Abstract The safety behavior of lithium-ion cells using high contents of silicon as new anode active material was barely investigated. This work investigates the short-circuit behavior of self-manufactured single-layered pouch cells using 70%wt microscale silicon and NCA cathodes in a novel dual reference cell setup consisting of a gold wire and a lithium metal reference electrode. Six cells were externally shortened at three different compression levels using a novel developed quasi-isothermal calorimetric shortcircuit test bench. The same current plateaus and transition zones were observed for all pressure settings, as reported in the literature for graphite-containing anodes. In addition, a direct dependency of the short-circuit intensity and the heat generation is measured for the differently compressed cells. This higher short-circuit intensity was quantitatively explained by the decreasing impedance at increased pressure levels. The built-in reference electrodes allow for monitoring of the negative terminal voltage, revealing potentials of up to 3:508 V versus Li+/Li and thus explaining the measured over-discharge in the range of ≈25% SoC. The post-mortem analysis reveals copper deposition on both electrodes and the separator, confirming the electrochemically measured over-discharge. Linear scans and potential trajectories reveal 3.379 V versus Li+/Li as oxidation potential for copper dissolution using copper||lithium-metal coin cells.
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