Spent Lithium Ion Batteries Research Articles

Catalytic pyrolysis of rape straw to produce light aromatic hydrocarbons over HZSM-5 loaded by metal ions from spent lithium batteries extracted with citric acid

In this study, metal-loaded HZSM-5 was prepared with metal ion extracted from the cathode materials of spent lithium batteries (lithium iron phosphate, LFP; lithium nickel-cobalt manganate, NCM) with citric acid for the improved production of light aromatic hydrocarbons by catalytic pyrolysis of rape straw. Because of the dealuminization effect of citric acid on HZSM-5, mesopores were introduced, and the diffusion and conversion of pyrolysis gas over acid sites were improved. After metal loading with acid-leaching solution, the amount of weak and total acids in metal-loaded HZSM-5 increased a lot, which was conducive to the dehydration, deoxygenation, decarbonylation and aromatization of pyrolysis, and the production of monocyclic aromatic hydrocarbons (MAHs). With 0.1 mol/L citric acid for LFP and NCM treatment, the metal-loaded catalyst showed a higher yield of benzene, toluene and xylene (BTX) of 11.10 wt% during catalytic pyrolysis of rape straw. Compared with 0.1-NCM-H5, a higher yield of MAHs was obtained over 0.1-LFP-H5 with a more favorable pore structure and higher amounts of weak and total acid sites. In general, the high-valued utilization of agricultural wastes and spent lithium batteries was realized in this study to produce clean energy.

Valorization of waste graphite in spent lithium-ion batteries to graphene via modified mechanical exfoliation and the mechanism exploration

In the electrodes of spent lithium-ion batteries, graphite, due to its layered structure and crystalline composition, presents significant recyclable value, yet it has not been fully utilized. This study proposes a modified mechanical exfoliation method (MEM), which employs leaching-drying pretreatment to transform waste graphite into two-dimensional graphene. Three drying methods were evaluated, among which freeze drying was found to be the most conducive for exfoliation. Pneumatic drying, being basic and simple, did not exhibit any special effects that benefit exfoliation. XRD results showed that leaching restores the lamellar structure of graphite, with peak intensity ( × 105) increasing from 6.5 to 8.9–10.1. XPS analysis revealed that vacuum roasting drying leads to dehydration condensation of hydroxyl groups between layers, resulting in the obtained graphite having the best dehydration effect and the lowest oxygen content, at only 1.89%, but this enhances interlayer forces, which is counterproductive for exfoliation. In contrast, freeze drying, through the volumetric expansion caused by the freezing of water, disrupts the interlayer forces, achieving an interlayer spacing of 337.5 nm, which facilitates the exfoliation of graphene. This was confirmed by TEM results. This method effectively overcomes the problem of impurity contamination in waste graphite, providing a new approach for the high-value utilization and green recycling of graphite in spent lithium batteries.

Influencing factor analysis and enterprise evaluation of lithium-ion battery recycling based on improved DEMATEL method

Spent lithium-ion battery (LIB) recycling can create great pollution to the environment. Understanding the safety, environment, technique, and regulation factors’ impact on the recycling process is crucial. Due to the complexity of the relevant factors, and there is a certain degree of correlation and dependence between the factors, the Decision Making Trial and Evaluation Laboratory (DEMATEL) method is used to analyze the factors’ degree of impact in this study. As the experts are ambiguous about some relations between the factors, it is impossible to conduct integrated evaluation. The improved DEMATEL method is proposed in this study to make up the missing relations. Further, the weights of the factors will be calculated. In the improved DEMATEL method, the numerical scale of a linguistic term set is introduced. Therefore, the numerical scale used by experts can not only be uniform and symmetrical, but can also be non-uniform symmetric, non-uniform asymmetric, etc. Finally, both reusing and recycling companies are included in this study and their factors’ importance weights were analyzed with the fuzzy comprehensive evaluation method.

Synergistic Approach for Selective Leaching and Separation of Strategic Metals from Spent Lithium-Ion Batteries.

