Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

PubMed

García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

2010-07-20

A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images.

Fabrication of low-temperature solid oxide fuel cells with a nanothin protective layer by atomic layer deposition

PubMed Central

2013-01-01

Anode aluminum oxide-supported thin-film fuel cells having a sub-500-nm-thick bilayered electrolyte comprising a gadolinium-doped ceria (GDC) layer and an yttria-stabilized zirconia (YSZ) layer were fabricated and electrochemically characterized in order to investigate the effect of the YSZ protective layer. The highly dense and thin YSZ layer acted as a blockage against electron and oxygen permeation between the anode and GDC electrolyte. Dense GDC and YSZ thin films were fabricated using radio frequency sputtering and atomic layer deposition techniques, respectively. The resulting bilayered thin-film fuel cell generated a significantly higher open circuit voltage of approximately 1.07 V compared with a thin-film fuel cell with a single-layered GDC electrolyte (approximately 0.3 V). PMID:23342963

One-Step Electrochemical Preparation of Multilayer Graphene Functionalized with Nitrogen

NASA Astrophysics Data System (ADS)

Ustavytska, Olena; Kurys, Yaroslav; Koshechko, Vyacheslav; Pokhodenko, Vitaly

2017-03-01

A new environmentally friendly one-step method for producing multilayer (preferably 7-9 layers) nitrogen-doped graphene (N-MLG) with a slight amount of oxygen-containing defects was developed. The approach is based on the electrochemical exfoliation of graphite electrode in the presence of azide ions under the conditions of electrolysis with pulse changing of the electrode polarization potential. It was found that usage of azide anions lead not only to the exfoliation of graphite but also to the simultaneous functionalization of graphene sheets by nitrogen atoms (as a result of electrochemical decomposition of azide anions with ammonia evolution). Composition, morphology, structure, and electrochemical properties of N-MLG were characterized by C,H,N analysis, transmission electron microscopy, atomic force microscopy, FTIR, UV-Vis, and Raman spectroscopy, as well as cyclic voltammetry. The perspective of using N-MLG as oxygen reduction reaction electrocatalyst and for the electrochemical analysis of biomarkers (dopamine, ascorbic acid, and uric acid) in their mixtures was shown.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

NASA Astrophysics Data System (ADS)

Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

Atomic layer deposition of ultrathin blocking layer for low-temperature solid oxide fuel cell on nanoporous substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Wonjong; Cho, Gu Young; Noh, Seungtak

2015-01-15

An ultrathin yttria-stabilized zirconia (YSZ) blocking layer deposited by atomic layer deposition (ALD) was utilized for improving the performance and reliability of low-temperature solid oxide fuel cells (SOFCs) supported by an anodic aluminum oxide substrate. Physical vapor-deposited YSZ and gadolinia-doped ceria (GDC) electrolyte layers were deposited by a sputtering method. The ultrathin ALD YSZ blocking layer was inserted between the YSZ and GDC sputtered layers. To investigate the effects of an inserted ultrathin ALD blocking layer, SOFCs with and without an ultrathin ALD blocking layer were electrochemically characterized. The open circuit voltage (1.14 V) of the ALD blocking-layered SOFC was visiblymore » higher than that (1.05 V) of the other cell. Furthermore, the ALD blocking layer augmented the power density and improved the reproducibility.« less

First-principles calculations of the thermodynamic properties of transuranium elements in a molten salt medium

NASA Astrophysics Data System (ADS)

Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan

2014-03-01

We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.

Core-shell structured ceramic nonwoven separators by atomic layer deposition for safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shen, Xiu; Li, Chao; Shi, Chuan; Yang, Chaochao; Deng, Lei; Zhang, Wei; Peng, Longqing; Dai, Jianhui; Wu, Dezhi; Zhang, Peng; Zhao, Jinbao

2018-05-01

Safety is one of the most factors for lithium-ion batteries (LIBs). In this work, a novel kind of ceramic separator with high safety insurance is proposed. We fabricated the core-shell nanofiber separators for LIBs by atomic layer deposition (ALD) of 30 nm Al2O3 on the electrospinning nonwoven fiber of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). The separators show a pretty high heat resistance up to 200 °C without any shrinkage, an excellent fire-resistant property and a wide electrochemical window. Besides, with higher uptake and ionic conductivity, cells assembled with the novel separator shows better electrochemical performance. The ALD produced separators exhibit great potential in elaborate products like 3C communications and in energy field with harsh requirements for safety such as electric vehicles. The application of ALD on polymer fiber membranes brings a new strategy and opportunity for improving the safety of the advanced LIBs.

Atomic-Scale Simulation of Electrochemical Processes at Electrode/Water Interfaces under Referenced Bias Potential.

PubMed

Bouzid, Assil; Pasquarello, Alfredo

2018-04-19

Based on constant Fermi-level molecular dynamics and a proper alignment scheme, we perform simulations of the Pt(111)/water interface under variable bias potential referenced to the standard hydrogen electrode (SHE). Our scheme yields a potential of zero charge μ pzc of ∼0.22 eV relative to the SHE and a double layer capacitance C dl of ≃19 μF cm -2 , in excellent agreement with experimental measurements. In addition, we study the structural reorganization of the electrical double layer for bias potentials ranging from -0.92 eV to +0.44 eV and find that O down configurations, which are dominant at potentials above the pzc, reorient to favor H down configurations as the measured potential becomes negative. Our modeling scheme allows one to not only access atomic-scale processes at metal/water interfaces, but also to quantitatively estimate macroscopic electrochemical quantities.

Nano-scaled top-down of bismuth chalcogenides based on electrochemical lithium intercalation

NASA Astrophysics Data System (ADS)

Chen, Jikun; Zhu, Yingjie; Chen, Nuofu; Liu, Xinling; Sun, Zhengliang; Huang, Zhenghong; Kang, Feiyu; Gao, Qiuming; Jiang, Jun; Chen, Lidong

2011-12-01

A two-step method has been used to fabricate nano-particles of layer-structured bismuth chalcogenide compounds, including Bi2Te3, Bi2Se3, and Bi2Se0.3Te2.7, through a nano-scaled top-down route. In the first step, lithium (Li) atoms are intercalated between the van der Waals bonded quintuple layers of bismuth chalcogenide compounds by controllable electrochemical process inside self-designed lithium ion batteries. And in the second step, the Li intercalated bismuth chalcogenides are subsequently exposed to ethanol, in which process the intercalated Li atoms would explode like atom-scaled bombs to exfoliate original microscaled powder into nano-scaled particles with size around 10 nm. The influence of lithium intercalation speed and amount to three types of bismuth chalcogenide compounds are compared and the optimized intercalation conditions are explored. As to maintain the phase purity of the final nano-particle product, the intercalation lithium amount should be well controlled in Se contained bismuth chalcogenide compounds. Besides, compared with binary bismuth chalcogenide compound, lower lithium intercalation speed should be applied in ternary bismuth chalcogenide compound.

Perspective: Maintaining surface-phase purity is key to efficient open air fabricated cuprous oxide solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoye, Robert L. Z., E-mail: rlzh2@cam.ac.uk, E-mail: jld35@cam.ac.uk; Ievskaya, Yulia; MacManus-Driscoll, Judith L., E-mail: rlzh2@cam.ac.uk, E-mail: jld35@cam.ac.uk

2015-02-01

Electrochemically deposited Cu{sub 2}O solar cells are receiving growing attention owing to a recent doubling in efficiency. This was enabled by the controlled chemical environment used in depositing doped ZnO layers by atomic layer deposition, which is not well suited to large-scale industrial production. While open air fabrication with atmospheric pressure spatial atomic layer deposition overcomes this limitation, we find that this approach is limited by an inability to remove the detrimental CuO layer that forms on the Cu{sub 2}O surface. Herein, we propose strategies for achieving efficiencies in atmospherically processed cells that are equivalent to the high values achievedmore » in vacuum processed cells.« less

Electrochemical sensors and biosensors based on less aggregated graphene.

