The electronegative filling in skutterudites not only broadened the scope of filling atoms, but also facilitated the preparation of p-type skutterudites. However, the introduction of a single sulfur atom in the Co₄Sb₁₂ cannot be achieved without charge compensation through the traditional equilibrium method. In the present study, the dual occupations of S-atoms by self-charge compensation were shown as the most stable forms under high pressure, and a series of p-type S_yCo₄Sb_12−2yS_2y skutterudites was successfully prepared by high-pressure-high-temperature (HPHT) method. The electronic structures and transport properties of as-obtained materials were investigated, and the related mechanisms were explored. The results suggested that the presence of S-impurities led to flattening of the electronic band that led to a higher Seebeck coefficient. The S-doped Co₄Sb₁₂ displayed lower elastic modulus, elastic constant, and Debye temperature, thus indicating the chemical bond softening in skutterudites. The thermal conductivities of S_yCo₄Sb_12−2yS_2y compounds reduced monotonously with the increase in S-content. This study provides a new and promising avenue for optimizing the thermoelectric properties of p-type Co₄Sb₁₂.

方钴矿中的电负性填充不仅拓宽了填充原子的范围，而且有利于p型方钴矿的制备。然而，通过传统的平衡方法，在没有电荷补偿的情况下无法在Co ₄ Sb _{12 中}引入单个硫原子。在本研究中，自电荷补偿对 S 原子的双重占据是高压下最稳定的形式，一系列p型 S _y Co ₄ Sb _{12−2 y} S _{2 y}通过高压高温（HPHT）法成功制备方钴矿。研究了所获得材料的电子结构和输运特性，并探索了相关机制。结果表明 S 杂质的存在导致电子带变平，从而导致更高的塞贝克系数。S掺杂的Co ₄ Sb ₁₂显示出较低的弹性模量、弹性常数和德拜温度，因此表明方钴矿中的化学键软化。S _y Co ₄ Sb _{12−2 y} S _{2 y}的热导率化合物随着 S 含量的增加而单调减少。该研究为优化p型Co ₄ Sb ₁₂的热电性能提供了一条新的、有前景的途径。