Stereolithography-Derived Three-Dimensional Pyrolytic Carbon/Mn₃O₄ Nanostructures for Free-Standing Hybrid Supercapacitor Electrodes

The development of permeable three-dimensional (3D) macroporous carbon architectures loaded with active pseudocapacitive nanomaterials offers hybrid supercapacitor (SC) materials with higher energy density, shortened diffusion length for ions, and higher charge-discharge rate capability and thereby is highly relevant for electrical energy storage (EES). Herein, structurally complex and tailorable 3D pyrolytic carbon/Mn₃O₄ hybrid SC electrode materials are synthesized through the self-assembly of MnO₂ nanoflakes and nanoflowers onto the surface of stereolithography 3D-printed architectures via a facile wet chemical deposition route, followed by a single thermal treatment. Thermal annealing of the MnO₂ nanostructures concurrent with carbonization of the polymer precursor leads to the formation of a 3D hybrid SC electrode material with unique structural integrity and uniformity. The microstructural and chemical characterization of the hybrid electrode reveals the predominant formation of crystalline hausmannite-Mn₃O₄ after the pyrolysis/annealing process, which is a favorable pseudocapacitive material for EES. With the combination of the 3D free-standing carbon architecture and self-assembled binder-free Mn₃O₄ nanostructures, electrochemical capacitive charge storage with very good rate capability, gravimetric and areal capacitances (186 F g^-1 and 968 mF cm^-2, respectively), and a long lifespan (>92% after 5000 cycles) is demonstrated. It is worth noting that the gravimetric capacitance value is obtained by considering the full mass of the electrode including the carbon current collector. When only the mass of the pseudocapacitive nanomaterial is considered, a capacitance value of 457 F g^-1 is achieved, which is comparable to state-of-the-art Mn₃O₄-based SC electrode materials.