Recycling of Spent Lithium-ion Batteries used in Electric Vehicles by Physical Treatment and Acid Leaching

( Jeongsoo Sohn ),( Sookyung Kim ),( Donghyo Yang ),( Kangin Rhee ),( Hongin Kim ),( Kiwoong Lee ) 한국폐기물자원순환학회(구 한국폐기물학회) 2015 한국폐기물자원순환학회 3RINCs초록집 Vol.2015 No.-

The final goal of this research is to develop the commercialized technologies of recycling process on the spent lithium-ion battery used in electric vehicles. The contents and scope of this paper are demonstration on the pilot scale physical treatment process of the spent lithium-ion battery, developing recycling technology with the chemical leaching process on the crushed lithium-ion batteries, and the removal of impurities in leaching solution such as Fe and Al ions. The spent lithium-ion battery pack(227 kg) is made of 12 modules which are composed of 11 cells. This pack was dismantled manually in the dismantling line which is composed of lift, conveyor belt and hood system with the dismantling capacity of 50 packs/day. After dismantling, cells are crushed and separated. The result by crushing and separation showed that over 95% of valuable metals such as Co, Ni, Mn were concentrated into fine powders with 1-3 mm particle size. On the other hand over 95% of aluminum foils are separated from fine powders with 65 mesh screen. Through reductive leaching with H₂O₂ and H₂SO₄, leaching efficiency of valuable metals with -65mesh powder was almost 99 % Co, Mn, Ni and Li under the condition of 2M H₂SO₄, 5 vol. % H₂O₂, 60 ℃, 300 rpm, 50 g/500 ml, and 2 h. After removing some impurities such as Cu, Al, and Fe the leaching solutions containing Co, Mn, Ni, and Li could be utilized for the source material of Li-ion battery. In this paper Taylor reactor was introduced to precipitate Fe and Al into hydroxides.

Valuable Metals Recovery from Spent Lithium-ion Batteries by using Organic Chlorinated Compounds in Subcritical Water

( T. Nshizirungu ),( D. Shin ),( Y. T. Jo ),( J. H. Park ) 한국폐기물자원순환학회(구 한국폐기물학회) 2019 ISSE 초록집 Vol.2019 No.-

In this study, we are based on an effective and environmental friendly recovery of valuable metals such as Lithium (Li) and Cobalt (Co) from the spent Lithium-ion batteries and at the same time dechlorination of waste plastic chlorinated polyvinyl chloride (CPVC) in hydrothermal subcritical water process. Therefore, the process includes 2 main steps: (1) pre-treatment; from Li-ion battery full discharge until LiCoO₂ powder formed. (2) Co-treatment; from leaching process until recovery of Li and Co in form of Li₂CO₃ and Co(OH)₃. Waste plastic Chlorinated polyvinyl chloride was grinded and sieved to obtain fine CPVC powder. In Pre-treatment stage, spent lithium-ion batteries were full discharged in 20(wt. %) NaCl solution and followed by dismantling. Afterwards, Al foil was removed from cathode electrodes by using 50ml of N-methyl-2- pyrrolidone (NMP) solvent. Then the LiCoO₂ slurry was filtrated and dried. The LiCoO₂ powder was measured by inductively coupled plasma optical emission spectrometer (ICP-OES) after digestion with aquaregia. The results indicated that Li was accounted for 4.99% and 54.90% for Co. In Co-treatment stage, LiCoO₂ powder and waste plastic CPVC will be co-treated in temperature range of 100°C to 350°C by subcritical water oxidation, in which CPVC will be used as a hydrochloride acid (HCl) source to promote metal leaching. The expected results from ICP-OES will show us that more than 96% Cobalt and nearly 97% Lithium will be recovered under the optimum conditions of 300°C, CPVC/LiCoO₂ ratio 3:1 and time 40min respectively. This innovative work of hydrothermal subcritical water technology is sufficient, environmental friendly and appropriate for Co and Li recovery from spent lithium-ion batteries.

