Cell formation is an energy and time-intensive empirically-guided process crucial to manufacturing secondary lithium-ion batteries. As the rechargeable battery industry moves towards manufacturing lithium metal batteries—where a metallic lithium negative electrode is used instead of a porous graphite composite—the cell formation process may need reconsidering. The effects of formation rate and cycling protocol on lithium metal battery performance are poorly understood. In this work, we used operando acoustic transmission to measure physical changes during the formation cycles and the effect of formation cycling protocols on the long-term cycling of anode-free lithium metal pouch cells—where all the lithium inventory comes from the positive electrode and is deposited as metallic lithium on copper foil during initial charge. We show that a faster C/3 formation protocol results in comparable cycling performance and cell stiffness change to a slower C/10 formation step. Variations in acoustic metrics across different electrolytes tested are attributed to differences in gas formation, cell swelling, and lithium deposition morphology. NMC811 cathodes paired with a high-concentration ether electrolyte are shown to be particularly prone to gas formation, which is mitigated by using a localized high-concentration ether electrolyte and single-crystal NMC532. The results highlight differences in formation behavior between anode-free lithium metal cells and lithium-ion cells. These are important to consider when bringing new manufacturing plants online for lithium metal batteries.
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