Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “VOLTAMETRY”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Ultra-thin g-C{sub 3}N{sub 4} nanosheets wrapped silicon nanowire array for improved chemical stability and enhanced photoresponse

Highlights: • g-C{sub 3}N{sub 4}, as an oxygen free and metal free protective material for Si, was proposed. • g-C{sub 3}N{sub 4} nanosheets wrapped Si nanowire array was synthesized. • SiNW/g-C{sub 3}N{sub 4} exhibited enhancement of photoelectrochemical stability and photocurrent. - Abstract: In order to inhibit the oxidation of Si materials in aqueous solution, Si nanowire array was wrapped by ultra-thin g-C{sub 3}N{sub 4} nanosheets via an electrophoresis process. Scanning electron microscopy and transmission electron microscopy images showed that g-C{sub 3}N{sub 4} nanosheets were evenly distributed on the surface of Si nanowire array. X-ray diffraction patterns indicated that Si nanowire array/g-C{sub 3}N{sub 4} nanosheets were composed of Si (4 0 0 crystal plane) and g-C{sub 3}N{sub 4} (0 0 2 and 1 0 0 crystal planes). The cyclic voltammetry curves revealed that the corrosion of Si nanowire array was restrained under the protection of g-C{sub 3}N{sub 4} nanosheets. Furthermore, the photocurrent density of Si nanowire array/g-C{sub 3}N{sub 4} nanosheets increased by nearly 3 times compared to that of bare Si nanowire array due to the effective charge separation caused by the built-in electric field at the interface. This work will facilitate the applications of Si materials in aqueous solution, such as solar energy harvest and photocatalytic pollution control.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synthesis, characterization and electrochemical studies of nanostructured CaWO{sub 4} as platinum support for oxygen reduction reaction

Highlights: • Nanostructured CaWO{sub 4} was fabricated by co-precipitation method. • Platinum was electrodeposited onto the surface prepared nanostructured CaWO{sub 4}. • Pt/CaWO{sub 4}-graphite demonstrate good oxygen reduction reaction activity. - Abstract: In the present work, we employed nanostructured calcium tungstate as a supporting material for platinum, a well-known electrocatalyst for oxygen reduction. The co-precipitation method has been utilized to synthesize nanostructured calcium tungstate from aqueous solution. The structure and morphology of the obtained CaWO{sub 4} were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Preparation of the Pt/CaWO{sub 4}-graphite catalyst was carried out by electrodeposition of Pt onto the surface of CaWO{sub 4}/graphite electrode. The physical properties of the catalyst were determined by scanning electron microscopy analysis and energy dispersive X-ray (SEM/EDX). The electrochemical activity of the Pt/CaWO{sub 4}-graphite for the oxygen reduction reaction (ORR) was investigated in acid solution by cyclic voltammetry measurements, linear sweep voltammetry, and electrochemical impedance spectroscopy. The results revealed that the Pt/CaWO{sub 4}-graphite has higher electrocatalytic activity for oxygen reduction in comparison with Pt/graphite catalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Highly efficient dye-sensitized solar cell with GNS/MWCNT/PANI as a counter electrode

Highlights: • High-performance PANI/MWCNT-CE was incorporated in a Pt-CE in DSSCs. • GNS/MWCNT/PANI-CE exhibits a high power conversion efficiency (PCE) of 7.52%. • GNS/MWCNT/PANI composite has a high catalytic activity for the reduction of I{sub 3}{sup −}. • GNS/MWCNT/PANI composite has a low R{sub CT} on the electrolyte/CE interface. - Abstract: A graphene-based nanosheet composite/multiwalled carbon nanotube/polyaniline (GNS/MWCNT/PANI) was synthesized via an in situ polymerization technique and applied by the spin-coating method as a counter electrode (CE) in dye-sensitized solar cells (DSSCs). The combination of the high catalytic activity of PANI and outstanding conductivity of GNS/MWCNT improved the photovoltaic performance of the hybrid CE. The cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) showed that the GNS/MWCNT/PANI composite has high catalytic activity for the reduction of triiodide to iodide and low charge-transfer resistance at the electrolyte/electrode interface. Transmission electron microscopy (TEM) images showed that the GNS/MWCNT/PANI-CE has a rough and porous structure and X-ray diffraction analysis confirmed the formation of PANI coating on the surface of the GNS/CNT. In particular, current–voltage measurements showed the superior power conversion efficiency (PCE) of 7.52% of the DSSC based on GNS/MWCNT/PANI-CE compared to the PCE of 6.69% of the DSSC based on Pt-CE.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Sodium doping effect on physicochemical properties of K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) for the determination of mercury(II): Application in seawater samples

