Document Type : Original Research Paper


School of Mining Engineering, Faculty of Engineering, University of Tehran, Tehran, Iran


In this research work, with a simple, safe, and environmentally friendly approach to hydrometallurgy, a method for the recovery of lithium (Li), cobalt (Co), and nickel (Ni) from LIBs is suggested. The cathode materials are leached by malonic acid, as the leaching agent, and ascorbic acid, as the reducing agent in the first process, and by L-glutamic acid, as the leaching agent, and ascorbic acid, as the reducing agent in the second process. In order to optimize the leaching parameters including temperature, organic acid concentration, ascorbic acid concentration, type of organic acid, pulp density, and time, response surface methodology (RSM) of the experimental design process is used. According to the results, compared to L-glutamic acid in the second process, the leaching recovery increase considerably with malonic acid in the first process. This normally occurs due to the higher solubility of malonic acid in water, which results in a better complexation and a higher chelation rate. By contrast, as solubility of L-glutamic acid in water is low, metal-acid surface reaction and poor complexation are unavoidable. According to the statistical analysis of the results and validation testing, optimal experimental leaching occurs at the reaction temperature of 88 °C, organic acid concentration of 0.25 M, ascorbic acid concentration of 0.03 M, pulp density of 10 g/L, and leaching time of 2 h, via which metal recovery of 100% Li, 81% Co, and 99% Ni is achieved. Before and after acidic leaching, the sample active materials are qualitatively and quantitatively analyzed using X-ray diffraction, X-ray fluorescence, particle size analyzer, scanning electron microscope, energy dispersive spectroscopy, and atomic absorption spectroscopy.


[1]. He, L.P., Sun, S.Y., and Yu, J.G. (2018). Performance of LiNi1/3Co1/3Mn1/3O2 prepared from spent lithium-ion batteries by a carbonate co-precipitation method. Ceramics International. 44 (1): 351-357.
[2]. Nayaka, G., Zhang, Y., Dong, P., Wang, D., Pai, K., Manjanna, J., and Xiao, J. (2018). Effective and environmentally friendly recycling process designed for LiCoO2 cathode powders of spent Li-ion batteries using mixture of mild organic acids. Waste Management, 78, 51-57.
[3]. Meshram, P., Pandey, B.D., Mankhand, T.R., and Deveci, H. (2016). Acid baking of spent lithium ion batteries for selective recovery of major metals: a two-step process. Journal of Industrial and Engineering Chemistry, 43, 117-126.
[4]. Li, L., Dunn, J.B., Zhang, X.X., Gaines, L., Chen, R.J., Wu, F., and Amine, K. (2013). Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment. Journal of Power Sources, 233, 180-189.
[5]. Tang, X., Tang, W., Duan, J., Yang, W., Wang, R., Tang, M., and Li, J. (2021). Recovery of valuable metals and modification of cathode materials from spent lithium-ion batteries. Journal of Alloys and Compounds, 874, 159853.
[6]. Xiao, J., Niu, B., Song, Q., Zhan, L., and Xu, Z. (2021). Novel targetedly extracting lithium: An environmental-friendly controlled chlorinating technology and mechanism of spent lithium ion batteries recovery. Journal of hazardous materials, 404, 123947.
[7]. Gao, W., Liu, C., Cao, H., Zheng, X., Lin, X., Wang, H., and Sun, Z. (2018). Comprehensive evaluation on effective leaching of critical metals from spent lithium-ion batteries. Waste management, 75, 477-485.
[8]. Liu, F., Peng, C., Ma, Q., Wang, J., Zhou, S., Chen, Z., and Lundström, M. (2021). Selective lithium recovery and integrated preparation of high-purity lithium hydroxide products from spent lithium-ion batteries. Separation and Purification Technology, 259, 118181.
[9]. Chen, X., Guo, C., Ma, H., Li, J., Zhou, T., Cao, L., and Kang, D. (2018). Organic reductants based leaching: A sustainable process for the recovery of valuable metals from spent lithium ion batteries. Waste Management, 75, 459-468.
[10]. Billy, E., Joulié, M., Laucournet, R., Boulineau, A., De Vito, E., and Meyer, D. (2018). Dissolution mechanisms of LiNi1/3Mn1/3Co1/3O2 positive electrode material from lithium-ion batteries in acid solution. ACS applied materials & interfaces. 10 (19): 16424-16435.
