• Resources Recycling
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• v.32 no.1
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• pp.21-32
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• 2023

Because the application of lithium has gradually increased for the production of lithium ion batteries (LIBs), more research studies about recycling using solvent extraction (SX) should focus on Li⁺ recovery from the waste solution obtained after the removal of the valuable metals nickel, cobalt and manganese (NCM). The raffinate obtained after the removal of NCM metal contains lithium ions and other impurities such as Na ions. In this study, we optimized a selective SX system using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and tri-n-butyl phosphate (TBP) as a modifier in kerosene for the recovery of lithium from a waste solution containing lithium and a high concentration of sodium (Li⁺ = 0.5 ~ 1 wt%, Na⁺ = 3 ~6.5 wt%). The extraction of lithium was tested in different solvent compositions and the most effective extraction occurred in the solution composed of 20% D2EHPA + 20% TBP + and 60% kerosene. In this SX system with added NaOH for saponification, more than 95% lithium was selectively extracted in four extraction steps using an organic to aqueous ratio of 5:1 and an equilibrium pH of 4 ~ 4.5. Additionally, most of the Na⁺ (92% by weight) remained in the raffinate. The extracted lithium is stripped using 8 wt% HCl to yield pure lithium chloride with negligible Na content. The lithium chloride is subsequently treated with high purity ammonium bicarbonate to afford lithium carbonate powder. Finally the lithium carbonate is washed with an adequate amount of water to remove trace amounts of sodium resulting in highly pure lithium carbonate powder (purity > 99.2%).

• Archives of Metallurgy and Materials
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• v.66 no.4
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• pp.987-990
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• 2021

As the amount of high-capacity secondary battery waste gradually increased, waste secondary batteries for industry (high-speed train & HEV) were recycled and materialization studies were carried out. The precipitation experiment was carried out with various conditions in the synthesis of LiNi_0.6Co_0.2Mn_0.2O₂ material using a Taylor reactor. The raw material used in this study was a leaching solution generated from waste nickel-based batteries. The nickel-cobalt-manganese (NCM) precursor was prepared by the Taylor reaction process. Material analysis indicated that spherical powder was formed, and the particle size of the precursor was decreased as the reaction speed was increased during the preparation of the NCM. The spherical NCM powder having a particle size of 10 ㎛ was synthesized using reaction conditions, stirring speed of 1000 rpm for 24 hours. The NCM precursor prepared by the Taylor reaction was synthesized as a cathode material for the LIB, and then a coin-cell was manufactured to perform the capacity evaluation.

• Journal of Surface Science and Engineering
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• v.56 no.4
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• pp.259-264
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• 2023

As the demand for lithium-ion batteries, a key power source in electric vehicles and energy storage systems, continues to increase for achieving global carbon neutrality, there is a growing concern about the environmental impact of disposing of spent batteries. Extensive research is underway to develop efficient recycling methods. While hydrometallurgy and pyrometallurgy methods are commonly used to recover valuable metals from spent cathode materials, they have drawbacks including hazardous waste and complex processes. Hence, alternative recycling methods that are environmentally friendly are being explored. However, recycling spent cathode materials still remains complex and energy-intensive. This study focuses on a novel approach called solid-state synthesis, which aims at regenerating the performance of spent cathode materials. The method offers a simpler process and reduces energy consumption. Optimal heat treatment conditions were identified based on experimental results, contributing to the development of sustainable recycling technologies for lithium-ion batteries.

• Resources Recycling
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• v.28 no.5
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• pp.30-41
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• 2019

Global production of zinc is about 13 million tons and zinc is the fourth-most widely used primary metal in the world following iron, aluminum and copper. When zinc is recycled to produce secondary zinc, it can save about 75 % of the total energy that is needed to produce the primary zinc from ore, and in therms of $CO_2$ emissions reduced by about 40 %. However, since zinc is mainly used for galvanizing of steel, the recycling rate of zinc is about 25 %, which is lower than other metals. The raw materials for recycling of zinc include dusts generated in the production of steel and brass, sludge in the production process of non-ferrous metals, dross in the melting of zinc ingots or hot dip galvanizing, waste batteries, and metallic scrap. Among them, steelmaking dust and waste batteries are most actively recycled up to now. Most of the recycling process uses pyrometallurgical methods. Recently, however, much attention has been given to a combined process of pyrometallurgical and hydrometallurgical processes.

• Resources Recycling
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• v.32 no.6
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• pp.25-33
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• 2023

With the growth of the battery industry, a rapid increase in the production and usage of lithium-ion batteries is expected, and in line with this, much interest and effort is being paid to recycle waste batteries, including production scrap. Although much effort has been made to recycle cathode material, much attention has begun to recycle anode material to secure the supply chain of critical minerals and improve recycling rates. The proximate analysis that measures the content of coal can be used to analyze graphite in anode material, but it cannot accurately analyze due to the interaction between the components of the black mass. Therefore, in this study, thermogravimetric analysis of each component of black mass was measured as the temperature increased up to 950℃ in an oxygen atmosphere. As a result, in the case of cathode material, no change in mass was measured other than a mass reduction of about 5% due to oxidation of the binder and conductive material. In the case of anode material, except for a mass reduction of about 2% due to the binder, all mass reduction were due to the graphite(fixed carbon). In addition, metal conductors (Al, Cu) were oxidized and their mass increased as the temperature increased. Thermal analysis results of mixed samples of cathode/anode show similar results to the predictive values that can be calculated through each cathode and anode analysis results.