PubMed

Bo, Xiangjie; Zhou, Ming; Guo, Liping

2017-03-15

As a novel single-atom-thick sheet of sp 2 hybridized carbon atoms, graphene (GR) has attracted extensive attention in recent years because of its unique and remarkable properties, such as excellent electrical conductivity, large theoretical specific surface area, and strong mechanical strength. However, due to the π-π interaction, GR sheets are inclined to stack together, which may seriously degrade the performance of GR with the unique single-atom layer. In recent years, an increasing number of GR-based electrochemical sensors and biosensors are reported, which may reflect that GR has been considered as a kind of hot and promising electrode material for electrochemical sensor and biosensor construction. However, the active sites on GR surface induced by the irreversible GR aggregations would be deeply secluded inside the stacked GR sheets and therefore are not available for the electrocatalysis. So the alleviation or the minimization of the aggregation level for GR sheets would facilitate the exposure of active sites on GR and effectively upgrade the performance of GR-based electrochemical sensors and biosensors. Less aggregated GR with low aggregation and high dispersed structure can be used in improving the electrochemical activity of GR-based electrochemical sensors or biosensors. In this review, we summarize recent advances and new progress for the development of electrochemical sensors based on less aggregated GR. To achieve such goal, many strategies (such as the intercalation of carbon materials, surface modification, and structural engineering) have been applied to alleviate the aggregation level of GR in order to enhance the performance of GR-based electrochemical sensors and biosensors. Finally, the challenges associated with less aggregated GR-based electrochemical sensors and biosensors as well as related future research directions are discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly Reversible Water Oxidation at Ordered Nanoporous Iridium Electrodes Based on an Original Atomic Layer Deposition.

PubMed

Schlicht, Stefanie; Haschke, Sandra; Mikhailovskii, Vladimir; Manshina, Alina; Bachmann, Julien

2018-05-01

Nanoporous iridium electrodes are prepared and electrochemically investigated towards the water oxidation (oxygen evolution) reaction. The preparation is based on 'anodic' aluminum oxide templates, which provide straight, cylindrical nanopores. Their walls are coated using atomic layer deposition (ALD) with a newly developed reaction which results in a metallic iridium layer. The ALD film growth is quantified by spectroscopic ellipsometry and X-ray reflectometry. The morphology and composition of the electrodes are characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. Their catalytic activity is quantified for various pore geometries by cyclic voltammetry, steady-state electrolysis, and electrochemical impedance spectroscopy. With an optimal pore length of L ≈17-20 μm, we achieve current densities of J =0.28 mA cm -2 at pH 5 and J =2.4 mA cm -2 at pH 1. This platform is particularly competitive for achieving moderate current densities at very low overpotentials, that is, for a high degree of reversibility in energy storage.

Multilayer Regulation of Atomic Boron Nitride Films to Improve Oxidation and Corrosion Resistance of Cu.

PubMed

Ren, Siming; Cui, Mingjun; Pu, Jibin; Xue, Qunji; Wang, Liping

2017-08-16

The boron nitride (BN) monolayer (1L) with high impermeability and resistivity seems to hold promise as a long-term corrosion barrier for Cu under ambient condition, which is supported by recent researches. Here, we perform a complete study of the alternating temperature tests (the sample is exposed in air for 30 days and subsequently heated at 200 °C for 2 h) and electrochemical measurements on 1L and multilayer BN-coated Cu foils. Results imply that the BN-coated Cu foils are less oxidized than uncoated Cu foils after alternating temperature tests, regardless of the layers of BN. Particularly, the oxidation process proceeds slowly in multilayers because most of the underlying defects are covered with BN layers to suppress the oxygen diffusion in the vertical direction and the oxidation mainly occurs on the wrinkled region of BN films. Electrochemical analyses reveal that the BN layers provide an effective physical barrier against the corrosive medium and inhibit the electron diffusion because of their high electrical insulating behavior and the corrosion resistance of the samples increases with increasing BN layers. These findings indicate that BN films with adequate layers are good candidates for oxidation and corrosion protection at the atomic level, which is vital to many industrial and academic applications.

Thermal treatment effects on charge storage performance of graphene-based materials for supercapacitors.

PubMed

Zhang, Hongxin; Bhat, Vinay V; Gallego, Nidia C; Contescu, Cristian I

2012-06-27

Graphene materials were synthesized by reduction of exfoliated graphite oxide and then thermally treated in nitrogen to improve the surface area and their electrochemical performance as electrical double-layer capacitor electrodes. The structural and surface properties of the prepared reduced graphite oxide (RGO) were investigated using atomic force microscopy, scanning electron microscopy, Raman spectra, X-ray diffraction pattern analysis, and nitrogen adsorption/desorption studies. RGO forms a continuous network of crumpled sheets, which consist of large amounts of few-layer and single-layer graphenes. Electrochemical studies were conducted by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge measurements. The modified RGO materials showed enhanced electrochemical performance, with maximum specific capacitance of 96 F/g, energy density of 12.8 Wh/kg, and power density of 160 kW/kg. These results demonstrate that thermal treatment of RGO at selected conditions is a convenient and efficient method for improving its specific capacitance, energy, and power density.

Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

PubMed

Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

2016-10-26

To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

Synthesis of ZnTe dendrites on multi-walled carbon nanotubes/polyimide nanocomposite membrane by electrochemical atomic layer deposition and photoelectrical property research

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Yimin; Kou, Huanhuan; Li, Jiajia

2012-10-15

We report on the electrochemical atomic layer deposition (EC-ALD) of ZnTe dendrites on the carboxyl-functionalized multi-walled carbon nanotubes/polyimide (COOH-MWCNTs/PI) membrane. Electrochemical characteristics were studied by cyclic voltammetry (CV) and the deposition of ZnTe dendrites was completed using amperometric method (I-t). The prepared ZnTe dendrites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The growth mechanism of ZnTe dendrites was elucidated to give a deep understanding of crystal growth. The concentration of reagents and deposition cycle had a significant effect on the morphology and structure of deposits. UV-vis transmission study indicated a direct bandmore » gap of 2.26 eV. Photoelectrical measurement confirmed the p-type conductivity of ZnTe dendrites, which indicated that the dendritic ZnTe crystals may have potential practical application in optoelectronic devices. - Graphical abstract: Representative SEM images of ZnTe dendrites. (a) Panorama of ZnTe dendrites; (b) a single dendrite. The regular branches appeared like leaves and showed a parallel arrangement layer upon layer between each other. Highlights: Black-Right-Pointing-Pointer ZnTe dendrites were successfully synthesized on CNTs/PI membrane by electrodeposition. Black-Right-Pointing-Pointer The growth mechanism of ZnTe dendritic structures was investigated in detail. Black-Right-Pointing-Pointer The concentration and deposition cycle greatly affected the morphology of ZnTe. Black-Right-Pointing-Pointer OCP and I-t studies showed that ZnTe can be beneficial to photoelectric applications.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benson, David M.; Tsang, Chu F.; Sugar, Joshua Daniel

One method for the formation of nanofilms of materials, is Electrochemical atomic layer deposition (E-ALD), one atomic layer at a time. It uses the galvanic exchange of a less noble metal, deposited using underpotential deposition (UPD), to produce an atomic layer of a more noble element by reduction of its ions. This process is referred to as surface limited redox replacement and can be repeated in a cycle to grow thicker deposits. Previously, we performed it on nanoparticles and planar substrates. In the present report, E-ALD is applied for coating a submicron-sized powder substrate, making use of a new flowmore » cell design. E-ALD is used to coat a Pd powder substrate with different thicknesses of Rh by exchanging it for Cu UPD. Furthermore, cyclic voltammetry and X-ray photoelectron spectroscopy indicate an increasing Rh coverage with increasing numbers of deposition cycles performed, in a manner consistent with the atomic layer deposition (ALD) mechanism. Cyclic voltammetry also indicated increased kinetics of H sorption and desorption in and out of the Pd powder with Rh present, relative to unmodified Pd.« less

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized using a Direct Electrochemical Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lapp, Aliya S.; Duan, Zhiyao; Marcella, Nicholas

In this report we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2-, a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H-atom capping layer prevents deposition of Pt multilayers. We applied this method to ~1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to themore » well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).« less

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized using a Direct Electrochemical Method

DOE PAGES

Lapp, Aliya S.; Duan, Zhiyao; Marcella, Nicholas; ...

