A recent approach for solar-to-hydrogen generation has been water electrolysis using efficient, stable, and inexpensive bifunctional electrocatalysts within strong electrolytes. Herein, the direct growth of 1D NiCo2S4 nanowire (NW) arrays on a 3D Ni foam (NF) is described. This NiCo2S4 NW/NF array functions as an efficient bifunctional electrocatalyst for overall water splitting with excellent activity and stability. The 3D-Ni foam facilitates the directional growth, exposing more active sites of the catalyst for electrochemical reactions at the electrode–electrolyte interface. The binder-free, self-made NiCo2S4 NW/NF electrode delivers a hydrogen production current density of 10 mA cm–2 at an overpotential of 260 mV for the oxygen evolution reaction and at 210 mV (versus a reversible hydrogen electrode) for the hydrogen evolution reaction in 1 m KOH. This highly active and stable bifunctional electrocatalyst enables the preparation of an alkaline water electrolyzer that could deliver 10 mA cm–2 under a cell voltage of 1.63 V. Because the nonprecious-metal NiCo2S4 NW/NF foam-based electrodes afford the vigorous and continuous evolution of both H2 and O2 at 1.68 V, generated using a solar panel, they appear to be promising water splitting devices for large-scale solar-to-hydrogen generation.

Hierarchical NiCo2S4 Nanowire Arrays Supported on Ni Foam: An Efficient and Durable Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

While the synthesis of hollow structures of transition metal oxides is well established, it is extremely challenging to fabricate complex hollow structures for mixed transition metal sulfides. Here we report an anion exchange method to synthesize a complex ternary metal sulfides hollow structure, namely nickel cobalt sulfide ball-in-ball hollow spheres. Uniform nickel cobalt glycerate solid spheres are first synthesized as the precursor and subsequently chemically transformed into nickel cobalt sulfide ball-in-ball hollow spheres. When used as electrode materials for electrochemical capacitors, these nickel cobalt sulfide hollow spheres deliver a specific capacitance of 1,036 F g(-1) at a current density of 1.0 A g(-1). An asymmetric supercapacitor based on these ball-in-ball structures shows long-term cycling performance with a high energy density of 42.3 Wh kg(-1) at a power density of 476 W kg(-1), suggesting their potential application in high-performance electrochemical capacitors.

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Formation of nickel cobalt sulfide ball-in-ball hollow spheres with enhanced electrochemical pseudocapacitive properties

As new members of carbon material family, carbon and graphene quantum dots (CDs, GQDs) have attracted tremendous attentions for their potentials for biological, optoelectronic, and energy related applications. Among these applications, bio-imaging has been intensively studied, but optoelectronic and energy devices are rapidly rising. In this Feature Article, recent exciting progresses on CD- and GQD-based optoelectronic and energy devices, such as light emitting diodes (LEDs), solar cells (SCs), photodetctors (PDs), photocatalysis, batteries, and supercapacitors are highlighted. The recent understanding on their microstructure and optical properties are briefly introduced in the first part. Some important progresses on optoelectronic and energy devices are then addressed as the main part of this Feature Article. Finally, a brief outlook is given, pointing out that CDs and GQDs could play more important roles in communication- and energy-functional devices in the near future.

Carbon and Graphene Quantum Dots for Optoelectronic and Energy Devices: A Review

To push the energy density limit of supercapacitors, a new class of electrode materials with favorable architectures is strongly needed. Binary metal sulfides hold great promise as an electrode material for high-performance energy storage devices because they offer higher electrochemical activity and higher capacity than mono-metal sulfides. Here, the rational design and fabrication of NiCo2S4 nanosheets supported on nitrogen-doped carbon foams (NCF) is presented as a novel flexible electrode for supercapacitors. A facile two-step method is developed for growth of NiCo2S4 nanosheets on NCF with robust adhesion, involving the growth of Ni-Co precursor and subsequent conversion into NiCo2S4 nanosheets through sulfidation process. Benefiting from the compositional features and 3D electrode architectures, the NiCo2S4/NCF electrode exhibits greatly improved electrochemical performance with ultrahigh capacitance (877 F g−1 at 20 A g−1) and excellent cycling stability. Moreover, a binder-free asymmetric supercapacitor device is also fabricated by using NiCo2S4/NCF as the positive electrode and ordered mesoporous carbon (OMC)/NCF as the negative electrode; this demonstrates high energy density (≈45.5 Wh kg−1 at 512 W kg−1).

