Hydrothermally synthesized Ni(OH)<Subscript>2</Subscript>@Zn(OH)<Subscript>2</Subscript> composite with enhanced electrochemical performance for supercapacitors

Two kinds of electrode materials Ni(OH)₂ and Ni(OH)₂@Zn(OH)₂ composite are fabricated on nickel foam. Electrochemical experiments indicate Ni(OH)₂@Zn(OH)₂ composite deserves further study due to high specific capacitance and good cycle stability, so that it can achieve energy storage and conversion as much as possible. When the hydrothermal time is different, the electrochemical performance of the sample is also different. Accurately, samples can obtain better electrochemical performance at 15 h, and the maximum specific capacitance of Ni(OH)₂@Zn(OH)₂ is 7.87 F cm^?2 compared to Ni(OH)₂ (0.61 F cm^?2) at 5 mA cm^?2. Even at 50 mA cm^?2, specific capacitance is 5.24 F cm^?2 and rate capability is 66.6%. Furthermore, Ni(OH)₂@Zn(OH)₂-15 h loses 19.8% after 1000 cycles, revealing the composite has an outstanding stable cycle. These properties also indicate Ni(OH)₂@Zn(OH)₂-15 h is a promising electrode material.     

Cation-anion interactions in [Mo<Subscript>3</Subscript>S<Subscript>7</Subscript>(Et<Subscript>2</Subscript>dtc)<Subscript>3</Subscript>](Et<Subscript>2</Subscript>dtc) solutions

Quantum chemical calculations of the [Mo₃S₇(Et₂dtc)₃](Et₂dtc) complex in different solvents are performed. It is shown that the binding energy between the cluster [Mo₃S₇(Et₂dtc)₃]⁺ cation and the outersphere (Et₂dtc)^? anion exponentially decreases with increase in the solvent dielectric permittivity. By DOSY NMR it is determined that in chloroform, the cationic and anionic moieties of the complex form an associate (contact ion pair), while in strongly polar dimethyl sulfoxide these moieties move independently of one another.     

Effect of anionic and cationic micelles on the oxidation of <Emphasis Type="SmallCaps">D</Emphasis>-glucose by cerium(IV) in presence of H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

The influence of surfactants (anionic and cationic) on the reactivity of the redox couple cerium(IV) and D-glucose was examined spectrophotometerically. Various kinetic parameters have been determined in the absence and presence of surfactants. The kinetics were followed by monitoring the disappearance of the absorbance of cerium(IV) at 385 nm. The reaction obeyed first-order kinetics with respect to [D-glucose] in both media. No effect of anionic micelles of sodium dodecyl sulfate (SDS) was observed due to electrostatic repulsion between the negative head group of SDS and reactive species of cerium(IV) (Ce(SO₄) ₃ ²⁻ ). A twofold increase in the oxidation rate was observed in the presence of cationic micelles of cetyltrimethylammonium bromide (CTAB). The observed catalytic role has been analyzed in terms of the Menger–Portnoy model. The effects of various inorganic salts (Na₂SO₄, NaNO₃ and NaCl) were also studied in micellar media.     

Electrodeposited Ni(OH)<Subscript>2</Subscript> nanostructures on electro-etched carbon fiber paper for highly stable supercapacitors

Herein, we introduce a facile, inexpensive and fast, and additive-/template-free method to fabricate highly stable nickel hydroxide nanofibers for supercapacitor applications. Ni(OH)₂ nanofibers were electrodeposited on electro-etched carbon fiber paper by a potential step method (Ni(OH)₂-ECFs) and characterized using scanning electron microscopy and X-ray diffraction analysis. Electrochemical performance of Ni(OH)₂-ECF was studied in symmetric two-electrode assembly by cyclic voltammetry, galvanostatic charge–discharge method, and electrochemical impedance spectroscopy. A specific capacitance of 277.5 F g^?1 was achieved for the symmetric supercapacitor based on two identical Ni(OH)₂-ECFs. Our findings demonstrate high-rate capability with excellent stability (approximately 100 % capacitance retention) for Ni(OH)₂-ECF supercapacitor, originated from the intimate contact between Ni(OH)₂ and ECF. Our studies suggest the Ni(OH)₂-ECF electrode as an excellent material for supercapacitor applications.     

