The recycling of spent lithium-ion batteries can effectively mitigate the environmental and resource challenges arising from the escalating generation of battery waste and the soaring demand for battery metals. The existing mixing-then-separating recycling process is confronted with high entropy-increasing procedures, including crushing and leaching, which result in irreversible entropy production due to the decrease in material orderliness or heavy chemical consumption, thereby hindering its thermodynamic efficiency and economic viability of the entire recycling process. Herein, we propose a galvanic leaching strategy that leverages the self-assembly of LiNi