Electrodialysis of Lithium Sulfate Solutions from Hydrometallurgical Recycling of Spent Lithium-Ion Batteries
Authors: Zhu Jiyong , Kang Dongxin , Jung Joey Chung-Yen , Sui Pang-Chieh 
Published: February 2024

Recycling lithium-ion battery materials is a crucial step to achieving a circular economy. A hydrometallurgical recycling process of spent lithium-ion battery materials involves leaching by acids and precipitation by bases. A large amount of Li2SO4 leachate solution is generated at the end of the recycling process. Such Li2SO4 solution can be separated by electrodialysis (ED) to form H2SO4 and LiOH solutions, which are reused for leaching and precipitation, respectively, making the recycling a closed-loop process. In this study, an ‘electrodialysis stack constructed with bipolar membranes’ (EDBM) is built with repetitive unit cells consisting of a bipolar membrane, anion exchange membrane (AEM), and cation exchange membrane (CEM), see Fig. 1(a). The effective area for each membrane is 121.8 cm2 (70mm×174mm). The gap between these membranes is 0.8mm, with a mesh inserted to allow flow mixing. All experiments were operated at constant current mode. The feed, acid, and base solutions were recirculated through their tanks at initial concentrations of 1.1, 0.1, and 0.1 mol/L. The ion concentrations of the solutions were measured with Inductively coupled plasma mass spectrometry periodically. The weight and the pH value of the solution tanks were also recorded.
The trend of concentration variations of the present stack with up to 6 cell pairs is found to be consistent with that observed with a three-compartment configuration in our previous study [1]. The concentration of H2SO4 increases with time linearly, whereas that of LiOH levels off due to a significant electro-osmosis that drags water through the CEM into the concentrate channel. The present setup differs from the three-compartment design in the bipolar membrane, which splits water to produce H+ and OH- at the internal interface, eliminating the formation of bubbly flows in the unit cell. It is found that the voltage loss across the bipolar membrane ca. 1V accounts for a major part of the unit cell of about 1.27V.
The effects of current density, number of cell pairs, and flow rates on the overall stack performance are investigated. Increasing the stack current density accelerates the separation process at the cost of higher voltage losses. It is found that increasing the number of cell pairs can improve the overall production efficiency and reduce energy consumption per cell pair. For instance, at 800 A/m2, the specific energy consumption for LiOH production is reduced to 3.40 kWh/kg with five cell pairs versus 5.83 kWh/kg with two cell pairs. It is also found that increasing the solution flow rate can result into the increase of LiOH solution concentration, ion recovery rate, and current efficiency (Fig. 1b), although the impact of flow rate is low.
A small EDBM stack is constructed and tested for Li2SO4 separation in the present study. This work demonstrates that EDBM can be a simple and energy-saving alternative to the current chemical precipitation method to produce LiOH from Li2SO4. The present study provides new insights into optimal operation and design for Li2SO4 EDBM. The findings are helpful in determining how the stack can be scaled up for practical application. Furthermore, a 2D multiphysics model is currently under development to elucidate the coupled transport processes within the unit cell. The model will be validated with experimental data of the present setup.

Figure 1