• Clean Technology
• /
• v.29 no.2
• /
• pp.87-94
• /
• 2023

The recovery of valuable metals from waste lithium-based secondary batteries is very important in terms of efficiently utilizing earth's limited number of resources. Currently, the cathode material of a LiFePO₄ battery, a type of battery which is widely used in automobiles, contains approximately 5% lithium. After use, the lithium in these batteries can be used again as a raw material for new batteries through lithium recycling. In this study, low-concentration sulfuric acid, a commonly used type of inorganic acid, was used to selectively leach the lithium contained in a waste LiFePO₄ cathode material powder. In addition, in order to compare and analyze the leaching efficiency and separation efficiency of each component, the optimalleaching conditions were derived by applying a two-step leaching process with pulp density being used as a variable during leaching. When leaching with pulp density as a variable, it was confirmed that at a pulp density of 200 g/L, the separation efficiency was approximately 200 times higher than at other pulp densities because the iron and phosphorus components were hardly leached at this pulp density. Accordingly, the pulp density of 200 g/L was used tooptimize the leaching conditions for the selective leaching and recovery of lithium.

• Resources Recycling
• /
• v.31 no.4
• /
• pp.40-48
• /
• 2022

In waste lithium iron phosphate (LFP) batteries, the cathode material contains approximately 4% lithium. Recycling the constituent elements of batteries is important for resource circulation and for mitigating the environmental pollution. Li contained in the waste LFP cathode powder was selectively leached using persulfate-based oxidizing agents, such as sodium persulfate, potassium persulfate, and ammonium persulfate. Leaching efficiency and waste LFP powder properties were compared and analyzed. Pulp density was used as a variable during leaching, which was performed for 3 h under each condition. The leaching efficiency was calculated using the inductively coupled plasma (ICP) analysis of the leachate. All types of persulfate-based oxidizing agents used in this study showed a Li leaching efficiency over 92%. In particular, when leaching was performed using (NH₄)₂S₂O₈, the highest Li leaching percentage of 93.3% was observed, under the conditions of 50 g/L pulp density and an oxidizing agent concentration of 1.1 molar ratio.

• Resources Recycling
• /
• v.28 no.6
• /
• pp.79-86
• /
• 2019

Recently, the use of lithium ion battery(LIB) has increased. As a result, the price of lithium and the amount spent lithium on ion battery has increased. For this reason, research on recycling lithium in waste LIBs has been conducted1). In this study, the effect of roasting for the selective lithium leaching from the spent LIBs is studied. Chemical transformation is required for selective lithium leaching in NCM LiNi_xCo_yMn_zO₂) of the spent LIBs. The carbon in the waste EV cell powder reacts with the oxygen of the oxide at high temperature. After roasting at 550 ~ 850 ℃ in the Air/N₂ atmosphere, the chemical transformation is analysed by XRD. The heat treated powders are leached at a ratio of 1:10 in D.I water for ICP analysis. As a result of XRD analysis, Li₂CO₃ peak is observed at 700 ℃. After the heat treatment at 850 ℃, a peak of Li₂O was confirmed because Li₂CO₃ is decomposed into Li₂O and CO₂ over 723 ℃. The produced Li₂O reacted with Al at high temperature to form LiAlO₂, which does not leach in D.I water, leading to a decrease in lithium leaching ratio. As a result of lithium leaching in water after heat treatment, lithium leaching ratio was the highest after heat treatment at 700 ℃. After the solid-liquid separation, over 45 % of lithium leaching was confirmed by ICP analysis. After evaporation of the leached solution, peak of Li₂CO₃ was detected by XRD.

• Resources Recycling
• /
• v.30 no.6
• /
• pp.43-52
• /
• 2021

In this study, the optimal nitration process for selective lithium leaching from powder of a spent battery cell (LiNi_xCo_yMn_zO₂, LiCoO₂) was studied using Taguchi method. The nitration process is a method of selective lithium leaching that involves converting non-lithium nitric compounds into oxides via nitric acid leaching and roasting. The influence of pretreatment temperature, nitric acid concentration, amount of nitric acid, and roasting temperature were evaluated. The signal-to-noise ratio and analysis of variance of the results were determined using L₁₆(4⁴) orthogonal arrays. The findings indicated that the roasting temperature followed by the nitric acid concentration, pretreatment temperature, and amount of nitric acid used had the greatest impact on the lithium leaching ratio. Following detailed experiments, the optimal conditions were found to be 10 h of pretreatment at 700℃ with 2 ml/g of 10 M nitric acid leaching followed by 10 h of roasting at 275℃. Under these conditions, the overall recovery of lithium exceeded 80%. X-ray diffraction (XRD) analysis of the leaching residue in deionized water after roasting of lithium nitrate and other nitrate compounds was performed. This was done to determine the cause of rapid decrease in lithium leaching rate above a roasting temperature of 400℃. The results confirmed that lithium manganese oxide was formed from lithium nitrate and manganese nitrate at these temperatures, and that it did not leach in deionized water. XRD analysis was also used to confirm the recovery of pure LiNO₃ from the solution that was leached during the nitration process. This was carried out by evaporating and concentrating the leached solution through solid-liquid separation.