Highlights: • The apatite, K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1), was synthesized using reaction solid. • The obtained apatite was used to determine mercury in seawater samples from Morocco. • The effect of doping sodium into apatite on physic-chemical parameters was studied. • The influence of the electrochemical variables was investigated to determine mercury. - Abstract: A new chemically modified electrode was synthesized for the determination of mercury(II) using differential pulse anodic stripping voltammetry (DPASV). The electrode was modified by lacunar apatite K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) synthesized using solid reaction. These powders were crystallized in the hexagonal system, space group P6{sub 3}/m. The effect of sodium content on structural, thermodynamic and electrochemical properties of prepared apatite has been studied. Therefore, the best results was obtained using NaCaPb{sub 3}(PO{sub 4}){sub 3} (x = 1) as modifier of carbon paste electrode for the electrochemical detection of mercury(II). The later ions were preconcentrated on the surface of the modified electrode and oxidized at 0.06 V vs. Ag/AgCl. The electroanalytical procedure comprises of two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using differential pulse voltammetry. The different parameters that govern the two steps were optimized. A linear response was obtained in the concentration range from 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} to 2.0 mol L{sup −1} × 10{sup −7} mol L{sup −1} Hg(II) after activation of the electrode surface under the optimized conditions. The standard deviation was evaluated in a high and low concentration of mercury(II). The values ​​obtained for seven consecutive measurements were 1.24% and 5.07% of 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} and 5.0 mol L{sup −1} × 10{sup −6} mol L{sup −1} mercury(II) solutions respectively. The detection limit and quantification limit for mercury(II), calculated from nine times standard deviation of blank/slope of the calibration graph, were 1.086 mol L{sup −1} × 10{sup −8} mol L{sup −1} and 3.62 mol L{sup −1} × 10{sup −8} mol L{sup −1}, respectively. The proposed chemically modified electrode was applied to determine mercury(II) in seawater samples.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electrochemical performance studies of MnO{sub 2} nanoflowers recovered from spent battery

Highlights: • MnO{sub 2} is recovered from spent zinc–carbon batteries as nanoflowers structure. • Recovered MnO{sub 2} nanoflowers show high specific capacitance. • Recovered MnO{sub 2} nanoflowers show stable electrochemical cycling up to 900 cycles. • Recovered MnO{sub 2} nanoflowers show low resistance in EIS data. - Abstract: The electrochemical performance of MnO{sub 2} nanoflowers recovered from spent household zinc–carbon battery is studied by cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy. MnO{sub 2} nanoflowers are recovered from spent zinc–carbon battery by combination of solution leaching and electrowinning techniques. In an effort to utilize recovered MnO{sub 2} nanoflowers as energy storage supercapacitor, it is crucial to understand their structure and electrochemical performance. X-ray diffraction analysis confirms the recovery of MnO{sub 2} in birnessite phase, while electron microscopy analysis shows the MnO{sub 2} is recovered as 3D nanostructure with nanoflower morphology. The recovered MnO{sub 2} nanoflowers exhibit high specific capacitance (294 F g{sup −1} at 10 mV s{sup −1}; 208.5 F g{sup −1} at 0.1 A g{sup −1}) in 1 M Na{sub 2}SO{sub 4} electrolyte, with stable electrochemical cycling. Electrochemical data analysis reveal the great potential of MnO{sub 2} nanoflowers recovered from spent zinc–carbon battery in the development of high performance energy storage supercapacitor system.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Simultaneous determination of hydrazine and phenyl hydrazine using 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine diacetonitrile triphenylphosphine ruthenium(II) tetrafluoroborate complex functionalized multiwalled carbon nanotubes modified electrode

