An electrorefining process for refining relatively purer lithium metal from a lithium-alloy feedstock material using a three-layer electrorefining apparatus can include a) providing an anode layer comprising a molten, lithium-alloy feedstock material that includes a combination of lithium metal having a first purity and a carrier material; b) providing an electrolyte layer comprising a molten salt electrolyte material; c) providing a product layer comprising molten lithium metal having a second purity that is greater than the first purity above the electrolyte layer; and d) applying an activation electric potential that is sufficient to electrolyze the lithium-alloy feedstock material between an anode layer and the product layer that is electrically isolated from the anode layer, whereby lithium metal is liberated from the lithium-alloy feedstock material, migrates through the electrolyte layer and collects in the product layer.