Anode-free Li-metal batteries are of significant interest to energy storage industries due to their intrinsically high energy. However, the accumulative Li dendrites and dead Li continuously consume active Li during cycling. That results in a short lifetime and low Coulombic efficiency of anode-free Li-metal batteries. Introducing effective electrolyte additives can improve the Li deposition homogeneity and solid electrolyte interphase (SEI) stability for anode-free Li-metal batteries. Herein, we reveal that introducing dual additives, composed of LiAsF₆ and fluoroethylene carbonate, into a low-cost commercial carbonate electrolyte will boost the cycle life and average Coulombic efficiency of NMC||Cu anode-free Li-metal batteries. The NMC||Cu anode-free Li-metal batteries with the dual additives exhibit a capacity retention of about 75% after 50 cycles, much higher than those with bare electrolytes (35%). The average Coulombic efficiency of the NMC||Cu anode-free Li-metal batteries with additives can maintain 98.3% over 100 cycles. In contrast, the average Coulombic efficiency without additives rapidly decline to 97% after only 50 cycles. In situ Raman measurements reveal that the prepared dual additives facilitate denser and smoother Li morphology during Li deposition. The dual additives significantly suppress the Li dendrite growth, enabling stable SEI formation on anode and cathode surfaces. Our results provide a broad view of developing low-cost and high-effective functional electrolytes for high-energy and long-life anode-free Li-metal batteries.

Lithium-rich oxide compounds have been recognized as promising cathode materials for high performance Li-ion batteries, owing to their high specific capacity. However, it remains a great challenge to achieve the fully reversible anionic redox reactions to realize high capacity, high stability, and low voltage hysteresis for lithium-rich cathode materials. Therefore, it is critically important to comprehensively understand and control the anionic redox chemistry of lithium-rich cathode materials, including atomic structure design, and nano-scale materials engineering technologies. Herein, we summarize the recent research progress of lithium-rich cathode materials with a focus on redox chemistry. Particularly, we highlight the oxygen-based redox reactions in lithium-rich metal oxides, with critical views of designing next generation oxygen redox lithium cathode materials. Furthermore, we purposed the most promising strategies for improving the performances of lithium-rich cathode materials with a technology-spectrum from the atomic scale to nano-scale.