Highlights: • A nanocomposite of ruthenium(II) terpyridine, triphenylphosphine based complex and multiwalled carbon nanotubes have been used first time for simultaneous detection of hydrazine and phenyl hydrazine. • The detection limit reported is lower as compared to other reported works. • The paper also focuses towards effect of ligand variation attached to ruthenium(II) terpyridine based complexes complex for the hydrazine and phenyl hydrazine detection. • Nanocomposite does not involve any biological entity hence high stability. - Abstract: A nanocomposite based on the incorporation of the complex 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine triphenylphosphine diacetonitrile ruthenium(II) tetrafluoroborate with multiwalled carbon nanotubes and ionomer supported upon a glassy carbon electrode substrate is reported and characterized with scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The electrochemical behavior and stability of the composite electrode was investigated via cyclic voltammetry. The modified electrode exhibits an electro-catalytic activity towards the oxidation of both hydrazine and phenyl hydrazine in 0.1 M phosphate buffer solution (PBS, pH 7.4). The oxidation of hydrazine and phenyl hydrazine occurs at 0.81 V and 0.32 V with limit of detection found to be 3.7 × 10{sup −7} M and 1.15 × 10{sup −7} M and having a linear range from 5 × 10{sup −6} M to 6.5 × 10{sup −3} M, and 5 × 10{sup −6} M to 0.2 × 10{sup −3} M, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Vanadium oxides nanostructures: Hydrothermal synthesis and electrochemical properties

Highlights: • Vanadium oxides nanostructures were synthesized hydrothermally. • Reversible redox behavior with doping/dedoping process. • Doping/dedoping is easier for Li{sup +} to Na{sup +}. • Energy-related applications such as cathodes in lithium batteries. - Abstract: A facile and template-free one-pot strategy is applied to synthesize nanostructured vanadium oxide particles via a hydrothermal methodology. X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transforms infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the structure and morphology of the samples. The products are gradually changed from sheet-shaped VO{sub 2}(B) to rod-like V{sub 3}O{sub 7}·H{sub 2}O with decreasing cyclohexanediol as both protective and reducing agent. The specific surface area of the VO{sub 2}(B) nanosheets and V{sub 3}O{sub 7}·H{sub 2}O nanorods was found to be 22 and 16 m{sup 2} g{sup −1}, respectively. Thin films of VO{sub 2}(B) and V{sub 3}O{sub 7}·H{sub 2}O deposited on ITO substrates were electrochemically characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The voltammograms show reversible redox behavior with doping/dedoping process corresponding to reversible cation intercalation/de-intercalation into the crystal lattice of the nanorods/nanosheets. This process is easier for the small Li{sup +} cation than larger ones Na{sup +}.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Synthesis of polyaniline/SnO{sub 2} nanocomposite and its improved electrochemical performance

Highlights: • Supercapacitors based on PANI/SnO{sub 2} nanocomposite were reported. • Supercapacitors using this material gave a specific capacitance of 501 F g{sup −1}. • Capacitance retention was 85.8% over 2000 charge–discharge cycles. - Abstract: SnO{sub 2} was prepared by the hydrothermal route. Aniline monomer was polymerized in the suspension of SnO{sub 2} to form inorganic–organic nanocomposite materials, in which SnO{sub 2} particles were embedded within polyaniline (PANI). Morphological and structural characterizations of the prepared samples were carried out using scanning electron microscope; transmission electron microscope; power X-ray diffraction and Fourier transform infrared spectroscopy. Their electrochemical properties were also investigated using cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The as-prepared nanocomposites had excellent properties in the capacitance, and its specific capacitance was up to 501 F g{sup −1} with a specific energy density of 66.8 W h kg{sup −1} at a power density of 960.6 W kg{sup −1}. The device fulfilled the requirement of long durability necessary for an energy storage system, since after 2000 galvanostatic charge–discharge cycles, retention of 85.8% in capacitance was observed. These results indicated that the PANI/SnO{sub 2} had a synergistic effect of the complementary properties of both components.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electrodeposited manganese dioxide nanostructures on electro-etched carbon fibers: High performance materials for supercapacitor applications

Highlights: • We report a facile method for fabrication of MnO{sub 2} nanostructures on electro-etched carbon fiber. • MnO{sub 2}-ECF electrode shows outstanding supercapacitive behavior even at high discharge rates. • Exceptional cycle stability was achieved for MnO{sub 2}-ECF electrode. • The coulombic efficiency of MnO{sub 2}-ECF electrode is nearly 100%. - Abstract: In this article we introduce a facile, low cost and additive/template free method to fabricate high-rate electrochemical capacitors. Manganese oxide nanostructures were electrodeposited on electro-etched carbon fiber substrate by applying a constant anodic current. Nanostructured MnO{sub 2} on electro-etched carbon fiber was characterized by scanning electron microscopy, X-ray diffraction and energy dispersive X-ray analysis. The electrochemical behavior of MnO{sub 2} electro-etched carbon fiber electrode was investigated by electrochemical techniques including cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. A maximum specific capacitance of 728.5 F g{sup −1} was achieved at a scan rate of 5 mV s{sup −1} for MnO{sub 2} electro-etched carbon fiber electrode. Also, this electrode showed exceptional cycle stability, suggesting that it can be considered as a good candidate for supercapacitor electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Facile synthesis and electrochemical performance of Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} nanocomposite for lithium-ion batteries

