On the oxidation state of manganese ions in li-ion battery electrolyte solutions

We demonstrate herein that Mn³⁺ and not Mn²⁺, as commonly accepted, is the dominant dissolved manganese cation in LiPF6-based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn³⁺ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn³⁺ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn3+ occurs at a very slow rate.