LiMO<Subscript>2</Subscript>@Li<Subscript>2</Subscript>MnO<Subscript>3</Subscript> positive-electrode material for high energy density lithium ion batteries

Li[Ni_1/3Co_1/3Mn_1/3]O₂ (NCM 111) is a promising alternative to LiCoO₂, as it is less expensive, more structurally stable, and has better safety characteristics. However, its capacity of 155 mAh g^?1 is quite low, and cycling at potentials above 4.5 V leads to rapid capacity deterioration. Here, we report a successful synthesis of lithium-rich layered oxides (LLOs) with a core of LiMO₂ (R-3m, M?=?Ni, Co) and a shell of Li₂MnO₃ (C2/m) (the molar ratio of Ni, Co to Mn is the same as that in NCM 111). The core–shell structure of these LLOs was confirmed by XRD, TEM, and XPS. The Rietveld refinement data showed that these LLOs possess less Li⁺/Ni²⁺ cation disorder and stronger M*–O (M*?=?Mn, Co, Ni) bonds than NCM 111. The core–shell material Li_1.15Na_0.5(Ni_1/3Co_1/3)_core(Mn_1/3)_shellO₂ can be cycled to a high upper cutoff potential of 4.7 V, delivers a high discharge capacity of 218 mAh g^?1 at 20 mA g^?1, and retains 90 % of its discharge capacity at 100 mA g^?1 after 90 cycles; thus, the use of this material in lithium ion batteries could substantially increase their energy density.

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Graphical Abstract Average voltage vs. number of cycles for the core–shell and pristine materials at 20 mA g^?1 for 10 cycles followed by 90 cycles at 100 mA g^?1

     

Surfactant effect on electrochemical-induced synthesis of α-Ni(OH)2

Nickel hydroxide films were electrosynthesized in the presence of different diluted surfactant solutions by galvanostatic electroprecipitation. Lamellar α-Ni(OH)₂ films are obtained using cationic surfactant cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecyl sulfate (SDS), and also neutral surfactant Tween® 80. The films were structurally and morphologically characterized by X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy, and electrochemically by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The results evidenced that SDS remains intercalated between the lamellae of α-Ni(OH)₂. Albeit the presence of CTAB and Tween® 80, it was noticed in FTIR spectra that the surfactants did not intercalate. The morphology was affected by the presence of different surfactants. All studied surfactants displaced the oxidation potential (E _O) of Ni²⁺/Ni³⁺ process to less positive values. Also, the presence of surfactants improved the electrode charge efficiency and the charge response for the same number of moles of nickel ions deposited. The ratio of the charge and frequency change is 4.4 times bigger for films deposited with SDS when compared with pure α-Ni(OH)₂ films.     

TiO<Subscript>2</Subscript> nanotube arrays: a study on the surface electrochemical reactions during the photoelectrochemical process

The surface electrochemical reactions of TiO₂ nanotube arrays (NTAs) corresponding to different active species of TiO₂ NTAs (·OH, h⁺, and ·O₂ ^?) play key roles during the photoelectrochemical process. Effect of the active species and surface electrochemical reactions are studied by adding capture agents of isopropyl alcohol (IPA) for ·OH, ammonium oxalate ((NH₄)₂C₂O₂) for h⁺, and benzoquinone (BQ) for ·O₂ ^? radicals. The changes of photocurrent with addition of capture agents confirm the existence of ·OH, h⁺, and ·O₂ ^? during photoelectrochemical process. IPA and (NH₄)₂C₂O₂ additions are found to enhance the photocurrent by accelerating the consumption velocity of h⁺ indirectly and directly and restricting the chargers recombination. BQ can decrease the photocurrent stepwise to 0 due to the indirect consumption of e^? on surface of TiO₂ NTAs. The consumption of h⁺ by forming ·OH is 38% that of the whole consumption of h⁺. The ratio of chargers recombination is higher than 80.8% that of the whole photogenerated chargers.     