[11]. Sommerville, R., Zhu, P., Rajaeifar, M. A., Heidrich, O., Goodship, V., and Kendrick, E. (2021). A qualitative assessment of lithium ion battery recycling processes. Resources, Conservation and Recycling, 165, 105219.
[12]. Li, J., He, Y., Fu, Y., Xie, W., Feng, Y., and Alejandro, K. (2021). Hydrometallurgical enhanced liberation and recovery of anode material from spent lithium-ion batteries. Waste Management, 126, 517-526.
[13]. Meng, F., Liu, Q., Kim, R., Wang, J., Liu, G., and Ghahreman, A. (2020). Selective recovery of valuable metals from industrial waste lithium-ion batteries using citric acid under reductive conditions: Leaching optimization and kinetic analysis. Hydrometallurgy, 191, 105160.
[14]. Zhang, X., Bian, Y., Xu, S., Fan, E., Xue, Q., Guan, Y., and Chen, R. (2018). Innovative application of acid leaching to regenerate Li (Ni1/3Co1/3Mn1/3) O2 cathodes from spent lithium-ion batteries. ACS Sustainable Chemistry & Engineering. 6 (5): 5959-5968.
[15]. Zheng, Y., Song, W., Mo, W.t., Zhou, L., and Liu, J.W. (2018). Lithium fluoride recovery from cathode material of spent lithium-ion battery. RSC advances. 8 (16): 8990-8998.
[16]. Wang, C., Wang, S., Yan, F., Zhang, Z., Shen, X., and Zhang, Z. (2020). Recycling of spent lithium-ion batteries: Selective ammonia leaching of valuable metals and simultaneous synthesis of high-purity manganese carbonate. Waste Management, 114, 253-262.
[17]. Tang, Y., Zhang, B., Xie, H., Qu, X., Xing, P., and Yin, H. (2020). Recovery and regeneration of lithium cobalt oxide from spent lithium-ion batteries through a low-temperature ammonium sulfate roasting approach. Journal of Power Sources, 474, 228596.
[18]. Zhang, X., Li, L., Fan, E., Xue, Q., Bian, Y., Wu, F., and Chen, R. (2018). Toward sustainable and systematic recycling of spent rechargeable batteries. Chemical Society Reviews. 47 (19): 7239-7302.
[19]. Guo, Y., Li, F., Zhu, H., Li, G., Huang, J., and He, W. (2016). Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl). Waste Management, 51, 227-233.
[20]. He, L.P., Sun, S.Y., Song, X.F., and Yu, J.G. (2017). Leaching process for recovering valuable metals from the LiNi1/3Co1/3Mn1/3O2 cathode of lithium-ion batteries. Waste management, 64, 171-181.
[21]. Chen, X., Ma, H., Luo, C., and Zhou, T. (2017). Recovery of valuable metals from waste cathode materials of spent lithium-ion batteries using mild phosphoric acid. Journal of hazardous materials, 326, 77-86.
[22]. Lee, C.K., and Rhee, K.I. (2003). Reductive leaching of cathodic active materials from lithium ion battery wastes. Hydrometallurgy. 68 (1-3): 5-10.
[23]. Yao, L., Feng, Y., and Xi, G. (2015). A new method for the synthesis of LiNi 1/3 Co 1/3 Mn 1/3 O 2 from waste lithium ion batteries. RSC advances. 5 (55): 44107-44114.
[24]. Nayaka, G., Pai, K., Santhosh, G., and Manjanna, J. (2016). Dissolution of cathode active material of spent Li-ion batteries using tartaric acid and ascorbic acid mixture to recover Co. Hydrometallurgy, 161, 54-57.
[25]. Roshanfar, M., Golmohammadzadeh, R., and Rashchi, F. (2019). An environmentally friendly method for recovery of lithium and cobalt from spent lithium-ion batteries using gluconic and lactic acids. Journal of Environmental Chemical Engineering. 7 (1): 102794.
[26]. Li, L., Ge, J., Chen, R., Wu, F., Chen, S., and Zhang, X. (2010). Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries. Waste Management. 30 (12): 2615-2621.
[27]. Chen, X., Luo, C., Zhang, J., Kong, J., and Zhou, T. (2015). Sustainable recovery of metals from spent lithium-ion batteries: a green process. ACS Sustainable Chemistry & Engineering. 3 (12): 3104-3113.