Comparison of Two Acidic Leaching Processes for Selecting the Effective Recycle Process of Spent Lithium ion Battery

Sohn, Jeong-Soo,Shin, Shun-Myung,Yang, Dong-Hyo,Kim, Soo-Kyung,Lee, Churl-Kyoung 한국암반공학회 2006 Geosystem engineering Vol.9 No.1

Physical treatment and chemical treatment of spent lithium-ion battery were studied in our research team. Especially we developed two types of acidic leaching for crushed powders containing $LiCoO_2$ of spent lithium ion battery. One of them is sulfuric acid leaching with $H_2O_2$ as a reducing agent. The leaching rates of cobalt, lithium and the other metals were above 99 % at the condition of 2 M $H_2SO_4$, 10 vol. % $H_2O_2$, $75^{\circ}C$, 300 rpm agitation speed, 250 g/5L solid liquid ratio and 75 minutes reaction time. And the other leaching process is the oxalic acid leaching. In this process more than 99% of Li and less than 1% of Co were dissolved at the condition of 3M oxalic acid, $80^{\circ}C$ reaction temperature, 300rpm agitation speed, 50g/L initial solid/liquid ratio and 90min extraction time. Each process has its advantage and disadvantage. In sulfuric acid leaching, leaching reagent is very cheap and cobalt could be recovered into cobalt hydroxide. On the other hand, oxalic acid is more expensive than sulfuric acid but lithium could be dissolved selectively. Also cobalt could be recovered into cobalt oxalate and it could be changed into cobalt oxide after heat treatment. In order to select the effective recycling process, recovery rate and purity of cobalt hydroxide and cobalt oxalate were compared and it was investigated which process was more environment-friendly and economical.

Physical Treatment of Non-battery Components from Spent Battery Pack in Electric Vehicles

( Jeong-soo Sohn ),( Hong-in Kim ),( Dong-hyo Yang ),( Soo-kyung Kim ),( Kwang-hyun Bae ) 한국폐기물자원순환학회(구 한국폐기물학회) 2019 ISSE 초록집 Vol.2019 No.-

The lithium-ion batteries used in electric vehicle are composed of one pack. This pack is composed of several modules and each module is composed of several cells. The weight of battery pack is above 200 kg but the weight percent of cell is only 60%. The other 40% is not lithium-ion cells but another components such as BMS(battery management system), PRA(power relay assembly), safety plug, cable, cooling system and pack case. Recycling technologies for valuable metals such as cobalt, nickel, manganese and lithium are now commercialized but non-battery components in battery pack of electric vehicles are not fully recycled. In order to complete the recycling of spent battery pack in electric vehicles, recycling of non-battery components is necessary in addition to lithium-ion cell recycling. So in this study, we introduced the physical treatment processes such as dismantlement, crushing, grinding, magnetic separation and size separation for non-battery components recycling. Some of nonbattery components are plastic materials and the others are plastics mixed with metals. These non-battery components are too bulky to transport and sometimes metal components should be separated from the plastics. After dismantling the spent battery pack, each parts were treated by shredder. Volume changes of each non-battery component wastes were measured before and after shredding and volume reducing ratio was examined. Also in the case of plastics mixed with metals such as BMS, PRA and cooling system, the separation between metal and non-metal was examined after crushing, size separation and magnetic separation.

Effective leaching and extraction of valuable metals from electrode material of spent lithium-ion batteries using mixed organic acids leachant

Yuanpeng Fu,Yaqun He,Hangchao Chen,Cuiling Ye,Qichang Lu,Rongnian Li,Weining Xie,Jie Wang 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.79 No.-

The present work focuses on simultaneous recycling of Li and Co from crushed products of mixedelectrode materials using mixed organic acids, in which benzenesulfonic acid and formic acid werecooperatively used as the leaching reagents. Results show that the optimal leaching efficiency of 97% Coand 99% Li were obtained under the conditions of 1.3 mol/L benzenesulfonic acid, 1.5 mol/L formic acid, asolid to liquid (S/L) ratio of 30 g/L, and 40 min reaction time at 50 C. Meanwhile, the leaching of Li and Cofits well to logarithmic rate model with apparent activation energy of 32.7 and 47.0 kJ/mol in this givenleaching system, respectively. Besides, cobalt was directly recovered from the leach liquor as pure cobaltbenzene sulfonic with the recovery efficiency of 99%, and lithium can be entirely precipitated by addingphosphoric acid. Further, the reaction mechanism involves the leaching-hydrating-complexing model ofLiCoO2 particles was proposed based on the dissolution behavior of metals and then verified bymorphological and phase characterization (i.e. FT-IR, XRD and SEM-EDS) of the recycling product. Thewhole process is found to be effective and sustainable for recovery of Li, Co and graphite from mixedindustrial crushing product of spent LIBs.

