Synthesis and electrochemical performance of mixed phase α/β nickel hydroxide by codoping with Ca<Superscript>2+</Superscript> and PO<Subscript>4</Subscript><Superscript>3−</Superscript>

Nickel hydroxide with a unique mixed phase α/β-Ni(OH)₂ was prepared by partially substituting Ca²⁺ for Ni²⁺ with supersonic co-precipitating method firstly. The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The results show that the Ca-substituted Ni(OH)₂ by adding PO₄ ^3? is α/β mixed phase, while the undoped Ni(OH)₂ and the Ca-substituted Ni(OH)₂ without adding PO₄ ^3? are pure β phase. Furthermore, the Ca-substituted Ni(OH)₂ by adding PO₄ ^3? exhibits irregular shape and contains many intercalated water molecules and anions as proven by SEM and FT-IR. Meanwhile, the prepared samples were added into micro-sized beta nickel hydroxide to form biphase electrode materials for Ni-MH battery. The electrochemical performances of the biphase electrodes were characterized by cyclic voltammetry (CV) and charge/discharge tests. The results demonstrate that the biphase electrode with mixed phase α/β-Ni(OH)₂ exhibits higher electrochemical activity, better electrochemical reversibility and charge efficient, higher discharge potential, and better cyclic stability. The specific discharge capacity of Ca-substituted α/β-Ni(OH)₂ electrode can retain 271.7 and 238 mAh/g after 80 cycles at 0.2 and 0.5 C, respectively. This indicates that it may be a promising positive active material for alkaline secondary batteries. The results reported in this work may be useful for the designing and synthesizing of nickel hydroxide materials with superior performance.     

Electrochemical preparation of Ni-La alloys from the EMIC-EG eutectic-based ionic liquid

The electrodeposition behavior of Ni-La alloys was investigated in 1-ethyl-3-methylimidazolium chloride-ethylene glycol (EMIC-EG; 1:2-M ratio) eutectic-based ionic liquid containing 0.1 M NiCl₂ and 0.2 M LaCl₃. Cyclic voltammograms revealed that La could be co-deposited with Ni under the inducement of Ni(II) species in this solvent. The analysis of the chronoamperometric transients showed that, as with deposition of metal Ni, the co-deposition of Ni-La alloy on a glassy carbon electrode followed an instantaneous nucleation and three-dimensional growth controlled by diffusion. Galvanostatically deposited Ni-La alloys with different composition and morphology were characterized by inductively coupled plasma–atomic emission spectrometry (ICP-AES), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM). The current density and temperature were found to play an important role in controlling the composition and surface morphology of the resultant Ni-La alloys. The structure of these deposits depended on the La content. Alloys containing less than 4 at.% La could be indexed to a disordered face-centered cubic structure similar to pure Ni, whereas alloys containing about 9 at.% Ni were completely amorphous (metallic glass).     

Continuous one-step synthesis of N-doped titania under supercritical and subcritical water conditions for photocatalytic reaction under visible light

N-doped titania was prepared continuously by one-step synthetic method under supercritical and subcritical water conditions using titanium(IV)tetraisopropoxide (TTIP) and nitric acid as a titania precursor and nitrogen source, respectively. The synthesized N-doped titania particles were characterized by XRD, N₂-adsorption, TEM, XPS, UV-vis diffuse reflectance spectroscopy. N-doped titania was successfully synthesized and its crystalline structure was homogenous anatase phase with high surface area. The absorption edge of synthesized N-doped titania shifted into the visible light region compared with commercial titania P25. All synthesized N-doped titania have higher photocatalytic activity than P25 under visible light irradiation. The photocatalytic activity of N-doped titania synthesized under supercritical water condition was the highest for the degradation of methyl orange under visible light due to the larger crystallite size compared with the N-doped titania synthesized under subcritical water condition.     

