Important Impact of the Slurry Mixing Speed on Water-Processed Li₄Ti₅O₁₂ Lithium-Ion Anodes in the Presence of H₃PO₄ as the Processing Additive

The aqueous processing of lithium transition metal oxides into battery electrodes is attracting a lot of attention as it would allow for avoiding the use of harmful N-methyl-2-pyrrolidone (NMP) from the cell fabrication process and, thus, render it more sustainable. The addition of slurry additives, for instance phosphoric acid (PA), has been proven to be highly effective for overcoming the corresponding challenges such as aluminum current collector corrosion and stabilization of the active material particle. Herein, a comprehensive investigation of the effect of the ball-milling speed on the effectiveness of PA as a slurry additive is reported using Li4Ti5O12 (LTO) as an exemplary lithium transition metal oxide. Interestingly, at elevated ball-milling speeds, rod-shaped lithium phosphate particles are formed, which remain absent at lower ball-milling speeds. A detailed surface characterization by means of SEM, EDX, HRTEM, STEM-EDX, XPS, and EIS revealed that in the latter case, a thin protective phosphate layer is formed on the LTO particles, leading to an improved electrochemical performance. As a result, the corresponding lithium-ion cells comprising LTO anodes and LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes reveal greater long-term cycling stability and higher capacity retention after more than 800 cycles. This superior performance originates from the less resistive electrode–electrolyte interphase evolving upon cycling, owing to the interface-stabilizing effect of the lithium phosphate coating formed during electrode preparation. The results highlight the importance of commonly neglected─frequently not even reported─electrode preparation parameters.