황산용액에서 용매추출에 의한 코발트(II), 니켈(II) 및 구리(II) 분리

문현승,송시정,Thanh Tuan Tran,이만승 한국자원리싸이클링학회 2022 資源 리싸이클링 Vol.31 No.1

폐리튬이온배터리를 고온에서 용융환원시키면 코발트, 니켈 및 구리 금속합금상을 얻을 수 있다. 이러한 금속합금상으로부터 금속을분리회수하기 위한 공정을 개발하기 위해 코발트, 니켈 및 구리 금속을 혼합한 금속혼합물을 3% 과산화수소를 함유한 2 M 황산용액으로침출하면 9.6%의 구리와 함께 코발트와 니켈이 모두 침출된다. 침출용액에서 Cyanex 301로 구리(II)가 선택적으로 추출되었으며, 30% 왕수로 구리(II)를 탈거했다. 구리가 분리된 여액에서 이온성액체인 ALi-SCN으로 Co(II)를 선택적으로 추출했으며, 15%의 암모니아용액으로 3단의 교차식 탈거를 통해 모두 탈거했다. 본 연구를 통해 코발트, 니켈 및 구리 금속혼합물의 황산침출액에서 용매추출로 세 금속을 분리할 수 있는 공정을 제안했다. 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.

Use of grape seed as reductant for leaching of cobalt from spent lithium-ion batteries

Ying-Jie Zhang,Qi Meng,Peng Dong,Jianguo Duan,Yan Lin 한국공업화학회 2018 Journal of Industrial and Engineering Chemistry Vol.66 No.-

The grape seed was novelly used as reductant for leaching of spent LiCoO2 material, which is idea of “waste + waste → resources”. About 92% Co and 99% Li could be leached under the optimized conditions of grape seed 0.6 g/g, malic acid 1.5 mol/L, 180 min, 80 °C, and slurry density 20 g/L. The catechin, EC and EGCG contained in grape seed could be employed as efficient reductants during leaching. The leaching process is controlled by combination of surface chemical reaction and diffusion with apparent activation energy of 11.96 kJ/mol, which is related to the form of Co(OH)3.

규소(IV)가 함유된 염산용액으로부터 침전법에 의한 고순도 니켈(II)화합물의 회수

문현승,송시정,Thanh Tuan Tran,이만승 한국자원리싸이클링학회 2021 資源 리싸이클링 Vol.30 No.6

Spent lithium-ion batteries are treated by reduction-smelting at high temperatures to recover valuable metals. Solvent extraction and precipitation of the HCl leaching solution of reduction-smelted metallic alloys resulted in a filtrate containing Ni(II) and a small amount of Si(IV). Adsorption and precipitation experiments were conducted to recover pure Ni(II) compounds from the filtrate. Si(IV) was selectively loaded onto polyacrylamide, but this method did not efficiently filter the solution due to an increase in viscosity. The addition of Na2CO3 as a precipitant to the filtrate led to the simultaneous precipitation of Ni(II) and Si(IV). However, it was possible to recover nickel oxalate with a purity higher than 99.99% by selectively precipitating Ni(II) with the addition of Na2C2O4 as a precipitant. 폐리튬이온배터리에 함유된 유가금속을 회수하기 위해 고온에서 용융환원처리한다. 용융환원된 금속상을 염산용액으로 침출한 다음용매추출과 침전으로 유가금속을 분리한 여과액에는 니켈(II)과 미량의 규소(IV)가 함유되어 있다. 여액으로부터 고순도 니켈화합물을회수하기 위해 흡착법에 의한 규소(IV)의 분리와 니켈(II)의 선택적 침전에 대해 조사했다. Polyacrylamide는 규소(IV)를 선택적으로 흡착했으나 용액의 점도 역시 증가하여 여과가 어렵다. 침전제로 탄산나트륨을 첨가하면 니켈(II)과 미량의 규소(IV)가 공침되었다. 반면옥살산나트륨은 상온에서 니켈(II)만을 선택적으로 침전시켜 순도 99.99% 이상의 니켈옥살산염 결정상을 회수할 수 있었다.