Physical and electrochemical characterizations of Ni-SiO2 nanocomposite coatings

Advances in materials performance often require the development of composite system. In the present investigation, SiO₂-reinforced nickel composite coatings were deposited on a mild steel substrate using direct current electrodeposition process employing a nickel acetate bath. Surface morphology, composition, microstructure and crystal orientation of the Ni and Ni-SiO₂ nanocomposite coatings were investigated by scanning electron microscope, energy dispersive X-ray spectroscopy and X-ray diffraction analysis, respectively. The effect of incorporation of SiO₂ particles in the Ni nanocomposite coating on the microhardness and corrosion behaviour has been evaluated. Smooth composite deposits containing well-distributed silicon oxide particles were obtained. The preferred growth process of the nickel matrix in crystallographic directions <111>, <200> and <220> is strongly influenced by SiO₂ nanoparticles. The average crystallite size was calculated by using X-ray diffraction analysis and it was ~23 nm for electrodeposited nickel and ~21 nm for Ni-SiO₂ nanocomposite coatings. The crystallite structure was fcc for electrodeposited nickel and Ni-SiO₂ nanocomposite coatings. The incorporation of SiO₂ particles into the Ni matrices was found to improve corrosion resistance of pure Ni coatings. The corrosion potential (E _corr) in the case of Ni-SiO₂ nanocomposite coatings had shown a negative shift, confirming the cathodic protective nature of the coating. The Ni-SiO₂ composite coatings have exhibited significantly improved microhardness (615 HV) compared to pure nickel coatings (265 HV)     

High-performance hierarchical cypress-like CuO/Cu<Subscript>2</Subscript>O/Cu anode for lithium ion battery

Composite CuO/Cu₂O/Cu anode for lithium ion battery was designed and synthesized via facile electrodeposition and the subsequent in situ thermal oxidation in air at 300 °C for 1 h. The as-prepared composite CuO/Cu₂O/Cu anode was studied in terms of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), galvanostatic charge/discharge, cyclic voltammetry (CV), and AC impedance. As expected, the composite CuO/Cu₂O/Cu with CuO-rich surface displayed hierarchical cypress-like morphology; furthermore, the hierarchical cypress-like CuO/Cu₂O/Cu anode also delivered satisfactory electrochemical performances. For example, the reversible discharge capacity remained at 534.1 mAh/g even after 100 cycles. The enhanced electrochemical performances were attributed to the hierarchical cypress-like porous structure and the synergistic effect among the composite active copper oxides and highly conductive Cu current collector.     

Visible-light-induced degradation of formaldehyde over titania photocatalyst co-doped with nitrogen and nickel

Titanium isopropoxide, ammonium carbonate and nickelous nitrate were used as the sources of titanium, nitrogen, and nickel to prepare titania photocatalyst co-doped with nitrogen and nickel by means of the modified sol-gel method. The photocatalyst was characterized by X-ray diffraction (XRD), UV-vis diffusive reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). The prepared N-Ni co-doped photocatalyst showed optical absorption in the visible light area and exhibited excellent photocatalytic ability for the degradation of formaldehyde under visible light irradiation. The effects of annealing temperature and component on the phase composition and photocatalytic activity were investigated. The results demonstrated that nitrogen atoms was weaved into the structure of titania and led to the response to visible light. However, nickel atoms existed in the form of Ni₂O₃, dispersed on the surface of TiO₂, suppressed the recombination of photo-induced electron-hole pairs, raised the photo quantum efficiency, and led to the enhancement of photocatalytic performance. The increase of photoactivity was attributed to the synergistic effects of co-doping.     

