There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Supercapacitors have drawn considerable attention in recent years due to their high specific power, long cycle life, and ability to bridge the power/energy gap between conventional capacitors and batteries/fuel cells. Nanostructured electrode materials have demonstrated superior electrochemical properties in producing high-performance supercapacitors. In this review article, we describe the recent progress and advances in designing nanostructured supercapacitor electrode materials based on various dimensions ranging from zero to three. We highlight the effect of nanostructures on the properties of supercapacitors including specific capacitance, rate capability and cycle stability, which may serve as a guideline for the next generation of supercapacitor electrode design.

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Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions

Charge kinetics is highly critical in determining the quantum efficiency of solar-to-chemical conversion in photocatalysis, and this includes, but is not limited to, the separation of photoexcited electron–hole pairs, utilization of plasmonic hot carriers and delivery of photo-induced charges to reaction sites, as well as activation of reactants by energized charges. In this review, we highlight the recent progress on probing and steering charge kinetics toward designing highly efficient photocatalysts and elucidate the fundamentals behind the combinative use of controlled synthesis, characterization techniques (with a focus on spectroscopic characterizations) and theoretical simulations in photocatalysis studies. We first introduce the principles of various processes associated with charge kinetics that account for or may affect photocatalysis, from which a set of parameters that are critical to photocatalyst design can be summarized. We then outline the design rules for photocatalyst structures and their corresponding synthetic approaches. The implementation of characterization techniques and theoretical simulations in different steps of photocatalysis, together with the associated fundamentals and working mechanisms, are also presented. Finally, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.

Steering charge kinetics in photocatalysis: intersection of materials syntheses, characterization techniques and theoretical simulations

The controlled synthesis of nanohybrids composed of noble metals (Au, Ag, Pt and Pd, as well as AuAg alloy) and metal oxides (ZnO, TiO2, Cu2O and CeO2) have received considerable attention for applications in photocatalysis, solar cells, drug delivery, surface enhanced Raman spectroscopy and many other important areas. The overall architecture of nanocomposites is one of the most important factors dictating the physical properties of nanohybrids. Noble metals can be coupled to metal oxides to yield diversified nanostructures, including noble metal decorated-metal oxide nanoparticles (NPs), nanoarrays, noble metal/metal oxide core/shell, noble metal/metal oxide yolk/shell and Janus noble metal–metal oxide nanostructures. In this review, we focus on the significant advances in tailored nanostructures of noble metal–metal oxide nanohybrids. The improvement in performance in the representative solar energy conversion applications including photocatalytic degradation of organic pollutants, photocatalytic hydrogen generation, photocatalytic CO2 reduction, dye-sensitized solar cells (DSSCs) and perovskite solar cells (PSCs) are discussed. Finally, we conclude with a perspective on the future direction and prospects of these controllable nanohybrid materials.

Noble metal–metal oxide nanohybrids with tailored nanostructures for efficient solar energy conversion, photocatalysis and environmental remediation

Three-dimensional (3D) graphene materials (3DGMs) are of great importance due to their unique properties and practical applications. A number of 3DGMs with novel structures have been developed in recent years. This review presents the current progress of 3DGMs. After introducing the preparation strategies of 3DGMs, we summarize the reported 3DGMs based on their different structures, and then focus on the description of their preparation methods, properties and applications. Lastly, the applications of 3D graphene-based materials in supercapacitors are described.

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Three-dimensional graphene materials: preparation, structures and application in supercapacitors

NiO nanostructures with three distinct morphologies were fabricated by a sol–gel method and their morphology-dependent supercapacitor properties were exploited. The nanoflower- shaped NiO with a distinctive three-dimensional (3D) network and the highest pore volume shows the best supercapacitor properties. The nanopores in flower-shaped nanostructures, offering advantages in contact with and transport of the electrolyte, allow for 3D nanochannels in NiO structure, providing longer electron pathways. The XPS and EIS data of the NiO nanostructure confirm that the flower-shaped NiO, which has the lowest surface area among the three morphologies, was effectively optimized as a superior electrode and yielded the greatest pseudocapacitance. This study indicates that forming a 3D nanonetwork is a straightforward means of improving the electrochemical properties of a supercapacitor.