Ionic liquid assisted recovery of cobalt and nickel metals from spent lithium-ion batteries (LIBs)

( Raj Tirath ),( Raj Morya ),( Ashutosh Kumar Pandey ),( Sang-hyoun Kim ) 한국폐기물자원순환학회 2022 ISSE 초록집 Vol.2022 No.-

Lithium-ion batteries (LIBs) have become an essential component of the energy supply chain for transportation (in electric vehicles) and renewable energy storage systems. This surge in demand necessitates an increase in production, which, in turn, results in a large number of waste LIBs. LIB cathode material primarily contains heavy metal elements such as nickel (Ni) and cobalt (Co), which are potentially hazardous to human health and the environment if discarded improperly. The leaching of Co and Ni into various water streams has become an environmental hazard and is continuously affecting human health through the food chain. Thus, recycling spent LIBs has gotten a lot of attention because it provides a cost-effective way to ensure a steady supply of these metals for LIB remanufacturing. Thus, recycling spent LIBs has received a lot of attention because it offers a cost-effective way to ensure a steady supply of these metals for LIB remanufacturing while also encouraging safer environmental load reduction. Solvent extraction is the most widely accepted method for separating these metals, but traditional extractants employed in conjunction with molecular diluents often lack selectivity and cause major environmental hurdles. Thus, the present study demonstrated a state-of-the-art approach for the recovery of cobalt and nickel from waste LIBs using green ionic liquids, which is such as recycling from a sustainable perspective. Ionic liquids are molten salts of organic cation and inorganic/ organic anion and are considered as green solvents. Here in, two halogen-free, low viscous, biocompatible fatty acid-based hydrophobic ionic liquids (ILs) were synthesized, characterized, and used to recover cobalt, Co(II), and nickel, Ni(II), from aqueous solutions. The extraction behaviors of Co(II) and Ni(II) were studied further by varying the equilibrium time, ILs molar concentration, metal loading, and temperature. Thermodynamic parameters such as enthalpy change and Gibbs free energy change were also investigated showed that metal recovery is governed by metal transfer phenomenon. Study revealed that fatty acid-based ILs were found to be capable of extracting > 99 % Co(II) and Ni(II) from aqueous solutions at 298 K in 15 minutes using a 1:1 (org: aq.) ratio at low concentrations of 2.5 to 10 g L^-1. Furthermore, when the metal concentration was greater than 10 g L^-1, Co(II) extraction was preferred over Ni(II) extraction for methyltrioctylammonium oleate IL.

황산과 염산 합성용액에서 이온교환에 의한 니켈(II), 코발트(II), 망간(II) 및 실리케이트(IV)의 분리

Thi Thu Huong Nguyen,Jiangxian Wen,이만승 한국자원리싸이클링학회 2022 資源 리싸이클링 Vol.31 No.3

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 폐리튬이온전지를 고온에서 용융환원하면 금속혼합물을 얻을 수 있다. 금속혼합물을 황산이나 염산으로 침출한 다음 용매추출로 분리한 여액에는 니켈(II), 코발트(II), 망간(II)과 실리케이트(IV)가 함유되어 있다. 본 논문에서는 양이온교환수지인 Diphonix와 P204를사용하여 황산과 염산 합성용액에 함유된 상기 이온들의 이온교환거동을 조사했다. 용액의 pH가 3인 황산용액에서 니켈(II), 코발트(II) 와 망간(II)이 선택적으로 Diphonix에 흡착되었다. 용액의 pH가 6인 염산용액에서는 망간(II)이 P204수지에 선택적으로 흡착되어 분리가 가능했다. Diphonix와 P204에 흡착된 금속이온은 황산이나 염산용액으로 세출할 수 있었다