Preparation of superhydrophobic films on titanium as effective corrosion barriers

Stable superhydrophobic films were prepared on the electrochemical oxidized titania/titanium substrate by a simple immersion technique into a methanol solution of hydrolyzed 1H,1H,2H,2H-perfluorooctyltriethoxysilane [CF₃(CF₂)₅(CH₂)₂Si(OCH₂CH₃)₃, PTES] for 1 h at room temperature followed by a short annealing at 140 °C in air for 1 h. The surface morphologies and chemical composition of the film were characterized by means of water contact angle (CA), field emission scanning electron microscopy (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The water contact angle on the surface of this film was measured to be as high as 160°. SEM images showed that the resulting surfaces exhibited special hierarchical structure. The special hierarchical structure along with the low surface energy leads to the high surface superhydrophobicity. The corrosion resistance ability and durance property of the superhydrophobic film in 3.5 wt.% NaCl solution was evaluated by the electrochemical impedance spectroscopy (EIS). The anticorrosion properties of the superhydrophobic film are compared to those of unmodified pure titanium and titania/titanium substrates. The results showed that the superhydrophobic film provides an effective corrosion resistant coating for the titanium metal even with immersion periods up to 90 d in the 3.5 wt.% NaCl solution, pointing to promising future applications.     

Electrodeposition of platinum on tourmaline and application as an electrocatalyst for oxidation of methanol

A composite electrode of Pt nanoparticles coupled with tourmaline is prepared on glassy carbon (GC) disk electrode via electrodeposition. The nanocomposite of Pt/tourmaline is characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, and transmission electron microscopy examinations linked with energy dispersive X-ray analysis. The electrocatalytic performance of the composite electrode (Pt/tourmaline/GC) is investigated in electrocatalysis oxidation of methanol at room temperature by cyclic voltammetry and chronoamperometry. It is indicated that Pt nanoparticles with size of ∼5 nm are uniformly assembled along the tourmaline particles and Pt exists in metallic and oxidated states confirmed by XPS. The results of electro-oxidation of methanol show that Pt/tourmaline catalyst is catalytically more active and stable than platinum-modified GC electrode, and the onset potential of Pt/tourmaline shifts 0.15 V to the negative side, and also the current density is significantly enhanced.     

Nanogravel structured NiO/Ni foam as electrode for high-performance lithium-ion batteries

Nanogravel structured NiO/Ni electrodes were fabricated by using two-step thermal oxidation method of commercial nickel (Ni) foam in air for lithium-ion batteries (LIBs). The macro- and micro-structures of the NiO/Ni foam were characterized using X-ray diffraction (XRD), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX), and Raman spectroscopy. Galvanostatic tests revealed that the electrode exhibits no obvious capacity fading over 40 cycles at 1 C (718 mAg^?1) and 2.5 C (1.8 Ag^?1) current rate. The discharge capacity was higher than the theoretical capacity of NiO even at a high-current rate of 2.5 C. The electrodes can deliver a reversible capacity of 1116.65 mAh g^?1 after 20th cycle at 1 C rate and 1026.20 mAh g^?1 after 40th cycle at 2.5 C rate. The cyclic voltammograms and impedance spectra analysis indicated that a redox reaction of NiO–Ni⁰ with formation and decomposition of Li₂O. The excellent electrochemical performance is mainly attributed to the nanogravel structure of the NiO/Ni foam electrodes as well as its excellent electrical contact between NiO and Ni. The unique nanostructured NiO on the highly conductive metallic Ni in core resulted in the enhanced discharge capacity, coulombic efficiency, cyclic stability, and rate capability when utilized as negative electrodes in LIBs.     

The composite of ZnSn(OH)<Subscript>6</Subscript> and Zn–Al layered double hydroxides used as negative material for zinc–nickel alkaline batteries