• Resources Recycling
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• v.32 no.3
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• pp.9-17
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• 2023

Efforts are currently underway to develop a method for efficiently recovering lithium from the cathode material of waste lithium iron phosphate batteries (LFP). The successful application of lithium battery recycling can address the regional ubiquity and price volatility of lithium resources, while also mitigating the environmental impact associated with both waste battery material and lithium production processes. The isomorphic substitution leaching process was used to recover lithium from spent lithium iron phosphate batteries. Lithium was leached by the isomorphic substitution of Fe²⁺ in LFP using a relatively inexpensive ferric chloride etching solution as a leaching agent. In the study, the leaching rate of lithium was compared using the ferric chloride etching solution at various multiples of the LFP molar ratio: 0.7, 1.0, 1.3, and 1.6 times. The highest lithium leaching rate was shown at about 98% when using 1.3 times the LFP molar ratio. Subsequently, to eliminate Fe, the leachate was treated with NaOH. The Fe-free solution was then used to synthesize lithium carbonate, and the harvested powder was characterized and validated. The surface shape and crystal phase were analyzed using SEM and XRD analysis, and impurities and purity were confirmed using ICP analysis.

• Resources Recycling
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• v.28 no.1
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• pp.23-31
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• 2019

Cementation is one of economical and efficient recycling method precipitating the metal ion in solution by adding another active metal. In this study for optimizing cadmium recovery efficiency, it was performed as a function of the effect of pH, temperature, particle size, and input amount of zinc in 0.1 M $CdSO_4$ solution and Ni-Cd battery leaching solutions, respectively. The particle size of zinc and temperature were key factors for Cd cementation and it was confirmed that the input amount of 2.6 of Zn/Cd ratio using granular-type zinc was optimal condition for selective Cd recovery efficiency at $25^{\circ}C$.

• Journal of Surface Science and Engineering
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• v.55 no.4
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• pp.231-235
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• 2022

As environmental pollution becomes more serious, the demand for electric vehicles (EVs) and lithium-ion batteries for electric vehicles is rapidly increasing worldwide. Accordingly, the amount of waste batteries is also increasing, and a technology for recycling and reusing them is required. In order to reuse a used battery, it is necessary to non-destructively diagnose the deterioration condition of the battery. Therefore, in this study, we investigate the diagnosis of degradation for parallel-connected lithium-ion battery cells through non-constructive electrochemical approach. As the number of parallel-connected cells increased, in addition to linear degradation, abrupt step-like degradation occurred, which is attributed to the predominant degradation of specific cells. In addition, it is confirmed that deteriorated cells among multiple cells can be distinguished through a simple measurement of open circuit voltage (OCV).

• Clean Technology
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• v.27 no.1
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• pp.33-38
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• 2021

Demand for lithium-based secondary batteries is greatly increasing with the explosive growth of related industries, such as mobile devices and electric vehicles. In Korea, there are several top-rated global lithium-ion battery manufacturers accounting for 40% of the global secondary battery business. Most discarded lithium secondary batteries are recycled as scrap to recover valuable metals, such as Nickel and Cobalt, but residual wastes are disposed of according to the residual lithium-ion concentration. Furthermore, there has not been an attempt on the possibility of water discharge system contamination due to the concentration of lithium ions, and the effluent water quality standards of public sewage treatment facilities are becoming stricter year after year. In this study, the as-received waste water generated from the cathode electrode coating process in the manufacturing of high-nickel-based NCM cathode material used for high-performance and long-term purposes was analyzed. We suggested a facile recycling process chart for waste water treatment. We revealed a correlation between lithium-ion concentration and pH effect according to the proposed waste water of each recycling process through analyzing standard water quality tests and daphnia ecological toxicity. We proposed a realistic waste water treatment plan for lithium electrode manufacturing plants via comparison with other industries' ecotoxicology.

• Journal of the Korea Organic Resources Recycling Association
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• v.30 no.4
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• pp.59-66
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• 2022

Lithium-ion batteries have greatly expanded along with the mobile phone market, and as the electric vehicle business is activated in earnest, they will attract many people's attention even afterwards. Until now, many people have attracted attention to the recovery of valuable metals inside lithium-ion batteries, but graphite, which is mainly used as an anode material, is also worth recycling. Therefore, in order to recover graphite with high purity and valuable metals, graphite that can be used as an anode material of a secondary battery may be generated again through a regeneration process of purifying and separating graphite from a waste lithium-ion battery and recovering electrical characteristics of graphite. This paper describes the process of converting waste graphite into regenerated graphite and the environmental and economic effects of regenerated graphite.