Recycling spent Li-ion batteries (LIBs) is paramount to pursuing resource efficiency and environmental sustainability. This study introduces a synergistic approach for selectively leaching and separating strategic metals from waste LIBs, representing a more efficient alternative to traditional single-acid-based leaching methods. The research also thoroughly analyzes diverse extraction parameters, aiming to achieve clean metal separation through synergistic concepts rather than single-phase extraction. The outcome of this study is developing a comprehensive downstream process, advancing the cause of sustainable waste management in the LIB industry. Under specific conditions with 0.6 mol/L total acid content (0.5 mol/L tartaric acid + 0.1 mol/L ascorbic acid), 99.9% cobalt and 100% lithium were effectively leached. The subsequent extraction process achieved a clean separation, with 48.3% of cobalt extracted using a mixture of 0.1 mol/L Alamine-336-Cyanex-272 (A-336-Cy-272) from the leach liquor with no coextraction of lithium, and this efficiency was improved to 67.3% by adjusting the pH from 2.44 to 7.5. However, it is worth noting that increasing the extractant concentration led to an antagonistic effect. To further enhance cobalt enrichment in the organic phase, the McCabe-Thiele plot method was recommended, employing saponified Cy-272. Moreover, the regeneration of saponified Cy-272 was investigated, and the stripped solution was processed with NaOH to form Co(OH)2, subsequently converting it into cobalt oxide (Co3O4) through calcination.

Water as a Sustainable Leaching Agent for the Selective Leaching of Lithium from Spent Lithium-Ion Batteries.

The development of a sustainable recycling process for lithium from spent lithium-ion batteries is an essential step to reduce the environmental impact of batteries. So far, the industrial implementation of a recycling process for lithium has been hindered by low recycling efficiencies and impurities in the recycled material. The aim of this study is thus to develop an easy-to-implement recycling concept for the selective leaching of lithium from spent lithium-ion batteries with water as a sustainable leaching reagent. With this highly selective process, the quantity of chemicals used can be substantially decreased. The influence of the leaching temperature, the solid/liquid-ratio, the mixing rate, and the number of stages in multistage operation were investigated utilizing NCM-material. High leaching efficiencies and a high selectivity were achieved at moderate temperatures of 40 °C and a solid/liquid-ratio of 100 g L-1. In multistage operation, a selectivity for lithium higher than 98% was achieved with 57% leaching performance of lithium. XRD-measurements showed that lithium carbonate was quantitatively leached, while lithium metal oxides remained in the black mass. Finally, the leaching kinetics were determined, proving that the first leaching period is diffusion controlled and, in the second period, the leaching rate is rate controlling. This work confirms the concept of a green leaching process by which lithium can be recycled with a high degree of purity.

From spent lithium ion battery to supercapacitors: a green and facile approach for recovering carbon-based anode materials

With the rapid development of electric vehicles and boosting lithium-ion battery production, recycling waste lithium-ion batteries has been the focus for researchers all over the world. In this study, carbon material was recovered via forming lithium graphite intercalated compound through charging and followed by high energy ball milling. The recovered carbon sample was then prepared as electrodes for symmetric supercapacitors. Electrochemical tests and material characterizations showed that the recovered carbon has a porous graphene-like sheet structure, and the specific surface area and specific capacitance can be effectively increased to 155 m²/g, which is over 10 times higher than that of the untreated carbon. The maximum specific capacitance of recovered carbon material was 41.66 F/g at a scan rate of 100 mV/s with a voltage range of 0-2V, which is 10 times higher than that of untreated carbon. The green and facile recovery method of batteries proposed in this paper provides a new idea and method for the recycling and utilization of waste lithium-ion battery anode materials.

High-Selectivity Recycling of Valuable Metals from Spent Lithium-Ion Batteries Using Recyclable Deep Eutectic Solvents.

The recovery of valuable metals from spent lithium-ion batteries using deep eutectic solvents (DESs) is an environmentally and economically beneficial process. In this study, a method has been developed for recovering LiNi0.33Co0.33Mn0.33O2. Our process operates under mild conditions and with a little oxalic acid as a reducing agent, dissolving lithium, cobalt, manganese, and nickel completely utilizing a DES that is composed of tetrabutylammonium chloride and of monochloroacetic acid. Lithium and nickel were selectively precipitated using oxalic acid. Cobalt and manganese were precipitated as oxalates by adding an oxalic acid aqueous solution. Finally, the DES can be regenerated by evaporating the water. Importantly, valuable metals can be recovered with a 100 % yield through the process of DES recycling. This environmentally friendly and recyclable process is suitable for the recycling of spent lithium-ion batteries industry.

Short-Process Regeneration of Highly Stable Spherical LiCoO2 Cathode Materials from Spent Lithium-Ion Batteries through Carbonate Precipitation.