2018-06-01

In this report we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2-, a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H-atom capping layer prevents deposition of Pt multilayers. We applied this method to ~1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to themore » well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).« less

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized Using a Direct Electrochemical Method.

PubMed

Lapp, Aliya S; Duan, Zhiyao; Marcella, Nicholas; Luo, Long; Genc, Arda; Ringnalda, Jan; Frenkel, Anatoly I; Henkelman, Graeme; Crooks, Richard M

2018-05-11

In this report, we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2- , a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H atom capping layer prevents deposition of Pt multilayers. We applied this method to ∼1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to the well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).

Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, June Key, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.

2015-05-14

Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ∼35%. Further removal of hydrogen seems to be involved in the breaking ofmore » Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.« less

Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

NASA Astrophysics Data System (ADS)

Lee, June Key; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok; Ryu, Sang-Wan; Jeong, Tak; Jung, Eunjin; Kim, Hyunsoo

2015-05-01

Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ˜35%. Further removal of hydrogen seems to be involved in the breaking of Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.

Plasma-assisted atomic layer deposition of Al(2)O(3) and parylene C bi-layer encapsulation for chronic implantable electronics.

PubMed

Xie, Xianzong; Rieth, Loren; Merugu, Srinivas; Tathireddy, Prashant; Solzbacher, Florian

2012-08-27

Encapsulation of biomedical implants with complex three dimensional geometries is one of the greatest challenges achieving long-term functionality and stability. This report presents an encapsulation scheme that combines Al(2)O(3) by atomic layer deposition with parylene C for implantable electronic systems. The Al(2)O(3)-parylene C bi-layer was used to encapsulate interdigitated electrodes, which were tested invitro by soak testing in phosphate buffered saline solution at body temperature (37 °C) and elevated temperatures (57 °C and 67 °C) for accelerated lifetime testing up to 5 months. Leakage current and electrochemical impedance spectroscopy were measured for evaluating the integrity and insulation performance of the coating. Leakage current was stably about 15 pA at 5 V dc, and impedance was constantly about 3.5 MΩ at 1 kHz by using electrochemical impedance spectroscopy for samples under 67 °C about 5 months (approximately equivalent to 40 months at 37 °C). Alumina and parylene coating lasted at least 3 times longer than parylene coated samples tested at 80 °C. The excellent insulation performance of the encapsulation shows its potential usefulness for chronic implants.

Photoelectrochemical Water Oxidation by GaAs Nanowire Arrays Protected with Atomic Layer Deposited NiO x Electrocatalysts

NASA Astrophysics Data System (ADS)

Zeng, Joy; Xu, Xiaoqing; Parameshwaran, Vijay; Baker, Jon; Bent, Stacey; Wong, H.-S. Philip; Clemens, Bruce

2018-02-01

Photoelectrochemical (PEC) hydrogen production makes possible the direct conversion of solar energy into chemical fuel. In this work, PEC photoanodes consisting of GaAs nanowire (NW) arrays were fabricated, characterized, and then demonstrated for the oxygen evolution reaction (OER). Uniform and periodic GaAs nanowire arrays were grown on a heavily n-doped GaAs substrates by metal-organic chemical vapor deposition selective area growth. The nanowire arrays were characterized using cyclic voltammetry and impedance spectroscopy in a non-aqueous electrochemical system using ferrocene/ferrocenium (Fc/Fc+) as a redox couple, and a maximum oxidation photocurrent of 11.1 mA/cm2 was measured. GaAs NW arrays with a 36 nm layer of nickel oxide (NiO x ) synthesized by atomic layer deposition were then used as photoanodes to drive the OER. In addition to acting as an electrocatalyst, the NiO x layer served to protect the GaAs NWs from oxidative corrosion. Using this strategy, GaAs NW photoanodes were successfully used for the oxygen evolution reaction. This is the first demonstration of GaAs NW arrays for effective OER, and the fabrication and protection strategy developed in this work can be extended to study any other nanostructured semiconductor materials systems for electrochemical solar energy conversion.

The role of terminations and coordination atoms on the pseudocapacitance of titanium carbonitride monolayers.

PubMed

Zhang, Wenqiang; Cheng, Chuan; Fang, Peilin; Tang, Bin; Zhang, Jindou; Huang, Guoming; Cong, Xin; Zhang, Bao; Ji, Xiao; Miao, Ling

2016-02-14

Nowadays, MXenes have received extensive concern as a prominent electrode material of electrochemical capacitors. As two important factors to the capacitance, the influence of the intrinsical terminations (F, O and OH) and coordination atoms (C and N) is investigated using first-principles calculations. According to the density of states aligned with the standard hydrogen electrode, it turns out that a Ti3CNO2 monolayer is proven to show an obvious pseudocapacitive behavior, while the bare, F and OH terminated Ti3CN monolayers may only present electrochemical double layer characters in an aqueous electrolyte. Moreover, the illustration of molecular orbitals over the Fermi level are mainly contributed by the d-orbitals of Ti atoms coordinated with O and N atoms, indicating that the redox pseudocapacitance of the Ti3CNO2 monolayer is promoted by the coordination N atoms. Then the superiority of N bonded Ti atoms in accepting charges can be visualized through the charge population. Further, the larger ratio of C/N in the coordination environment of Ti atoms indicates that more electrons can be stored. Our investigation can give an instructional advice in the MXenes-electrode production.

Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts

DOE PAGES

Gearba, Raluca I.; Mueller, Kory M.; Veneman, Peter A.; ...

2015-05-09

Owing to its high conductivity, graphene holds promise as an electrode for energy devices such as batteries and photovoltaics. However, to this end, the work function and doping levels in graphene need to be precisely tuned. One promising route for modifying graphene’s electronic properties is via controlled covalent electrochemical grafting of molecules. We show that by employing diaryliodonium salts instead of the commonly used diazonium salts, spontaneous functionalization is avoided. This then allows for precise tuning of the grafting density. Moreover, by employing bis(4-nitrophenyl)iodonium(III) tetrafluoroborate (DNP) salt calibration curves, the surface functionalization density (coverage) of glassy carbon was controlled usingmore » cyclic voltammetry in varying salt concentrations. These electro-grafting conditions and calibration curves translated directly over to modifying single layer epitaxial graphene substrates (grown on insulating 6H-SiC (0 0 0 1)). In addition to quantifying the functionalization densities using electrochemical methods, samples with low grafting densities were characterized by low-temperature scanning tunneling microscopy (LT-STM). We show that the use of buffer-layer free graphene substrates is required for clear observation of the nitrophenyl modifications. Furthermore, atomically-resolved STM images of single site modifications were obtained, showing no preferential grafting at defect sites or SiC step edges as supposed previously in the literature. Most of the grafts exhibit threefold symmetry, but occasional extended modifications (larger than 4 nm) were observed as well.« less

A Step toward High-Energy Silicon-Based Thin Film Lithium Ion Batteries.

PubMed

Reyes Jiménez, Antonia; Klöpsch, Richard; Wagner, Ralf; Rodehorst, Uta C; Kolek, Martin; Nölle, Roman; Winter, Martin; Placke, Tobias

2017-05-23

The next generation of lithium ion batteries (LIBs) with increased energy density for large-scale applications, such as electric mobility, and also for small electronic devices, such as microbatteries and on-chip batteries, requires advanced electrode active materials with enhanced specific and volumetric capacities. In this regard, silicon as anode material has attracted much attention due to its high specific capacity. However, the enormous volume changes during lithiation/delithiation are still a main obstacle avoiding the broad commercial use of Si-based electrodes. In this work, Si-based thin film electrodes, prepared by magnetron sputtering, are studied. Herein, we present a sophisticated surface design and electrode structure modification by amorphous carbon layers to increase the mechanical integrity and, thus, the electrochemical performance. Therefore, the influence of amorphous C thin film layers, either deposited on top (C/Si) or incorporated between the amorphous Si thin film layers (Si/C/Si), was characterized according to their physical and electrochemical properties. The thin film electrodes were thoroughly studied by means of electrochemical impedance spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. We can show that the silicon thin film electrodes with an amorphous C layer showed a remarkably improved electrochemical performance in terms of capacity retention and Coulombic efficiency. The C layer is able to mitigate the mechanical stress during lithiation of the Si thin film by buffering the volume changes and to reduce the loss of active lithium during solid electrolyte interphase formation and cycling.

