Three-dimensional heterostructured MnO2/graphene/carbon nanotube composite on Ni foam for binder-free supercapacitor electrode

In this article, three-dimensional (3D) heterostructured of MnO₂/graphene/carbon nanotube (CNT) composites were synthesized by electrochemical deposition (ELD)-electrophoretic deposition (EPD) and subsequently chemical vapour deposition (CVD) methods. MnO₂/graphene/CNT composites were directly used as binder-free electrodes to investigate the electrochemical performance. To design a novel electrode material with high specific area and excellent electrochemical property, the Ni foam was chosen as the substrate, which could provide a 3D skeleton extremely enhancing the specific surface area and limiting the huge volume change of the active materials. The experimental results indicated that the specific capacitance of MnO₂/graphene/CNT composite was up to 377.1 F g^?1 at the scan speed of 200 mV s^?1 with a measured energy density of 75.4 Wh kg^?1. The 3D hybrid structures also exhibited superior long cycling life with close to 90% specific capacitance retained after 500 cycles.     

Cr-doped MnO<Subscript>2</Subscript> nanostructure: morphology evolution and electrochemical properties

Cr-doped MnO₂ nanostructure has been fabricated via a facile hydrothermal method and its morphology and electrochemical properties was discussed systematically. In this process, flower-like MnO₂ transforms into the self-assembled orchid structure under the influence of Cr-doped. Moreover, electrochemical behaviors of the Cr-doped MnO₂ nanostructure electrode were clarified by cyclic voltammograms, galvanostatic charge/discharge tests and electrochemical impedance spectroscopy, which shows a high specific capacitance of 202.5 F g^?1 and superior cycling stability (6.8 % capacitance decay after 1000 cycling test). These remarkable and excellent results prove it has a great potential of application in future energy storage device.     

Improvement of hydrothermally synthesized MnO2 electrodes on Ni foams via facile annealing for supercapacitor applications

Nanostructured manganese dioxide (MnO₂) is deposited on nickel foams by a hydrothermal synthesis route. As-deposited MnO₂ thin films are largely amorphous. Facile post-deposition annealing significantly improves the electrochemical performance of the MnO₂ thin films via changing their morphology, phase, and crystallinity. The specific capacitance of the MnO₂ electrode increases with the annealing temperature and reaches an optimal value of 244 F g^?1 (at the current density of 1 A g^?1) in a neutral 1 M Na₂SO₄ electrolyte for a specimen annealed at 500 °C. Furthermore, when an alkaline 5 M KOH electrolyte is used, an exceptionally high capacitance of 950 F g^?1 is achieved at the current density of 2 A g^?1. The cost-effective facile synthesis, high specific capacitance, and good cycle stability of these MnO₂-based electrodes enable their applications in high-performance supercapacitors.     

Preparation of MnO<Subscript>2</Subscript>/graphene composite as electrode material for supercapacitors

MnO₂/graphene composite was synthesized by a facile and effective polymer-assisted chemical reduction method. The nanosized MnO₂ particles were homogeneously distributed on graphene nanosheets, which have been confirmed by scanning electron microscopy and transmission electron microscopy analysis. The capacitive properties of the MnO₂/graphene composite have been investigated by cyclic voltammetry(CV). MnO₂/graphene composite exhibited a high specific capacitance of 324 F g⁻¹ in 1 M Na₂SO₄ electrolyte. In addition, the MnO₂/graphene composite electrode shows excellent long-term cycle stability (only 3.2% decrease of the specific capacitance is observed after 1,000 CV cycles).     

Investigation for the synthesis of hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@MnO<Subscript>2</Subscript> nanoarrays materials and their application for supercapacitor

We designed and fabricated hierarchical Co₃O₄@MnO₂ nanoarrays directly grown on nickel foam by hydrothermal and calcination methods. After the investigation of growth mechanism, we found that the deposition of MnO₂ was based on the self-decomposition of KMnO₄ and the reducibility of Co₃O₄ during the hydrothermal process. Thanks to the hierarchical structure, the obtained electrode exhibited excellent capacitive performance in supercapacitor. It delivered 21.72 F cm^?2 at a current density of 5 mA cm^?2 and retained ~94 % capacitance of initial value after 5000 cycles.     

Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles embedded in 3D reduced graphene oxide network as anode for high-performance lithium ion batteries

Mn₃O₄ nanoparticles were in-situ synthesized in the 3D framework of reduced graphene oxide (RGO) by a facile one-step hydrothermal method. In the reduced graphene-Mn₃O₄ (RGM) composite, the RGO network not only serves as a mechanical support to construct a self-supported and binder-free electrode, but also offers 3D continuous conductive network for effective electron transfer. The Mn₃O₄ nanoparticles anchored uniformly across the RGO framework, which provided high capacity and prevented the restacking of the RGO thin sheets. Based on the unique composite structures, strong synergistic effect was achieved between Mn₃O₄ and RGO, resulting in superior specific capacity, enhanced rate capability, stable cycling performance and nearly 100% Coulombic efficiency in the RGM2 composites. With an optimal Mn₃O₄ composition of 44% by weight (similarly hereinafter), the composite exhibits high specific capacities of 696–795 mAh g¹ based on the overall weight of the electrode in 60 cycles at 200 mA g^?1, with a large coulombic efficiency of around 98%. Even at a high current density of 10,000 mA g^?1, the composite can still deliver a capacity of 383 mAh g^?1, demonstrating its excellent rate performance. The outstanding performances of the composites are attributed to the synergistic effect of both components and the hierarchical structure of the composite.     

Electrochemical co-deposition and characterization of MnO2/SWNT composite for supercapacitor application

Manganese oxide/single-wall carbon nanotubes (MnO₂/SWNT) composite was co-deposited by the potentiostatic method on a graphite slice. Morphological and structural performances for MnO₂/SWNT composite were characterized by means of scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The wall surface of SWNT was wrapped by ramsdellite MnO₂ nanoparticles to fabricate MnO₂/SWNT coaxial nanotubes, which further interconnected other MnO₂ particles to form the porous MnO₂/SWNT composite. The electrochemical properties were examined by cyclic voltammograms, galvanostatic charge and discharge and electrochemical impedance spectrum. A high specific capacitance of 421 F g^?1 was obtained for overall MnO₂/SWNT composite electrode at the constant current density of 1 A g^?1 in 3 mol L^?1 KCl solution.     

Facile synthesis of graphene@NiMoO<Subscript>4</Subscript> nanosheet arrays on Ni foam for a high-performance asymmetric supercapacitor

Honeycomb-like NiMoO₄ with nanosheet arrays is grown on reduced graphene oxide, which is supported on Ni foam having successfully fabricated by a simple hydrothermal treatment followed by a calcined process. In the as-synthesized Ni foam@reduced graphene oxide@NiMoO₄, Ni foam served as “skeleton” to support reduced graphene oxide and reduced graphene oxide directly grown on Ni foam served as the “skin” to provide high passway of electrons and ions, which simultaneously accommodated the volume change during the process of charge–discharge and NiMoO₄ acted as active substance to provide high areal capacitance. It shows a high areal capacitance of 2165.9 mF cm^?2 at a current density of 1 mA cm^?2 and long cycle stability with 93.8% capacitance retained over 1000 charge–discharge cycles. Moreover, an asymmetric supercapacitor has been constructed by using Ni foam@reduced graphene oxide and Ni foam@reduced graphene oxide@NiMoO₄ as negative and positive electrodes. The energy density of this asymmetric supercapacitor is 0.579 mWh cm^?2, and it retains 93.1% capacitance over charge–discharge 5000 cycles. Therefore, it reveals great promise for practical applications in energy storage devices.     

