Li‐CO ₂ batteries could skillfully combine the reduction of “greenhouse effect” with energy storage systems. However, Li‐CO ₂ batteries still suffer from unsatisfactory electrochemical performances and their rechargeability is challenged. Here, it is reported that a composite of Ni nanoparticles highly dispersed on N‐doped graphene (Ni‐NG) with 3D porous structure, exhibits a superior discharge capacity of 17 625 mA h g ⁻¹ , as the air cathode for Li‐CO ₂ batteries. The batteries with these highly efficient cathodes could sustain 100 cycles at a cutoff capacity of 1000 mA h g ⁻¹ with low overpotentials at the current density of 100 mA g ⁻¹ . Particularly, the Ni‐NG cathodes allow to observe the appearance/disappearance of agglomerated Li ₂ CO ₃ particles and carbon thin films directly upon discharge/charge processes. In addition, the recycle of CO ₂ is detected through in situ differential electrochemical mass spectrometry. This is a critical step to verify the electrochemical rechargeability of Li‐CO ₂ batteries. Also, first‐principles computations further prove that Ni nanoparticles are active sites for the reaction of Li and CO ₂ , which could guide to design more advantageous catalysts for rechargeable Li‐CO ₂ batteries.

IrO₂ nanoparticles highly dispersed on N-doped carbon nanotubes pave a promising way to deploy an efficient cathode catalyst for ultralong-life Li–CO₂ batteries.

In this work, we present a facile sol–gel method to prepare a composite of Co nanoparticles highly dispersed on N-rich carbon substrates (Co–C composite). The assembled Li–O₂ batteries with the composite as a cathode catalyst showed lower overpotential and better cyclability, and the improved performance may be attributed to the superior electrocatalytic activity of the Co–C composite.