Structured Nanowires for Spectra-Tuned and Spectra-Multiplexed Sensing THZ Generation

DTIC Science & Technology

2015-04-08

anodic aluminum oxide membranes ( AAO ) as templates. We...nanowires were fabricated by direct current electrochemical deposition technique using diameter-modulated anodic aluminum oxide membranes ( AAO ) as...throughout this project was the technique of atomic layer deposition (ALD) into anodized alumina oxide ( AAO ) templates. Aluminum , when

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media

PubMed Central

Al-Harbi, Albandaree K.

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution. PMID:29337992

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media.

PubMed

Emran, Khadijah M; Al-Harbi, Albandaree K

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution.

Study of Cu2O\\ZnO nanowires heterojunction designed by combining electrodeposition and atomic layer deposition

NASA Astrophysics Data System (ADS)

Makhlouf, Houssin; Weber, Matthieu; Messaoudi, Olfa; Tingry, Sophie; Moret, Matthieu; Briot, Olivier; Chtoutou, Radhouane; Bechelany, Mikhael

2017-12-01

Cu2O/ZnO nanowires (NWs) heterojunctions were successfully prepared by combining Atomic layer Deposition (ALD) and Electrochemical Deposition (ECD) processes. The crystallinity, morphology and photoconductivity properties of the Cu2O/ZnO nanostructures have been investigated. The properties of the Cu2O absorber layer and the nanostructured heterojunction were studied in order to understand the mechanisms lying behind the low photoconductivity measured. It has been found that the interface state defects and the high resistivity of Cu2O film were limiting the photovoltaic properties of the prepared devices. The understanding presented in this work is expected to enable the optimization of solar cell devices based on Cu2O/ZnO nanomaterials and improve their overall performance.

Misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ for the hydrogen evolution reaction: beyond van der Waals heterostructures.

PubMed

Chua, Chun Kiang; Sofer, Zdeněk; Jankovský, Ondřej; Pumera, Martin

2015-03-16

Recent research on stable 2D nanomaterials has led to the discovery of new materials for energy-conversion and energy-storage applications. A class of layered heterostructures known as misfit-layered chalcogenides consists of well-defined atomic layers and has previously been applied as thermoelectric materials for use as high-temperature thermoelectric batteries. The performance of such misfit-layered chalcogenides in electrochemical applications, specifically the hydrogen evolution reaction, is currently unexplored. Herein, a misfit-layered chalcogenide consisting of CoO2 layers interleaved with an SrO-BiO-BiO-SrO rock-salt block and having the formula Bi1.85 Sr2 Co1.85 O7.7-δ is synthesized and examined for its structural and electrochemical properties. The hydrogen-evolution performance of misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ , which has an overpotential of 589 mV and a Tafel slope of 51 mV per decade, demonstrates the promising potential of misfit-layered chalcogenides as electrocatalysts instead of classical carbon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinrich, Henning; Come, Jérémy; Tempel, Hermann

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topographymore » changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.« less

Investigation of hexagonal boron nitride as an atomically thin corrosion passivation coating in aqueous solution.

PubMed

Zhang, Jing; Yang, Yingchao; Lou, Jun

2016-09-09

Hexagonal boron nitride (h-BN) atomic layers were utilized as a passivation coating in this study. A large-area continuous h-BN thin film was grown on nickel foil using a chemical vapor deposition method and then transferred onto sputtered copper as a corrosion passivation coating. The corrosion passivation performance in a Na2SO4 solution of bare and coated copper was investigated by electrochemical methods including cyclic voltammetry (CV), Tafel polarization and electrochemical impedance spectroscopy (EIS). CV and Tafel analysis indicate that the h-BN coating could effectively suppress the anodic dissolution of copper. The EIS fitting result suggests that defects are the dominant leakage source on h-BN films, and improved anti-corrosion performances could be achieved by further passivating these defects.

Passivation of Si(111) surfaces with electrochemically grafted thin organic films

NASA Astrophysics Data System (ADS)

Roodenko, K.; Yang, F.; Hunger, R.; Esser, N.; Hinrichs, K.; Rappich, J.

2010-09-01

Ultra thin organic films (about 5 nm thick) of nitrobenzene and 4-methoxydiphenylamine were deposited electrochemically on p-Si(111) surfaces from benzene diazonium compounds. Studies based on atomic force microscopy, infrared spectroscopic ellipsometry and x-ray photoelectron spectroscopy showed that upon exposure to atmospheric conditions the oxidation of the silicon interface proceed slower on organically modified surfaces than on unmodified hydrogen passivated p-Si(111) surfaces. Effects of HF treatment on the oxidized organic/Si interface and on the organic layer itself are discussed.

Excellent Resistive Switching Performance of Cu-Se-Based Atomic Switch Using Lanthanide Metal Nanolayer at the Cu-Se/Al2O3 Interface.

PubMed

Woo, Hyunsuk; Vishwanath, Sujaya Kumar; Jeon, Sanghun

2018-03-07

The next-generation electronic society is dependent on the performance of nonvolatile memory devices, which has been continuously improving. In the last few years, many memory devices have been introduced. However, atomic switches are considered to be a simple and reliable basis for next-generation nonvolatile devices. In general, atomic switch-based resistive switching is controlled by electrochemical metallization. However, excess ion injection from the entire area of the active electrode into the switching layer causes device nonuniformity and degradation of reliability. Here, we propose the fabrication of a high-performance atomic switch based on Cu x -Se 1- x by inserting lanthanide (Ln) metal buffer layers such as neodymium (Nd), samarium (Sm), dysprosium (Dy), or lutetium (Lu) between the active metal layer and the electrolyte. Current-atomic force microscopy results confirm that Cu ions penetrate through the Ln-buffer layer and form thin conductive filaments inside the switching layer. Compared with the Pt/Cu x -Se 1- x /Al 2 O 3 /Pt device, the optimized Pt/Cu x -Se 1- x /Ln/Al 2 O 3 /Pt devices show improvement in the on/off resistance ratio (10 2 -10 7 ), retention (10 years/85 °C), endurance (∼10 000 cycles), and uniform resistance state distribution.

The smallest quaternary ammonium salts with ether groups for high-performance electrochemical double layer capacitors† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02755a Click here for additional data file.

PubMed Central

Han, Taihee; Park, Min-Sik; Kim, Jeonghun; Kim, Jung Ho

2016-01-01

Electrochemical double layer capacitors (EDLCs) are energy storage devices that have been used for a wide range of electronic applications. In particular, the electrolyte is one of the important components, directly related to the capacitance and stability. Herein, we first report a series of the smallest quaternary ammonium salts (QASs), with ether groups on tails and tetrafluoroborate (BF4) as an anion, for use in EDLCs. To find the optimal structure, various QASs with different sized head groups and ether-containing tail groups were systematically compared. Comparing two nearly identical structures with and without ether groups, QASs with oxygen atoms showed improved capacitance, proving that ions with oxygen atoms move more easily than their counterparts at lower electric fields. Moreover, the ether containing QASs showed low activation energy values of conductivities, leading to smaller IR drops during the charge and discharge processes, resulting in an overall higher capacitance. PMID:28959391

Enhanced electronic and electrochemical properties of core-shelled V2O5-Pt nanowires

NASA Astrophysics Data System (ADS)

Pan, Ko-Ying; Wei, Da-Hua

2018-01-01

Platinum nanoparticles (Pt NPs) were decorated on vanadium pentoxide nanowires (V2O5 NWs) to form the core-shelled vanadium-platinum nanowires (Pt@V2O5 NWs) and their electrochemical activities for methanol oxidation were investigated. The synthetic procedure involved the synthesis of abundant vanadium pentoxide nanowires (V2O5 NWs) by a direct vapor-solid growth process (VS method), followed by atomic layer depositions (ALD) of platinum nanoparticles (Pt NPs) onto the V2O5 NWs. After the physical examinations, three designed deposition parameters (50, 100 and 150 cycles) of Pt NPs onto the V2O5 NWs by ALD process were successful. From the measurements of current-voltage (I-V) and cyclic voltammetry (CV) curves respectively, both the conductivity and the ratio of the forward anodic peak current (IF) to the reverse anodic peak current (IR) are enhancing proportionately to the deposition cycles of ALD process, which denotes that coating Pt atomic layers onto V2O5 nanowires indeed improves the catalytic performances than that of pure V2O5 nanowires.