Graphical abstract: TEM of Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite and the discharge curves of pure Co{sub 3}O{sub 4}, pure Co{sub 2}SnO{sub 4} and Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite. - Highlights: • Novel Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite has been prepared by simple co-precipitation method. • Small spherical nanocrystals adhering to the surface of large polyhedral particles. • Formation mechanism is relate to solubility of Sn(OH){sub 6}{sup 2−} in high concentration OH{sup −} . • The composite shows better electrochemical performance than Co{sub 2}SnO{sub 4} and Co{sub 3}O{sub 4} - Abstract: A novel dispersed structure Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite has been successfully synthesized by a conventional co-precipitation method with certain amount of NaOH concentration. The obtained composite exhibits dispersed structure with small spherical nanocrystals adhering to the surface of large polyhedral particles, which has been studied as an anode material in lithium-ion battery. Galvanostatic charge–discharge and cyclic voltammetry has been conducted to measure the electrochemical properties of the material. The results show that Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite demonstrates good reversible capacity of 702.5 mA h g{sup −1} after 50 cycles at a current density of 100 mA h g{sup −1}, much better than that of pure Co{sub 3}O{sub 4} (375.1 mA h g{sup −1}) and pure Co{sub 2}SnO{sub 4} (194.1 mA h g{sup −1}). This material also presents improved rate performance with capacity retention of 71.1% when the current ranges from 100 mA g{sup −1} to 1000 mA g{sup −1}. The excellent electrochemical performance of the as-prepared dispersed structure Co{sub 2}SnO{sub 4}/Co{sub 3}O{sub 4} composite could be attributed to the good dispersibility of nanoparticles which can effectively alleviate the volume expansion and improve the conductivity, thus enhance the cycling stability.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electrochemical and microstructural characterization of magnetron-sputtered ATO thin films as Li–ion storage materials

Highlights: • Nano-structured ATO thin films prepared by RF magnetron sputtering at 25 °C, 100 °C and 200 °C, respectively. • ATO thin films show a high reversible capacity and high rate performance. • Electrochemical reaction mechanism of the ATO thin film was revealed by transmission electron microscopy. - Abstract: Sb-doped SnO{sub 2} (ATO) nanostructured thin films were prepared by using radio frequency magnetron sputtering at the substrate temperatures of 25 °C, 100 °C and 200 °C, respectively. All the ATO thin films have the similar redox characteristics in the cyclic voltammetry measurements. The ATO thin film sputtered at 200 °C shows the lowest charge transfer resistance and best electrochemical performance, and has a high reversible capacity of 679 mA h g{sup −1} at 100 mA g{sup −1} after 200 charge–discharge cycles and high rate performance of 483 mA h g{sup −1} at 800 mA g{sup −1}. The electrochemical mechanisms were investigated by analyzing the phase evolution of the ATO electrodes that had been electrochemically induced at various stages. The results reveal that the ATO underwent reversible lithiation/delithiation processes during the electrochemical cycles, i.e., the SnO{sub 2} reacted with Li{sup +} to produce metallic Sn and followed by the formation of the Li{sub x}Sn alloys during discharge process, and then Li{sub x}Sn alloys de-alloyed, Sn reacted with Li{sub 2}O, and even partially formed SnO{sub 2} during charge process.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Effects of lithium salt concentration on graphited carbon microbead anodes in the piperidinium-based hybrid electrolytes