High-efficacy recycling of spent lithium cobalt oxide (LiCoO2 ) batteries is one of the key tasks in realizing a global resource security strategy due to the rareness of lithium (Li) and cobalt (Co) resources. However, it is of great significance to develop the innovative recycle methods for spent LiCoO2 , simultaneously realizing the efficient recovery of valuable elements and the regeneration of high-performance LiCoO2 . Herein, a novel strategy of regenerating LiCoO2 cathode is proposed, which involves the preparation of micro-spherical aluminum (Al)-doped lithium-lacked precursor (Li2x Co1-x-y Al2/3y CO3, remarked as "PLCAC") via ammonium bicarbonate coprecipitation. The comprehensive conditions affecting particle growth kinetics, morphology and particle size the has been investigated in detail by physical characterizations and electrochemical measurements. And the optimized Al-doped LiCoO2 materials with high-density sphericity (LiCo1-z Alz O2 , remarked as "LCAO") shows a high initial specific capacity of 161 mAh g-1 at 0.1 C and excellent capacity retention of 99.5 % within 100 cycles at 1 C in the voltage range of 2.8 to 4.3 V. Our work provides valuable insights into the featured design of LiCoO2 precursors and cathode materials from spent LiCoO2 batteries, potentially guaranteeing the high-efficacy recycling and utilization of strategic resources.

Rapid Degrading Carbamazepine in a Novel Advanced Oxidation Process of Bisulfite Activated by Lithium Cobaltate Recovered from Spent Lithium-ion Battery

Rapid Degrading Carbamazepine in a Novel Advanced Oxidation Process of Bisulfite Activated by Lithium Cobaltate Recovered from Spent Lithium-ion Battery

Co-Precipitation of Metal Oxalates from Organic Leach Solution Derived from Spent Lithium-Ion Batteries (LIBs)

Recent studies in hydrometallurgy are focused on developing eco-friendly and selective leach agents such as organic acids. These agents can extract metal ions, which are usually separated through precipitation methods. When traditional methods are used, the separation is complex and time-consuming, and each metal cation is required to be isolated separately. Moreover, extracted metal salts are subsequently recombined in the regeneration of cathode materials. To simplify this, a novel simultaneous precipitation approach has been developed, allowing the separation of metal salts that can directly contribute to regenerating novel cathode materials, bypassing the need for separate isolation. This study aimed to recover cobalt, nickel, and manganese from the organic leach solution of spent lithium-ion batteries (LIBs) through co-precipitation of metal oxalates. The investigation includes the selection of organic acids and the best parameters for the leaching process, as well as testing different molar ratios of the metals M2+ (M = Co, Ni, Mn) to oxalic acid (1:3, 1:4.5, 1:6, and 1:7.5) to examine the effects of the precipitating agent on the recovery percentages of the metals. The findings indicate that 2 M citric acid and 4 vol% H2O2 is the optimal parameter in the leaching process. Meanwhile, in the co-precipitation process, an increase in the molar ratio leads to a corresponding rise in the resulting metal recoveries. At the ratio of 1:7.5, cobalt, nickel, and manganese were recovered to the extent of 99.26%, 98.93%, and 94.01%, respectively. Nevertheless, at the increased molar ratio, the co-extraction of lithium and aluminum was observed, resulting in reduced selectivity and decreased precipitate purity.

Recovery of Electrode Materials from a Spent Lithium-Ion Battery through a Pyrolysis-Coupled Mechanical Milling Method

Recovery of Electrode Materials from a Spent Lithium-Ion Battery through a Pyrolysis-Coupled Mechanical Milling Method

Leaching Li from mixed cathode materials of spent lithium-ion batteries via carbon thermal reduction.

The use of a carbon thermal reduction roasting method to recover lithium resources from spent lithium-ion batteries (S-LIBs) provides an important opportunity for recycling S-LIBs. The preferential extraction of Li via reduction roasting has been widely studied; however, the extraction of Li from mixed cathode materials has been rarely reported. Herein, we propose a method based on carbon thermal reduction to preferentially extract Li from mixed cathode materials. It was confirmed that there are differences in carbon thermal reduction products at 700 °C-850 °C by the thermodynamic analysis of the carbon thermal reduction process. At the same time, the effects of factors such as roasting temperature, roasting time, and material ratio on Li leaching efficiency were investigated. The Li recovery rate reached 98.86% under the optimal conditions of holding at 750 °C for 4 h with a molar ratio of mixed cathode materials to graphite of 1 : 0.25. Recovered Li2CO3 can be directly used as a lithium source for the regeneration of cathode materials. This study will provide new opportunities for the efficient recycling of spent lithium-ion batteries (S-LIB) mixtures.