Corrosion Protection of Copper Using Al2O3, TiO2, ZnO, HfO2, and ZrO2 Atomic Layer Deposition.

PubMed

Daubert, James S; Hill, Grant T; Gotsch, Hannah N; Gremaud, Antoine P; Ovental, Jennifer S; Williams, Philip S; Oldham, Christopher J; Parsons, Gregory N

2017-02-01

Atomic layer deposition (ALD) is a viable means to add corrosion protection to copper metal. Ultrathin films of Al 2 O 3 , TiO 2 , ZnO, HfO 2 , and ZrO 2 were deposited on copper metal using ALD, and their corrosion protection properties were measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Analysis of ∼50 nm thick films of each metal oxide demonstrated low electrochemical porosity and provided enhanced corrosion protection from aqueous NaCl solution. The surface pretreatment and roughness was found to affect the extent of the corrosion protection. Films of Al 2 O 3 or HfO 2 provided the highest level of initial corrosion protection, but films of HfO 2 exhibited the best coating quality after extended exposure. This is the first reported instance of using ultrathin films of HfO 2 or ZrO 2 produced with ALD for corrosion protection, and both are promising materials for corrosion protection.

SELF ALIGNED TIP DEINSULATION OF ATOMIC LAYER DEPOSITED AL2O3 AND PARYLENE C COATED UTAH ELECTRODE ARRAY BASED NEURAL INTERFACES

PubMed Central

Xie, Xianzong; Rieth, Loren; Negi, Sandeep; Bhandari, Rajmohan; Caldwell, Ryan; Sharma, Rohit; Tathireddy, Prashant; Solzbacher, Florian

2014-01-01

The recently developed alumina and Parylene C bi-layer encapsulation improved the lifetime of neural interfaces. Tip deinsulation of Utah electrode array based neural interfaces is challenging due to the complex 3D geometries and high aspect ratios of the devices. A three-step self-aligned process was developed for tip deinsulation of bilayer encapsulated arrays. The deinsulation process utilizes laser ablation to remove Parylene C, O2 reactive ion etching to remove carbon and Parylene residues, and buffered oxide etch to remove alumina deposited by atomic layer deposition, and expose the IrOx tip metallization. The deinsulated iridium oxide area was characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy to determine the morphology, surface morphology, composition, and electrical properties of the deposited layers and deinsulated tips. The alumina layer was found to prevent the formation of micro cracks on iridium oxide during the laser ablation process, which has been previously reported as a challenge for laser deinsulation of Parylene films. The charge injection capacity, charge storage capacity, and impedance of deinsulated iridium oxide were characterized to determine the deinsulation efficacy compared to Parylene-only insulation. Deinsulated iridium oxide with bilayer encapsulation had higher charge injection capacity (240 vs 320 nC) and similar electrochemical impedance (2.5 vs 2.5 kΩ) compared to deinsulated iridium oxide with only Parylene coating for an area of 2 × 10−4 cm2. Tip impedances were in the ranges of 20 to 50 kΩ, with median of 32 KΩ and standard deviation of 30 kΩ, showing the effectiveness of the self-aligned deinsulation process for alumina and Parylene C bi-layer encapsulation. The relatively uniform tip impedance values demonstrated the consistency of tip exposures. PMID:24771981

Low-dimensional carbon and MXene-based electrochemical capacitor electrodes.

PubMed

Yoon, Yeoheung; Lee, Keunsik; Lee, Hyoyoung

2016-04-29

Due to their unique structure and outstanding intrinsic physical properties such as extraordinarily high electrical conductivity, large surface area, and various chemical functionalities, low-dimension-based materials exhibit great potential for application in electrochemical capacitors (ECs). The electrical properties of electrochemical capacitors are determined by the electrode materials. Because energy charge storage is a surface process, the surface properties of the electrode materials greatly influence the electrochemical performance of the cell. Recently, graphene, a single layer of sp(2)-bonded carbon atoms arrayed into two-dimensional carbon nanomaterial, has attracted wide interest as an electrode material for electrochemical capacitor applications due to its unique properties, including a high electrical conductivity and large surface area. Several low-dimensional materials with large surface areas and high conductivity such as onion-like carbons (OLCs), carbide-derived carbons (CDCs), carbon nanotubes (CNTs), graphene, metal hydroxide, transition metal dichalcogenides (TMDs), and most recently MXene, have been developed for electrochemical capacitors. Therefore, it is useful to understand the current issues of low-dimensional materials and their device applications.

All-Diamond Microelectrodes as Solid State Probes for Localized Electrochemical Sensing.

PubMed

Silva, Eduardo L; Gouvêa, Cristol P; Quevedo, Marcela C; Neto, Miguel A; Archanjo, Braulio S; Fernandes, António J S; Achete, Carlos A; Silva, Rui F; Zheludkevich, Mikhail L; Oliveira, Filipe J

2015-07-07

The fabrication of an all-diamond microprobe is demonstrated for the first time. This ME (microelectrode) assembly consists of an inner boron doped diamond (BDD) layer and an outer undoped diamond layer. Both layers were grown on a sharp tungsten tip by chemical vapor deposition (CVD) in a stepwise manner within a single deposition run. BDD is a material with proven potential as an electrochemical sensor. Undoped CVD diamond is an insulating material with superior chemical stability in comparison to conventional insulators. Focused ion beam (FIB) cutting of the apex of the ME was used to expose an electroactive BDD disk. By cyclic voltammetry, the redox reaction of ferrocenemethanol was shown to take place at the BDD microdisk surface. In order to ensure that the outer layer was nonelectrically conductive, a diffusion barrier for boron atoms was established seeking the formation of boron-hydrogen complexes at the interface between the doped and the undoped diamond layers. The applicability of the microelectrodes in localized corrosion was demonstrated by scanning amperometric measurements of oxygen distribution above an Al-Cu-CFRP (Carbon Fiber Reinforced Polymer) galvanic corrosion cell.

Shape-Controlled Synthesis of Colloidal Metal Nanocrystals by Replicating the Surface Atomic Structure on the Seed.

PubMed

Gilroy, Kyle D; Yang, Xuan; Xie, Shuifen; Zhao, Ming; Qin, Dong; Xia, Younan

2018-06-01

Controlling the surface structure of metal nanocrystals while maximizing the utilization efficiency of the atoms is a subject of great importance. An emerging strategy that has captured the attention of many research groups involves the conformal deposition of one metal as an ultrathin shell (typically 1-6 atomic layers) onto the surface of a seed made of another metal and covered by a set of well-defined facets. This approach forces the deposited metal to faithfully replicate the surface atomic structure of the seed while at the same time serving to minimize the usage of the deposited metal. Here, the recent progress in this area is discussed and analyzed by focusing on the synthetic and mechanistic requisites necessary for achieving surface atomic replication of precious metals. Other related methods are discussed, including the one-pot synthesis, electrochemical deposition, and skin-layer formation through thermal annealing. To close, some of the synergies that arise when the thickness of the deposited shell is decreased controllably down to a few atomic layers are highlighted, along with how the control of thickness can be used to uncover the optimal physicochemical properties necessary for boosting the performance toward a range of catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Atomic Layer Processing

DTIC Science & Technology

1994-06-25

small parastaltic pumps were used. The solution reservoirs were made with Pyrex glass bottles and Teflon valves. The design of the flow-cell (FIG. 1...cells were used, as well (6). These electrodes consist of an Au rod set in a fitted glass cavity. The glass walls were designed to be on the order of...0.001" from the Au rod. Two pin holes were ground into the bottom of the glass in order for the solution to be flushed in and out of the thin-layer

Electrochemical Formation of Germanene: pH 4.5

DOE PAGES

Ledina, M. A.; Bui, N.; Liang, X.; ...

