Samarium-doped Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles with improved magnetic and supercapacitive performance: a novel preparation strategy and characterization

Sm³⁺-doped magnetite (Fe₃O₄) nanoparticles were synthesized through a one-pot facile electrochemical method. In this method, products were electrodeposited on a stainless steel (316L) cathode from an additive-free 0.005 M Fe(NO₃)₃/FeCl₂/SmCl₃ aqueous electrolyte. The structural characterizations through X-ray diffraction, field-emission electron microscopy, and energy-dispersive X-ray indicated that the deposited material has Sm³⁺-doped magnetite particles with average size of 20 nm. Magnetic analysis by VSM revealed the superparamagnetic nature of the prepared nanoparticles (Ms = 41.89 emu g^?1, Mr = 0.12 emu g^?1, and H _Ci = 2.24 G). The supercapacitive capability evaluation of the prepared magnetite nanoparticles through cyclic voltammetry and galvanostat charge–discharge showed that these materials are capable to deliver specific capacitances as high as 207 F g^?1 (at 0.5 A g^?1) and 145 F g^?1 (at 2 A g^?1), and capacity retentions of 94.5 and 84.6% after 2000 cycling at 0.5 and 1 A g^?1, respectively. The results proved the suitability of the electrosynthesized nanoparticles for use in supercapacitors. Furthermore, this work provides a facile electrochemical route for the synthesis of lanthanide-doped magnetite nanoparticles.     

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.     

Vertically-aligned Mn(OH)<Subscript>2</Subscript> nanosheet films for flexible all-solid-state electrochemical supercapacitors

The arrangement of the electrode materials is a significant contributor for constructing high performance supercapacitor. Here, vertically-aligned Mn(OH)₂ nanosheet thin films were synthesized by cathodic electrodeposition technique on flexible Au coated polyethylene terephthalate substrates. Morphologies, microstructures, chemical compositions and valence state of the nanosheet films were characterized systematically. It shows that the nanosheets arranged vertically to the substrate, forming a porous nanowall structures and creating large open framework, which greatly facilitate the adsorption or diffusion of electrolyte ions for faradaic redox reaction. Electrochemical tests of the films show the specific capacitance as high as 240.2 F g^?1 at 1.0 A g^?1. The films were employed to assemble symmetric all-solid-state supercapacitors with LiCl/PVA gel severed as solid electrolyte. The solid devices exhibit high volumetric capacitance of 39.3 mF?cm^?3 at the current density 0.3 mA cm^?3 with robust cycling stability. The superior performance is attributed to the vertically-aligned configuration.     

Facile synthesis and characterization of MnO<Subscript>2</Subscript> nanomaterials as supercapacitor electrode materials

MnO₂ nanomaterials are synthesized via calcinations in air at various temperatures. Amorphous MnO₂ masses appear between 100 and 300 °C and nanorods form above 400 °C. Transmission and scanning electron microscopy are used to observe the geometries of each material, with further structural analyses conducted using X-ray photoelectron spectroscopy, X-ray diffraction, and BET method. The electrochemical properties are investigated through galvanostatic charge/discharge cycling, electrochemical impedance spectra, and cyclic voltammetry within a three-electrode test cell filled with 1 mol L^?1 Na₂SO₄ solution. The slightly asymmetric galvanostatic cycling curves suggest that the reversibility of the Faradaic reactions are imperfect, requiring a larger time to charge than discharge. The specific capacitances of each sample are calculated and trends are identified, proving that the samples synthesized at higher temperatures exhibit poorer electrochemical behaviors. The highest calculated specific capacitance is 175 F g^?1 by the sample calcinated at 400 °C. However, the lower temperature samples exhibit more favorable geometric properties and higher overall average specific capacitances. For future research, it is suggested that surface modifications such as a carbon coating could be used in conjunction with the MnO₂ nanorods to reach the electrochemical properties required by contemporary industrial applications.     