Layered LiNi<Subscript>0.80</Subscript>Co<Subscript>0.15</Subscript>Al<Subscript>0.05</Subscript>O<Subscript>2</Subscript> as cathode material for hybrid Li<Superscript>+</Superscript>/Na<Superscript>+</Superscript> batteries

LiNi_0.80Co_0.15Al_0.05O₂ (NCA) is explored to be applied in a hybrid Li⁺/Na⁺ battery for the first time. The cell is constructed with NCA as the positive electrode, sodium metal as the negative electrode, and 1 M NaClO₄ solution as the electrolyte. It is found that during electrochemical cycling both Na⁺ and Li⁺ ions are reversibly intercalated into/de-intercalated from NCA crystal lattice. The detailed electrochemical process is systematically investigated by inductively coupled plasma-optical emission spectrometry, ex situ X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The NCA cathode can deliver initially a high capacity up to 174 mAh g^?1 and 95% coulombic efficiency under 0.1 C (1 C?=?120 mA g^?1) current rate between 1.5–4.1 V. It also shows excellent rate capability that reaches 92 mAh g^?1 at 10 C. Furthermore, this hybrid battery displays superior long-term cycle life with a capacity retention of 81% after 300 cycles in the voltage range from 2.0 to 4.0 V, offering a promising application in energy storage.     

Highly stable asymmetric supercapacitors based on Ni(OH)<Subscript>2</Subscript> deposited on electro-etched carbon paper

Herein, we introduce the application of nickel hydroxide nanosheets on the electro-etched carbon fiber (ECF) formed via a direct electrodeposition, for fabrication of asymmetric supercapacitor. To confirm the practical applicability of prepared Ni(OH)₂–ECF, an asymmetric device was assembled using Ni(OH)₂–ECF in combination with an activated carbon (AC) electrode. Our results showed a substantial cycling stability (96% capacitance retention after 10000 cycles) and considerable rate capability at large discharge currents (60% capacitance retention at 8 A g^??1) for this asymmetric supercapacitor that may have originated from the good contact between Ni(OH)₂ and ECF. A maximum specific capacitance of 88.1 F g^??1 was achieved for Ni(OH)₂–ECF//AC/CF device and showed considerable rate capability at large discharge currents (60% capacitance retention at 8 A g^??1). The results of this study suggest the Ni(OH)₂–ECF electrode is an excellent material for fabrication of supercapacitor electrodes.     

Synthesis details and solubility product for cobalt hydroxo salt Co(OH)<Subscript>1.8</Subscript>Cl<Subscript>0.2</Subscript>

The hydroxo salt Co(OH)_1.8Cl_0.2 is precipitated by a deficit of OH^? ions from dilute CoCl₂ solutions under the conditions that inhibit the appearance of local excesses of OH^? ions. The three-variable method is used to determine the solubility product for this compound. A linear correlation between the composition and solubility product is found for Co(OH)₂, Co(OH)_1.8Cl_0.2, and Co(OH)_1.5Cl_0.5.     

Correlation between the structural,electrical and electrochemical performance of layered Li(Ni<Subscript>0.33</Subscript>Co<Subscript>0.33</Subscript>Mn<Subscript>0.33</Subscript>)O<Subscript>2</Subscript> for lithium ion battery

The Li(Ni_0.33Co_0.33Mn_0.33)O₂ (LNCMO) cathode material is prepared by poly(vinyl pyrrolidone) (PVP)-assisted sol-gel/hydrothermal and poly(ethylene glycol)-block-poly(propylene glycol)-block-poly (ethylene glycol) (Pluronic-P123)-assisted hydrothermal methods. The compound prepared by PVP-assisted hydrothermal method shows a comparatively higher electrical conductivity of ~2?×?10^?5 S cm^?1 and exhibits a discharge capacity of 152 mAh g^?1 in the voltage range of 2.5 to 4.4 V, for a C-rate of 0.2 C, whereas the compounds prepared by P123-assisted hydrothermal method and PVP-assisted sol-gel method show a total electrical conductivity in the order of 10^?6 S cm^?1 and result in poor electrochemical performance. The structural and electrical properties of LNCMO (active material) and its electrochemical performance are correlated. The difference in percentage of ionic and electronic conductivity contribution to the total electrical conductivity is compared by transference number studies. The cation disorder is found to be the limiting factor for the lithium ion diffusion as determined from ionic conductivity values.     

