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Journal ArticleDOI: 10.1039/D0TA11606H

Hybrid layered double hydroxides as multifunctional nanomaterials for overall water splitting and supercapacitor applications

02 Mar 2021-Journal of Materials Chemistry (Royal Society of Chemistry)-Vol. 9, Iss: 8, pp 4528-4557
Abstract: Global demand for energy conversion and storage technologies such as fuel cells, water electrolyzers, batteries, and supercapacitors is increasing, yet their commercial and environmental viability are critically dependent on the performance of their electrode materials and catalysts, which are the indispensable components that drive these systems. Among various materials, layered double hydroxides (LDHs) are considered promising candidates for catalysts and electrodes for electrochemical energy conversion and storage systems. Their diverse range of chemical properties make them highly versatile platforms for developing hybrid nanostructures, including flexible two-dimensional LDH nanostructures with various di-/tri-valent metals. Hybrid LDHs also exhibit unique structural attributes, including 3D hierarchical porous features and heterointerfaces, as well as optimized electrical conductivity and stability, which are crucial to achieving highly efficient multifunctional nanomaterials for electrochemical energy device applications. This review presents recent developments in the design, synthetic routes, structural/chemical modification strategies, and applications of hybrid LDHs as multifunctional nanomaterials for overall water splitting and electrochemical supercapacitors. Recent advances in modification strategies are critically assessed to determine their effect on the physicochemical properties of hybrid LDHs. The hybrid nanostructures' alteration of energy barriers in the electrocatalytic reactions is also discussed. Finally, this review concludes with future outlooks for hybrid LDH nanostructures.

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12 results found

Open access
01 Sep 2016-
Abstract: The synthesis of layered double hydroxide (LDH) as electroactive material has been well reported; however, fabricating an LDH electrode with excellent electrochemical performance at high current density remains a challenge. In this paper, we report a 3D hierarchical porous flower-like NiAl-LDH grown on nickel foam (NF) through a liquid-phase deposition method as a high-performance binder-free electrode for energy storage. With large ion-accessible surface area as well as efficient electron and ion transport pathways, the prepared LDH-NF electrode achieves high specific capacity (1250 C g−1 at 2 A g−1 and 401 C g−1 at 50 A g−1) after 5000 cycles of activation at 20 A g−1 and high cycling stability (76.7% retention after another 5000 cycles at 50 A g−1), which is higher than those of most previously reported NiAl-LDH-based materials. Moreover, a hybrid supercapacitor with LDH-NF as the positive electrode and porous graphene nanosheet coated on NF (GNS-NF) as the negative electrode, delivers high energy density (30.2 Wh kg−1 at a power density of 800 W kg−1) and long cycle life, which outperforms the other devices reported in the literature. This study shows that the prepared LDH-NF electrode offers great potential in energy storage device applications.

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Topics: Electrode (54%), Nanosheet (53%), Supercapacitor (52%)

143 Citations

Journal ArticleDOI: 10.1016/J.ENSM.2021.04.023
Abstract: Herein, a solution-free dry strategy for the growth of self-assembled ordered tricopper phosphide (Cu3P) nanorod arrays is developed and the product is employed as a high-energy, stable positive electrode for a solid-state hybrid supercapacitor (HSC). The ordered Cu3P nanorod arrays grown on the copper foam deliver an excellent specific capacity of 664 mA h/g with an energy efficiency of 88% at 6 A/g and an ultra-long cycling stability over 15,000 continuous charge–discharge cycles. These electrochemical features are attributed to the ordered growth of the Cu3P nanorod arrays, which offers a large number of accessible electroactive sites, a reduced number of ion transfer paths, and reversible redox activity. The potential of the Cu3P nanorod arrays is further explored by engineering solid-state HSCs in which the nanorods are paired with an activated carbon-based negative electrode. The constructed cell is shown to convey a specific energy of 76.85 Wh/kg at a specific power of 1,125 W/kg and an 88% capacitance retention over 15,000 cycles. Moreover, the superior energy storing and delivery capacity of the cell is demonstrated by an energy efficiency of around 65%. The versatile solution-free dry strategies developed here pave the way towards engineering a range of electrode materials for next-generation energy storage systems.

