Chunhua Tang

Superior performance asymmetric supercapacitors based on a directly grown commercial mass 3D Co3O4@Ni(OH)2 core-shell electrode.

Pseudocapacitors based on fast surface Faradaic reactions can achieve high energy densities together with high power densities. Usually, researchers develop a thin layer of active materials to increase the energy density by enhancing the surface area; meanwhile, this sacrifices the mass loading. In this work, we developed a novel 3D core-shell Co3O4@Ni(OH)2 electrode that can provide high energy density with very high mass loading. Core-shell porous nanowires (Co3O4@Ni(OH)2) were directly grown on a Ni current collector as an integrated electrode/collector for the supercapacitor anode. This Co3O4@Ni(OH)2 core-shell nanoarchitectured electrode exhibits an ultrahigh areal capacitance of 15.83 F cm(-2). The asymmetric supercapacitor prototypes, assembled using Co3O4@Ni(OH)2 as the anode, reduced graphene oxide (RGO) or active carbon (AC) as the cathode, and 6 M aqueous KOH as the electrolyte, exhibit very high energy densities falling into the energy-density range of Li-ion batteries. Because of the large mass loading and high energy density, the prototypes can drive a minifan or light a bulb even though the size is very small. These results indicate that our asymmetric supercapacitors have outstanding potential in commercial applications. Systematic study and scientific understanding were carried out.

Hierarchical porous Cu2ZnSnS4 films for high-capacity reversible lithium storage applications

Sulphide-based materials have attracted much attention as high performance electrode candidates for lithium batteries. However, a serious irreversible capacity decay after the first cycle of such materials inhibits their widespread applications in rechargeable batteries. In this work, a highly porous (3D) quaternary Cu2ZnSnS4 (CZTS) film was synthesized through a facile solution pyrolysis method. An initial discharge capacity of 1154 mA h g−1 and a stabilised value of about 680 mA h g−1 after 40 cycles at a current rate of 100 mA g−1 were achieved. Such significantly improved capacity and stability (especially for the first several cycles) indicate the great advantages of this 3D nanostructured CZTS electrode for advanced secondary lithium batteries.

Intercalating graphene with clusters of Fe3O4 nanocrystals for electrochemical supercapacitors

A hierarchical nanostructure consisting of graphene sheets intercalated by clusters of Fe3O4 nanocystals is developed for high-performance supercapacitor electrode. Here we show that the negatively charged graphene oxide (GO) and positively charged Fe3O4 clusters enable a strong electrostatic interaction, generating a hierarchical 3D nanostructure, which gives rise to the intercalated composites through a rational hydrothermal process. The electrocapacitive behavior of the resultant composites is systematically investigated by cyclic voltammeter and galvanostatic charge-discharge techniques, where a positive synergistic effect between graphene and Fe3O4 clusters is identified. A maximum specific capacitance of 169 F g−1 is achieved in the Fe3O4 clusters decorated with effectively reduced graphene oxide (Fe3O4-rGO-12h), which is much higher than those of rGO (101 F g−1) and Fe3O4 (68 F g−1) at the current density of 1 Ag−1. Moreover, this intercalated hierarchical nanostructure demonstrates a good capacitance retention, retaining over 88% of the initial capacity after 1000 cycles.

Cobalt monoxide-doped porous graphitic carbon microspheres for supercapacitor application

A novel design and facile synthesis process for carbon based hybrid materials, i.e., cobalt monoxide (CoO)-doped graphitic porous carbon microspheres (Co-GPCMs), have been developed. With the synthesis strategy, the mixture of cobalt gluconate, α-cyclodextrin and poly (ethylene oxide)106-poly (propylene oxide)70-poly (ethylene oxide)106 is treated hydrothermally, followed by pyrolysis in argon. The resultant Co-GPCMs exhibits a porous carbon matrix with localized graphitic structure while CoO nanodots are embedded in the carbon frame. Thus, the Co-GPCMs effectively combine the electric double-layer capacitance and pseudo-capacitance when used as the electrode in supercapacitor, which lead to a higher operation voltage (1.6 V) and give rise to a significantly higher energy density. This study provides a new research strategy for electrode materials in high energy density supercapacitors.