3D composites of ZnSnO<Subscript>3</Subscript> nanoplates/reduced graphene oxide aerogels as an advanced lithium-ion battery anode

Zinc-based bimetal oxides have received considerable attention as anode for lithium-ion batteries (LIBs). A one-pot self-assembly hydrothermal method is developed for the fabrication of 3D hierarchical structure aerogels from zinc stannate (ZnSnO₃) and reduced graphene oxide (rGO). 3D interconnected porous structure with ZnSnO₃ hexagon nanoplates uniformly dispersed on graphene sheets has been constructed successfully, in which the crystalline hexagon nanoplates ZnSnO₃ are firstly used to prepare ZnSnO₃-based anode materials for LIBs. The as-prepared ZnSnO₃ nanoplates/reduced graphene oxide aerogels (ZnSnO₃–rGAs) electrode demonstrates an excellent reversible capacity (780 mAh g^?1) after 200 cycles at a certain current density (100 mA g^?1) and still delivers a specific capacity of 460 mAh g^?1 even at 1000 mA g^?1. The superior performance of lithium storage is attributed to the 3D porous hierarchical structure and the synergistic effects of uniform hexagon nanoplates ZnSnO₃ and rGO sheets.     

Successful synthesis of interconnected Co<Subscript>0.85</Subscript>Se nanosheets with high pore volume and its electrochemical performance in supercapacitors

Interconnected Co_0.85Se nanosheets have been prepared by a facile hydrothermal method via tuning reaction time to control the chemical constitution and the morphology. The nanosheets morphology of Co_0.85Se offers sufficient electron transfer and short ion diffusion pathway, which can favor the fast transfer of electrolyte ions. The Co_0.85Se electrode exhibits specific capacitance of 980 F g^??1 at 10 A g^??1 with high cycling life stability (8.3% loss after 5000 cycles) and good conductivity. The assembled Co_0.85Se//AC asymmetric supercapacitor (ASC) device exhibits a high energy density of 46.2 Wh kg^??1 at a power density of 807.4 W kg^??1 and still maintained 29.3 Wh kg^??1 at a power density of 15981.8 W kg^??1 with excellent cycling performance (90.01% capacitance retention over 5000 cycles). The impressive results indicate that such unique interconnected Co_0.85Se nanosheets are promising electrode materials for high-performance supercapacitors.     

Growth of cobalt–nickel layered double hydroxide on nitrogen-doped graphene by simple co-precipitation method for supercapacitor electrodes

Nitrogen-doped graphene/Co–Ni layered double hydroxide (RGN/Co–Ni LDH) is synthesized by a facile co-precipitation method. Transmission electron microscopy images indicated that the formation of Co–Ni(OH)₂ nanoflakes with the good dispersion anchored on the surfaces of the nitrogen-doped graphene sheets. The nitrogen-doped graphene composites delivered the enhanced electrochemical performances compared to the pure Co–Ni LDH due to the improved electronic conductivity and its hierarchical layer structures. The high specific capacitance of 2092 F g^?1 at current density of 5 mA cm^?2 and the rate retention of 86.5% at current density of 5–50 mA cm^?2 are achieved by RGN/Co–Ni LDH, higher than that of pure Co–Ni LDH (1479 F g^?1 and 76.5%). Moreover, the two-electrode asymmetric supercapacitor, with the RGN/Co–Ni LDH composites as the positive electrode and active carbon as the negative electrode material, exhibits energy density of 49.4 Wh kg^?1 and power density of 101.97 W kg^?1 at the current density of 5 mA cm^?2, indicating the composite has better capacitive behavior.     

