the cycling of the Li metal anode, it is difficult for the conventional electrolyte to form stable and homogeneous solid electrolyte interphase (SEI) layer on the electrode to protect the interface, and the consequent incomplete SEI will further induce the growth of Li dendrites and finally cause cell failure. [7,8] Poor recyclability and serious safety problems have greatly hindered the commercialization of LMBs.So far, tremendous efforts have been invested to inhibit the growth of Li dendrites and boost the Coulombic efficiency (CE) of LMB, multiple methods such as constructing artificial SEI, [9] using 3D porous current collectors, [10] modifying separators, [11,12] optimizing electrolyte composition and forming Li-based alloys have been adopted. [13][14][15] From the perspective of commercialization potential, electrochemical performance, and environmental protection, adding the appropriate amount of additives to commercial carbonate electrolytes is undoubtedly the most advantageous way to optimize the performance of LMBs. [16] To date, additives like some sulfur-containing compounds, [17] inorganic salts, [18][19][20] and fluorine-containing materials [21,22] have been found with high Li-metal compatibility and proved effective in forming stable SEI layer. Nevertheless, most additives will preferentially participate in the interfacial reactions that cause their concentration to drop, leading to the gradual failure of the additives during cycling. [23] It should be noted that increasing the dosage of additives will not only raise the cost, but also accelerate the unfavored side reactions due to the increased concentration of unstable active groups (such as -F, -S(O) 2 -, etc.) and higher viscosity, leading to electrolyte deterioration and gas production (Figure 1a). [24,25] To conquer the above issues, several LiNO 3containing additives have been successfully developed recently inspired by the sustained-release strategy, and their impressive performances demonstrate the great application potential of this method. [26,27] Therefore, optimizing the overall performance and cost of additives designed based on this strategy is of great research significance.Herein, we adopt cheap, environment-friendly CaCO 3 nanoparticles (40-80 nm) as a novel solid additive for LMBs. The added nano CaCO 3 additive exhibits a unique sustainedrelease mechanism as is shown in Figure 1b, which can absorb the decomposition by-products of electrolyte continuously and release active substances containing LiPO 2 F 2 and Ca 2+ , thus