As the currently available methods for recycling of valuable metals from batteries and old electronics (commonly called eWaste) are in need of improvement, this project focuses on the development of a novel valuable metals recovery method by electrolysis in molten salts. The process proposed consists of three steps: metal oxides dissolution in borate salts, liquid-liquid interface ion transfer between the borate and chloride layer, and electrodeposition from the chloride phase. Inherent borate salts stability and its affinity to metals, coupled with the chloride salts large electrochemical window enables a stable and efficient (semi)-continuous process concept to be explored. Two electrolytic cell concepts akin to an industrial set-up were designed. The first composed of three interconnected chambers each for one of the three steps of the process, or a simpler, single-vessel solution relying on the immiscibility of the molten phases. For the needs of a laboratory scale testing the smaller, one vessel solution has been assembled. The proposed recycling method is a novel solution for the recovery of valuable metals considered and evaluated in this work; Co, Cu, Ni, and Mn, present in most Li-ion and Ni-MH batteries, but also other metals suitable for electrodeposition present in the eWaste or other metal-rich waste streams. The process proposed was designed, evaluated and resulted in a successful recovery of all of the metals considered. Novel and promising experimental data on the metal oxides dissolution in molten borate salts is reported. Boron oxide salts were assessed, with the sodium borate achieving significant metals concentrations ranging from 4-20 wt%. Metals distribution between the oxide and halide layers was evaluated, and was found to be biased towards the borate layer due to its structure resulting in high metal affinity, with the metal ions concentration in the chloride layer around 1 wt% for the evaluated salts combination. This enables the sodium borate phase to work as a buffer, feeding the dissolved metal required for the electrodeposition into the chloride layer sustaining the process. Liquid-liquid interface transfer and diffusion phenomena in the melt as well as the metal electrodeposition parameters were studied using a range of (electro)-analytical methods, validating the main steps of the proposed metal recovery process. The system was evaluated in a three-electrode set-up (WE: tungsten, CE; graphite, QRE: tungsten) and the formal redox reaction potentials were reported for the following feedstock: Co2O3 [-0.733/-1.848 V], CuO [-1.297/-2.375 V], Mn2O3 [-1.552 V] and NiO [-1.734 V] versus chlorine evolution. The recovered metals were analysed and found to form high purity (~99 %) dendritic deposits (SA/V of 950 cm-1), which also supports the assumption of a diffusion controlled process. This marks the successful outcome of this proof-of-concept process, providing a feasible, alternative valuable metals recovery method design.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:714916 |
| Date | January 2016 |
| Creators | Amietszajew, Tazdin |
| Publisher | University of Warwick |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://wrap.warwick.ac.uk/88531/ |
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