NiCo2S4 Nanosheets Grown on Nitrogen‐Doped Carbon Foams as an Advanced Electrode for Supercapacitors

A facile one-step electrodeposition method is developed to prepare ternary nickel cobalt sulfide interconnected nanosheet arrays on conductive carbon substrates as electrodes for supercapacitors, resulting in exceptional energy storage performance. Taking advantages of the highly conductive, mesoporous nature of the nanosheets and open framework of the three-dimensional nanoarchitectures, the ternary sulfide electrodes exhibit high specific capacitance (1418 F g–1 at 5 A g–1 and 1285 F g–1 at 100 A g–1) with excellent rate capability. An asymmetric supercapacitor fabricated by the ternary sulfide nanosheet arrays as positive electrode and porous graphene film as negative electrode demonstrates outstanding electrochemical performance for practical energy storage applications. Our asymmetric supercapacitors show a high energy density of 60 Wh kg–1 at a power density of 1.8 kW kg–1. Even when charging the cell within 4.5 s, the energy density is still as high as 33 Wh kg–1 at an outstanding power density of ...

One-Step Electrodeposited Nickel Cobalt Sulfide Nanosheet Arrays for High-Performance Asymmetric Supercapacitors

In situ growth of NiCo2S4 nanotube arrays on Ni foam for supercapacitors: Maximizing utilization efficiency at high mass loading to achieve ultrahigh areal pseudocapacitance

Nickel cobalt sulphides with different stoichiometric nickel and cobalt contents have been synthesized and used as pseudocapacitive materials for supercapacitors. The as-employed polyol method is robust enough to use a one-pot synthesis of nickel cobalt sulphides with similar porous morphology and crystal structure at different nickel and cobalt ratios. The electrochemical performance of the nickel cobalt sulphides can be easily tuned by the varying the Ni and Co content. Owing to the combined contributions from both Ni and Co ions, the bimetallic Ni–Co sulphides show a superior pseudocapacitance compared to monometallic Co and Ni sulphides in terms of high specific capacitance, excellent rate capability and long cycle stability. In particular, the Ni1.5Co1.5S4 sample shows the highest specific capacitance of 1093 F g−1 at 1 A g−1, superior rate capability of 69% capacitance retention after a 50-fold increase in current densities, and longer cycle stability with increased specific capacitance of 108% of capacitance retention after 2000 cycles. In addition, the Ni1.5Co1.5S4 was also used to assemble an asymmetric supercapacitor with reduced graphene oxide and attains excellent capacitive performance with high specific capacitance (113 F g−1 at 1 A g−1), high energy density (37.6 W h kg−1 at 775 W kg−1) and high power density (23.25 kW kg−1 at 17.7 W h kg−1).

One-pot synthesis of porous nickel cobalt sulphides: tuning the composition for superior pseudocapacitance

Facilely synthesized α phase nickel–cobalt bimetallic hydroxides: Tuning the composition for high pseudocapacitance

A novel and facile one-step method for growing α-phase nickel–cobalt hydroxides is developed. The use of 1-methyl-2-pyrrolidone (NMP) in the mixed solvent plays the decisive role in the precipitation of metal ions and the formation of α-phase hydroxides. The synthetic method is robust enough to synthesize Ni–Co hydroxides with different stoichiometric ratios of Ni and Co, and can be extended to the fabrication of Ni0.67Zn0.33 hydroxide in the α phase. More encouragingly, the method employed can be further used to grow layered nickel-cobalt hydroxides on Ni foam. As the electroactive materials for pseudocapacitors, the Ni–Co hydroxides deliver an ultrahigh specific capacitance (1337.4 F g−1 at 1 A g−1 for Ni0.67Co0.33 hydroxide) with improved rate capability and cycling stability. Moreover, a greatly increased specific capacitance (2248.9 and 2286.7 F g−1 at 1 A g−1 for Ni0.5Co0.5 and Ni0.67Co0.33 hydroxides, respectively) with superior cycling stability is obtained after growth on Ni foam.

Yuandong Zhao

Papers

In situ growth of NiCo2S4 nanotube arrays on Ni foam for supercapacitors: Maximizing utilization efficiency at high mass loading to achieve ultrahigh areal pseudocapacitance

One-pot synthesis of porous nickel cobalt sulphides: tuning the composition for superior pseudocapacitance

Facilely synthesized α phase nickel–cobalt bimetallic hydroxides: Tuning the composition for high pseudocapacitance

One-Pot Fabrication of Layered α-Phase Nickel–Cobalt Hydroxides as Advanced Electrode Materials for Pseudocapacitors