Addressing preliminary challenges in upscaling the recovery of lithium from spent lithium ion batteries by the electrochemical method: a review.

The paramount importance of lithium (Li) nowadays and the mounting volume of untreated spent LIB have imposed pressure on innovators to tackle the near-term issue of Li resource depletion through recycling. The trajectory of research dedicated to recycling has skyrocketed in this decade, reflecting the global commitment to addressing the issues surrounding Li resources. Although metallurgical methods, such as pyro- and hydrometallurgy, are presently prevalent in Li recycling, they exhibit unsustainable operational characteristics including elevated temperatures, the utilization of substantial quantities of expensive chemicals, and the generation of emissions containing toxic gases such as Cl2, SO2, and NOx. Therefore, the alternative electrochemical method has gained growing attention, as it involves a more straightforward operation leveraging ion-selective features and employing water as the main reagent, which is seen as more environmentally benign. Despite this, intensive efforts are still required to advance the electrochemical method toward commercialisation. This review highlights the key points in the electrochemical method that demand attention, including the feasibility of a large-scale setup, consideration of the substantial volume of electrolyte consumption, the design of membranes with the desired features, a suitable layout of the membrane, and the absence of techno-economic assessments for the electrochemical method. The perspectives presented herein provide a crucial understanding of the challenges of advancing the technological readiness level of the electrochemical method.

Extraction of Lithium from Spent Lithium-ion Batteries (LIBs) using Cation Exchange Resin

Considering the lithium (Li) supply crisis and the regulations around recycling, sustainable extraction of Li from spent lithium-ion batteries (LiBs) is critical. Recently, recovery of Li from spent LiBs by water leaching has been investigated, and a high leaching selectivity towards Li is reported by fine-tuning the pH among other factors leading to the introduction of Na+ ions, which complicates selective Li recovery. Further, the low Li concentration makes the downstream precipitation challenging without an intermediate energy-intensive evaporative step. Herein, we employ Amberlite-H+, a commercially available cation exchange resin to investigate its suitability in the extraction of Li from water leachates of black mass. The water leachate containing 135 mg/L Li was prepared at optimized conditions of 25 °C, S/L (black mass/water) of 20 g/L, and a pH of 10. The extraction of Li from this water leachate by Amberlite-H+ was studied to optimize the reaction time, and various S/L ratios of Amberlite-H+ to leachate were investigated. The kinetic experiments showed that the extraction of Li from the water leachate reaches equilibrium before 30 minutes. The effect of S/L ratios was investigated at the optimized reaction time and the results showed that at S/L (g/L) of 20, 40, and 60, the uptake capacity of Li (mgLi+/gresin) is 5.34, 3.06, and 2.15, respectively. The Li-loaded resins were washed with 100 mL of 1 M HCl to desorb Li, achieving 97 – 99 % desorption yield.

Sustainable Lithium and Cobalt Recovery from Spent Lithium-ion Batteries: Best Practices for the Future. A review

Sustainable Lithium and Cobalt Recovery from Spent Lithium-ion Batteries: Best Practices for the Future. A review

Resilience in waste management: A socioeconomic context for managing spent lithium batteries in Southeastern Nigeria

The global value chain (GVC) recognizes post production processes that involve socio economic engagements of stakeholders with electrical and electronic equipment (EEE or e-products) at their near or end of life. This paper attempts to measure some of the key social, economic, environmental, and sustainability indicators in line with GVC for lithium-ion batteries from e-products at their near or end of life. The assessment was based on the socioeconomic impacts on the battery sector for managing spent lithium-ion (Li-ion) batteries in Southeastern Nigeria. The study methodology highlighted strategic features in line with socioeconomic assessment by deploying questionnaire administration. Ten (10) local government areas (LGAs) were purposely selected from five mutually exclusive States, with 100 stakeholders investigated. Descriptive statistics were used to analyze data for innovation potentials for the battery recycling/refurbishing sector, and discussed accordingly under sustainability, social, economic and environmental impacts. The socioeconomic drivers (or outcomes) for the recycling and refurbishing of lithium ion batteries touched on self-sustainability, institutionalization, service demand, service utilization and prevalence.

