Spent Battery Flows, Characterization and Recycling Processes

Spent Battery Flows, Characterization and Recycling Processes

N. Vieceli F. Pedrosa  F. Margarido  C.A. Nogueira 

Center for Innovation, Technology and Policy Research–IN+, Instituto Superior Técnico, University of Lisbon

LNEG - Laboratório Nacional de Energia e Geologia, I.P

30 September 2016
| Citation



Spent batteries are an important waste flow regarding the recovery of the contained metals motivated by economic, environmental and strategic reasons. The portable battery market is dominated by primary Zn-Mn cells, but the market of secondary batteries are continuously growing, with particular relevance for Li-ion batteries, used in practically all electronic devices. The batteries are metal concentrates, having metal grades such as 20%–30% of Zn, Mn, Co, Ni, depending on the battery system. These metals are specifically concentrated in the electrodes, which are the most important component of a battery. The most usual chemical forms of these metals in the electrodes are oxides or hydrated oxides, but other solid phases can be found such as metal alloys. The recycling of batteries can be done by pyrometallurgical and hydrometallurgical processes. The first one usually involves the distillation of some more volatile metals, such as Zn in Zn-Mn cells and Cd in Ni-Cd cells. For Ni-MH and Li-ion batteries, some pyrometallurgical approaches involve the melting and recovery of Ni or Co, but with losses of other metals (like lithium and rare earths). The hydrometallurgical alternative allows higher metal recovery rates, as practised industrially for Zn-Mn and Li-ion batteries. Many studies on alternative processes for recycling Li-ion batteries have been intensively carried out due to the special interest on these batteries nowadays and in the future.


battery characterization, battery market, battery processing, recycling, spent batteries


[1] Linden, D., (Chapters 8 and 10). Handbook of Batteries, 2nd ed., McGraw-Hill Inc.: New York, 1995.

[2] Nayaka, G.P.,Manjanna, J., Pai, K.V., Vadavi, R., Keny, S.J. & Tripathi, V.S., Recovery of valuable metal ions from the spent lithium-ion battery using aqueous mixture of mild organic acids as alternative to mineral acids. Hydrometallurgy, 151, pp. 73–77, 2015.

[3] Castillo, S., Ansart, F., Laberty-Robert, C. & Portal, J., “Advances in the recovering of spent lithium battery compounds”. Journal of Power Sources, 112(1), pp. 247–254, 2002. http://dx.doi.org/10.1016/S0378-7753(02)00361-0

[4] Chen, X., Zhou, T., Kong, J., Fang, H. & Chen, Y., Separation and recovery of metal values from leach liquor of waste lithium nickel cobalt manganese oxide based cathodes. Separation and Purification Technology, 141, pp. 76–83, 2015. http://dx.doi.org/10.1016/j.seppur.2014.11.039

[5] Ordoñez, J., Gago, E.J. & Girard,A., Processes and technologies for the recycling and recovery of spent lithium-ion batteries. Renewable and Sustainable Energy Reviews, 60, pp. 195–205, 2016.

[6] http://dx.doi.org/10.1016/j.rser.2015.12.363

[7] Cabral, M., Pedrosa, F., Margarido, F. & Nogueira, C.A., End-of-life Zn-MnO2batteries: electrode materials characterization. Environmental Technology, 34(10), pp. 1283–1295, 2013. http://dx.doi.org/10.1080/09593330.2012.745621

[8] Nogueira, C.A. & Margarido, F., Chemical and physical characterization of electrode materials of spent sealed Ni–Cd batteries. Waste Management, 27(11), pp. 1570–1579, 2007. http://dx.doi.org/10.1016/j.wasman.2006.10.007

[9] Cabral, M., Margarido, F. & Nogueira, C.A., Characterisation of spent Ni-MH batteries. Materials Science Forum, 730, pp. 569–574, 2013.

[10] Bertuol, D.A., Toniasso, C., Jimenez, B.M., Meili, L., Dotto, G.L., Tanabe, E.H. & Aguiar, M.L., Application of spouted bed elutriation in the recycling of lithium ion batteries. Journalof Power Sources, 275, pp. 627–632, 2015. http://dx.doi.org/10.1016/j.jpowsour.2014.11.036

[11] Li, L., Dunn, J.B., Zhang, X.X., Gaines, L., Chen, R.J., Wu, F. & Amine,K.,Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment. Journalof Power Sources, 233, pp. 180–189, 2013. http://dx.doi.org/10.1016/j.jpowsour.2012.12.089

[12] Chen, X., Chen, Y., Zhou, T., Liu, D., Hu,H. & Fan, S., Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries.Waste Management, 38, pp. 349–356, 2015. http://dx.doi.org/10.1016/j.wasman.2014.12.023

[13] Kang, J., Senanayake, G., Sohn, J. & Shin, S.M., Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272. Hydrometallurgy, 100(3–4), pp. 168–171, 2010. http://dx.doi.org/10.1016/j.hydromet.2009.10.010

[14] Espinosa, D.C.R., Bernardes, A.M. & Tenório, J.A.S., An overview on the current processes for the recycling of batteries. Journalof Power Sources, 135, pp. 311–319, 2004. http://dx.doi.org/10.1016/j.jpowsour.2004.03.083

[15] Sayilgan, E., Kukrer, T., Civelekoglu, G., Ferella, F., Akcil, A., Veglio,F. & Kitis, M., A review of technologies for the recovery of metals from spent alkaline and zinc–carbon batteries.Hydrometallurgy, 97, pp. 158–166, 2009. http://dx.doi.org/10.1016/j.hydromet.2009.02.008

[16] Beck, M., Batrec: recovering metals.Recycling International, pp. 24–27, 2004.

