Li metal can potentially deliver much higher specific capacity than commercially used anodes. Nevertheless, because of its poor reversibility, abundant excess Li (usually more than three times) is required in Li metal batteries, leading to higher costs and decreased energy density. Here, a concentrated lithium bis(trifluoromethane sulfonyl) imide (LiTFSI)–lithium nitrate (LiNO3)–lithium bis(fluorosulfonyl)imide (LiFSI) ternary‐salts electrolyte is introduced to realize a high stable Li metal full‐cell with only a slight excess of Li. LiNO3 and LiFSI contribute to the formation of stable Li2O–LiF‐rich solid electrolyte interface layers, and LiTFSI helps to stabilize the electrolyte under high concentration. Li metal in the electrolyte remains stable over 450 cycles and the average Coulombic efficiency reaches 99.1%. Moreover, with 0.5 × excess Li metal, the Coulombic efficiency of Li metal in the LiTFSI–LiNO3–LiFSI reaches 99.4%. The electrolyte also presents high stability to the LiFePO4 cathode, the capacity retention after 500 cycles is 92.0% and the Coulombic efficiency is 99.8%. A Li metal full‐cell with only 0.44 × excess Li is also assembled, it remains stable over 70 cycles and 83% of the initial capacity is maintained after 100 cycles.

Metal–CO2 batteries, especially Li–CO2 and Na–CO2 batteries, offer a novel and attractive strategy for CO2 capture as well as energy conversion and storage with high specific energy densities. However, some scientific issues and challenges existing restrict their practical applications. Here, recent progress of crucial reaction mechanisms on cathodes in Li–CO2 and Na–CO2 batteries are summarized. The detailed reaction pathways can be modified by operation conditions, electrolyte compositions, and catalysts. Besides, specific discussions from aspects of catalyst design, stability of electrolytes, and anode protection are presented. Perspectives of several innovative directions are also put forward. This review provides an intensive understanding of Li–CO2 and Na–CO2 batteries and gives a useful guideline for the practical development of metal–CO2 batteries and even metal–air batteries.

The Li-CO 2 battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. However, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber-shaped Li-CO 2 batteries with ultralong cycle-life, high rate capability, and large specific capacity are fabricated, employing bamboo-like N-doped carbon nanotube fiber (B-NCNT) as flexible, durable metal-free catalysts for both CO 2 reduction and evolution reactions. Benefiting from high N-doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo-like nodes, the fabricated Li-CO 2 battery shows outstanding electrochemical performance with high fulldischarge capacity of 23 328 mAh g −1 , high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g −1 , stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B-NCNT is used as the counter electrode for a fiber-shaped dye-sensitized solar cell to fabricate a self-powered fiber-shaped Li-CO 2 battery with overall photochemicalelectric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearable electronics with a breath monitor as an example.