• Resources Recycling
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• v.31 no.3
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• pp.73-80
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• 2022

Reduction smelting of spent lithium-ion batteries at high temperature produces metallic alloys. Following solvent extraction of the leaching solutions of these metallic alloys with either sulfuric or hydrochloric acid, the raffinate is found to contain Ni(II), Co(II), Mn(II), and Si(IV). In this study, two cationic exchange resins (Diphonix and P204) were employed to investigate the loading behavior of these ions from synthetic sulfate and chloride solutions. Experimental results showed that Ni(II), Co(II), and Mn(II) could be selectively loaded onto the Diphonix resin from a sulfate solution of pH 3.0. With a chloride solution of pH 6.0, Mn(II) was selectively loaded onto the P204 resin, leaving Ni(II) and Si(IV) in the effluent. Elution experiments with H₂SO₄ and/or HCl resulted in the complete recovery of metal ions from the loaded resin.

• Resources Recycling
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• v.16 no.6
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• pp.10-19
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• 2007

The mechanical process followed by hydrometallurgical treatment has been developed in order to recover cobalt and lithium from spent lithium ion battery. In the previous study, a citrate precursor combustion process to prepare cathodic active materials from the leaching solution was elucidated. Resynthesis of electrode materials should be more valuable in spent battery recycling. Conventional slurry mixing of $LiCoO_2$ and carbon cannot make uniform distribution, and therefore the cathode cannot reach the theoretical charge-discharge capacity and is easily degraded during the charge-discharge cycling. In this study, ultra-fine $LiCoO_2$ powders has been prepared by modification of the combustion process and fabricated the enhanced cathode by modification of mixing method of $LiCoO_2$ and carbon added.

• 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%).

• Resources Recycling
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• v.10 no.6
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• pp.9-14
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• 2001

A sulfuric acid leaching of $LiCoO_2$as cathodic active materials of lithium ion secondary batteries was investigated in terms of reaction variables. In the absence of a reducing agent, the extraction of cobalt was less than 40% in 2 M sulfuric acid at $75^{\circ}C$ instead of that of lithium could be almost 100% in the same conditions. To improve the Co extraction, hydrogen peroxide was used as a reducing agent in the range 2~20 vol%. When over 10vo1% hydrogen peroxide was added, the extractions of both metals were improved to about 95%. It seems to be due to the reduction of Co(III) to Co(II) that can be readily dissolved. The extractions of Co and Li were increased with increasing $H_2$$SO_4$concentration and temperature, and amount of hydrogen peroxide and with decreasing of pulp density. The optimum leaching conditions were determined at $2 M H_2$$SO_4$concentration, $75^{\circ}C$ operating temperature, 100 g/L. initial pulp density, 20 vol% $H_2$$O_2$addition and 30 min.

• Resources Recycling
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• v.14 no.6 s.68
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• pp.37-43
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• 2005

[ $LiCoO_{2}$ ] nanoparticles were synthesized from leach liquor of lithium ion battery waste using flame spray pyrolysis. Electrode Materials containing lithium and cobalt could be concentrated with thermal and mechanical treatment. After dissolution of used cathode materials of the lithium battery with nitric acid, the molar ratio of Li/Co in the leach liquor was adjusted at 1.0 by adding a fresh $LiNO_{3}$ solution. The nanoparticles synthesized by the flame spray pyrolysis showed clear crystallinity and were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm. The average particle diameter increased with an increase in the molar concentration of the precursor. Raising the maximum flame temperature by controlling the gas flow rates also led to an increase in the average diameter of the particles. The $LiCoO_{2}$ powder was proved to have good characteristics as cathode active materials in charge/discharge capacity and cyclic performance.

• Applied Chemistry for Engineering
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• v.34 no.5
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• pp.515-521
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• 2023

In this study, waste carbon fiber obtained by pyrolysis of carbon fiber reinforced plastic (CFRP) was used to produce carbon fluoride through vapor phase fluorination and recycled as a reducing electrode material for lithium primary batteries. First, the physicochemical properties of the waste carbon fiber obtained by pyrolysis were determined, and the structural and chemical properties of carbon fluoride were analyzed to evaluate the effect of vapor phase fluorination on the waste carbon fiber. XRD analysis confirmed that the hexagonal network carbon laminated structure (002 peak) of the waste carbon fiber was gradually converted into a carbon fluoride structure (CF_X, 001 peak) as the temperature of gas phase fluorination increased. The discharge capacity of the lithium primary battery produced using this carbon fluoride was up to 862 mAh/g. This was compared to the discharge capacity of carbon fluoride-based Li-ion batteries made of other carbon materials. These results suggest that carbon fluoride made from waste CFRP-based carbon fibers can be used as a reducing electrode material for Li-ion batteries.

