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

Abstract

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/Mn 3 O 4 hybrid SC electrode materials are synthesized through the self-assembly of MnO 2 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 MnO 2 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-Mn 3 O 4 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 Mn 3 O 4 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 Mn 3 O 4 -based SC electrode materials.

Triethanolamine assisted synthesis of bimetallic nickel cobalt nitride/nitrogen-doped carbon hollow nanoflowers for supercapacitor

“…As expected, all the precursors show no sharp and distinct peaks, exhibiting salient amorphous characteristics [28] . The wide peak bulge at 15°-25° is assigned to the (002) crystal face of carbon, indicating the successful formation of nitrogen-doped carbon after calcining [Figure 2A] [29] . The peaks at 38.9°, 42.1°, 44.5°, 58.5°, 70.6° and 78.4° could be attributed to the (110), (002), ( 111), ( 112), (300) and (113) 002), ( 101), ( 102), ( 110) and ( 103) crystal faces of Co 2 N 0.67 (JCPDS:10-0280).…”

A Review on 3D Architected Pyrolytic Carbon Produced by Additive Micro/Nanomanufacturing

“…Typically an acrylate-based photoresin is used in SLA printing for carbon structures. Most of the published articles used commercial resins as the starting photoresin, [41,[59][60][61][62] whereas customized resins, including biopolymer-based resins, have also been demonstrated for SLA-based 3D PyC. [63,64] The precursor material plays the most important role in determining the final shape, size, and macrostructural properties of the final 3D PyC.…”

“…PyC, Rezaei et al decorated the SLA-printed 3D PyC surface with electroactive manganese oxide (MnO x ) nanoparticles. [61] Hybrid architected electrodes were fabricated by wet chemical bath deposition of MnO 2 on SLA-printed 3D resin structures, followed by a calcination/carbonization process, which led to the decoration of highly electroactive crystalline hausmannite-Mn 3 O 4 on 3D PyC (Figure 8b(i)). The electrochemical performances of the hybrid electrode were significantly higher than pristine 3D PyC and highly dependent on the loading of MnO x precursor, as demonstrated by their cyclic voltammograms and electrochemical impedance spectroscopy in Figure 8b(ii,iii), respectively.…”

In Situ Mineralization of Biomass‐Derived Hydrogels Boosts Capacitive Electrochemical Energy Storage in Free‐Standing 3D Carbon Aerogels

“…The development of three-dimensional (3D) hierarchical porous carbon structures ranging from macroscopic carbonized monoliths to microscopic carbon nanomaterials is attracting a great degree of interest for energy storage and environmental applications. [1][2][3][4] Specifically, these hierarchical carbons possess a unique 3D network with a wellinterconnected hierarchical porous structure in terms of macropores (>50 nm), mesopores (2-50 nm), and micropores (<2 nm) that are more beneficial than carbon materials with simple or dual pore structures. The minimized diffusive resistance of mass transport through macropores and larger accessible surface area with effective dispersion of active sites on macro-, meso-, and micropore channels make them attractive as electrode materials for various electrochemical applications.…”