Dendrite formation in Li-metal anodes: an atomistic molecular dynamics study

Lithium-metal is a desired material for anodes of Li-ion and beyond Li-ion batteries because of its large theoretical specific capacity of 3860 mA h g^-1 (the highest known so far), low density, and extremely low potential. Unfortunately, there are several problems that restrict the practical application of lithium-metal anodes, such as the formation of dendrites and reactivity with electrolytes. We present here a study of lithium dendrite formation on a Li-metal anode covered by a cracked solid electrolyte interface (SEI) of LiF in contact with a typical liquid electrolyte composed of 1 M LiPF₆ salt solvated in ethylene carbonate. The study uses classical molecular dynamics on a model nanobattery. We tested three ways to charge the nanobattery: (1) constant current at a rate of one Li⁺ per 0.4 ps, (2) pulse train 10 Li⁺ per 4 ps, and (3) constant number ions in the electrolyte: one Li⁺ enters the electrolyte from the cathode as one Li⁺ exits the electrolyte to the anode. We found that although the SEI does not interfere with the lithiation, the mere presence of a crack in the SEI boosts and guides dendrite formation at temperatures between 325 K and 410.7 K at any C-rate, being more favorable at 325 K than at 410.7 K. On the other hand, we find that a higher C-rate (2.2C) favors the lithium dendrite formation compared to a lower C-rate (1.6C). Thus the battery could store more energy in a safe way at a lower C-rate.