Variation in structure and Li<Superscript>+</Superscript>-ion migration in argyrodite-type Li<Subscript>6</Subscript>PS<Subscript>5</Subscript>X (X = Cl,Br, I) solid electrolytes

All-solid-state rechargeable lithium-ion batteries (AS-LIBs) are attractive power sources for electrochemical applications due to their potentiality in improving safety and stability over conventional batteries with liquid electrolytes. Finding a solid electrolyte with high ionic conductivity and compatibility with other battery components is a key factor in raising the performance of AS-LIBs. In this work, we prepare argyrodite-type Li₆PS₅X (X = Cl, Br, I) using mechanical milling followed by annealing. X-ray diffraction characterization reveals the formation and growth of crystalline Li₆PS₅X in all cases. Ionic conductivity of the order of 7?×?10^?4 S cm^?1 in Li₆PS₅Cl and Li₆PS₅Br renders these phases suitable for AS-LIBs. Joint structure refinements using high-resolution neutron and laboratory X-ray diffraction provide insight into the influence of disorder on the fast ionic conductivity. Besides the disorder in the lithium distribution, it is the disorder in the S^2?/Cl^? or S^2?/Br^? distribution that we find to promote ion mobility, whereas the large I^? cannot be exchanged for S^2? and the resulting more ordered Li₆PS₅I exhibits only a moderate conductivity. Li⁺ ion migration pathways in the crystalline compounds are modelled using the bond valence approach to interpret the differences between argyrodites containing different halide ions.     

Fabrication of a New Self-assembly Compound of CsTi<Subscript>2</Subscript>NbO<Subscript>7</Subscript> with Cationic Cobalt Porphyrin Utilized as an Ascorbic Acid Sensor

A novel sandwich-structured nanocomposite based on Ti₂NbO₇^? nanosheets and cobalt porphyrin (CoTMPyP) was fabricated through electrostatic interaction, in which CoTMPyP has been successfully inserted into the lamellar spacing of layered titanoniobate. The resultant Ti₂NbO₇/CoTMPyP nanocomposite was characterized by XRD, SEM, TEM, EDS, FT-IR, and UV-vis. It is demonstrated that the intercalated CoTMPyP molecules were found to be tilted approximately 63° against Ti₂NbO₇^? layers. The glass carbon electrode (GCE) modified by Ti₂NbO₇/CoTMPyP film showed a fine diffusion-controlled electrochemical redox process. Furthermore, the Ti₂NbO₇/CoTMPyP-modified electrode exhibited excellent electrocatalytic oxidation activity of ascorbic acid (AA). Differential pulse voltammetric studies demonstrated that the intercalated nanocomposite detects AA linearly over a concentration range of 4.99?×?10^?5 to 9.95?×?10^?4 mol L^?1 with a detection limit of 3.1?×?10^?5 mol L^?1 at a signal-to-noise ratio of 3.0.     

Effect of ionic and non-ionic surfactants on the reduction of water soluble colloidal MnO<Subscript>2</Subscript> by glycolic acid

Kinetics of the redox reaction between colloidal MnO₂ and glycolic acid have been studied spectrophotometrically by monitoring the decay in the absorbance of colloidal MnO₂ in absence and presence of surfactants. Anionic sodium dodecyl sulfate has no effect, non-ionic Triton X-100 catalyzed the reaction and experiments were not possible in presence of cationic cetyltrimethylammonium bromide due to the precipitation of MnO₂.The reaction followed the same type of kinetic behavior, i.e., fractional-, first- and fractional-order dependencies, respectively, in [glycolic acid], [MnO₂] and [H⁺ ] in both the media. Effects of gum arabic and manganese(II) have also been studied and discussed. Mechanisms in accordance with the experimental data are proposed for the reaction.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Crystalline Vanadium Pentoxide with Hierarchical Mesopores and Its Capacitive Behavior

Crystalline vanadium pentoxide with hierarchical mesopores was synthesized by using a CTAB/BMIC cotemplate (CTAB=cetyltrimethylammonium bromide, BMIC=1‐butyl‐3‐methylimidazolium chloride). The material was fully characterized by SEM, TEM, N₂ adsorption–desorption, XRD, XPS, and CV methods. By elaborate adjustment of the template proportions, the distribution and size of the hierarchical pores were tuned successfully. CTAB cationic surfactant contributed more to the larger mesopores, whereas BMIC ionic liquid was beneficial in forming the smaller nanopores. The vanadium‐containing anions combined with CTA⁺ micelles and BMI⁺ rings through electrostatic interactions. The CTA⁺–O(VO)O^?–BMI⁺ entities built up an orderly array, which finally formed the hierarchical mesoporous framework during thermal treatment. The mesoporous vanadium pentoxide directed by the cotemplate of CTAB/BMIC=1:1 showed many orderly crystalline structures and demonstrated a large capacitance (225 F g^?1); it is thus a promising material for electrochemical capacitors. Two alternative solutions to the disappearance of capacitance due to insertion of K⁺ are proposed in view of possible future applications.     