A series of Zn–Al layered double hydroxides (LDHs) and ZnSn(OH)₆ composites were successfully synthesized by hydrothermal method. The characteristic diffraction peaks of composites analyzed by X-ray diffraction (XRD) display that Zn–Al LDHs have been coupled with ZnSn(OH)₆, among which the composite containing 10% ZnSn(OH)₆ shows the best crystallinity. Besides, scanning electron microscopy (SEM) was conducted to observe the crystal morphologies. The electrodes were carried out by electrochemical measurements such as cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and cycling performance. The results suggest that the discharge specific capacity of composite containing 10% ZnSn(OH)₆ is basically kept at 354 mAh g^?1 with a capacity retention rate about 98.3% after 800 cycles. Meanwhile, the CV measurement manifests that this material has the smallest redox peak potential difference (0.31 V) than that of others. And the electrode reaction of composite containing 10% ZnSn(OH)₆ occurs easily because the EIS test implies that its charge transfer resistance has been declined by 11.57 Ω cm², accompanied by the ohmic resistance decreasing by 0.48 Ω cm². The findings mentioned above can be attributed to the high electron mobility and electrical conductivity of ZnSn(OH)₆. All the results show that the electrode of LDHs with 10% ZnSn(OH)₆ has quite outstanding electrochemical performances when used as the negative material for zinc–nickel alkaline batteries.     

Nanoparticles of nickel oxide: growth and organization on zinc-substituted anionic clay matrix by one-pot route at room temperature

A room temperature nanocarving strategy is developed for the fabrication of nanoparticles of nickel oxide on zinc-substituted anionic clay matrix (Ni/ZnLDH). It is based on the growth and organization of nanoparticles of nickel oxide which occur during the structural reconstruction of the layered structure of the anionic clay in NiSO₄ aqueous solution. No organic compounds are used during the fabrication. The described material was characterized by X-ray diffraction (XRD), IR spectroscopy (FTIR), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that the nickel-clay nanoarchitecture consists of small nanoparticles of nickel oxide (average size 7 nm) deposited on the larger nanoparticles (average size 90 nm) of zinc-substituted clay. The optical properties of the new nickel-zinc formulation are studied by UV–Vis.     

Improved Pt/C electrocatalysts for methanol oxidation prepared by different reducing agents and surfactants and DFT studies on it

In this work, PtCl₄ as precursor; sodium borohydride (Cat I), hydrazinium hydroxide (Cat II), and formaldehyde (Cat III) as reducing agents; and 1-heptanamine (a), N-methyl-1-heptanamine (b), and N,N-dimethyl-1-heptanamine (c) as surfactants were used to prepare platinum nanoparticles which were then dispersed on carbon XC-72 for use as catalysts in the methanol oxidation reaction. XRD and TEM results indicate that the platinum has a face-centered cubic structure and is found as small and agglomerated particles in different shapes, sizes, and densities. Cat I comprises small (~?5 nm) cubic and formless agglomerated (~?20–~?300 nm) particles, Cat II is composed of small (~?5 nm) and a significant number of quite dense spherical agglomerated (~?20–~?150 nm) particles, and Cat III contains large number of small (~?5 nm) and a small number of spherical, less dense, and agglomerated (~?20–~?200 nm) particles. XPS data shows that the platinum exists in two different oxidation states Pt(0) (~?64.5–~?69.6%) and Pt(IV) (~?35.5–~?30.4%), and platinum surface also contains OH, H₂O, C–O, C=O, and carbon. DFT and FTIR show that the surfactants decompose to form partially crystalline carbon. Electrochemical studies reveal that performance order of the catalysts towards the methanol oxidation reaction is Cat II < Cat I < Cat III, and that Cat IIIc has the highest performance, which is 2.23 times larger than E-TEK catalysts. It was found that the performance of the catalysts depends on the kind of surfactant, reducing agent, electrochemical surface area, percent platinum utility, roughness factor, and I_f/I_r ratio.

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Synthesis of Titania-supported Copper Nanoparticles via Refined Alkoxide Sol-gel Process

