As one of the most promising supercapacitor electrode materials, transition metal sulfides (TMSs) with unique hollow structural features and multiple functional compositions have attracted tremendous interest in the scientific community. Herein, by rationally design a Ni-LDH@Co-BTC yolk-shelled-structure as a template, we successfully fabricate a chemically coupled 0D-3D hetero-structure of Co₉S₈-Ni₃S₄ hollow spheres (Co₉S₈-Ni₃S₄ HS). During the sulfidation process, the free Co²⁺ ions derived from the hydrolysis Co-BTC core are anchored by S-rich hierarchical Ni₃S₄ hollow microsphere shell and further reacted with emerging S²⁻ ion from the hydrolysis of TAA to form the chemically coupled Co₉S₈ and Ni₃S₄. The optimized Co₉S₈-Ni₃S₄ HS-13 shows prominent supercapacitor performance (239.30 mAh g⁻¹ (1723 F g⁻¹) at 1 A g⁻¹) and excellent cycling stability (94.7 % capacitance retention after 3000 cycles). The as-fabricated Co₉S₈-Ni₃S₄ HS-13//rGO-Zn hybrid Zn-based supercapacitor presented a high energy density of 381.63 Wh kg⁻¹ at 1.67 kW kg⁻¹ and excellent cycling durability (91.7 % capacitance retention after 5000 cycles). Then, through the ex-situ XPS measurements, the energy storage mechanism of the Co₉S₈-Ni₃S₄ HS-13//rGO-Zn device is proved to be a novel double ions (OH⁻ and Zn(Ⅱ)) intercalation/deintercalation reaction.

作为最有前途的超级电容器电极材料之一，过渡金属硫化物（TMSs）具有独特的空心结构特征和多种功能成分，引起了科学界的极大兴趣。在此，通过合理设计 Ni-LDH@Co-BTC 蛋黄壳结构作为模板，我们成功地制备了 Co ₉ S ₈ -Ni ₃ S ₄空心球（Co ₉ S ₈ -Ni ₃ S ₄ HS)。在硫化过程中，来自水解 Co-BTC 核心的游离 Co ²⁺离子被富含 S 的分层 Ni ₃ S ₄锚定空心微球壳并进一步与来自 TAA 水解的S ^2-离子反应，形成化学偶联的 Co ₉ S ₈和 Ni ₃ S ₄。优化的 Co ₉ S ₈ -Ni ₃ S ₄ HS-13 显示出突出的超级电容器性能（239.30 mAh g ^-1 (1723 F g ^-1 ) at 1 A g ^-1）和优异的循环稳定性（3000 次循环后电容保持率为 94.7 % ）。制成的 Co ₉ S ₈ -Ni ₃ S ₄HS-13//rGO-Zn 混合锌基超级电容器在 1.67 kW kg ^{-1 时}具有381.63 Wh kg ^-1的高能量密度和出色的循环耐久性（5000 次循环后电容保持率为 91.7%）。然后，通过非原位XPS 测量，证明Co ₉ S ₈ -Ni ₃ S ₄ HS-13//rGO-Zn 器件的储能机制是一种新型的双离子（OH ^-和 Zn(Ⅱ) ) 嵌入/脱嵌反应。