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Topics: Nanorod (58%), Supercapacitor (52%), Specific energy (51%)

9 Citations

Journal ArticleDOI: 10.1016/J.CCR.2021.214103
Zhongzhu Yang1, Chang Zhang1, Guangming Zeng1, Xiaofei Tan1  +7 moreInstitutions (2)
Abstract: Photocatalytic (PC) and Photoelectrochemical (PEC) water splitting have been regarded as an attainable and sustainable strategy to obtain hydrogen and oxygen. Developing earth-abundant H2/O2-production catalysts with high catalytic activity and robust stability has attracted much attention. Due to the flexible multiple metal cations in the host layers, intercalated anions with interlayer spaces, and good chemical/physical stability, Layered double hydroxides (LDHs) have been proved as versatile and robust catalysts/co-catalysts in PC/PEC water splitting. In this article, recent progress in the rational design of LDH-based catalysts toward PC/PEC are well reviewed. Firstly, the characteristic of LDH is briefly introduced. Then, we specifically addressed the recent research efforts toward the application of pristine LDHs and semiconductor/LDH materials as photocatalytic catalysts in photocatalytic H2-generation, O2-evolution and photoelectrochemical water splitting. Finally, the remaining challenges to investigate and optimize the catalyzing ability of LDH based catalysts are stated to promote possible future development of LDH.

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7 Citations

Open accessJournal ArticleDOI: 10.1038/S41598-021-87823-6
16 Apr 2021-Scientific Reports
Abstract: Manganese ferrite (MnFe2O4) nanoparticles were synthesized via a hydrothermal method and combined with exfoliated MoS2 nanosheets, and the nanocomposite was studied as a supercapacitor. X-ray diffractometry and Raman spectroscopy confirmed the crystalline structures and structural characteristics of the nanocomposite. Transmission electron microscopy images showed the uniform size distribution of MnFe2O4 nanoparticles (~ 13 nm) on few-layer MoS2 nanosheets. UV-visible absorption photospectrometry indicated a decrease in the bandgap of MnFe2O4 by MoS2, resulting in a higher conductivity that is suitable for capacitance. Electrochemical tests showed that the incorporation of MoS2 nanosheets largely increased the specific capacitance of MnFe2O4 from 600 to 2093 F/g (with the corresponding energy density and power density of 46.51 Wh/kg and 213.64 W/kg, respectively) at 1 A/g, and led to better charge-discharge cycling stability. We also demonstrated a real-world application of the MnFe2O4/MoS2 nanocomposite in a two-cell asymmetric supercapacitor setup. A density functional theory study was also performed on the MnFe2O4/MoS2 interface to analyze how a MoS2 monolayer can enhance the electronic properties of MnFe2O4 towards a higher specific capacitance.

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Topics: Nanocomposite (53%)

2 Citations

Open accessJournal ArticleDOI: 10.3389/FMATS.2021.781900
Abstract: Multifunctional nanomaterials have been attracting increasing attention as solutions to the existing challenges in energy systems and sensing technologies. In this regards, multifunctional NiVCe-layered double hydroxide (NiVCe-LDH) nanoparticles were synthesized by modified sol-gel method. The analysis of this material demonstrated excellent potential for its utilization as electrode materials for hybrid supercapacitor, oxygen evolution reaction (OER) and sensor applications. The NiVCe-LDH nanoparticles delivered a specific charge of 740 C g-1 at 10 A g-1 and decent rate performance (charge retention of 68.7% at 100 A g−1), showing excellent prospects as electrode material for hybrid energy storage devices. In addition, NiVCe-LDH nanoparticles have also been successfully applied as proof-of-concept for OER, as confirmed by their low Tafel slope of 47 mV dec−1. Finally, trimetallic NiVCe-LDH-based screen-printed electrodes were developed for the sensing of hydrogen peroxide directly in a real complex mouthwash sample, achieving a satisfactory recovery value around 98% employing a fast and simple BIA procedure. These results allow us to predict the great potential of this trimetallic hydroxide for building electrochemical sensors with good perspectives as electroactive material for OER processes and energy storage technologies.