• Clean Technology
• /
• v.30 no.2
• /
• pp.105-112
• /
• 2024

Globally, the demand for electric vehicles has surged due to greenhouse gas regulations related to climate change, leading to an increase in the production of used batteries as a consequence of the battery life issue. This study aims to selectively leach and recover valuable metal lithium from the cathode material of spent LFP (LiFePO₄) batteries among lithium-ion batteries. Generally, the use of inorganic acids results in the emission of toxic gases or the generation of large quantities of wastewater, causing environmental issues. To address this, research is being conducted to leach lithium using organic acids and other leaching agents. In this study, selective leaching was performed using the organic acid methane sulfonic acid (MSA, CH₃SO₃H). Experiments were conducted to determine the optimal conditions for selectively leaching lithium by varying the MSA concentration, pulp density, and hydrogen peroxide dosage. The results of this study showed that lithium was leached at approximately 100%, while iron and phosphorus components were leached at about 1%, verifying the leaching efficiency and the leaching rates of the main components under different variables.

• Resources Recycling
• /
• v.11 no.3
• /
• pp.10-16
• /
• 2002

In the leaching of $LiCoO_2$with a strong acid such as sulfuric and nitric acid, an additional step was needed to recover cobalt and lithium separately from spent lithium ion batteries (LIBs). The leaching of $LiCoO_2$in an oxalic acid solution was investigated to recover cobalt selectively using a low solubility of cobalt oxalate at low pH. Leaching efficiency of 95% of lithium and less than 1% of cobalt were obtained when pure $LiCoO_2$powder was leached in 3M oxalic acid at $80^{\circ}C$ and 50 g/L pulpdensity. Under the above leaching conditions, complete dissolution of lithium was accomplished with mere 0.25% of cobalt in the solution when the cathodic active material collected from spent LIBs was employed. The lithium in the leaching solution can be recovered as a form of carbonate or hydroxide depending on the addition of $Na_2$$CO_3$or LiOH.

• Clean Technology
• /
• v.30 no.1
• /
• pp.28-36
• /
• 2024

As demand for electric vehicles increases, the market for lithium-ion batteries is also rapidly increasing. The battery life of lithium-ion batteries is limited, so waste lithium-ion batteries are inevitably generated. Accordingly, lithium was selectively preleached from waste lithium iron phosphate (LiFePO₄, hereafter referred to as the LFP) cathode material powder among lithium ion batteries, and iron phosphate (FePO₄) powder was recovered. The recovered iron phosphate powder was mixed with alkaline sodium carbonate (Na₂CO₃) powder and heat treated to confirm its crystalline phase. The heat treatment temperature was set as a variable, and then the leaching rate and powder characteristics of each ingredient were compared after water leaching using Di-water. In this study, lithium showed a leaching rate of approximately 100%, and in the case of powder heat-treated at 800 ℃, phosphorus was leached by approximately 99%, and the leaching residue was confirmed to be a single crystal phase of Fe₂O₃. Therefore, in this study, lithium, phosphorus, and iron components were individually separated and recovered from waste LFP powder.

• Resources Recycling
• /
• v.24 no.3
• /
• pp.44-50
• /
• 2015

Recycling technologies would be required in consideration of increasing demand in lithium ion batteries (LIBs). In this study, the leaching behavior of Ni, Co and Mn is investigated with ammoniacal medium for spent cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles. The leaching behavior of each metal is analyzed in the presence of reducing agent and pH buffering agent. The existence of reducing agent is necessary to increase the leaching efficiency of Ni and Co. The leaching of Mn is insignificant even with the existence of reducing agent in contrast to Ni and Co. The most conspicuous difference between acid and ammoniacal leaching would be the selective leaching behavior between Ni/Co and Mn. The ammoniacal leaching can reduce the cost of basic reagent that makes the pH of leachate higher for the precipitation of leached metals in the acid leaching.

• Resources Recycling
• /
• v.29 no.5
• /
• pp.73-80
• /
• 2020

In order to develop a process for the recovery of valuable metals from spent LiBs, solvent extraction experiments were performed to separate Cu(II) and/or Co(II) from synthetic hydrochloric acid solutions containing Li(I), Mn(II), and Ni(II). Commercial amines (Alamine 336 and Aliquat 336) were employed and the extraction behavior of the metals was investigated as a function of the concentration of HCl and extractants. The results indicate that HCl concentration affected remarkably the extraction efficiency of the metals. Only Cu(II) was selectively at 1 M HCl concentration, while both Co(II) and Cu(II) was extracted by the amines when HCl concentration was higher than 5 M, leaving the other metal ions in the raffinate. Therefore, it was possible to selectively extract either Cu(II) or Co(II)/Cu(II) by adjusting the HCl concentration.

• Resources Recycling
• /
• v.31 no.1
• /
• pp.21-28
• /
• 2022

The smelting reduction of spent lithium-ion batteries results in metallic alloys of cobalt, nickel, and copper. To develop a process to separate the metallic alloys, leaching of the metallic mixtures of these three metals with H₂SO₄ solution containing 3% H₂O₂ dissolved all the cobalt and nickel, together with 9.6% of the copper. Cyanex 301 selectively extracted Cu(II) from the leaching solution, and copper ions were completely stripped with 30% aqua regia. Selective extraction of Co(II) from a Cu(II)-free raffinate was possible using the ionic liquid ALi-SCN. Three-stage cross-current stripping of the loaded ALi-SCN by a 15% NH₃ solution resulted in the complete stripping of Co(II). A process was proposed to separate the three metal ions from the sulfuric acid leaching solutions of metallic mixtures by employing solvent extraction.