Binder-free polyaniline interconnected metal hexacyanoferrates nanocomposites (Metal = Ni,Co) on carbon fibers for flexible supercapacitors

Improvement of the electrical conductivity, specific capacitance and binder-free polyaniline (PANI) interconnected with metal(II) hexacyanoferrate(III) (MHCF) nanocomposites (M?=?Ni, Co) on flexible carbon fibers (CF) were designed in our present research goal. PANI/MHCF/CF nanocomposites were prepared by one-step co-polymerization method. Electrochemical studies like cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy were analyzed. Under the optimized conditions, the nanocomposites demonstrated remarkable electrochemical performances as supercapacitor electrode with outstanding specific capacitances of ~725 F g^?1 at a current density of 1 A g^?1, and retained ~325 F g^?1 even at a high current density of 20 A g^?1 in 0.5 M H₂SO₄?+?0.5 M Na₂SO₄ solution. The excellent cycling stability with capacitance retention of 80% after 1000 cycles may be a potential electrode material for future supercapacitor when its cycling stability and rate performance are addressed.     

Multilayer super-short carbon nanotube/nickel hydroxide nanoflakes for enhanced supercapacitor properties

Multilayer super-short carbon nanotubes (SSCNTs) could be synthesized by tailoring the raw multiwalled carbon nanotubes with a simple ultrasonic oxidation-cut method. Nanostructured layered nickel hydroxide and SSCNTs have been successfully assembled to form Ni(OH)₂/SSCNTs composite by electrostatic force. Compared with pure Ni(OH)₂ (665 F g^?1), the Ni(OH)₂/SSCNTs composite exhibits the much better electrochemical performance with a specific capacitance of 1887 F g^?1 at 1 A g^?1, and demonstrates a good rate capability and excellent long-term cyclic stability (92 % capacity retention after 3000 cycles). It is the reason that the SSCNTs can form a conductive network onto the surface of Ni(OH)₂ nanoflakes, and their excellent electric conductivity is advantaged to the charge transport on the electrode in discharge process and charge process. Therefore, the greatly enhanced capacitive performance of Ni(OH)₂/SSCNTs can be attributed to a synergetic effect of Ni(OH)₂ and SSCNTs.     

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.     

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.     

Cathodic electrosynthesis of CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CuO composite nanostructures for high performance supercapacitor applications

In this work, CuFe₂O₄/CuO nanocomposites have been synthesized by galvanostatic cathodic electrodeposition. The obtained nanocomposites were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier Transform Infrared, and Brunauer–Emmett–Teller surface area analysis. The electrochemical properties of CuFe₂O₄/CuO nanocomposites were evaluated by cyclic voltammetry, galvanostatic charge–discharge cycling, and electrochemical impedance spectroscopy in 1.0 M KOH. The CuFe₂O₄/CuO nanocomposites have shown the high specific capacitance of 322.49 F g^?1 at the scan rate of 1 mV s^?1. After 5000 cycles, 92% of this specific capacitance was retained. Although the prepared nanocomposite has shown a mediocre specific capacitance compared to other metal oxide-based materials, the low cost of the starting materials and the ease of preparation make this nanocomposite a good candidate for supercapacitor applications.     

Impact of CTAB on morphology and electrochemical performance of MoS<Subscript>2</Subscript> nanoflowers with improved lithium storage properties

The search for high capacity, low-cost electrode materials for lithium-ion batteries is a significant challenge in energy research. Among the numerous potential candidates, layered compounds such as MoS₂ (Molybdenum Disulfide) have attracted increasing attention. A facile hydrothermal reduction process using hexadecyltrimethy ammonium bromide (CTAB) as surfactant was developed for the synthesis of lithium-ion battery anode material MoS₂ nanoflowers. The impact of CTAB on morphology and electrochemical performance of MoS₂ has been investigated. With the increase of CTAB content, MoS₂ ultrathin nanosheets with high specific surface area and more active sites have been successfully synthesized. Electrochemical measurements demonstrated that MoS₂ nanoflowers synthesized with 1% content of CTAB have better electrochemical performance than others as anode materials for Li-ion batteries, which yield a high discharge capacity of 1245 mAh g^?1 at a current density of 50 mA g^?1 and a stable capacity retention of 740 mAh g^?1 until 100 electrochemical cycles.     

