Solution Self-Assembly of an Alternating Copolymer toward Hollow Carbon Nanospheres with Uniform Micropores

Controllable preparation of porous hollow carbon spheres (HCSs) has attracted considerable attention due to their potential applications, e.g., in energy conversion and storage. We report for the first time the synthesis of narrowly size-distributed HCSs with uniform micropores in the wall, through a simple template-free approach, which employs the solution self-assembly of an alternating copolymer (poly(9,9'-bis(4-glycidyloxyphenyl)fluorene-alt-2,3-dihydroxy-butylene dithioether) (P(BGF-a-DHBDT))). This alternating copolymer first self-assembled into previously undocumented hollow polymeric spheres (HPSs) in an N,N-dimethylformamide (DMF)/H₂O solvent mixture. After the cross-linking of the BGF segments in the spheres, the stabilized HPSs (CL-HPSs) were carbonized at 800 °C under N₂ atmosphere, yielding porous HCSs with uniform micropores of very narrow size distribution (0.4-0.8 nm) in the wall, benefiting from the uniform DHBDT block length in the alternating copolymer. Through KOH activation, which made the internal pores fully interconnected, uniform micropores (0.5-1.0 nm) of a narrow size distribution were retained within the activated HCSs (A-HCSs), while their specific surface areas (SSAs) were much increased to 2580 m² g^-1. As a proof of concept, the A-HCSs were applied as electrode materials of supercapacitors. They exhibited superior electrochemical performance with a high specific capacitance (292 F g^-1 at 0.2 A g^-1), good rate capability, and outstanding cycling stability with no apparent capacitance loss after 10 000 cycles.