Insights from incorporating reference electrodes in symmetric lithium-ion cells with layered oxide or graphite electrodes

Symmetric cells provide complementary means to probe electrochemical processes in lithium-ion batteries. Here, positive and negative electrodes harvested from conventional oxide/graphite cells are cross-paired, and the assembled reference-electrode-bearing symmetric cells are cycled/aged. For graphite symmetric cells, the electrode potentials and impedances remain nearly constant during calendar aging and the parasitic currents are typically small. However, at higher cell voltages when the “positive” graphite potential exceeds 1.0 V vs. Li/Li+, the capacity loss is higher, indicating that even a mild (but prolonged) overdischarge can damage the SEI. For the layered-oxide symmetric cells there are strong parasitic currents and a persistent slide of the electrode potential over time during calendar aging. Significant cell impedance rise, especially at higher hold voltages, is also observed. Curiously, the impedance rise in the “negative” oxide electrode, which experiences potentials below 4.0 V vs. Li/Li+, is greater than in the “positive” oxide electrode that experiences much higher potentials. We postulate that electrolyte oxidation is responsible for the behavior of these oxide symmetric cells, as it supplies electrons (that bind more Li+ into the cathode, causing the potential slide) and protons (that contribute to impedance rise). These insights can guide the development of future lithium-ion cell chemistries.