The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes.

Much theoretical effort has been spent on the causes of dendrite formation in lithium metal batteries, but a decisive factor has been overlooked: Lithium is deposited on an electrode which carries a sizable negative charge, and this charge is not distributed homogeneously on the surface. We show by explicit model calculations that the excess charge accumulates on small protrusions and creates a strong electric field, which attracts the Li+ ions and induces further growth on the tip and finally the formation of dendrites. Even a small tip consisting of a few atoms will carry an excess charge of a tenth of a unit charge or more. In addition, the negative charge on the tips locally reduces the surface tension, which further fosters dendrite growth. The same principles can also explain dendrite formation on other metals with deposition potentials below the potential of zero charge.