• The unique layered structure and excellent photoelectric properties of MoS2 facilitate abundant generation and rapid transfer of photo-excited carriers, accelerating CO2 reduction and Li2CO3 decomposition upon illumination.
• MoS2-based photo-energized Li–CO2 battery displays ultra-low charge voltage of 3.27 V, high energy efficiency of 90.2%, superior cycling stability after 120 cycles, and high rate capability.
• The low-temperature Li–CO2 battery achieves an ultra-low charge voltage of 3.4 V at –30 °C with a round-trip efficiency of 86.6%.
• The photoelectric and photothermal synergistic mechanism of MoS2/CNT cathode enables wide-temperature operation without electrolyte replacement, addressing charge overpotential and energy efficiency challenges.