• Resources Recycling
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• v.28 no.5
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• pp.3-18
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• 2019

Due to the increasing demand for clean energy, the consumption of lithium ion batteries (LIBs) is expected to grow steadily. Therefore, stable supply of lithium is becoming an important issue globally. Commercially, most of lithium is produced from the brine and minerals viz., spodumene, although various processes/technologies have been developed to recover lithium from other resources such as low grade ores, clays, seawaters and waste lithium ion batteries. In particular, commercialization of such recycling technologies for end-of-life LIBs being generated from various sources including mobile phones and electric vehicles(EVs), has a great potential. This review presents the commercial processes and also the emerging technologies for exploiting minerals and brines, besides that of newly developed lithium-recovery-processes for the waste LIBs. In addition, the future lithium-supply is discussed from the technical point of view. Amongst the emerging processes being developed for lithium recovery from low-grade ores, focus is mostly on the pyro-cum-hydrometallurgical based approaches, though only a few of such approaches have matured. Because of low recycling rate (<1%) of lithium globally compared to the consumption of lithium ion batteries (56% of lithium produced currently), processing of secondary resources could be foresighted as the grand opportunity. Considering the carbon economy, environment, and energy concerns, the hydrometallurgical process may potentially resolve the issue.

• Resources Recycling
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• v.20 no.4
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• pp.65-70
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• 2011

Environmental friendly leaching process for the recovery of cobalt and lithium from the $LiCoO_2$ was investigated by organic acids as a leaching reagent. The experimental parameters, such as organic acid type, concentrations of leachant and hydrogen peroxide, reaction time and temperature as well as the pulp density were tested to obtain the most effective conditions for the leaching of cobalt and lithium. The results showed that the latic acid was the most effective leaching reagent for cobalt and lithium among the organic acids and was reached about 99.9% of leaching percentage respectively. With the increase of the concentration of citric acid, hydrogen peroxide and temperature, the leaching rate of cobalt and lithium increased. But the increase of pulp density decreased the leaching rate of cobalt and lithium.

• Clean Technology
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• v.27 no.2
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• pp.139-145
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• 2021

The purpose of this study is to recover valuable metals from spent batteries using a dry process. We focused on the effect of the smelting temperature on the composition of recovered solid and liquid products and collected gaseous products. After removal of the cover, the spent battery was left in NaCl solution and discharged. Then, the spent battery was made into a powder form through a crushing process. The smelting of the spent battery was performed in a tubular electric furnace in an oxygen atmosphere. For spent lithium-ion batteries, the recovery yield of the solid product was 80.1 wt% at a reaction temperature of 850 ℃, and the final product had 27.2 wt% of cobalt as well as other metals such as lithium, copper, and aluminum. Spent nickel-hydrogen batteries had a recovery yield of 99.2 wt% at a reaction temperature of 850 ℃ with about 37.6 wt% of nickel and other metals including iron. For spent nickel-cadmium batteries, the yield decreased to 65.4 wt% because of evaporation with increasing temperature. At 1050 ℃, the recovered metals were nickel (41 wt%) and cadmium (12.9 wt%). Benzene and toluene, which were not detected with the other secondary waste batteries, were detected in the gaseous product. The results of this study can be used as basic data for future research on the dry recycling process of spent secondary batteries.

• Resources Recycling
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• v.16 no.3 s.77
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• pp.50-60
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• 2007

There are several kinds of battery such as zinc-air battery, lithium battery, Manganese dry battery, silver oxide battery, mercury battery, sodium-sulphur battery, lead battery, nickel-hydrogen secondary battery, nickel-cadmium battery, lithium ion battery, alkaline battery, etc. These days it has been widely studied for the recycling technologies of the used battery from view points of economy and efficiency. In this paper, patents on the recycling technologies of the used lithium battery were analyzed. The range of search was limited in the open patents of USA(US), European Union(EP), Japan(JP), and Korea(KR) from 1986 to 2006. Patents were collected using key-words searching and filtered by filtering criteria. The trends of the patents was analyzed by the years, countries, companies, and technologies.