A1-Triple I: Any galvanic cell functions by compartmentalizing, via the electron-blocking electrolyte, an exothermic chemical reaction into two redox half-reactions to force release of the reaction free energy as electrical energy. The conventional electrolyte is an ion-conductor shuttling the operative ions and preventing any other chemical exchange to maintain the integrity and reversibility of the electrodes. In overcoming the capacity ceiling of layered intercalation hosts, conversion reactions between low-cost chalcogens (sulfur, selenium, and oxygen) and alkali metals (lithium and sodium) have been investigated for decades. However, parasitic crossover of soluble polychalcogenides limit battery cycle life. We conceptualize that selective solute transport at the interface of partially miscible solvents can be utilized in designing organic electrolytes to suppress parasitic crossover in precipitation-dissolution battery chemistries. This talk will discuss successful concept-demonstration experiments and highlight intriguing physical phenomena within such electrolyte system under the dynamics of electrochemistry.