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Topics: Supercapacitor (50%), Electrocatalyst (50%)


239 results found

Open accessJournal ArticleDOI: 10.1126/SCIENCE.1226419
21 Jun 2013-Science
Abstract: Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

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Topics: Exfoliation joint (55%), Nanosheet (51%), Carbon nanotube (51%)

2,647 Citations

Journal ArticleDOI: 10.1038/NMAT3313
Ram Subbaraman1, Dusan Tripkovic1, Kee-Chul Chang1, Dusan Strmcnik1  +6 moreInstitutions (1)
01 Jun 2012-Nature Materials
Abstract: Design and synthesis of materials for efficient electrochemical transformation of water to molecular hydrogen and of hydroxyl ions to oxygen in alkaline environments is of paramount importance in reducing energy losses in water–alkali electrolysers. Here, using 3d-M hydr(oxy)oxides, with distinct stoichiometries and morphologies in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) regions, we establish the overall catalytic activities for these reaction as a function of a more fundamental property, a descriptor, OH–M2+δ bond strength (0 ≤ δ ≤ 1.5). This relationship exhibits trends in reactivity (Mn < Fe < Co < Ni), which is governed by the strength of the OH–M2+δ energetic (Ni < Co < Fe < Mn). These trends are found to be independent of the source of the OH, either the supporting electrolyte (for the OER) or the water dissociation product (for the HER). The successful identification of these electrocatalytic trends provides the foundation for rational design of ‘active sites’ for practical alkaline HER and OER electrocatalysts. Efficient electrochemical transformation of water to molecular hydrogen and of hydroxyl ions to oxygen in alkaline environments is important for reducing energy losses in water–alkali electrolysers. Insight into the activities of hydr(oxy)oxides on platinum catalyst surfaces for hydrogen and oxygen evolution reactions should prove significant for designing practical alkaline electrocatalysts.

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Topics: Oxygen evolution (57%), Catalysis (53%), Electrocatalyst (53%) ... read more

1,728 Citations

Journal ArticleDOI: 10.1126/SCIENCE.1211934
Ram Subbaraman1, Dusan Tripkovic1, Dusan Strmcnik1, Kee-Chul Chang1  +4 moreInstitutions (1)
02 Dec 2011-Science
Abstract: Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.

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Topics: Water splitting (60%), Hydrogen (58%), Electrolysis of water (55%) ... read more

1,606 Citations

Open accessJournal ArticleDOI: 10.1038/NCOMMS5477
Fang Song1, Xile Hu1Institutions (1)
Abstract: The oxygen evolution reaction is a key reaction in water splitting. The common approach in the development of oxygen evolution catalysts is to search for catalytic materials with new and optimized chemical compositions and structures. Here we report an orthogonal approach to improve the activity of catalysts without alternating their compositions or structures. Specifically, liquid phase exfoliation is applied to enhance the oxygen evolution activity of layered double hydroxides. The exfoliated single-layer nanosheets exhibit significantly higher oxygen evolution activity than the corresponding bulk layered double hydroxides in alkaline conditions. The nanosheets from nickel iron and nickel cobalt layered double hydroxides outperform a commercial iridium dioxide catalyst in both activity and stability. The exfoliation creates more active sites and improves the electronic conductivity. This work demonstrates the promising catalytic activity of single-layered double hydroxides for the oxygen evolution reaction.

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Topics: Layered double hydroxides (64%), Oxygen evolution (58%), Exfoliation joint (56%) ... read more

1,510 Citations

Journal ArticleDOI: 10.1002/ADFM.201301747
Hao Chen1, Linfeng Hu1, Min Chen1, Yan Yan1  +1 moreInstitutions (1)
Abstract: A facile and novel one-step method of growing nickel-cobalt layered double hydroxide (Ni-Co LDH) hybrid films with ultrathin nanosheets and porous nanostructures on nickel foam is presented using cetyltrimethylammonium bromide as nanostructure growth assisting agent but without any adscititious alkali sources and oxidants. As pseudocapacitors, the as-obtained Ni-Co LDH hybrid film-based electrodes display a significantly enhanced specific capacitance (2682 F g−1 at 3 A g−1, based on active materials) and energy density (77.3 Wh kg−1 at 623 W kg−1), compared to most previously reported electrodes based on nickel-cobalt oxides/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni-Co LDH hybrid film as the positive electrode material and porous freeze-dried reduced graphene oxide (RGO) as the negative electrode material, exhibits an ultrahigh energy density (188 Wh kg−1) at an average power density of 1499 W kg−1 based on the mass of active material, which greatly exceeds the energy densities of most previously reported nickel or cobalt oxide/hydroxide-based asymmetric supercapacitors.

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Topics: Pseudocapacitor (55%), Cobalt oxide (55%), Hydroxide (53%) ... read more

1,029 Citations

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