Insertion of Molecular Oxygen in Transition‐Metal Hydride Bonds,Oxygen‐Bond Activation,and Unimolecular Dissociation of Metal Hydroperoxide Intermediates. Short Communication

Thermal activation of molecular oxygen is observed for the late‐transition‐metal cationic complexes [M(H)(OH)]⁺ with M=Fe, Co, and Ni. Most of the reactions proceed via insertion in a metal? hydride bond followed by the dissociation of the resulting metal hydroperoxide intermediate(s) upon losses of O, OH, and H₂O. As indicated by labeling studies, the processes for the Ni complex are very specific such that the O‐atoms of the neutrals expelled originate almost exclusively from the substrate O₂. In comparison to the [M(H)(OH)]⁺ cations, the ion? molecule reactions of the metal hydride systems [MH]⁺ (M=Fe, Co, Ni, Pd, and Pt) with dioxygen are rather inefficient, if they occur at all. However, for the solvated complexes [M(H)(H₂O)]⁺ (M=Fe, Co, Ni), the reaction with O₂ involving O? O bond activation show higher reactivity depending on the transition metal: 60% for the Ni, 16% for the Co, and only 4% for the Fe complex relative to the [Ni(H)(OH)]⁺/O₂ couple.     

A Conductometric Sensor Specific for Cationic Surfactants

In this work, a fast, sensitive and miniaturised conductometric sensor based on interdigitated electrodes, working in differential mode, was developed for the determination of cationic surfactants. The membrane was composed of a polymer (PVC), a plasticizer (dinonylphtalate (DNP)) and a carrier (sodium tetraphenylborate (NaBΦ₄)). The sensor response was linear from at least 10^?9 M to 10^?2 M for dodecyltrimethylammonium (DTA⁺). No significant loss of sensor response was observed after 8 weeks. The sensor exhibited a lower sensitivity and a narrower dynamic range for tetrabutylammonium, decyltrimethylammonium and cetyltrimethylammonium cationic surfactants. A ten times lower sensitivity was observed for laurylsulfate anionic surfactant, (LS^?).     

Crystal structure of osmium selenobromide OsSe<Subscript>2</Subscript>Br<Subscript>12</Subscript>

The crystal structure of the compound OsSe₂Br₁₂ obtained by the reaction of OsBr₄ with SeBr₄ or Se in liquid bromine at 100°C was studied by X-ray powder diffraction. The structure of osmium selenobromide corresponds to a specific type: space group C2/m, a = 14.0464(2) Å, b = 11.05398(14) Å, c = 6.50340(9) Å, β = 112.2645(11)°, Z = 2; R _B = 0.03946, R _wp = 0.05403, χ² = 4.261 for 479 reflections and 53 refinement parameters. The X-ray diffraction analysis confirmed the earlier assumption concerning the cation-anion structure of the compound representing a packing of nearly regular [OsBr₆]^2? octahedra as anionic complexes and deficient [:SeBr₃]⁺ tetrahedra as cationic complexes in which the missing vertex is occupied by the lone electron pair of selenium.     

Electrodeposition of three-dimensional Ni(OH)<Subscript>2</Subscript> nanoflakes on partially crystallized activated carbon for high-performance supercapacitors

Three-dimensional Ni(OH)₂ nanoflakes were prepared via a facile and cost-effective electrodeposition method using commercial activated carbon (AC) as substrate. Nitric acid treatment (NT) and partial crystallization (PC) by metal nickel catalysis were applied for AC. The effects of the oxygen-containing functional groups and the degree of crystallization on the electrochemical performance of the electrode were investigated. The resulting Ni(OH)₂/PC–NT–AC/nickel foam electrode exhibits distinct performance with a specific capacitance of 2971 F/g (scaled to the mass of active Ni(OH)₂) at a current density of 6 A/g. A high capacitance of 1919 F/g was still achieved even at 40 A/g, which is much higher than Ni(OH)₂/AC/nickel foam electrode and Ni(OH)₂/NT–AC/nickel foam electrode. The excellent performance of Ni(OH)₂/PC–NT–AC/nickel foam electrode can be attributed to the presence of large surface area and highly conductive PC–NT–AC network on nickel foam. This study presents an effective method to improve the dispersion and rate capability of Ni(OH)₂ nanostructure electrodes.