Building an interpenetrating network of Ni(OH)<Subscript>2</Subscript>/reduced graphene oxide composite by a sol–gel method

Herein, a facile sol–gel strategy for building the ordered interpenetrating network of Ni(OH)₂ and reduced graphene oxide (rGO) was proposed. In this strategy, rGO nanosheets were homogeneously fixed inside composite utilizing the pores of Ni(OH)₂ gel as template, forming rGO-interpenetrated gel network. It was found that the rGO nanosheets could effectively reduce the internal resistant of composites and provide mechanical support for the gel network of Ni(OH)₂. Therefore, the composite presented high electrochemical performance, especially high-rate performance, due to the interpenetrating of rGO nanosheets plus the supplementary role of acetylene black. It had high specific capacitance of 2163 F g^?1 at low current density of 2.9 A g^?1 and 733 F g^?1 at high current density of 86.8 A g^?1.     

Electrochemical performance of Sn-doped δ-MnO<Subscript>2</Subscript> hollow nanoparticles for supercapacitors

Sn-doped δ-MnO₂ (Sn-MnO₂) hollow nanoparticles have been synthesized via chemical process at room temperature. Many characterizations have been carried out to fully identify the intrinsic information of the as-prepared samples and investigate their electrochemical properties. The results indicate that the morphologies of the samples can be adjusted by changing the concentration of Sn while the capacitance of Sn-MnO₂ nanoparticles increased corresponded with that of the undoped δ-MnO₂ nanoparticles. The specific capacitance of Sn(1 at.%)-MnO₂ is up to 258.2 F g^??1 at a current density of 0.1 A g^??1. What’s more, over 90% of the initial specific capacitance still remains after 1000 cycles at a current density of 2.0 A g^??1, displaying excellent cycling stability.     

Li-ion storage performance and electrochemically induced phase evolution of layer-structured Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> cathode material

Li-rich Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ (LMNC) powders were synthesized by a gel-combustion method. The related microstructure, electrochemical performance and electrochemically induced phase evolution were characterized. The 900°C calcined powders have a hexagonal layered structure with high ordered degree and low cationic mixing level. The calcined materials as cathode electrode for Li-ion battery deliver the high electrochemical properties with an initial discharge capacity of 243.5 mA?h?g^–1 at 25 mA?g^–1 and 249.2 mA?h?g^–1 even after 50 cycles. The electrochemically induced phase evolution investigated by a transmission electron microscopy indicates that Li⁺ ions deintercalated first from the LiMO₂ (M = Mn, Co, Ni) component and then from Li₂MnO₃ component in the LMNC during the charge process, while Li⁺ ions intercalated into Li_1–xMO₂ component followed by into MnO₂ component during the discharge process.     

SnO<Subscript>2</Subscript>-based thin films with excellent photocatalytic performance

SnO₂ semiconductor is a new-typed promising photocatalyst, but wide application of SnO₂-based photocatalytic technology has been restricted by low visible light utilization efficiency and rapid recombination of photogenerated electrons–holes. To overcome these drawbacks, we prepared B/Fe codoped SnO₂–ZnO thin films on glass substrates through a simple sol–gel method. The photocatalytic activities of the films were evaluated by degradation of organic pollutants including acid naphthol red (ANR) and formaldehyde. UV–Vis absorption spectroscopy and photoluminescence (PL) spectra results revealed that the B/Fe codoped SnO₂–ZnO film not only enhanced optical absorption properties but also improved lifetime of the charge carriers. X-ray diffraction (XRD) results indicated that the nanocrystalline SnO₂ was a single crystal type of rutile. Field emission scanning electron microscopy (FE-SEM) results showed that the B/Fe codoped SnO2–ZnO film without cracks was composed of smaller nanoparticles or aggregates compared to pure SnO2 film. Brunauer–Emmett–Teller (BET) surface area results showed that the specific surface area of the B/Fe codoped SnO₂–ZnO was 85.2 m² g^?1, while that of the pure SnO₂ was 20.7 m² g^?1. Experimental results exhibited that the B/Fe codoped SnO₂–ZnO film had the best photocatalytic activity compared to a pure SnO₂ or singly-modified SnO₂ film.     

