<p>The mineralization method boasts advantages including high product purity, controllable crystal structure and good reproducibility, making it a promising approach for the preparation of black phosphorus (BP). However, the employed Sn₂₄P_19.3I₈ catalyst suffers from pronounced sintering during the preparation process, which severely compromises its catalytic activity and cycle period. The yield (56.0%) was significantly low after two cycles of BP preparation by using Sn₂₄P_19.3I₈. Herein, intrinsically low thermal conductivity (1.73&#xa0;W&#xa0;m⁻¹&#xa0;K⁻¹) was demonstrated to the decreased catalytic performance of Sn₂₄P_19.3I₈ catalyst. To overcome this issue, graphite was integrated with Sn₂₄P_19.3I₈ (Sn₂₄P_19.3I₈/Gra) for improving the thermal conductivity (15.75&#xa0;W&#xa0;m⁻¹&#xa0;K⁻¹), which effectively alleviated the issue of local heat accumulation and therefore overcame sintering of Sn₂₄P_19.3I₈. As expected, an exceptionally high yield of 83.3% was achieved even after nine cycles of BP preparation based on the Sn₂₄P_19.3I₈/Gra composite catalyst, highlighting the catalytic robustness. This work provided a feasible production of high-quality BP, paving the way for its broad industrial application.</p> Graphical Abstract <p></p>