Air leakage of closed wall in coal mine goaf would cause spontaneous combustion of remained coal. Most of measures to repair cracks are carried out after cracks are penetrated, which is not conducive to early prevention of spontaneous combustion. Repairing damage at the initial stage of cracking makes prevention effect to the best. Phenol-formaldehyde resin (PF) microcapsules embedded in closed wall to achieve self-healing of initial cracks, but the actual repair effect is often less than expected. PF microcapsules (PFM) of carbon nanotubes (CNTs) and silicon dioxide (SiO₂) decorated shell for self-healing of closed wall cracks were prepared by in-situ polymerization. The effects of nanomaterials on morphology, chemical constitution, thermal performance and mechanical properties of PF microcapsules were characterized by scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and nanoindentation test. The test results indicated that nanomaterials were successfully introduced into the shell of PF microcapsules. The CNTs-SiO₂@PF microcapsules were uniformly dispersed, the thermal decomposition was delayed, and the residual carbon was significantly increased, and the brittleness of PF microcapsules was significantly enhanced. The 0.2CNTs-SiO₂@PF microcapsules (0.2CNTs-SiO₂@PFM) had a uniform and full particle size, the initial decomposition temperature was 267.6 ℃, the residual mass was 41.3%, the maximum load on the capsule wall reached 94.79 mN, and the load dropped sharply after the capsule wall rupture. Finally, the self-healing mechanism of closed wall doped with microcapsules was discussed. The exploration of modified phenolic microcapsules provides a new idea for the repair of closed wall in goaf.