Electro-winning of active metal (e.g., lithium) ions from a variety of sources including industrial waste, and recycled lithium and lithium-ion batteries is accomplished with an electrolyzer having a protected cathode that is stable against aggressive solvents, including water, aqueous electrolytes, acid, base, and a broad range of protic and aprotic solvents. The electrolyzer has a highly ionically conductive protective membrane adjacent to the alkali metal cathode that effectively isolates (de-couples) the alkali metal electrode from solvent, electrolyte processing and/or cathode environments, and at the same time allows ion transport in and out of these environments. Isolation of the cathode from other components of a battery cell or other electrochemical cell in this way allows the use of virtually any solvent, electrolyte and/or anode material in conjunction with the cathode. The electrolyzer can be configured and operated to claim or reclaim lithium or other active metals from such sources.