[17] Vollrath, K., Battery recycling in Europe: confusion and high costs. Recycling International, pp. 18–23, 1999.

[18] Frías, C., Martín, D., Díaz, G., Falgueras, J. & Baylina, V., Highlights of domestic battery recycling plant based on the modified Zincex process sfter five years successful operation. Proceeding of the REWAS 2004–Global Symp. on Recycling, Waste Treatment and Clean Technology, vol III, eds. I. Gaballah, B. Mishra, R. Solcjzahal & M. Tifnaka, TMS: Warredale, USA and INASMET: S. Sebastián, Spain, pp. 2299–2308.

[19] Tedjar, F., Recycling used electric cells by hydrometallurgical treatment, Int Patent Appl. WO 021708 A3, March 13, 2003.

[20] Linck, F., SNAM company update and recycling service.Proceedings of the 4th International Battery Recycling Congress, Hamburg: Germany, 1998.

[21] Bärring, N.E., Recycling of nickel-cadmium batteries and process wastes – processes and operations of the new SAB NIFE plant. Proceeding of 4th Internatonal Cadmium Conference, eds. D. Wilson & R.A. Volfre, Intern. Cadmium Assoc.: Brussels, pp. 58–60, 1983.

[22] Tedjar, F. & Foudraz, J.C., Method for the mixed recycling of lithium-based anode batteries and cells.Int. Patent Appl. WO 101564, October 26, 2010.

[23] Meshram, P., Pandey, B.D. & Mankhand, T.R., Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: a comprehensive review. Hydrometallurgy, 150, pp. 192–208, 2014. http://dx.doi.org/10.1016/j.hydromet.2014.10.012

[24] Li, L., Qu, W., Zhang, X., Lu, J., Chen, R., Wu, F. & Amine, K., Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries.Journalof Power Sources,282, pp. 544–551, 2015. http://dx.doi.org/10.1016/j.jpowsour.2015.02.073

[25] Chen, X., Fan, B., Xu, L., Zhou, T. & Kong, J., An atom-economic process for the recovery of high value-added metals from spent lithium-ion batteries,Journal of the Cleaner Production,112, pp. 3562–3570, 2016. http://dx.doi.org/10.1016/j.jclepro.2015.10.132

[26] Fan, B., Chen, X., Zhou, T., Zhang, J. & Xu, B., A sustainable process for the recovery of valuable metals from spent lithium-ion batteries.Waste Management& Research,pp. 1–8, 2016. http://dx.doi.org/10.1177/0734242x16634454

[27] Zeng, X., Li,J. & Shen, B., Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid. Journal of Hazardous Materials,295, pp. 112–118, 2015. http://dx.doi.org/10.1016/j.jhazmat.2015.02.064

[28] Ku, H., Jung, Y., Jo, M., Park, S., Kim, S., Yang, D., Rhee, K., An, E., Sohn, J. & Kwon, K., Recycling of spent lithium-ion battery cathode materials byammoniacal leaching. Journal of Hazardous Materials, 313, pp. 138–146, 2016. http://dx.doi.org/10.1016/j.jhazmat.2016.03.062

[29] Swain, B., Separation and purification of lithium by solvent extraction and supported liquid membrane, analysis of their mechanism: a review.Journal of Chemical Technology andBiotechnology, 2016.

[30] Wang, M., Zhang, C. & Zhang, F.,An environmental benign process for cobalt and lithium recovery from spent lithium-ion batteries by mechanochemical approach.Waste Management, 51, pp. 239–244, 2016. http://dx.doi.org/10.1016/j.wasman.2016.03.006

[31] Xin, Y., Guo, X., Chen, S., Wang, J., Wu, F. & Xin, B., Bioleaching of valuable metals Li, Co, Ni and Mn from spent electric vehicle Li-ion batteries for the purpose of recovery.Journal of Cleaner Production, 116, pp. 249–258, 2016. http://dx.doi.org/10.1016/j.jclepro.2016.01.001

[32] Zeng, G., Deng, X., Luo, S., Luo, X. & Zou, J., A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries.Journal of Hazardous Materials, 199–200, pp. 164–169, 2012. http://dx.doi.org/10.1016/j.jhazmat.2011.10.063

[33] Niu, Z., Zou, Y., Xin, B., Chen, S., Liu, C. & Li, Y., Process controls for improving bioleaching performance of both Li and Co from spent lithium ion batteries at high pulp density and its thermodynamics and kinetics exploration, Chemosphere, 109, pp. 92–98, 2014. http://dx.doi.org/10.1016/j.chemosphere.2014.02.059

[34] Zeng, X., Li, J. & Singh, N., Recycling of spent lithium-ion battery: a critical review. Critical Reviews in Environmental Science and Technology, 44, pp. 1129–1165, 2014. http://dx.doi.org/10.1080/10643389.2013.763578

[35] Bertuol, D.A., Machado, C.M., Silva, M.L., Calgaro, C.O., Dotto, G.L. & Tanabe, E.H., Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction.Waste Management, 51, pp. 245–251, 2016. http://dx.doi.org/10.1016/j.wasman.2016.03.009

[36] Yang, L., Xi, G. & Xi, Y., Recovery of Co, Mn, Ni, and Li from spent lithium ion batteries for the preparation of LiNixCoyMnzO2 cathode materials Li.Ceramics International, 41, pp. 11498–11503, 2015. http://dx.doi.org/10.1016/j.ceramint.2015.05.115

[37] Zeng, X. &Li, J., Innovative application of ionic liquid to separate Al and cathode materials from spent high-power lithium-ion, batteries.Journal of Hazardous Materials, 271, pp. 50–56, 2014. http://dx.doi.org/10.1016/j.jhazmat.2014.02.001