJ g−1). Moreover, PCRE can effectively avoid the problem of salt deposition, and its evaporation rate can still be maintained at 3.0 kg m-2h−1 in the treatment of high-concentration brine (25 wt.%), and in long-term evaporation experiments, PCRE has demonstrated highly efficient and stable desalination performance and removal capability for real seawater and organic wastewater. Based on the excellent evaporation performance, simple preparation and low cost of this evaporator, this study provides a new idea for waste recycling in the application of interfacial photothermal evaporation.

Recycling and Reuse of Mn-Based Spinel Electrode from Spent Lithium-Ion Batteries

In this paper, we introduce an environmentally friendly approach to recycle used batteries and recover highly valuable manganese-based cathode materials. This study demonstrates the feasibility of fast plasma pyrolysis to recover LiMn2O4 electrode materials (e.g., lithium manganese oxide, LMO) and demonstrate their reuse in newly assembled Li-ion cells. The electrochemical performance of as-recycled cathodes shows an initial discharge capacity of 72 mAh/g and is stable for 100 cycles at 0.1 C. After adding 20 mole % of excess LiOH, the recycled LMO after relithiation at 660 °C can deliver an initial discharge capacity of 96 mAh/g and retain a decent discharge capacity of 88 mAh/g after 50 cycles at a 0.2 C rate. Without relithiation, the as-recycled LMO cathode after heating at 1000 °C delivers the best electrochemical cycling performance, including an initial discharge capacity of 94 mAh/g and 50th cycle capacity of 91 mAh/g at a 0.2 C rate. This study highlights a feasible approach for recycling electrode materials in spent LIBs. Recycling of lithium-ion batteries and especially electrode materials is crucial for the sustained growth of the lithium-ion battery industry and reduced environmental issues.

Repair and Reuse of Spent Lithium Battery Electrode Materials

With the popularity of new energy vehicles and various electronic devices, the use of lithium-ion batteries (LIBs) has shown explosive growth, which has resulted in a large number of spent LIBs. Spent LIBs contain a large amount of metal resources, and improper disposal will not only cause waste of resources, but also have potential environmental risks. The existing commercial recycling methods are mainly pyrometallurgy and hydrometallurgy recycling methods, both of which require re-extraction from the electrode material after destroying them to the atomic level for the preparation of new electrode materials, which is a long process with high cost, and involves the application of extreme conditions such as high temperature and strong acid, with inferior economic and environmental benefits. It is a major challenge in the field of battery recycling to develop innovative and clean recycling methods, to simplify the recycling process and to develop ways to reuse the recovered products. In view of the challenge of existing recycling methods, the reporters proposed the idea of direct recycling of electrode materials at the molecular scale, and designed innovative recycling methods such as direct repair of degraded lithium cobalt oxides with deep eutectic solvent (DES), repair of Ni-Mn-Co ternary (NCM) cathode with high failure degree by low temperature molten salt, and thermal regeneration of degraded lithium iron phosphate (LFP) with multifunctional solvent; and closed-loop design of the direct recycling process. In addition, we propose a high-value utilization path for the conversion of degraded electrode materials to high-performance electrode materials and nano-catalysts. It greatly simplifies the recycling process, avoids the use of extreme conditions, and provides a new technical system and theoretical guidance for battery recycling research and industry.

Efficient Regeneration of Graphite from Spent Lithium-Ion Batteries through Combination of Thermal and Wet Metallurgical Approaches.

With the large-scale application of lithium-ion batteries (LIBs) in various fields, spent LIBs are considered one of the most important secondary resources. Few studies have focused on recycling anode materials despite their high value. Herein, a new efficient recycling and regeneration method of spent anode materials through the combination of thermal and wet metallurgical approaches and restored graphite performance is presented. Using this method, the lithium recycling ratio from spent anode materials reaches 87%, with no metal impurities detected in the leaching solution. The initial Coulombic efficiency of the recycled graphite (RG) materials is 90.5%, with a reversible capacity of 350.2 mAh/g. Moreover, RG shows better rate performance than commercial graphite. The proposed method is simple and efficient and does not involve toxic substances. Thus, it has high economic value and application potential in graphite recycling from spent LIBs.