Short-term and High-performance Recycling of Cathode Material from Spent Lithium Ion Batteries

In the industrial practice of spent lithium-ion battery recycling, mechanical separation, pyrometallurgy and chemical dissolution technologies are often used to achieve the separation and recovery of cathode materials, but there are problems such as low material dissociation rate, low recovery rate, high energy consumption, serious lithium loss, and impurity ion embedding. In this paper, supercritical CO2 fluid was used to strengthen the separation of the cathode active material from the aluminum foil in the spent lithium-ion battery to achieve direct and efficient recovery of the active substance. The analysis of charge and discharge, AC impedance and differential capacitance curves show that the electrode of supercritical recovered material has higher ion diffusion coefficient and better redox reversibility, so it has higher charge and discharge capacity and better cycle stability than the traditional high-temperature calcined recovered material.

Sustainable Recovery, Surface Chemical Engineering, and Upcycling of Spent Graphite into Dual-Ion Battery

Recycling has become an absolute necessity. Spent Lithium-ion batteries (LIBs) are hazardous waste but a potential source of purified minerals. The industrial focus on LIB recycling is mostly centered on costly and scarce cathode materials recovery. Graphite is often overlooked as it fails to generate useful revenue. Herein, the waste LIBs are recycled following an all-components-recovery route that minimizes cross-contamination. However, the surface of the recovered graphite is covered with solid electrolyte interphase (SEI) formed during its first life application. Solvent wash followed by thermal treatment revives graphite for second-life applications. Three important things to consider here are the interaction of solvent media with the preformed SEI, the role of leftover SEI in forming the second-life SEI, and the effect of regenerated SEI on second-life electrochemistry. Therefore, the nature of the solvent plays a vital role in the overall process. Utilizing water is the go-to alternative but the obtained electrochemistry from water-washed graphite is below the mark. Organic solvent dimethyl carbonate (DMC) modifies the chemical composition of the interphase in such a way that it improves second-life electrochemistry. Strong inorganic acid HCl results in the highest carbon purity and makes recovered graphite suitable for non-electrochemical applications too. Electrochemically superior DMC-washed graphite is repurposed into a dual-ion full cell that delivers an average voltage of 4.5 V and an energy density of 110 Wh kg-1. Figure 1

Optimization of Synergistic Leaching of Valuable Metals from Spent Lithium-Ion Batteries by the Sulfuric Acid-Malonic Acid System Using Response Surface Methodology

A new environmentally friendly and economical recycling process for extracting metals from spent lithium-ion batteries (LIBs) using sulfuric acid and malonic acid as leaching agents is proposed. By applying Box-Behnken design (BBD) and response surface methodology (RSM) optimization techniques, the global optimal solution of the maximum leaching rate of metals in spent LIBs is realized. The results show that under the optimal conditions of 0.93 M H2SO4, 0.85 M malonic acid, liquid/solid ratio of 61 g·L–1, the temperature of 70 °C and 5 vol% of 30% H2O2, 99.79% Li, 99.46% Ni, 97.24% Co and 96.88% Mn are recovered within 81 min. The error between the theoretical value and the actual value of the metal leaching rate predicted by the regression model is less than 1.0%. Additionally, the study of leaching kinetics reveals that the leaching process of Li, Ni, Co, and Mn in spent cathode materials was affected by the synergistic effect of interfacial mass transfer and solid product layer diffusion. Economic analysis reveals that evaluation index should be fully considered when formulating recovery processes for different metals. This process can reduce the environmental risks of heavy metal disposal, and allow the reuse of metals recovered from spent LIBs.

Upcycling spent lithium battery cathodes into efficient PMS catalysts for organic contaminants degradation

The rapid accumulation of spent lithium-ion batteries (SLIBs) poses a global challenge in terms of their disposal and management. Considering the substantial quantity of transition metals contained in SLIBs, the preparation of derived catalysts for environmental remediation has emerged as a promising approach for the recycling of SLIBs. Herein, the citric acid-based sol-gel method was employed to synthesize the catalyst from SLIBs. The derived spent cathode material (LiNixCoyMn1−x-yO2, NCM) composites exhibit superior catalytic activity and display higher adaptability to the environment, effectively removing typical azo dye, methylene blue (MB), as well as various organic contaminants, sulfamethoxazole (SMX), levofloxacin (LVF) and rhodamine B (RhB) in 30 min. The Co2+ and Mn2+ ions in the catalyst play a crucial role in activating PMS to generate 1O2 and O2•−. The degradation of MB proceeds through several reaction pathways, including demethylation, oxidation, and ring-opening reactions, as confirmed by the Fukui function and UPLC-QTOF-MS analyses. The assessment of toxicity in the degradation products was conducted using T.E.S.T. and ECOSAR 2.0. This proposed method can be highly suggested as a promising strategy for the recycling and utilization of SLIBs, transforming them into efficient catalysts for PMS systems in environmental remediation.