Nanoparticles of titania and copper-loaded titania were synthesized by a refined sol-gel method using titanium butoxide. Unlike the conventional sol-gel procedure of adding water directly, the esterification of anhydrous butanol and glacial acetic acid provided the hydrolyzing water. In addition, acetic acid also served as a chelating ligand to stabilize the hydrolysis-condensation process and minimize the agglomeration of titania. Following the hydrolysis, Cu/TiO₂ was prepared by adding copper chloride to titania sol. The sol was dried, then calcined at 500^°C to remove organics and transformed to anatase titania which was verified by XRD. Cu/TiO₂ was further hydrogen-reduced at 300^°C. The recovery of Ti was exceeded by an average of 95% from titanium butoxide. TEM micrographs show that the Cu/TiO₂ particles are near uniform. The average crystallite sizes are 17–20 nm estimated from the peak broadening of XRD spectra. The bandgaps of TiO₂ and reduced Cu/TiO₂ range from 2.70 to 3.15 eV estimated from the diffusive reflective UV-Vis spectra. XPS analysis shows that Cu 2p_3/2 is 933.4 eV indicating primary Cu₂O form on the TiO₂ supports. The binding energy of Ti does not exhibit chemical shift suggesting negligible interaction of Cu cluster and TiO₂ support.     

Improvement of cycling and thermal stability of LiNi<Subscript>0.8</Subscript>Mn<Subscript>0.1</Subscript>Co<Subscript>0.1</Subscript>O<Subscript>2</Subscript> cathode material by secondly treating process

(Ni_0.8Mn_0.1Co_0.1)(OH)₂ and Co(OH)₂ secondly treated by LiNi_0.8Mn_0.1Co_0.1O₂ have been prepared via co-precipitation and high-temperature solid-state reaction. The residual lithium contents, XRD Rietveld refinement, XPS, TG-DSC, and electrochemical measurements are carried out. After secondly treating process, residual lithium contents decrease drastically, and occupancy of Ni in 3a site is much lower and Li/Ni disorder decreases. The discharge capacity is 193.1, 189.7, and 182 mAh g^?1 at 0.1 C rate, respectively, for LiNi_0.8Mn_0.1Co_0.1O₂-AP, -NT, and -CT electrodes between 3.0 and 4.2 V in pouch cell. The capacity retention has been greatly improved during gradual capacity fading of cycling at 1 C rate. The noticeably improved thermal stability of the samples after being treated can also be observed.     

Electrochemical performance of CeO<Subscript>2</Subscript> nanoparticle-decorated graphene oxide as an electrode material for supercapacitor

Cerium oxide nanoparticles and cerium oxide nanoparticle-decorated graphene oxide (GO) are synthesized via a facile chemical coprecipitation method in the presence of hexadecyltrimethylammonium bromide (CTAB). Nanostructure studies and electrochemical performances of the as-prepared samples were systematically investigated. The crystalline structure and morphology of the nanocomposites were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transition electron microscopy (TEM), Raman spectrum, and X-ray photoelectron spectroscopy (XPS). Electrochemical properties of the CeO₂ electrode, the GO electrode, and the nanocomposites electrodes were investigated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS) measurements. The CeO₂ nanoparticle-decorated GO (at the mole ratio of CeO₂/GO = 1:4) electrode exhibited excellent supercapacitive behavior with a high specific capacitance of 382.94 F/g at the current density of 3.0 A/g. These superior electrochemical features demonstrate that the CeO₂ nanoparticle-decorated GO is a promising material for next-generation supercapacitor systems.     

Biomimetic apatite induction on Ca-containing titania

To understand the apatite induction mechanism in SBF, Ca-containing titania film without CaTiO₃ phase was fabricated by micro-arc oxidation (MAO) at low voltage (230 V) in an electrolytic solution containing calcium acetate monohydrate. Macro-porous, Ca-containing titania film was formed on the titanium substrate and the oxidized layer was composed of anatase and rutile phase. When immersed in 1.5SBF, no apatite was induced in the MAO specimen similar to the CaTiO₃-containing titania. However, after hydrothermal treatment at 250 °C for 2 h, numerous precipitates, presumably calcium phosphates, were formed on the surface of the titania after 7 day immersion and titania surface was entirely covered with apatite after 14 days of immersion. This study clearly showed that Ca-containing titania has the capability to induce apatite in SBF and hydrothermal treatment plays a decisive role in apatite induction, particularly producing surface hydroxyl groups such as Ca–OH or Ti–OH.     

