Hydrometallurgical methods for the recycling of valuable metals from industrially produced lithium ion battery waste

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School of Chemical Engineering | Doctoral thesis (article-based) | Defence date: 2020-02-21
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Date

2020

Department

Kemian tekniikan ja metallurgian laitos
Department of Chemical and Metallurgical Engineering

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Mcode

Degree programme

Language

en

Pages

66 + app. 65

Series

Aalto University publication series DOCTORAL DISSERTATIONS, 29/2020

Abstract

With the continued growth in lithium ion batteries (LIBs) usage in recent years, the recycling of spent LIBs has become more urgent due to the increased demand for critical metals and growing environmental pressures. Although a wide range of investigations has been undertaken, the majority have focused on treatment of manually dismantled batteries that do not represent large-scale industrial practice. In the present work, industrially processed LIB waste was treated hydrometallurgically via reductive acid leaching and purification steps that allowed for the subsequent recovery of valuable metals. Acid leaching of industrial LIB waste containing both active materials and metallic components was compared with waste that contained only fine powders of cathode materials. Results revealed that metallic components present in LIB waste could act as reductants that increased Li and Co acid dissolution whereas, Cu was found in both the leaching solution (~60%) and leach residue (~40%). In order to improve the total recovery of valuable metals, ascorbic acid (C6H8O6) and large-size overflow fractions that contained 16 wt% Al, 12 wt% Cu, 8.4 wt% Co, and 1.4 wt% Li were investigated as additives. With ascorbic acid, selective extraction of Li and Co (> 99%) vs. Cu (0.1%) could be achieved, resulting in a Cu-rich leach residue (~12 wt% Cu). Addition of large-size overflow fractions, increased Co and Li dissolution to > 99% as the attached Li and Co in these fractions was also simultaneously recovered. The multi-metal pregnant leaching solution (PLS) produced was subsequently purified prior to Mn and Li recovery. High-purity MnO2 was obtained by oxidative precipitation with a stoichiometric amount of KMnO4 following the Mn separation from other elements - particularly Fe and Co - by solvent extraction and selective stripping. Co/Ni was then recovered via a solvent extraction-electrowinning process that resulted in a Li-rich raffinate. Recovery of Li2CO3 following evaporation was investigated, but due to LiNaSO4 crystal formation high losses occur. In comparison, Li recovery as high purity Li3PO4 was more efficient, as 92% was recovered under optimal conditions. Nevertheless, the residual waste solution after Li recovery has high Na+ and SO42- levels that pose a challenge to disposal. Consequently, a novel method that utilizes nickel-metal hydride (NiMH) waste into the LIB recycling system that results in the synergistic leaching of LIB and NiMH was explored. The PLS produced underwent rare earth elements (REEs) recovery by double sulfate precipitation, followed by Co, Ni, and Li. The resultant sulfate waste solution containing Na+, Li+, SO42- and OH-, was used to produce Na2SO4 and NaOH that can be utilized for REE recovery. Through this process, savings of up to 1.8 t of reducing additive (35% H2O2) and 0.8 t of precipitant (Na2SO4) were expected. Moreover, issues related to the disposal of Li-bearing leftover waste solution were solved.

Description

Supervising professor

Lundström, Mari, Prof., Aalto University, Department of Chemical and Metallurgical Engineering, Finland

Thesis advisor

Wilson, Benjamin, Dr., Aalto University, Department of Chemical and Metallurgical Engineering, Finland

Keywords

spent lithium-ion battery, hydrometallurgy, recycling, metal circular economy

Other note

Parts

  • [Publication 1]: Chao Peng, Joseph Hamuyuni, Benjamin P. Wilson, Mari Lundström. Selective reductive leaching of cobalt and lithium from industrially crushed waste Li-ion batteries in sulfuric acid system. Waste Management, 2018, volume 76, Page 582-590.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-201808014113
    DOI: 10.1016/j.wasman.2018.02.052 View at publisher
  • [Publication 2]: Chao Peng, Fupeng Liu, Arif T. Aji, Benjamin P. Wilson, Mari Lundström. Extraction of Li and Co from industrially produced Li-ion battery waste - Using the reductive power of waste itself. Waste Management, 2019, volume 95, Page 604-611.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-201907304450
    DOI: 10.1016/j.wasman.2019.06.048 View at publisher
  • [Publication 3]: Chao Peng, Cong Chang, Zulin Wang, Benjamin P. Wilson, Fupeng Liu, Mari Lundström. Recovery of high-purity MnO2 from the acid leaching solution of spent Li-ion batteries. JOM - The Journal of The Minerals, 2020, volume 72, Page 790-799.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-201910015552
    DOI: 10.1007/s11837-019-03785-1 View at publisher
  • [Publication 4]: Fupeng Liu, Chao Peng, Antti Porvali, Zulin Wang, Benjamin P. Wilson, Mari Lundström. Synergistic Recovery of Valuable Metals from Spent Nickel−Metal Hydride Batteries and Lithium-Ion Batteries. ACS Sustainable Chemistry and Engineering, 2019, volume 7, 16103-16111.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-201910015545
    DOI: 10.1021/acssuschemeng.9b02863 View at publisher

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https://urn.fi/URN:ISBN:978-952-60-8957-7

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[diss] Kemian tekniikan korkeakoulu / CHEM