Rietveld analysis of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films obtained by RF-sputtering

Calcium copper titanate, CaCu₃Ti₄O₁₂, CCTO, thin films with polycrystalline nature have been deposited by RF sputtering on Pt/Ti/SiO₂/Si (100) substrates at a room temperature followed by annealing at 600 °C for 2 h in a conventional furnace. The crystalline structure and the surface morphology of the films were markedly affected by the growth conditions. Rietveld analysis reveal a CCTO film with 100 % pure perovskite belonging to a space group Im3 and pseudo-cubic structure. The XPS spectroscopy reveal that the in a reducing N₂ atmosphere a lower Cu/Ca and Ti/Ca ratio were detected, while the O₂ treatment led to an excess of Cu, due to Cu segregation of the surface forming copper oxide crystals. The film present frequency -independent dielectric properties in the temperature range evaluated, which is similar to those properties obtained in single-crystal or epitaxial thin films. The room temperature dielectric constant of the 600-nm-thick CCTO films annealed at 600 °C at 1 kHz was found to be 70. The leakage current of the MFS capacitor structure was governed by the Schottky barrier conduction mechanism and the leakage current density was lower than 10^?7 A/cm² at a 1.0 V. The current–voltage measurements on MFS capacitors established good switching characteristics.     

Synthesis and electrochemical performances of a novel two-dimensional nanocomposite: polyaniline-coated laponite nanosheets

A novel two-dimensional nanocomposite, polyaniline-coated laponite (polyaniline/laponite) nanosheets, has been prepared by in situ oxidative polymerization of aniline on the surface of laponite nanosheets. These sheets present a loosely stacked structure with the formation of a great number of pores, which it can provide a larger electrode/electrolyte contact surface area, shorten the path for ions transport in the active material, and alleviate the expansion and contraction of the electrode material during the charge/discharge processes, leading to an improved electrochemical performance. As an active material for supercapacitors, the specific charge/discharge capacitance of polyaniline/laponite nanosheets is 375 and 330 F g^?1 (based on the total working electrode mass) at a current density of 0.5 A g^?1, respectively, with a coulombic efficiency of 88 % which is higher than that of pure polyaniline (28 %). Moreover, polyaniline/laponite nanosheets also show a good rate capability with a growth of current density from 0.5 to 30 A g^?1, a specific discharge capacitance of 266 F g^?1 remained at 30 A g^?1. This work suggests a strategy to improve the electrochemical performances of polyaniline.     

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.     

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.     

Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods with secondary plate-like nanostructures; preparation,characterization and application as high performance electrode material in supercapacitors

Mn₃O₄ nanorods with secondary plate-like structures were prepared through precipitation from a 0.005 M manganese chloride bath, under the applying direct current mode (i = 2 mA cm^?2). The structural analysis through XRD and FTIR confirmed that the deposited nanopowder has pure monoclinic phase of Mn₃O₄. Further morphological assessment through SEM proved the product to have the Mn₃O₄ nanorods in large quantity, which constructed the secondary plate-like building blocks. Cyclic voltammetric and charge–discharge experiments on the product indicated the prepared Mn₃O₄ to possess high specific capacitance (SC) values of 298 F g^?1, as well as an outstandingly durable cycling stability (95.1 % of initial capacity after discharging 1000 cycles).