Graphical abstract: “Lithium aggregates” usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. Therefore, as important as the problem of SEI, the content of lithium salt and the interaction between Li{sup +} and ILs’ anions should be taken into consideration in the optimization of ILs-based electrolytes for Li-ion batteries. - Highlights: • “Lithium aggregates” in piperidinium-based electrolytes are evidenced by IR and NMR. • High LiPF{sub 6} content could decrease Li{sup +} mobility due to “ionic aggregates”. • Lithium salt concentration is an important factor affecting graphite performances. - Abstract: The variations in LiPF{sub 6} concentration lead to the very different electrochemical performances of carbon microbeads anodes in the piperidinium-based hybrid electrolytes. The “two peaks” behaviors of lithium plating observed in cyclic voltammetry tests, and some detailed changes in infrared spectra and nuclear magnetic resonance indicates that the formation of “ionic aggregates” related to lithium ions”. Therefore, the excessive lithium salts in the piperidinium-based hybrid electrolytes, usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. The main behaviors are that, when LiPF{sub 6} concentrations increased from 0.2 to 1.2 mol kg{sup −1}, the apparent migration energies (E{sub a}) increase largely from 8.83 to 21.16 kJ mol{sup −1}, while the lithium transference numbers (t{sub Li{sup +}}) drop markedly from 0.538 to 0.292.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Enhanced electrochemical performances of PANI using redox additive of K{sub 4}[Fe(CN){sub 6}] in aqueous electrolyte for symmetric supercapacitors

Highlights: • Effect of K{sub 4}[Fe(CN){sub 6}] in H{sub 2}SO{sub 4} studied on the electrochemical properties of PANI. • The polaron band – π* transition reveals the emeraldine salt (conductive) form. • CV curves exhibit quasi-reversible redox behavior. • Symmetric PANI SC shows 228 F g{sup −1} at 1 mA cm{sup −2} in K{sub 4}[Fe (CN){sub 6}] added 1 M H{sub 2}SO{sub 4}. • PANI-1 symmetric supercapacitor shows almost 100% of capacity retention. - Abstract: Polyaniline (PANI) particles were prepared by reflux assisted chemical oxidative polymerization method with the aid of ammonium per sulfate/ferric chloride as oxidants and HCl/H{sub 2}SO{sub 4} as the medium. Amorphous nature and the emeraldine state of PANI were revealed from X-ray diffraction and Fourier transform infrared analysis. Moreover, ultra violet–visible spectra attributes to the polaron band – π* transition of polyaniline. The scanning electron microscopic image shows that the particle size is in the range of 0.2–2 μm. The electrochemical performances of the material were investigated in 1 M H{sub 2}SO{sub 4} and 0.08 M K{sub 4}[Fe(CN){sub 6}] added 1 M H{sub 2}SO{sub 4} aqueous electrolytes. Cyclic voltammetry and galvanostatic charge–discharge studies were carried out to find its suitability as a supercapacitor electrode material. The charge discharge analysis of the fabricated symmetric supercapacitors revealed the fact that the electrolyte containing redox additive (0.08 M K{sub 4}[Fe(CN){sub 6}]) delivered an enhanced specific capacitance of 228 F g{sup −1} (∼912 F g{sup −1} for single electrode) than that of 1 M H{sub 2}SO{sub 4} (100 F g{sup −1}) at 1 mA cm{sup −2}. Further cycling stability is performed at 5 mA cm{sup −2} ensures the durability of the supercapacitor.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The preparation and characterization of iron fluorides polymorphs FeF{sub 3}·0.33H{sub 2}O and β-FeF{sub 3}∙3H{sub 2}O as cathode materials for lithium-ion batteries

Graphical abstract: Better rate capability and cycling performance were observed for β-FeF{sub 3}·3H{sub 2}O/C prepared by mechano-chemical synthesis. - Highlights: • A novel mechano-chemical preparation method. • The use of NH{sub 4}F as starting material. • Better electro-chemical performance in the case of β-FeF{sub 3}·3H{sub 2}O/C. - Abstract: Two kinds of iron fluorides, FeF{sub 3}·0.33H{sub 2}O and β-FeF{sub 3}∙3H{sub 2}O, have been synthesized by different chemical routes using Fe(NO{sub 3}){sub 3}·9H{sub 2}O and NH{sub 4}F as precursors and investigated as cathode materials for secondary lithium batteries. β-FeF{sub 3}·3H{sub 2}O was obtained via a mechano-chemical process and FeF{sub 3}·0.33H{sub 2}O was obtained by a precipitation reaction from ethanol solution. To further improve their electrochemical properties, a ball milling process with carbon has been used to form composites. The fluorides were characterized by X-ray diffraction (XRD), thermal analysis, FTIR spectroscopy, galvanostatic charge/discharge and cyclic voltammetry measurements. The results showed that the as-prepared β-FeF{sub 3}·3H{sub 2}O/C exhibited better rate performance and cycling stability. It exhibited an initial discharge capacity of 199.6 mA h g{sup −1} at a current density of 20 mA g{sup −1} in a voltage range of 1.8–4.5 V and still reserved a discharge capacity of about 146.5 mA h g{sup −1} after 10 cycles. Only a capacity loss of 15 mA h g{sup −1} and 7 mA h g{sup −1} was observed when the current density was at 40 mA g{sup −1} and 80 mA g{sup −1}, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Preparation, temperature dependent structural, molecular dynamics simulations studies and electrochemical properties of LiFePO{sub 4}

