Gradient architecture to boost the electrochemical capacitance of hard carbon

Carbon-based supercapacitors with outstanding electrochemical performances are strongly desired for the development of portable and wearable electronics. From the free radical engineering point of view, this study innovatively developed carbon/carbon gradient-structured microspheres (CCGMs) by the strategy of “third-order graduation polymerization” and “dynamic radical oxidation”. Compared to conventional hybrid materials, for the first time, the gradient structure is proved to be extremely beneficial for improving the capacitive performance. Benefiting its gradient-structured advantages, the CCGMs exhibited “three-ultrahigh” performance with gravimetric, volumetric, and areal capacitances of 408.23 F g−1, 741.11 F cm−3, and 4390 μF cm−2, respectively. In addition, the assembled all-solids-state micro-supercapacitors delivered superior volumetric and areal specific capacitances (7.704 F cm−3 and 9.245 mF cm−2 at 5 μA cm−2), excellent life-span (100% after 12000 cycles), excellent volumetric and areal energy densities (1070 mWh cm−3 and 1284 μWh cm−2). This work paves a new way to develop unique carbon composites for high‐performance energy storage devices.