Towards an ultra-long lifespan Li-CO2: electron structure and charge transfer pathway regulation on hierarchical architecture

Strategies for changing the conductivity of Li 2 CO 3 is introduced into the fabrication of Li-CO 2 battery. Benefitting from the favorable hierarchical architecture constructed (CPM-MnO 2 ), facile charge transfer occurs between catalytic surface and Li 2 CO 3 by -OH…O hydrogen bonds improves the metallicity of Li 2 CO 3 , facilitating the formation/decomposition of Li 2 CO 3 and bestowing an ultra-long-term stability of 1087 cycles (4348 h). Taking into account its simplicity, scalable character and outstanding performance, this hierarchical composite electrode paves an effective trajectory for the future development of highly efficient cathodes for durable metal-CO 2 batteries. • Excellent hierarchical structure of MXene and MnO 2 on carbon paper was fabricated. • Enriched charge transfer occurred on MXene and the MnO 2 by OH…O hydrogen bonding. • The prepared batteries showed an ultra-long cycle lifetime and low overpotential. • The optimized electronic structure can improve the metallicity of Li 2 CO 3 . • The accelerated decomposition of discharge products promoted CRR and CER kinetics. Lithium-CO 2 batteries are recognized as an essential strategy for efficient carbon sequestration and energy storage to achieve carbon neutrality. Their cycle-ability and polarization voltage, however, are hindered by high decomposition voltage (≈ 4.3-4.5 V) of insulating Li 2 CO 3 . Herein, we report a significant advance toward the rational design of self-supporting and ultra-long cycle lifetime cathode for Li-CO 2 batteries, dependence on a favorable hierarchical architecture and rich charge transfer constructed by homogeneously distributed MnO 2 nanoplates rooted in the MXene surface supported by carbon paper. Detailedly, it exhibits impressive ultra-long-term stability of 1087 cycles (4348 h) with a low polarization gap (≈ 0.47 V) at a high current of 200 μA cm -2 , which is outperformed by all the liquid electrolyte-based Li-CO2 batteries reported previously. Electronic structure analysis reveals that facile charge transfer occurs between catalytic surface and Li 2 CO 3 , springing from the -OH functional group (in MXene) to MnO 2 by -OH…O hydrogen bonds, which acts as charge transfer channels, improving the metallicity of Li 2 CO 3 and facilitating its decomposition and extending battery cyclability. This work paves an effective trajectory for the future development of highly efficient cathodes for durable metal-CO 2 batteries.