• Resources Recycling
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• v.21 no.4
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• pp.16-25
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• 2012

There are several kinds of batteries such as zinc-air battery, lithium battery, Manganese dry battery, silver oxide battery, sodium-sulphur battery, lead acid battery, metal hydride 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 and published papers on the recycling technologies of the used battery were analyzed. The range of search was limited in the open patents of USA (US), European Union (EU), Japan (JP), Korea (KR) and SCI journal articles from 1972 to 2011. Patents and journal articles were collected using key-words searching and filtered by filtering criteria. The trends of the patents and journal articles were analyzed by the years, countries, companies, and technologies.

• Journal of Powder Materials
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• v.25 no.4
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• pp.296-301
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• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• 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.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.11
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• pp.603-610
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• 2016

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

• Resources Recycling
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• v.24 no.6
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• pp.9-16
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• 2015

In a recycling scheme of spent lithium ion batteries, a co-precipitation process for the re-synthesis of precursor is essential after the leaching of lithium ion battery scraps. In this study, the effect of ammonia as impurity during the co-precipitation process was investigated in order to re-synthesize a precursor of Ni-rich cathode active material $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ (NCM 622). As ammonia concentration increases from 1 M (the optimum condition for synthesis of the precursors based on 2 M of metal salt solution) to 4 M, the composition of obtained precursors deviates from the designed composition, most notably for Ni. The Ni co-precipitation efficiency gradually decreases from 100% to 87% when the concentration of ammonia solution increases from 1 M to 4 M. Meanwhile, the morphological properties of the obtained precursors such as sphericity, homogeneity and size distribution of particles were also investigated.

• Proceedings of the Korean Institute of Resources Recycling Conference
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• 2005.10a
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• pp.173-177
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• 2005

리튬이온 2차전지(Lithium ion battery, LIB)는 기존에 사용되던 전지에 비해 에너지 밀도가 높고 충방전 사이클이 우수하다. 이 때문에 휴대전화와 노트북 등에 수요가 급속하게 증가하고 있으며 1995년 LIB의 생산량은 4천만 개에서 2004년에는 약 8억 개로 20배 이상 증가하였다. 이에 따라 폐LIB도 급속하게 증가하게 되어 전국적인 재활용 시스템의 확보가 필요한 실정이다. 본 연구에서는 폐LIB에 함유되어 있는 유가금속 중에서 리튬코발트옥사이드(이하 $LiCoO_2$)를 회수하기 위하여 분쇄기(orient vertical cutting mill)와 진동 Screen을 사용하여 유기분리막, 금속류(Aluminium foil, Copper foil, case 등) 그리고 전극물질(lithium cobalt oxide와 graphite 등의 혼합 분말)로 분리하였다. 전극물질에서 $LiCoO_2$와 graphite 분리를 위한 전처리 단계로서 $500^{\circ}C$ 정도의 열처리를 하여 $LiCoO_2$의 표면 성질을 변화시켜 부유선별에 의해 $LiCoO_2$와 graphite의 분리가 가능하도록 하였다. 부유선별 실험 결과 93% 이상의 순도를 가지는 $LiCoO_2$를 92% 이상 회수할 수 있었다.

• Archives of Metallurgy and Materials
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• v.64 no.2
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• pp.481-485
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• 2019

This study was attempted to study for recovery of Li as Li₂CO₃ from cathode active material, especially NCA (LiNiCoAlO₂), recovered from spent lithium ion batteries. This consists of two major processes, carbonation using CO₂ and water leaching. Carbonation using CO₂ was performed at 600℃, 700℃ and 800℃, and NCA (LiNiCoAlO₂) was phase-separated into Li₂CO₃, NiO and CoO. The water leaching process using the differences in solubility was performed to obtain the optimum conditions by using the washing time and the ratio of the sample to the distilled water as variables. As a result, NCA (LiNiCoAlO₂) was phase-separated into Li₂CO₃ and NiO, CoO at 700℃, and Li₂CO₃ in water was recovered through vacuum filtration after 1 hour at a 1:30 weight ratio of the powder and distilled water. Finally, Li₂CO₃ containing Li of more than 98 wt.% was recovered.

• Resources Recycling
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• v.17 no.2
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• pp.3-15
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• 2008

Different toxic wastes are disposed of in our surroundings and these will ultimately threaten the existence of living organisms. Biohydrometallurgy, which includes the processes of bioleaching and bioremediation through the activities of microorganisms such as bacterial or fungal species, is a technology that has the potential to overcome many environmental problems at a reasonable economic cost. Bioleaching were carried out for dissolution of metals from different materials using most important metal mobilizing bacteria such as Thiobacillus ferrooxidans, Thiobacillus thiooxidans and Laptospirillum ferrooxidans. According to the reaction, bioleaching is parted as direct and indirect mechanism. In direct mechanism the bacteria oxidize the sulphides minerals by accepting electron and producing sulphuric acid in leaching media for their growth and metabolism. In other hand the indirect bioleaching is demonstrated as the oxidation of sulphides mineral by the oxidant like $Fe^{3+}$ produced by the iron oxidizing bacteria. Through this process, substantial amount of metal can be recovered from low-grade ores, concentrates, industrial wastes like sludge, tailings, fly ash, slag, electronic scrap, spent batteries and spent catalysts. This may be alternative technology to solve the high deposition of waste, which moves toward a healthy environment and green world.

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

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.517-520
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• 2006

The leaching behaviors of zinc and manganese oxides of spent alkaline manganeses battery in sulfuric acid solution by using $H_{2}O_{2}$ as a reducing agent were investigated according to the concentration of $H_{2}SO_{4}$, temperature, reaction time, and the amount of $H_{2}O_{2}$. The experimental results of zinc and manganeses dissolution rates obtained without a reducing agent at 100 g/L solid/liquid ratio, 3.0 M $H_{2}SO_{4}$, $60^{\circ}C$ and 200 r.p.m. were 97.7% and 43.5%, respectively. On the other hand, zinc and manganeses dissolution rates obtained by adding 30 mL reducing agent at $60^{\circ}C$ were 99.6% and 97.1%, respectively. The addition of the reducing agent increased the leaching of manganese by two-fold compared to the absence of a reducing agent. In case of adding over 30 mL $H_{2}O_{2}$, however, the leaching rates of zinc and manganeses were independent of reducing agent amounts.