Organic electrodes are promising as next generation energy storage materials originating from their enormous chemical diversity and electrochemical specificity. Although organic synthesis methods have been extended to a broad range, facile and selective methods are still needed to expose the corners of chemical space. Herein, we report the organopolysulfide, 1,4-bis(diphenylphosphanyl)tetrasulfide, which is synthesized by electrochemical oxidation of diphenyl dithiophosphinic acid featuring the cleavage of a P–S single bond and a sulfur radical addition reaction. Density functional theory proves that the external electric field triggers the intramolecular rearrangement of diphenyl dithiophosphinic acid through dehydrogenation and sulfur migration along the P–S bond axis. Impressively, the Li/bis(diphenylphosphanyl)tetrasulfide cell exhibits the high discharge voltage of 2.9 V and stable cycling performance of 500 cycles with the capacity retention of 74.8%. Detailed characterizations confirm the reversible lithiation/delithiation process. This work demonstrates that electrochemical synthesis offers the approach for the preparation of advanced functional materials.

有机电极因其巨大的化学多样性和电化学特异性而有望成为下一代储能材料。尽管有机合成方法已扩展到广泛的范围，但仍然需要简便和选择性的方法来暴露化学空间的角落。在此，我们报道了有机多硫化物，1,4-双(二苯基膦酰基)四硫化物，它是通过二苯基二硫代次膦酸的电化学氧化合成的，具有P-S单键的断裂和硫自由基加成反应。密度泛函理论证明，外部电场通过脱氢和沿P-S键轴的硫迁移引发二苯基二硫代次膦酸的分子内重排。令人印象深刻的是，Li/双(二苯基膦酰基)四硫化物电池表现出2.9 V的高放电电压和500次循环的稳定循环性能，容量保持率为74.8%。详细的表征证实了可逆的锂化/脱锂过程。这项工作表明电化学合成为制备先进功能材料提供了方法。