Presented in this article is the template-free fabrication of nitrogen-doped hollow carbon spheres (N-HCSs) as electrode materials for high-performance supercapacitors based on scalable homopolymer vesicles, which are self-assembled from an amphiphilic homopolymer, poly(amic acid) (PAA). This homopolymer can be massively produced by simple stepwise polymerization at room temperature with a fast polymerization rate. For the first time, PAA homopolymer vesicles are carbonized to form N-HCSs with tunable porous structures and nitrogen contents (from 1.3% to 7.4%) by controlling the content of the cross-linker (melamine). This template-free method for fabricating N-HCSs is more environmentally friendly and does not involve tedious synthetic procedures compared to traditional template-based methods. More importantly, the N-HCSs exhibit excellent electrochemical performance with a very high specific capacitance (266.9 F g⁻¹) after more than 1000 cycles when used as the active electrode material for the supercapacitor. The N-HCSs presented in this paper retain its specific capacitance as high as 84% at a very high current density (20 A g⁻¹). Given the potential massive production and excellent electrochemical properties, the N-HCSs based on the carbonization of scalable PAA homopolymer vesicles are promising candidate electrode materials for energy storage devices.

Asymmetric nanoparticles such as nanobowls have promising potential in many fields due to their interior asymmetric cavities and specific concave structure. However, the fabrication of nanobowls and control over their openings and interior holes are still challenging. Herein we demonstrate a versatile strategy for preparing nanobowls with precisely controlled openings and interior holes based on the synergy of hydrogen bonding and π–π interaction of homopolymers. We designed and synthesized a series of amphiphilic homopolymers with an amino alcohol moiety and azobenzene pendant (poly(2-hydroxy-3-((4-(phenyldiazenyl)phenyl)amino)propyl methacrylate) (PHAzoMA)). The homopolymers can self-assemble into nanobowls due to the heterogeneous shrinkage of the preformed spheres. Upon increasing the molecular weight of the homopolymers from 10.1 to 76.9 kg mol⁻¹, the sizes of the openings of nanobowls can be precisely controlled from 242 to 423 nm with a linear relationship as a result of the enhancement of the hydrogen bonding and π–π interaction between homopolymer chains. Overall, we have prepared finely controlled nanobowls by the synergy of non-covalent interactions such as hydrogen bonding and π–π interaction of polymers, which opens a new avenue for the preparation of asymmetric nanoparticles.