Highly porous nanostructures with large surface areas are typically employed for electrical double-layer capacitors to improve gravimetric energy storage capacity; however, high surface area carbon-based electrodes result in poor volumetric capacitance because of the low packing density of porous materials. Here, we demonstrate ultrahigh volumetric capacitance of 521 F cm−3 in aqueous electrolytes for non-porous carbon microsphere electrodes co-doped with fluorine and nitrogen synthesized by low-temperature solvothermal route, rivaling expensive RuO2 or MnO2 pseudo-capacitors. The new electrodes also exhibit excellent cyclic stability without capacitance loss after 10,000 cycles in both acidic and basic electrolytes at a high charge current of 5 A g−1. This work provides a new approach for designing high-performance electrodes with exceptional volumetric capacitance with high mass loadings and charge rates for long-lived electrochemical energy storage systems.

Oxygen vacancies (OVs) are important for changing the geometric and electronic structures as well as the chemical properties of MnO 2 . In this study, we performed a DFT+U calculation on the electronic structure and catalytic performance of a β-MnO 2 catalyst for oxygen reduction reaction (ORR) with different numbers and extents of OVs. Comparing to the experimental XRD analysis, we determined that OVs produce a new crystalline phase of β-MnO 2 . Changes in the electronic structure (Bader charges, band structure, partial density of states (PDOS), local density of states (LDOS), and frontier molecular orbital), proton insertion and oxygen adsorption in β-MnO 2 (110) were investigated as a function of the bulk OVs. The results show that a moderate concentration of bulk OVs reduced the band gap, increased the Fermi and HOMO levels of the MnO 2 (or MnOOH), and elongated the O-O bond of the adsorbed O 2 and co-adsorbed O 2 with H. These changes substantially increase the conductivity of MnO 2 for the catalysis of ORR. However, an excessively high concentration of OVs in β-MnO 2 (110) will work against the catalytic enhancement of MnO 2 for ORR. The DFT+U calculation reveals that a moderate concentration of OVs induced a large overlap of the surface Mn d z2 orbitals and thus introducing an extra donor level at the bottom of the conductive band (CB), which increased the conductivity of β-MnO 2 (110). Such a curvilinear change of the catalytic activity and electronic structure as a function of the oxygen vacancy concentration suggests that the β-MnO 2 with moderate concentration OVs exhibits the highest conductivity and catalytic activity for ORR.

Half metal, with moderate delocalized and parallelized arrangement of spin freedom, is crucial to optimize the bifunctional catalyst for both ORR and OER, and the atomic magnetization on the reaction center could serve as a activity descriptor.

A zinc-based single-atom catalyst has been recently explored with distinguished stability, of which the fully occupied Zn 2+ 3d 10 electronic configuration is Fenton-reaction-inactive, but the catalytic activity is thus inferior. Herein, we report an approach to manipulate the s-band by constructing a B,N co-coordinated Zn-B/N-C catalyst. We confirm both experimentally and theoretically that the unique N 2-Zn-B 2 configuration is crucial, in which Zn + (3d 10 4s 1) can hold enough delocalized electrons to generate suitable binding strength for key reaction intermediates and promote the charge transfer between catalytic surface and ORR reactants. This exclusive effect is not found in the other transition-metal counterparts such as M-B/N-C (M = Mn, Fe, Co, Ni and Cu). Consequently, the as-obtained catalyst demonstrates impressive ORR activity, along with remarkable long-term stability in both alkaline and acid media. This work presents a new concept in the further design of electrocatalyst.

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