2017-05-27

Germanene is a single layer allotrope of Ge, with a honeycomb structure similar to graphene. This report concerns the electrochemical formation of germanene in a pH 4.5 solution. The studies were performed using in situ Electrochemical Scanning Tunneling Microscopy (EC-STM), voltammetry, coulometry, surface X-ray diffraction (SXRD) and Raman spectroscopy to study germanene electrodeposition on Au(111) terraces. The deposition of Ge is kinetically slow and stops after 2–3 monolayers. EC-STM revealed a honeycomb (HC) structure with a rhombic unit cell, 0.44 ± 0.02 nm on a side, very close to that predicted for germanene in the literature. Ideally the HC structuremore » is a continuous sheet, with six Ge atoms around each hole. However, only small domains, surrounded by defects, of this structure were observed in this study. The small coherence length and multiple rotations domains made direct observation with surface X-ray diffraction difficult. Raman spectroscopy was used to investigate the multi-layer Ge deposits. A peak near 290 cm -1, predicted to correspond to germanene, was observed on one particular area of the sample, while the rest resembled amorphous germanium. Electrochemical studies of germanene showed limited stability when exposed to oxygen.« less

Application of poly (p-phenylene oxide) as blocking layer to reduce self-discharge in supercapacitors

NASA Astrophysics Data System (ADS)

Tevi, Tete; Yaghoubi, Houman; Wang, Jing; Takshi, Arash

2013-11-01

Supercapacitors are electrochemical energy storage devices with high power density. However, application of supercapacitors is limited mainly due to their high leakage current. In this work, application of an ultra-thin layer of electrodeposited poly (p-phenylene oxide) (PPO) has been investigated as a blocking layer to reduce the leakage current. The polymer was first deposited on a glassy carbon electrode. The morphology of the film was studied by atomic force microscopy (AFM), and the film thickness was estimated to be ˜1.5 nm by using the electrochemical impedance spectroscopy (EIS) technique. The same deposition method was applied to coat the surface of the activated carbon electrodes of a supercapacitor with PPO. The specific capacitance, the leakage current, and the series resistance were measured in two devices with and without the blocking layer. The results demonstrate that the application of the PPO layer reduced the leakage current by ˜78%. However, the specific capacitance was decreased by ˜56%, when the blocking layer was applied. Due to the lower rate of self-discharge, the suggested approach can be applied to fabricate devices with longer charge storage time.

First-Principles Study on the Thermal Stability of LiNiO2 Materials Coated by Amorphous Al2O3 with Atomic Layer Thickness.

PubMed

Kang, Joonhee; Han, Byungchan

2015-06-03

Using first-principles calculations, we study how to enhance thermal stability of high Ni compositional cathodes in Li-ion battery application. Using the archetype material LiNiO2 (LNO), we identify that ultrathin coating of Al2O3 (0001) on LNO(012) surface, which is the Li de-/intercalation channel, substantially improves the instability problem. Density functional theory calculations indicate that the Al2O3 deposits show phase transition from the corundum-type crystalline (c-Al2O3) to amorphous (a-Al2O3) structures as the number of coating layers reaches three. Ab initio molecular dynamic simulations on the LNO(012) surface coated by a-Al2O3 (about 0.88 nm) with three atomic layers oxygen gas evolution is strongly suppressed at T=400 K. We find that the underlying mechanism is the strong contacting force at the interface between LNO(012) and Al2O3 deposits, which, in turn, originated from highly ionic chemical bonding of Al and O at the interface. Furthermore, we identify that thermodynamic stability of the a-Al2O3 is even more enhanced with Li in the layer, implying that the protection for the LNO(012) surface by the coating layer is meaningful over the charging process. Our approach contributes to the design of innovative cathode materials with not only high-energy capacity but also long-term thermal and electrochemical stability applicable for a variety of electrochemical energy devices including Li-ion batteries.

An investigation on the electrochemical behavior of the Co/Cu multilayer system.

PubMed

Mahshid, S S; Dolati, A

2010-09-01

Co/Cu multilayers were deposited in a sulfate solution by controlling the current and potential for the deposition of cobalt and copper layer respectively. The electrochemical behavior of these multilayers was studied by cyclic voltammetry and current transients. In addition, a mathematical analysis was used to characterize the electrodeposition system. Simultaneously, the nucleation and growth mechanisms were monitored by these techniques. In this case, the results clearly showed that electrodeposition of cobalt layers was a kinetically controlled process while the reduction of copper ions was a diffusion-control process. Although nucleation mechanism of the single Co deposit was found as a progressive system, it was found as an instantaneous system with three-dimensional growth mechanism in the Co/Cu bilayer deposition. Atomic Forced Microscopy images of the Co/Cu multilayer also confirmed the aforementioned nucleation mechanism, where it was expected that the growth of multilayer films would form a laminar-type structure containing a large number of equally-sized rounded grains in each layer.

Multifunctional Core-Shell and Nano-channel Design for Nano-sized Thermo-sensor

DTIC Science & Technology

2015-04-01

185 (2012) 172. 3. X. Sun, X. Ming, G. K. Wang, et al., “Atomic Layer Deposition of TiO2 on Graphene for Supercapacitors ”, Journal of the...Electrochemical Supercapacitors ”, Small (2012) 452. 5. H. T. Sun, M. P. Yu, G. K. Wang, X. Sun and J. Lian, “Temperature-Dependent Morphology Evolution and

Synthesis of carbon nanotube-nickel nanocomposites using atomic layer deposition for high-performance non-enzymatic glucose sensing.

PubMed

Choi, Taejin; Kim, Soo Hyeon; Lee, Chang Wan; Kim, Hangil; Choi, Sang-Kyung; Kim, Soo-Hyun; Kim, Eunkyoung; Park, Jusang; Kim, Hyungjun

2015-01-15

A useful strategy has been developed to fabricate carbon-nanotube-nickel (CNT-Ni) nanocomposites through atomic layer deposition (ALD) of Ni and chemical vapor deposition (CVD) of functionalized CNTs. Various techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), were used to characterize the morphology and the structure of as-prepared samples. It was confirmed that the products possess uniform Ni nanoparticles that are constructed by finely controlled deposition of Ni onto oxygen or bromine functionalized CNT surface. Electrochemical studies indicate that the CNT-Ni nanocomposites exhibit high electrocatalytic activity for glucose oxidation in alkaline solutions, which enables the products to be used in enzyme-free electrochemical sensors for glucose determination. It was demonstrated that the CNT-Ni nanocomposite-based glucose biosensor offers a variety of merits, such as a wide linear response window for glucose concentrations of 5 μM-2 mM, short response time (3 s), a low detection limit (2 μM), high sensitivity (1384.1 μA mM(-1) cm(-2)), and good selectivity and repeatability. Copyright © 2014 Elsevier B.V. All rights reserved.

Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

PubMed

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2009-03-01

To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE PAGES

Zhang, Chenhao; Yang, Shize; Wu, Jingjie; ...

2018-03-25

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Chenhao; Yang, Shize; Wu, Jingjie

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Atomic Layer-Deposited Molybdenum Oxide/Carbon Nanotube Hybrid Electrodes: The Influence of Crystal Structure on Lithium-Ion Capacitor Performance.

PubMed

Fleischmann, Simon; Zeiger, Marco; Quade, Antje; Kruth, Angela; Presser, Volker

2018-06-06

Merging of supercapacitors and batteries promises the creation of electrochemical energy storage devices that combine high specific energy, power, and cycling stability. For that purpose, lithium-ion capacitors (LICs) that store energy by lithiation reactions at the negative electrode and double-layer formation at the positive electrode are currently investigated. In this study, we explore the suitability of molybdenum oxide as a negative electrode material in LICs for the first time. Molybdenum oxide-carbon nanotube hybrid materials were synthesized via atomic layer deposition, and different crystal structures and morphologies were obtained by post-deposition annealing. These model materials are first structurally characterized and electrochemically evaluated in half-cells. Benchmarking in LIC full-cells revealed the influences of crystal structure, half-cell capacity, and rate handling on the actual device level performance metrics. The energy efficiency, specific energy, and power are mainly influenced by the overpotential and kinetics of the lithiation reaction during charging. Optimized LIC cells show a maximum specific energy of about 70 W·h·kg -1 and a high specific power of 4 kW·kg -1 at 34 W·h·kg -1 . The longevity of the LIC cells is drastically increased without significantly reducing the energy by preventing a deep cell discharge, hindering the negative electrode from crossing its anodic potential limit.