Substrate-assisted self-organization of Ni–Cu spherical double hydroxide (SDH) and its excellent pseudo-capacitive performance

Ni–Cu spherical double hydroxide (SDH) was synthesized by a one-step, seedless and cost-effective chemical bath deposition method. It showed novel spherical morphology and an interesting composition, containing copper and nickel from elemental mapping. For comparison, when the substrates changed from a copper foam to a nickel foam or carbon paper, the deposited material became pure nickel hydroxide with a flower-like morphology. The SDH demonstrated a high specific capacitance of 1970 F g−1 after removing the contribution of the substrate (total 2282 F g−1).

(CH3NH3)2PdCl4: A Compound with Two‐Dimensional Organic–Inorganic Layered Perovskite Structure

The synthesis of previously unknown perovskite (CH3 NH3 )2 PdCl4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH3 NH3 )2 PdCl4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 104  cm-1 . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites.

A low-cost, ligand exchange-free strategy to synthesize large-grained Cu2ZnSnS4 thin-films without a fine-grain underlayer from nanocrystals

The first direct synthesis of CZTS nanocrystals in a formamide solvent system without using long hydrocarbon chain organic ligands is reported. The kesterite CZTS nanocrystals possess a mean size of 5.2 ± 1.2 nm. No secondary phases have been detected within the known limitations of XRD and Raman measurements. Experimental evidence suggests that excess S2− is present on the surface of the nanocrystals, accounting for their dispersibility in polar solvents. The nanocrystals also exhibit a smaller weight loss of 8.7% at 500 °C compared to 24.4% for those capped by oleylamine. A description of the formation of CZTS FA nanocrystals and the role of formamide during synthesis is proposed. Annealing of spin-coated nanocrystal thin-films highlighted the difficulty of forming dense films from loose nanocrystal films. This work shows that this can be overcome using compaction with a combination of a reasonably soft metal and silicone. A means to compact the film uniformly on a centimeter scale with reduced delamination is thus demonstrated. Annealed compacted films possess crystal grains with a favorable size on the order of microns. More significantly, a large-grain layer is formed without an unwanted residual fine-grain underlayer. The absence of a fine-grain underlayer shows that this ligand exchange-free strategy is effective in resolving a key challenge associated with the nanocrystal approach of making CZTS thin-films while simultaneously being low-cost and having a smaller environmental footprint. The strategy presented here is equally applicable to other nanocrystal approaches requiring the synthesis of dense thin-films from nanocrystal films.

Chemical insights into the roles of nanowire cores on the growth and supercapacitor performances of Ni-Co-O/Ni(OH)2 core/shell electrodes

Nanostructured core/shell electrodes have been experimentally demonstrated promising for high-performance electrochemical energy storage devices. However, chemical insights into the significant roles of nanowire cores on the growth of shells and their supercapacitor behaviors still remain as a research shortfall. In this work, by substituting 1/3 cobalt in the Co3O4 nanowire core with nickel, a 61% enhancement of the specific mass-loading of the Ni(OH)2 shell, a tremendous 93% increase of the volumetric capacitance and a superior cyclability were achieved in a novel NiCo2O4/Ni(OH)2 core/shell electrode in contrast to a Co3O4/Ni(OH)2 one. A comparative study suggested that not only the growth of Ni(OH)2 shells but also the contribution of cores were attributed to the overall performances. Importantly, their chemical origins were revealed through a theoretical simulation of the core/shell interfacial energy changes. Besides, asymmetric supercapacitor devices and applications were also explored. The scientific clues and practical potentials obtained in this work are helpful for the design and analysis of alternative core/shell electrode materials.

Influence of Ligands on the Formation of Kesterite Thin Films for Solar Cells: A Comparative Study.

The preparation of solar-cell-grade Cu2 ZnSnS4 (CZTS) thin films from ligand-capped small-grained CZTS particles remains hindered by problems of phase segregation, composition non-uniformity, and in particular carbon-layer formation. Herein, through a systematic comparative study of annealed films of CZTS nanocrystals prepared using conventional oleylamine and those prepared using formamide, these problems are found to be mainly attributable to the influence of the ligands, and mechanisms are proposed. Importantly, the origin of the carbon layer in oleylamine-capped CZTS films is revealed to be the reaction between oleylamine and sulfur. This carbon layer has a very poor electrical conductivity, which can be the reason for the limited performance of such films. Fortunately, these problems can almost all be avoided by replacing oleylamine with formamide to form CZTS films.