High-performance flexible supercapacitors based on C/Na<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>11</Subscript> nanocomposite electrode materials

A new solution method to synthesize Na₂Ti₅O₁₁ with titanium powder is presented, and the C/Na₂Ti₅O₁₁ nanocomposite with high specific surface area and tunnel structure as the electrode material has excellent electrochemical performance. The single electrode composed of the C/Na₂Ti₅O₁₁ nanocomposite based on carbon fiber fabric (CFF) has the highest area capacitance of 1066 mF cm^?2 at a current density of 2 mA cm^?2, which is superior to other titanates and Na-ion materials for supercapacitors (SCs). By scan-rate dependence cyclic voltammetry analysis, the capacity value shows both capacitive and faradaic intercalation processes, and the intercalation process contributed 81.7% of the total charge storage at the scan rate of 5 mV s^?1. The flexible symmetric solid-state SCs (C/Na₂Ti₅O₁₁/CFF//C/Na₂Ti₅O₁₁/CFF) based on different C/Na₂Ti₅O₁₁ mass were fabricated, and 7 mg SCs show the best supercapacitive characteristics with an area capacitance of 309 mF cm^?2 and a specific capacitance of 441 F g^?1, it has a maximum energy density of 22 Wh kg^?1 and power density of 1286 W kg^?1. As for practical application, three SCs in series can power 100 green light-emitting diodes (LEDs) to light up for 18 min, which is much longer than our previous work by Wang et al. lighting 100 LEDs for 8 min. Thus, the C/Na₂Ti₅O₁₁ nanocomposite has promising potential application in energy storage devices.     

Ordered mesoporous carbon-supported CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> composite with enhanced lithium storage properties

A high and stable reversible specific capacity (1277.7 mAh g^?1) was successfully achieved by the CoFe₂O₄/ordered mesoporous carbon nanohybrids (CFO/CMK-3) composite anode at the current density of 0.1 A g^?1 after 100 cycles. CFO/CMK-3 electrode also exhibited a stable capacity up to 733.2 and 482.6 mAh g^?1 at the current densities of 0.5 and 1 A g^?1 after 500 cycles, respectively. The CFO particles were found to be uniformly distributed inside the pore channels of CMK-3. Structure characterization before and after 100 tests revealed that the specific CMK-3 mesoporous structure and CFO crystallites remained unchanged. The stability of the anode composite stability and the rapid redox capability of CFO gave rise to superior lithium storage capacity and excellent cycling stability. CFO/CMK-3 showed a great promise to serve as anode for high-performance lithium-ion battery.     

Super-capacitive performance depending on different crystal structures of MnO2 in graphene/MnO2 composites for supercapacitors

In the present study, we synthesize nanoneedle structures of MnO₂/graphene nanocomposites (N-RGO/MnO₂) and birnessite-type MnO₂/graphene nanocomposites (B-RGO/MnO₂). The morphologies and microstructures of as-prepared composites are characterized by X-ray diffractometry, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Our characterizations indicate that nanoneedle structures of MnO₂ and birnessite-type MnO₂ are successfully formed on graphene surfaces. Capacitive properties of the N-RGO/MnO₂ and B-RGO/MnO₂ electrodes are measured using cyclic voltammetry, galvanostatic charge/discharge tests, and electrochemical impedance spectroscopy in a three-electrode experimental setup using a 1 M Na₂SO₄ aqueous solution as the electrolyte. The N-RGO/MnO₂ electrode displays a specific capacitance as high as 327.5 F g^?1 at 10 mV s^?1, which is higher than that of a B-RGO/MnO₂ electrode (248.5 F g^?1). It is believed that the nanoneedle structure of MnO₂ shows excellent electrochemical properties than birnessite-type MnO₂ for the electrode materials for supercapacitors.     

