With the large-scale application of lithium-ion batteries (LIBs), a huge amount of spent LIBs will be generated each year and how to realize their recycling and reuse in a clean and effective way poses a challenge to the society. In this work, using the electrolyte of spent LIBs as solvent, we in situ fluorinate the conductive three-dimensional porous copper foam by a facile solvent-thermal method and then coating it with a cross-linked sodium alginate (SA) layer. Benefiting from the solid-electrolyte interphase (SEI) that accommodating the volume change of internal CuF2 core and SA layer that inhibiting the dissolution of CuF2, the synthesized CuF2@void@SEI@SA cathode with a pomegranate-like structure (yolk-shell) exhibits a large reversible capacity of ~535 mAh g-1 at 0.05 A g-1 and superb cycling stability. This work conforms to the development concept of green environmental protection and comprehensively realizes the unity of environmental, social and economic benefits.