A new general approach to the direct formation of bipolar devices from heterogeneous colloids is suggested. By using surface-force theory and direct measurements, combinations of conductive device materials between which short-range repulsive forces exist in the presence of an intervening liquid, and use these interactions to self-form electrochemical junctions are identified. The inclusion of Lifshitz-van der Waals (LW) and acid-base (AB) interactions appears to be generally sufficient for the prediction of short-range interactions. Device concepts using repulsive and attractive short-range interactions to produce self-organizing colloidal-scale devices are proposed and demonstrated. A prototype self-organizing lithium rechargeable battery is demonstrated using lithium cobalt oxide (LiCoO2) and graphite as the active electrode materials.