Effect of Ti-ion non-stoichiometry on microstructure and microwave dielectric characteristic of Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> ceramics

This paper studies the microwave dielectric properties, microstructure, vibration and densification of Li₂ZnTi_3+xO_8+2x (\(- 0.04 \le {\text{x}} \le +0.06\)) ceramics, manufactured via a conventional mixed oxide route. The X-ray diffraction and Raman spectroscopy revealed the unit cell parameter and cation ordering in LZT non-stoichiometry in their vibrational modes. The densification and phase composition were characterized by the EDX and SEM methods. It was found that a slight Ti vacancy can improve the relative density to the maximum value (96.2%). The XRD results showed that the second phase of TiO₂ in the Li₂ZnTi_3.06O_8.12 composition is formed. The sintered samples were detected in the microwave frequency range by using the resonance technique. The \({\text{~}}{\tau _f}\) values of the ceramics within Ti excess adjusted to near zero. The Li₂ZnTi_2.96O_7.92 ceramic showed the best relative density, single phase and best microwave dielectric \({\varepsilon _r}~={\text{ }}25.98\), Q?×?f?=?61,000 GHz, \({\tau _f}={\text{ }} - 17.4{\text{ ppm/}}^\circ {\text{C}}\) sintered at 1100 °C for 4 h.     

MOF‐Derived Hollow Cage NixCo3−xO4 and Their Synergy with Graphene for Outstanding Supercapacitors

Highly optimized nickel cobalt mixed oxide has been derived from zeolite imidazole frameworks. While the pure cobalt oxide gives only 178.7 F g^?1 as the specific capacitance at a current density of 1 A g^?1, the optimized Ni:Co 1:1 has given an extremely high and unprecedented specific capacitance of 1931 F g^?1 at a current density of 1 A g^?1, with a capacitance retention of 69.5% after 5000 cycles in a three electrode test. This optimized Ni:Co 1:1 mixed oxide is further used to make a composite of nickel cobalt mixed oxide/graphene 3D hydrogel for enhancing the electrochemical performance by virtue of a continuous and porous graphene conductive network. The electrode made from GNi:Co 1:1 successfully achieves an even higher specific capacitance of 2870.8 F g^?1 at 1 A g^?1 and also shows a significant improvement in the cyclic stability with 81% capacitance retention after 5000 cycles. An asymmetric supercapacitor is also assembled using a pure graphene 3D hydrogel as the negative electrode and the GNi:Co 1:1 as the positive electrode. With a potential window of 1.5 V and binder free electrodes, the capacitor gives a high specific energy density of 50.2 Wh kg^?1 at a high power density of 750 W kg^?1.     

Intertwined Nanocarbon and Manganese Oxide Hybrid Foam for High‐Energy Supercapacitors

Rapid charging and discharging supercapacitors are promising alternative energy storage systems for applications such as portable electronics and electric vehicles. Integration of pseudocapacitive metal oxides with single‐structured materials has received a lot of attention recently due to their superior electrochemical performance. In order to realize high energy‐density supercapacitors, a simple and scalable method is developed to fabricate a graphene/MWNT/MnO₂ nanowire (GMM) hybrid nanostructured foam, via a two‐step process. The 3D few‐layer graphene/MWNT (GM) architecture is grown on foamed metal foils (nickel foam) via ambient pressure chemical vapor deposition. Hydrothermally synthesized α‐MnO₂ nanowires are conformally coated onto the GM foam by a simple bath deposition. The as‐prepared hierarchical GMM foam yields a monographical graphene foam conformally covered with an intertwined, densely packed CNT/MnO₂ nanowire nanocomposite network. Symmetrical electrochemical capacitors (ECs) based on GMM foam electrodes show an extended operational voltage window of 1.6 V in aqueous electrolyte. A superior energy density of 391.7 Wh kg^?1 is obtained for the supercapacitor based on the GMM foam, which is much higher than ECs based on GM foam only (39.72 Wh kg^?1). A high specific capacitance (1108.79 F g^?1) and power density (799.84 kW kg^?1) are also achieved. Moreover, the great capacitance retention (97.94%) after 13 000 charge–discharge cycles and high current handability demonstrate the high stability of the electrodes of the supercapacitor. These excellent performances enable the innovative 3D hierarchical GMM foam to serve as EC electrodes, resulting in energy‐storage devices with high stability and power density in neutral aqueous electrolyte.     