Humic acid-mediated mechanism for efficient biodissolution of used lithium batteries

Resource recovery of valuable metals from spent lithium batteries is an inevitable trend for sustainable development. In this study, external regulation was used to enhance the tolerance and stability of strains in the leaching of spent lithium batteries to radically improve the bioleaching efficiency. The leaching of Li, Ni, Co and Mn increased to 100 %, 85.06 %, 74.25 % and 69.44 % respectively after targeted cultivation with HA as compared to the undomesticated strain. In the process of microbial leaching of spent lithium batteries, the metabolites in the Ⅰ, Ⅳ, and Ⅴ regions of the metabolism of the undomesticated bacterial colony had a positive correlation to the dissolution of spent lithium batteries. The metabolites of Ⅰ, Ⅱ, and Ⅴ regions were directly affected by the HA domesticated flora on the dissolution of spent lithium batteries. The excess metabolism of protein substances can significantly promote the reduction of Ni, Co, Mn leaching, and at the same time in the role of a large number of humic substances complexed the toxic metal ions in the system, to ensure the activity of the bacterial colony. It can be seen that the bacteria were domesticated by humic acid, which promoted the bacteria's own metabolism, and the super-metabolised EPS promoted the solubilisation of spent lithium batteries.

Direct recovery of high-purity lithium via nanofiltration membranes from leaching solution of spent lithium batteries

The recycling of spent ternary lithium batteries (T-LIBs) promises scarce strategic resource recovery, however, efficient and selective recovery of Li+ from T-LIBs leaching solution with complex components is still a considerable challenge. Herein, we present a polyamide nanofiltration membrane based on the positively charged nanoscale dispersion interlayer for the first application in recycling lithium from the leaching solution of spent T-LIBs. The electronegativity is weakened by positive charge within the interlayer, which enhance the effect of Donnan exclusion. The pos-TFNi membrane can effectively permeate Li+ while the interfering divalent ions are almost completely separated, achieving the high purity (separation factor ≥ 93.5) and high recovery rate (79.2%) of Li+ from leaching solution simultaneously, with a 6.2-fold improvement in the separation factor over the pristine TFC membrane, and outperformed the majority of the NF membranes. This work represents a reference for the recycling of the massive accumulation of spent T-LIBs worldwide.

Effective peroxymonosulfate activation by lithium cobaltite recovered from spent lithium-ion batteries for enhanced carbamazepine degradation in a wide pH range.

Considering the high cost and complicated recycling process of spent lithium-ion batteries (SLIBs), transforming SLIBs into environment functional materials may be a wise approach. Herein, lithium cobaltite (LCO) cathode powders recovered from SLIBs were used to activate peroxymonosulfate (PMS) for removing carbamazepine (CBZ). The recovered LCO enables a 98.2% removal efficiency of CBZ (2.5mg/L) within 10min, which was effective at a broader pH range (pH = 5.0-11.0). The influence of key factors (initial pH, PMS, and catalyst dosage) and coexisting substances (SO42-, H2PO4-, NO3-, Cl-, HCO3-, and HA) on CBZ degradation were examined in detail. The primary radical species during the degradation of CBZ were proved to be 1O2, SO4-, and.OH that generated from PMS activation initiated by the valence change of Co in recovered LCO. The recovered LCO displayed excellent reusability with about 80.0% removal of CBZ after six cycles. Homogeneous activation of PMS mainly contributed to CBZ degradation in the first run, but the recovered LCO catalyst dominated the heterogeneous activation of PMS for the degradation of CBZ in the second to sixth run. Finally, the CBZ degradation pathways were presented based on the identified intermediates. This research has offered a new strategy of "treating wastes with wastes" to maximize the recycling of electronic wastes to remove emerging pollutants.

Recent and Novel Leaching Processes for Recovery of Metals from Spent Lithium-ion Batteries: A Review

Recent and Novel Leaching Processes for Recovery of Metals from Spent Lithium-ion Batteries: A Review

Pre-separation combined with reduction roasting for high-quality recovery of graphite and lithium from spent lithium ion batteries

The recycling of spent lithium ion batteries is of great significance because it contains large amounts of valuable metals. But current recovery methods exhibit limited efficiency in selectively extracting lithium from spent electrode materials and spent graphite becomes metallurgical residues. In this study, we propose a novel recycling flowchart that combines flotation with multi-stage water-leaching to enhance the recovery of graphite and lithium from black mass derived from spent lithium ion batteries. Removal of organics can be conducted by pyrolysis, at the same time, the spent ternary cathode material was decomposed into CoO, NiO, and MnO at a temperature of 600 °C for 60 min using pyrolysis product-derived reductant. The sub-microlevel migration behavior of lithium ions in electrode materials was also examined. The electrode material aggregates were broken up by water crushing, and 38.67 % lithium dissolves into water for recycling. Bubble flotation was used to recycle the excess graphite from the black mass while the residual graphite was used as reductant for the carbothermal reduction. Using the developed scheme, we were able to recover 95.51 % of lithium after carbothermal reduction with 12.31 % carbon residue. Based on basic research, a novel recycling flowchart of spent lithium-ion batteries has been proposed.