Highlights: • LiFePO{sub 4} compound was prepared by carbothermal reduction method. • In-situ XRD studies were carried out on LiFePO{sub 4} at various temperatures. • Dedicated imperial potentials used to explain the variation of lattice constants. • It exhibited reversible capacity of 140 (±5) mAh g{sup −1}, stable up to 400 cycles. - Abstract: LiFePO{sub 4} was prepared using carbothermal reduction method. In-situ temperature dependent structural studies were carried using X-ray diffraction. Molecular dynamics simulations were conducted for the LiFePO{sub 4} using empirical potentials developed using bond valence approach to investigate the structural variations. Electrochemical behaviour of LiFePO{sub 4} was evaluated using cyclic voltammetry and galvanostatic cycling studies at room temperature. Charge–discharge cycling studies showed a reversible capacities 140 (±5) mAh g{sup −1} at the end of 50th cycle and these capacity values were stable up to 400 cycles and almost nil capacity fade between 50 and 400 cycles, showing excellent capacity retention, low capacity fading. The cyclic voltammetry studies showed a main cathodic and anodic redox peaks at 3.34 and 3.5 V vs. Li, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11

Highlights: • Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were prepared from ZIF-11. • The activated N-PCMPs with fused KOH (N-PCMPs-A) have high specific surface area. • N-PCMPs-A exhibits high specific capacitance. • N-PCMPs-A reveals good cycling performance even at a high current density. - Abstract: Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were successfully prepared by direct carbonization of ZIF-11 polyhedra and further activated with fused KOH to obtain N-PCMPs-A. The morphology and microstructure of samples were examined by scanning electron microscopy, X-ray diffraction, and micropore and chemisorption analyzer. Electrochemical properties were characterized by cyclic voltammetry and galvanostatic charge/discharge method in 1.0 M H{sub 2}SO{sub 4} aqueous solution on a standard three-electrode system. Results show that, compared with N-PCMPs, N-PCMPs-A has higher specific surface area (2188 m{sup 2} g{sup −1}) and exhibits improved electrochemical capacitive properties (307 F g{sup −1} at 1.0 A g{sup −1}). The mass specific capacitance of N-PCMPs-A is also higher than that of most MOF-derived carbons, some carbide-derived carbons and carbon aerogel-derived carbons. In addition, the capacitance of the N-PCMPs-A retains 90% after 4000 cycles even at a high current density of 10 A g{sup −1}. These imply that N-PCMPs-A is the promising materials for the construction of a high-performance supercapacitor.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Efficient electrocatalytic performance of thermally exfoliated reduced graphene oxide-Pt hybrid

Highlights: • Synthesis of Pt–RGO nanohybrids of very high electrochemically active surface area. • Electrocatalytic activity-cum-stability: ∼10 times that of commercial Pt-C catalyst. • TEM confirms narrow size distribution and excellent dispersion of Pt nanoparticles. • SAED and XRD indicate (1 1 1) orientation of Pt nanoparticles. • Methanol oxidation EIS reveal decrease in charge transfer resistance with potential - Abstract: High quality thermally exfoliated reduced graphene oxide (RGO) nanosheets decorated with platinum nanocrystals have been synthesized using a simple environmentally benign process. The electrocatalytic behaviour of the Pt–RGO nanohybrid for methanol oxidation was studied using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. High resolution transmission electron microscopy shows uniform dispersion of Pt nanoparticles of ∼2–4 nm size. X-ray diffraction and selected area diffraction studies reveal (1 1 1) orientation of the platinum nanoparticles. The cyclic voltammetry and chronoamperometry results indicate higher catalytic activity and stability for Pt–RGO compared to commercial Pt-C. The electrochemical active surface area of Pt–RGO (52.16 m{sup 2}/g) is found to be 1.5 times that of commercial Pt-C. Impedance spectroscopy shows different impedance behaviour at different potential regions, indicating change in methanol oxidation reaction mechanism with potential. The reversal of impedance pattern to the second quadrant, at potentials higher than ∼0.40 V, indicates change in the rate determining reaction.

36 MATERIALS SCIENCE↗