Flexible carbon@graphene composite cloth for advanced lithium–sulfur batteries and supercapacitors with enhanced energy storage capability

Flexible carbon@graphene composite cloth was fabricated, and the resultant composite cloth consists of core–shell hollow structured carbon/graphene hybrid fibers with abundant micro- and mesoporosity and hydrophilic functionality. These unique features enable the composite cloth to be a promising material for energy storage application. As an efficient polysulfide adsorbent, the composite can be applied in lithium–sulfur batteries by being sandwiched between the sulfur cathode and polymeric separator. With this novel configuration, a high reversible capacity of ca. 900 mAh g^?1 and excellent cycle-life has been achieved, which is ascribed to the excellent polysulfides adsorption and confinement capability of the special core–shell and hollow structured porous hybrid fibers. Additionally, the composite cloth can be applied in supercapacitors as a flexible binder-free electrode, exhibiting a high specific capacitance of 271 F g^?1 (360 F cm^?3) at 0.1 A g^?1 in 6 M KOH, as well as excellent rate capability and cycling stability. The assembled symmetric supercapacitor supplies a high energy density of up to 9.4 Wh kg^?1 (12.5 Wh L^?1) with a power density of 25.0 W kg^?1 (33.3 W L^?1) and remains 5.7 Wh kg^?1 (7.6 Wh L^?1) with 4.5 kW kg^?1 (6.0 kW L^?1).     

Systematic investigation of the effect of oxygen mobility on CO oxidation over AgPt nanoshells supported on CeO<Subscript>2</Subscript>, TiO<Subscript>2</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Here, we have systematically investigated how the nature of the support influenced the oxygen mobility and activities in catalysts comprised of AgPt nanoshells deposited over inorganic oxides. We first synthesized AgPt nanoshells by galvanic replacement reaction between Ag nanospheres and PtCl₆ ^2? _(aq) combined with Pt reduction using hydroquinone as an auxiliary reducing agent. The nanoshells were then supported over TiO₂, Al₂O₃ and CeO₂. Through this methodology, we prepared materials with similar metallic nanoparticle AgPt compositions (~0.99 wt% Pt), sizes (43 ± 2 nm diameter), spherical shapes, surface morphologies, number of active sites \( (\sim4.5\;\upmu{\text{mol}}\;{\text{g}}_{{{\text{cat}} .}}^{ - 1} ) \) and uniform distribution over the supports, differing only in terms of the nature of the support. The oxide reduction temperature, its capability of re-oxidation and the presence of oxygen mobility were strongly dependent on the metal–support interaction between AgPt nanoshells and oxide supports. These properties have significantly influenced their catalytic performances toward the CO oxidation. At 230 °C, the CO oxidation TOF was 40.4 ± 0.4, 6.9 ± 1, 1.4 ± 0.8 min^?1 for AgPt/CeO₂, AgPt/TiO₂, AgPt/Al₂O₃, respectively. These differences were attributed to the concentration of oxygen vacancies in each catalyst, which presented exactly the same trend as that of the catalytic activities. Our results may have important contributions to the design of highly active metal oxide-based catalysts toward gas-phase oxidation transformations.     

Fabrication of a 3D Hierarchical Sandwich Co9S8/α‐MnS@N–C@MoS2 Nanowire Architectures as Advanced Electrode Material for High Performance Hybrid Supercapacitors

Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co₉S₈/α‐MnS@N–C@MoS₂ nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co₉S₈/α‐MnS@N–C@MoS₂ electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g^?1/1938 F g^?1 at 1 A g^?1, and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g^?1. Moreover, the fabricated asymmetric supercapacitor device using Co₉S₈/α‐MnS@N–C@MoS₂ as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg^?1 at 729.2 W kg^?1, and a promising energy density of 23.5 Wh kg^?1 is still attained at a high power density of 11 300 W kg^?1. The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.