[28]. Li, L., Fan, E., Guan, Y., Zhang, X., Xue, Q., Wei, L., and Chen, R. (2017). Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system. ACS Sustainable Chemistry & Engineering, 5(6): 5224-5233.
[29]. Gao, W., Zhang, X., Zheng, X., Lin, X., Cao, H., Zhang, Y., and Sun, Z. (2017). Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: a closed-loop process. Environmental science and technology. 51 (3): 1662-1669.
[30]. He, L.P., Sun, S.Y., Mu, Y.Y., Song, X.F., and Yu, J.G. (2017). Recovery of lithium, nickel, cobalt, and manganese from spent lithium-ion batteries using L-tartaric acid as a leachant. ACS Sustainable Chemistry and Engineering. 5 (1): 714-721.
[31]. Li, L., Qu, W., Zhang, X., Lu, J., Chen, R., Wu, F., and Amine, K. (2015). Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries. Journal of Power Sources, 282, 544-551.
[32]. Meshram, P., Pandey, B., and Mankhand, T. (2015). Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching. Chemical Engineering Journal, 281, 418-427.
[33]. Sung, M.H., Park, C., Kim, C.J., Poo, H., Soda, K., and Ashiuchi, M. (2005). Natural and edible biopolymer poly‐γ‐glutamic acid: synthesis, production, and applications. The Chemical Record. 5 (6): 352-366.
[34]. Fu, Y., He, Y., Li, J., Qu, L., Yang, Y., Guo, X., and Xie, W. (2020). Improved hydrometallurgical extraction of valuable metals from spent lithium-ion batteries via a closed-loop process. Journal of Alloys and Compounds, 847, 156489.
[35]. Ku, H., Jung, Y., Jo, M., Park, S., Kim, S., Yang, D., and Kwon, K. (2016). Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching. Journal of hazardous materials, 313, 138-146.
[36]. Zhu, B., Zhang, Y., Zou, Y., Yang, Z., Zhang, B., Zhao, Y., and Dong, P. (2021). Leaching kinetics and interface reaction of LiNi0. 6Co0. 2Mn0. 2O2 materials from spent LIBs using GKB as reductant. Journal of Environmental Management, 300, 113710.
[37]. Dutta, D., Kumari, A., Panda, R., Jha, S., Gupta, D., Goel, S., and Jha, M.K. (2018). Close loop separation process for the recovery of Co, Cu, Mn, Fe and Li from spent lithium-ion batteries. Separation and Purification Technology, 200, 327-334.
[38]. Zhou, S., Zhang, Y., Meng, Q., Dong, P., Fei, Z., and Li, Q. (2021). Recycling of LiCoO2 cathode material from spent lithium ion batteries by ultrasonic enhanced leaching and one-step regeneration. Journal of Environmental Management, 277, 111426.
[39]. Weissman, S.A., and Anderson, N.G. (2015). Design of experiments (DoE) and process optimization. A review of recent publications. Organic Process Research & Development. 19 (11): 1605-1633.
[40]. Yang, Y., Huang, G., Xu, S., He, Y., and Liu, X. (2016). Thermal treatment process for the recovery of valuable metals from spent lithium-ion batteries. Hydrometallurgy, 165, 390-396.
[41]. Kettler, R.M., Wesolowski, D.J., and Palmer, D.A. (1992). Dissociation quotients of malonic acid in aqueous sodium chloride media to 100 C. Journal of solution chemistry. 21 (8): 883-900.
[42]. Hamborg, E.S., Niederer, J.P., and Versteeg, G.F. (2007). Dissociation constants and thermodynamic properties of amino acids used in CO2 absorption from (293 to 353) K. Journal of Chemical & Engineering Data. 52 (6): 2491-2502.
[43]. Chen, W.S., and Ho, H.J. (2018). Recovery of valuable metals from lithium-ion batteries NMC cathode waste materials by hydrometallurgical methods. Metals. 8 (5): 321.
[44]. Golmohammadzadeh, R., Faraji, F., and Rashchi, F. (2018). Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review. Resources, Conservation and Recycling, 136, 418-435.
[45]. Aboyeji, O., Oloke, J., Arinkoola, A., Oke, M., and Ishola, M. (2020). Optimization of media components and fermentation conditions for citric acid production from sweet potato peel starch hydrolysate by Aspergillus niger. Scientific African, 10, e00554.