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In a typical battery, the inert electrolyte functions solely as the ionic conductor without contribution to the cell capacity. Here we demonstrate that the most energy-dense Li-CF_x battery delivers a capacity exceeding the theoretical maximum of CF_x with a solid electrolyte of Li₃PS₄ (LPS) that has dual functions: as the inert electrolyte at the anode and the active component at the cathode. Such a bifunctional electrolyte reconciles both inert and active characteristics through a synergistic discharge mechanism of CF_x and LPS. The synergy at the cathode is through LiF, the discharge product of CF_x, which activates the electrochemical discharge of LPS at a close electrochemical potential of CF_x. Therefore, the solid-state Li-CF_x batteries output 126.6% energy beyond their theoretic limits without compromising the stability of the cell voltage. The additional energy comes from the electrochemical discharge of LPS, the inert …