Can Layered Oxide/Hard Carbon Sodium-Ion Pouch Cells with Simple Electrolyte Additives Achieve Better Cycle Life than LFP/Graphite Cells?

Abstract

This study explores the impact of simple electrolyte additives on the performance of layered oxide/hard carbon sodium-ion pouch cells. The cycle life of these cells between 2.0 and 3.8 V is assessed at various temperatures (20, 40, and 55 °C) with different solvent systems based on ethylene carbonate, diethyl carbonate, and dimethyl carbonate. A particular challenge in these cells is gas generation at high temperature. Pouch bag experiments which separate the charged electrodes to measure their gas generation from reactions with the electrolyte show that hard carbon generates no gas, but the sodium layered oxide produces large amounts of gas. Isothermal microcalorimetry corroborates these results with parasitic heat flow measurements of pouch bags and full pouch cells. A crosstalk mechanism is revealed which lowers gas generation and reduces parasitic heat flows in full cells. The electrolyte additives prop-1-ene-1,3-sultone, sodium difluorophosphate, and 1,3,2-dioxathiolane-2,2-dioxide (DTD) are effective at reducing gas generation and heat flow from the positive electrode. They also reduce self-discharge in elevated temperature storage tests. Overall, 1 M NaFSI in EC:DMC (15:85) with 2% DTD is the best electrolyte for the sodium-ion pouch cells in this work. Eventually, the performance of these cells is compared to optimized LiFePO4/graphite cells.