Sputtering graphite coating to improve the elevated-temperature cycling ability of the LiMn2O4 electrode.

PubMed

Wang, Jiexi; Zhang, Qiaobao; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Xu, Daguo; Zhang, Kaili

2014-08-14

To improve the cycle performance of LiMn2O4 at elevated temperature, a graphite layer is introduced to directly cover the surface of a commercial LiMn2O4-based electrode via room-temperature DC magnetron sputtering. The as-modified cathodes display improved capacity retention as compared to the bare LiMn2O4 cathode (BLMO) at 55 °C. When sputtering graphite for 30 min, the sample shows the best cycling performance at 55 °C, maintaining 96.2% capacity retention after 200 cycles. Reasons with respect to the graphite layer for improving the elevated-temperature performance of LiMn2O4 are systematically investigated via the methods of cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectrometry, scanning and transmission electron microscopy, X-ray diffraction and inductively coupled plasma-atomic emission spectrometry. The results demonstrate that the graphite coated LiMn2O4 cathode has much less increased electrode polarization and electrochemical impedance than BLMO during the elevated-temperature cycling process. Furthermore, the graphite layer is able to alleviate the severe dissolution of manganese ions into the electrolyte and mitigate the morphological and structural degradation of LiMn2O4 during cycling. A model for the electrochemical kinetics process is also suggested for explaining the roles of the graphite layer in suppressing the Mn dissolution.

Facile Phase Control of Multivalent Vanadium Oxide Thin Films (V2O5 and VO2) by Atomic Layer Deposition and Postdeposition Annealing.

PubMed

Song, Gwang Yeom; Oh, Chadol; Sinha, Soumyadeep; Son, Junwoo; Heo, Jaeyeong

2017-07-19

Atomic layer deposition was adopted to deposit VO x thin films using vanadyl tri-isopropoxide {VO[O(C 3 H 7 )] 3 , VTIP} and water (H 2 O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VO x . The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO 2 and V 2 O 5 phases, respectively. The possible band structures of the crystalline VO 2 and V 2 O 5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V 2 O 5 and VO 2 films, respectively.

Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale

DOE PAGES

Wu, Yan; Ma, Cheng; Yang, Jihui; ...

2015-01-21

Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 tomore » 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.« less

Graphene by one-step chemical vapor deposition from ferrocene vapors: Properties and electrochemical evaluation

NASA Astrophysics Data System (ADS)

Pilatos, George; Perdikaki, Anna V.; Sapalidis, Andreas; Pappas, George S.; Giannakopoulou, Tatiana; Tsoutsou, Dimitra; Xenogiannopoulou, Evangelia; Boukos, Nikos; Dimoulas, Athanasios; Trapalis, Christos; Kanellopoulos, Nick K.; Karanikolos, Georgios N.

2016-02-01

Growth of few-layer graphene using ferrocene as precursor by chemical vapor deposition is reported. The growth did not involve any additional carbon or catalyst source or external hydrocarbon gases. Parametric investigation was performed using different conditions, namely, varying growth temperature from 600 to1000 °C, and growth duration from 5 min to 3 h, as well as using fast quenching or gradual cooling after the thermal treatment, in order to examine the effect on the quality of the produced graphene. The growth took place on silicon wafers and resulted, under optimal conditions, in formation of graphene with 2-3 layers and high graphitic quality, as evidenced by Raman spectroscopy, with characteristic full width at half maximum of the 2D band of 49.46 cm-1, and I2D/IG and ID/IG intensity ratios of 1.15 and 0.26, respectively. Atomic force microscopy and X-ray photoelectron spectroscopy were employed to further evaluate graphene characteristics and enlighten growth mechanism. Electrochemical evaluation of the developed material was performed using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge measurements.

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

DOE PAGES

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo; ...

2016-01-19

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

Vanadium based materials as electrode materials for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Yan, Yan; Li, Bing; Guo, Wei; Pang, Huan; Xue, Huaiguo

2016-10-01

As a kind of supercapacitors, pseudocapacitors have attracted wide attention in recent years. The capacitance of the electrochemical capacitors based on pseudocapacitance arises mainly from redox reactions between electrolytes and active materials. These materials usually have several oxidation states for oxidation and reduction. Many research teams have focused on the development of an alternative material for electrochemical capacitors. Many transition metal oxides have been shown to be suitable as electrode materials of electrochemical capacitors. Among them, vanadium based materials are being developed for this purpose. Vanadium based materials are known as one of the best active materials for high power/energy density electrochemical capacitors due to its outstanding specific capacitance and long cycle life, high conductivity and good electrochemical reversibility. There are different kinds of synthetic methods such as sol-gel hydrothermal/solvothermal method, template method, electrospinning method, atomic layer deposition, and electrodeposition method that have been successfully applied to prepare vanadium based electrode materials. In our review, we give an overall summary and evaluation of the recent progress in the research of vanadium based materials for electrochemical capacitors that include synthesis methods, the electrochemical performances of the electrode materials and the devices.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Facile fabrication of ultrathin Pt overlayers onto nanoporous metal membranes via repeated Cu UPD and in situ redox replacement reaction.

PubMed

Liu, Pengpeng; Ge, Xingbo; Wang, Rongyue; Ma, Houyi; Ding, Yi

2009-01-06

Ultrathin Pt films from one to several atomic layers are successfully decorated onto nanoporous gold (NPG) membranes by utilizing under potential deposition (UPD) of Cu onto Au or Pt surfaces, followed by in situ redox replacement reaction (RRR) of UPD Cu by Pt. The thickness of Pt layers can be controlled precisely by repeating the Cu-UPD-RRR cycles. TEM observations coupled with electrochemical testing suggest that the morphology of Pt overlayers changes from an ultrathin epitaxial film in the case of one or two atomic layers to well-dispersed nanoislands in the case of four and more atomic layers. Electron diffraction (ED) patterns confirm that the as-prepared NPG-Pt membranes maintain a single-crystalline structure, even though the thickness of Pt films reaches six atomic layers, indicating the decorated Pt films hold the same crystallographic relationship to the NPG substrate during the entire fabrication process. Due to the regular modulation of Pt utilization, the electrocatalytic activity of NPG-Pt exhibits interesting surface structure dependence in methanol, ethanol, and CO electrooxidation reactions. These novel bimetallic nanocatalysts show excellent electrocatalytic activity and much enhanced poison tolerance as compared to the commercial Pt/C catalysts. The success in the fabrication of NPG-Pt-type materials provides a new path to prepare electrocatalysts with ultralow Pt loading and high Pt utilization, which is of great significance in energy-related applications, such as direct alcohol fuel cells (DAFCs).

Covalent functionalization of MoS2 nanosheets synthesized by liquid phase exfoliation to construct electrochemical sensors for Cd (II) detection.

PubMed

Gan, Xiaorong; Zhao, Huimin; Wong, Kwok-Yin; Lei, Dang Yuan; Zhang, Yaobin; Quan, Xie

2018-05-15

Surface functionalization is an effective strategy in the precise control of electronic surface states of two-dimensional materials for promoting their applications. In this study, based on the strong coordination interaction between the transition-metal centers and N atoms, the surface functionalization of few-layer MoS 2 nanosheets was successfully prepared by liquid phase exfoliation method in N, N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone, and formamide. The cytotoxicity of surface-functionalized MoS 2 nanosheets was for the first time evaluated by the methylthiazolyldiphenyl-tetrazoliumbromide assays. An electrochemical sensor was constructed based on glass carbon electrode (GCE) modified by MoS 2 nanosheets obtained in DMF, which exhibits relatively higher sensitivity to Cd 2+ detection and lower cytotoxicity against MCF-7 cells. The mechanisms of surface functionalization and selectively detecting Cd 2+ were investigated by density functional theory calculations together with various spectroscopic measurements. It was found that surface-functionalized MoS 2 nanosheets could be generated through Mo-N covalent bonds due to the orbital hybridization between the 5 s orbitals of Mo atoms and the 2p orbitals of N atoms of the solvent molecules. The high selectivity of the sensor is attributed to the coordination reaction between Cd 2+ and O donor atoms of DMF adsorbed on MoS 2 nanosheets. The robust anti-interference is ascribed to the strong binding energy of Cd 2+ and O atoms of DMF. Under the optimum conditions, the electrochemical sensor exhibits highly sensitive and selective assaying of Cd 2+ with a measured detection limit of 0.2 nM and a linear range from 2 nM to 20 μM. Copyright © 2018 Elsevier B.V. All rights reserved.

