context: Polyanionic materials are a series of compounds containing polyhedral anionic structural units, which are linked to construct a three-dimensional network structure by strong covalent bonds. The unique structure endows the compounds with a stable crystal structure, moderate capacity, high operating voltage, and safety. Among them, monoclinic LiV2(PO4)3 (discharges to be Li3V2(PO4)3) is one of the most attractive cathode materials for primary batteries, which has stable voltage plateaus between 3.0 V and 4.3 V (vs. Li+/Li) and a suitable theoretical specific capacity (133 mA h g−1) corresponding to the insertion of two Li ions per formula unit. Most importantly, the unique NASICON structure of Li3V2(PO4)3 facilitates Li+ conduction and delivers faster Li+ diffusion kinetics when compared with traditional cathode materials such as LiFePO4, LiCoO2, and LiNi1/3Co1/3Mn1/3O2, ensuring superior rate capability and low-temperature performance. Thus, LiV2(PO4)3 has great potential for application as a cathode material for lithium primary batteries. For practical application, the shelf life of the Li/LiV2(PO4)3 batteries should be long enough; this means that the self-discharge rate should be as low as possible. Since the Li/LiV2(PO4)3 primary battery possesses a high open-circuit voltage (OCV) of about 4.1 V, the side reactions among electrode materials, electrolyte, and even current collectors can severely affect the shelf life of these batteries. In addition, the corrosion of the current collector leads to self-discharge. Therefore, stabilizing the interface between the electrode and electrolyte is essential.