context: In order to understand the relationship between self-discharge and electrolyte composition, the Li/LiV2(PO4)3 batteries were disassembled after one-week storage. The images of the Al current collectors and metallic Li of the disassembled battery are shown in Fig. 2. As shown in Fig. 2a and j, the Al current collector was obviously corroded, and many black precipitates were formed at the edge of the metallic Li electrode with the LPE-EC electrolyte. However, the appearances of the Al current collector and metallic Li electrode of the batteries with the LPE-PC and LPE-PC–LiBOB electrolytes were significantly better, as displayed in Fig. 2b, c, k and l, showing smooth Al current collectors and clean metallic Li surfaces. SEM was performed in order to verify the actual condition of the Al surface. As shown in the SEM images of the Al current collectors (Fig. 2d and g), the surface morphologies of the corroded Al current collector of the battery with the LPE-EC electrolyte displayed a high pit density, whereas those in the case of the batteries with the LPE-PC and LPE-PC–LiBOB electrolytes were smoother. The pits on the Al current collector were probably caused by the electrochemical oxidation of EC at high potentials generates a proton and triggers the chemical corrosion of aluminum foils. Pitting corrosion of the Al current collector can cause serious problems: passivation of cathode materials, increase of electrical resistance, contamination of the electrolyte, and reduction reactions of dissolved Al3+ on the anode side. Thus, the observed black precipitates on the metallic Li electrode could be the Li–Al alloy (LixAl) or a mixture of metallic Li and Li–Al alloy (cathodic: Al → Al3+ + 3e−; anodic: Al3+ + 3e− + Li → LixAl). The growth of precipitates can lead to separator piercing and internal short circuit of a battery, which is responsible for the rapid voltage drop and self-discharge of the Li/LiV2(PO4)3 batteries with the LPE-EC electrolyte (Fig. 1b). SEM images of the surface of the Al current collector of a battery with the LPE-PC and LPE-PC–LiBOB electrolytes after one-week storage are shown in Fig. 2e and h and Fig. 2f and i, respectively. Almost no obvious pitting corrosion was observed on the surfaces of the Al current collectors, confirming the better shelf stabilities of the Li/LiV2(PO4)3 batteries with the LPE-PC and LPE-PC–LiBOB electrolytes than that of the Li/LiV2(PO4)3 battery with the LPE-EC electrolyte (Fig. 1c and d), respectively. Therefore, the electrolyte composition can affect the stability of the current collector. The corrosion of the current collectors is a key reason for the self-discharge behavior of batteries.