context: Herein, a Li/LiV2(PO4)3 primary battery was proposed and studied for the first time. The unique NASICON structure of monoclinic LiV2(PO4)3 facilitated Li+ diffusion, ensuring superior rate capability and low-temperature performance of the battery. However, the short shelf life of the Li/LiV2(PO4)3 primary batteries hinders their practical applications. The shelf life of the Li/LiV2(PO4)3 primary batteries was improved by optimizing the electrolyte composition. It was found that the corrosion of the Al foil triggered by the organic radical cations generated from the electrochemical oxidation of EC at high potentials leads to the self-discharge of the Li/LiV2(PO4)3 primary battery. When EC was replaced by PC, the corrosion of the Al foil was alleviated, and the shelf life of the Li/LiV2(PO4)3 primary battery was significantly improved. However, the loss of capacity still occurred after storage, which is ascribed to the oxidation decomposition of the electrolyte on the surface of the LiV2(PO4)3 cathode. A slow two-phase transition process from the LiV2(PO4)3 phase to the Li3V2(PO4)3 phase with the reduction of V4+ to low-valence V was characterized by the in situ XRD of the LiV2(PO4)3 cathode during its storage; this process was accompanied by the spontaneous insertion of Li back into LiV2(PO4)3. It was found that LiBOB as an additive effectively helps to improve the shelf life of the Li/LiV2(PO4)3 primary battery by alleviating the side reaction between LiV2(PO4)3 and electrolyte according to the XPS results, 100% of capacity could be maintained after one-month storage. Meanwhile, the Li/LiV2(PO4)3 primary battery exhibited superior rate capability and low-temperature performance: 86% energy could be maintained at 50C and 63% energy could be maintained at −40 °C and 0.1C, which was substantially better than the performance of the Li/MnO2 primary battery. Thus, our Li/LiV2(PO4)3 primary battery is an ideal candidate for applications in extreme situations.
answer: LiV2(PO4)3