Formation and electronic properties of oxide and sulphide films of Co,Ni and Mo studied by XPS

Dry O₂ oxidation up to 400°C, water immersion at room temperature or H₂S sulphidation at 400°C forms oxide or sulphide films on polycrystalline Co and Ni foils. X-ray photoelectron spectra (XPS) of the Co 2p and Ni 2p core levels and valence band (VB) structure changes allow the identification of the chemical state of such films and their electronic properties. They are compared with the films obtained on Mo in similar conditions. Ni appears less reactive than Co during O₂ or water oxidation and is considered as a more noble metal. Dry oxidation mainly induces CoO while water immersion induces formation of CoO(OH). For Ni, phases like Ni₂O₃, Ni(OH)₂ and/or NiO(OH) are the most probable products, respectively. H₂S sulphidation always produces a sulphur-rich Co or Ni phase. The VB response to sulphidation of the three studied metals shows that Co or Ni sulphides are potential electron-donors to MoS₂. Such results are relevant to the synergy observed in hydrotreating catalysis with these sulphides.     

One-pot synthesized mesoporous Ni–Co hydroxide for high performance supercapacitors

Mesoporous Ni(OH)₂/Co(OH)₂ electrode materials were synthesized via a simple one-pot procedure by combining homogeneous precipitation and stepwise precipitation method. The configuration of the porous Ni(OH)₂/Co(OH)₂ electrode materials synthesized provides 3D electron transmission channels through a high conductive Co(OH)₂ distributed in the peripheral nanolayer of the composites, which is beneficial to rate capability and cycle stability. The Ni(OH)₂/Co(OH)₂ electrode materials have a specific surface area of 229 m² g^?1, which is approximately 40% higher than that of Ni(OH)₂ (163 m² g^?1). Their specific capacitance is up to 1202 and 1022 F g^?1 at the current densities of 10 and 20 A g^?1, respectively. Furthermore, the capacitance retention of the electrode materials at the current density of 10 A g^?1 is 98% after 5000 cycles. The synthesis method provides a novel simple route to fabricate heterostructure materials for capacitors with high electrochemical performance.

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Correlation between the mesoporous carbon sphere with Ni(OH)<Subscript>2</Subscript> nanoparticle contents for high-performance supercapacitor electrode

Ni(OH)₂ nanoparticles were decorated on mesoporous carbon spheres (MPCS) using a simple hard template method. The MPCS were derived from sodium carboxymethyl cellulose. As-prepared MPCS/Ni(OH)₂ nanocomposites were used as electrode materials for supercapacitors. These composites exhibited better electrochemical properties than a pristine mesoporous carbon sphere owing to the synergistic effect. However, the increase in Ni(OH)₂ is not proportional to the electrochemical performance improvement. The addition of an optimal amount of Ni(OH)₂, typically 1:20 by weight (MPCS:NiCl₂·6H₂O), showed an excellent specific capacitance of 1338.296 F g^?1 at a scan rate of 5 mV s^?1. These encouraging results indicate excellent potential for the development of highly capacitive energy storage devices for practical applications.     

Synthesis and structure refinement studies of LiNiVO4 electrode material for lithium rechargeable batteries

The lithium nickel vanadate (LiNiVO₄) cathode material has been synthesized by using sol-gel method. The thermal behavior of the material has been examined by thermogravimetric and differential thermal analysis (TG/DTA). The structure of LiNiVO₄ compound has been studied by the Rietveld refined x-ray diffraction (XRD) technique. The Brunauer–Emmett–Teller (BET) surface area of 0.79 m² g^?1 was estimated with N₂ absorption characteristics. The synthesized powder morphology was observed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) studies of synthesized LiNiVO₄ powder indicate that the oxidation states of nickel and vanadate are +2 and +5, respectively. The electrochemical properties were monitored using 2032 coin cells by cyclic voltammetry and EIS, which showed that the microscopic structural features were deeply related with the electrochemical performance.