Facile Route to an Efficient NiO Supercapacitor with a Three-Dimensional Nanonetwork Morphology

We report a robust and direct route to fabricate a three-dimensional nano-foam of few-layer graphene (3D-NFG) with large area coverage via a chemical vapor deposition (CVD) technique. Pyrolysis of polymer/nickel precursor film under a hydrogen environment, simply prepared by spin-coating, leads to the creation of nano-foam in the film and the reduction process of nickel ions. Carbonized-C and the nickel nano-frame formed from the pyrolysis are used as a solid carbon source and as a catalyst for the growth of graphene under CVD conditions, respectively. We investigate the use of 3D-NFG, with the advantage of large surface area and high conductivity, as an alternative to the Pt counter electrode material in dye sensitized solar cells. The excellent properties of 3D-NFG, fabricated in this simple and direct manner, suggest a great potential for interconnected graphene networks in electronic devices and photocatalytic sensors as well as in energy-related materials.

Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

The rapidly developing electronics industry is producing miniaturized electronic devices with flexible, portable and wearable characteristics, requiring high-performance miniature energy storage devices with flexible and light weight properties. Herein, we have successfully fabricated highly porous, binder free three-dimensional flower-like NiCo2O4/Ni nanostructures on Ni-wire as a fiber electrode for high-performance flexible fiber supercapacitors. Such a unique structure exhibited remarkable electrochemical performance with high capacitance (29.7 F cm−3 at 2.5 mA), excellent rate capability (97.5% retention at 20 mA), and super cycling stability (80% retention, even after 5000 cycles). The remarkable electrochemical performance is attributed to the large active area in the 3D porous architecture and direct contact between the active materials and 3D-Ni current collectors, which facilitate easy ionic/electronic transport. The symmetric fiber supercapacitor showed a gravimetric energy density of 2.18 W h kg−1 (0.21 mW h cm−3) and a power density of 21.6 W kg−1 (2.1 mW cm−3) with good flexibility and cycling performance, signifying potential applications in high-performance flexible energy storage devices. Further, performance in a self-powered system was demonstrated by charging these wire type NiCo2O4/Ni supercapacitors by serially wound DSSCs to drive commercial LEDs. These results suggest that the fabricated device has excellent potential as a power source for flexible, portable and wearable applications as well as self-powered systems.

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Realization of high performance flexible wire supercapacitors based on 3-dimensional NiCo2O4/Ni fibers

This study introduces an in situ fabrication of nanoporous hematite with a Ti-doped SiOx passivation layer for a high-performance water-splitting system. The nanoporous hematite with a Ti-doped SiOx layer (Ti-(SiOx/np-Fe2O3)) has a photocurrent density of 2.44 mA cm−2 at 1.23 VRHE and 3.70 mA cm−2 at 1.50 VRHE. When a cobalt phosphate co-catalyst was applied to Ti-(SiOx/np-Fe2O3), the photocurrent density reached 3.19 mA cm−2 at 1.23 VRHE with stability, which shows great potential of the use of the Ti-doped SiOx layer with a synergistic effect of decreased charge recombination, the increased number of active sites, and the reduced hole-diffusion pathway from the hematite to the electrolyte.

A Titanium-Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite-Based Photoelectrochemical System

In this report, we show that by creating a nanoporous haematite (α-Fe2O3) structure using boric acid (H3BO3) treatment, the chronic issue of the short diffusion length of carriers in α-Fe2O3 for photoelectrochemical (PEC) applications can be successfully addressed. The slow release of Fe3+ ions because of the presence of H3BO3 leads to the creation of smaller dimension FeOOH nanorods, creating nanoporous α-Fe2O3 nanorods, composed of ∼15 nm α-Fe2O3 domains. The nanoporous α-Fe2O3 suppresses recombination by providing the facile extraction of holes from the surface of favorably sized α-Fe2O3 domains. The optimized nanoporous sample showed a photocurrent density of 1.41 mA cm−2 at a reversible hydrogen electrode of 1.23 V, which is 1.7 times higher than that of pristine hematite. The electrochemical impedance spectroscopy and incident photon-to-current efficiency data, and Mott–Schottky plots confirmed the superior performance of the nanoporous samples. Our impressive results may pave the way for designing devices for advanced energy conversion applications as well as fabricating a high efficiency hematite-based PEC system.

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Hyo-Jin Ahn

Papers

Facile Route to an Efficient NiO Supercapacitor with a Three-Dimensional Nanonetwork Morphology

Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

Realization of high performance flexible wire supercapacitors based on 3-dimensional NiCo2O4/Ni fibers

A Titanium-Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite-Based Photoelectrochemical System

Nanoporous hematite structures to overcome short diffusion lengths in water splitting