Highly sensitive and selective electrochemical dopamine sensing properties of multilayer graphene nanobelts

NASA Astrophysics Data System (ADS)

Karthick Kannan, Padmanathan; Moshkalev, Stanislav A.; Sekhar Rout, Chandra

2016-02-01

In the present study, we report the electrochemical sensing property of multi-layer graphene nanobelts (GNBs) towards dopamine (DA). GNBs are synthesized from natural graphite and characterized by using techniques like field-emission scanning electron microscopy, atomic force microscopy and Raman spectroscopy. An electrochemical sensor based on GNBs is developed for the detection of DA. From the cyclic voltammetry and amperometry studies, it is found that GNBs possess excellent electrocatalytic activity towards DA molecules. The developed DA sensor showed a sensitivity value of 0.95 μA μM-1 cm-2 with a linear range of 2 μM to 0.2 mM. The interference data exhibited that GNB is highly selective to DA even in the presence of common interfering species like ascorbic acid, uric acid, glucose and lactic acid.

Highly sensitive and selective electrochemical dopamine sensing properties of multilayer graphene nanobelts.

PubMed

Kannan, Padmanathan Karthick; Moshkalev, Stanislav A; Rout, Chandra Sekhar

2016-02-19

In the present study, we report the electrochemical sensing property of multi-layer graphene nanobelts (GNBs) towards dopamine (DA). GNBs are synthesized from natural graphite and characterized by using techniques like field-emission scanning electron microscopy, atomic force microscopy and Raman spectroscopy. An electrochemical sensor based on GNBs is developed for the detection of DA. From the cyclic voltammetry and amperometry studies, it is found that GNBs possess excellent electrocatalytic activity towards DA molecules. The developed DA sensor showed a sensitivity value of 0.95 μA μM(-1) cm(-2) with a linear range of 2 μM to 0.2 mM. The interference data exhibited that GNB is highly selective to DA even in the presence of common interfering species like ascorbic acid, uric acid, glucose and lactic acid.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhao; Zhou, Daojin; Wang, Maoyu

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Introducing Fe2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity.

PubMed

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; Bak, Seongmin; Wu, Yueshen; Wu, Zishan; Tian, Yang; Xiong, Xuya; Li, Yaping; Liu, Wen; Siahrostami, Samira; Kuang, Yun; Yang, Xiao-Qing; Duan, Haohong; Feng, Zhenxing; Wang, Hailiang; Sun, Xiaoming

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel-iron layered double hydroxides (NiFe-LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe-O-Fe moieties. These Fe2+-containing NiFe-LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm2, which is among the best OER catalytic performance reported to date. In-situ X-ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe-O-Fe motifs could stabilize high-valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE PAGES

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; ...

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Atomic layer deposition of Al2O3 on V2O5 xerogel film for enhanced lithium-ion intercalation stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Dawei; Liu, Yanyi; Candelaria, Stephanie L.

V2O5 xerogel films were fabricated by casting V2O5 sols onto fluorine-doped tin oxide glass substrates at room temperature. Five, ten and twenty atomic layers of Al2O3 were grown onto as-fabricated films respectively. The bare film and Al2O3-deposited films all exhibited hydrous V2O5 phase only. Electrochemical impedance spectroscopy study revealed increased surface charge-transfer resistance of V2O5 films as more Al2O3 atomic layers were deposited. Lithium-ion intercalation tests at 600 mAg_1 showed that bare V2O5 xerogel film possessed high initial discharge capacity of 219 mAhg_1 but suffered from severe capacity degradation, i.e., having only 136 mAhg_1 after 50 cycles. After deposition ofmore » ten atomic layers of Al2O3, the initial discharge capacity was 195 mAhg_1 but increased over cycles before stabilizing; after 50 cycles, the discharge capacity was as high as 225 mAhg_1. The noticeably improved cyclic stability of Al2O3-deposited V2O5 xerogel film could be attributed to the improved surface chemistry and enhanced mechanical strength. During repeated lithium-ion intercalation/de-intercalation, atomic layers of Al2O3 which were coated onto V2O5 surface could prevent V2O5 electrode dissolution into electrolyte by reducing direct contact between active electrode and electrolyte while at the same time acting as binder to maintain good mechanical contact between nanoparticles inside the film. VC 2012 American Vacuum Society.« less

Atomic Layer Deposition of Aluminum Sulfide: Growth Mechanism and Electrochemical Evaluation in Lithium-Ion Batteries

DOE PAGES

Meng, Xiangbo; Cao, Yanqiang; Libera, Joseph A.; ...

2017-10-01

This work describes the synthesis of aluminum sulfide (AlS x) thin films by atomic layer deposition (ALD) using tris(dimethylamido)aluminum and hydrogen sulfide. We employed a suite of in situ measurement techniques to explore the ALD AlS x growth mechanism, including quartz crystal microbalance, quadrupole mass spectrometry, and Fourier transform infrared spectroscopy. A variety of ex situ characterization techniques were used to determine the growth characteristics, morphology, elemental composition, and crystallinity of the resultant AlS x films. This study revealed that the AlS x growth was self-limiting in the temperature range 100–250 °C, and the growth per cycle decreased linearly withmore » increasing temperature from ~0.45 Å/cycle at 100 °C to ~0.1 Å/cycle at 250 °C. The AlSx films were amorphous in this temperature range. We conducted electrochemical testing to evaluate the ALD AlS x as a potential anode material for lithium-ion batteries (LIBs). Finally, the ALD AlS x exhibited reliable cyclability over 60 discharge–charge cycles with a sustainable discharge capacity of 640 mAh/g at a current density of 100 mA/g in the voltage window of 0.6–3.5 V.« less

A combined approach for high-performance Li-O2 batteries: A binder-free carbon electrode and atomic layer deposition of RuO2 as an inhibitor-promoter

NASA Astrophysics Data System (ADS)

Shin, Hyun-Seop; Seo, Gi Won; Kwon, Kyoungwoo; Jung, Kyu-Nam; Lee, Sang Ick; Choi, Eunsoo; Kim, Hansung; Hwang, Jin-Ha; Lee, Jong-Won

2018-04-01

A rechargeable lithium-oxygen (Li-O2) battery is considered as a promising technology for electrochemical energy storage systems because its theoretical energy density is much higher than those of state-of-the-art Li-ion batteries. The cathode (positive electrode) for Li-O2 batteries is made of carbon and polymeric binders; however, these constituents undergo parasitic decomposition reactions during battery operation, which in turn causes considerable performance degradation. Therefore, the rational design of the cathode is necessary for building robust and high-performance Li-O2 batteries. Here, a binder-free carbon nanotube (CNT) electrode surface-modified by atomic layer deposition (ALD) of dual acting RuO2 as an inhibitor-promoter is proposed for rechargeable Li-O2 batteries. RuO2 nanoparticles formed directly on the binder-free CNT electrode by ALD play a dual role to inhibit carbon decomposition and to promote Li2O2 decomposition. The binder-free RuO2/CNT cathode with the unique architecture shows outstanding electrochemical performance as characterized by small voltage gaps (˜0.9 V) as well as excellent cyclability without any signs of capacity decay over 80 cycles.

Atomic Layer Deposition of Aluminum Sulfide: Growth Mechanism and Electrochemical Evaluation in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Xiangbo; Cao, Yanqiang; Libera, Joseph A.

This work describes the synthesis of aluminum sulfide (AlS x) thin films by atomic layer deposition (ALD) using tris(dimethylamido)aluminum and hydrogen sulfide. We employed a suite of in situ measurement techniques to explore the ALD AlS x growth mechanism, including quartz crystal microbalance, quadrupole mass spectrometry, and Fourier transform infrared spectroscopy. A variety of ex situ characterization techniques were used to determine the growth characteristics, morphology, elemental composition, and crystallinity of the resultant AlS x films. This study revealed that the AlS x growth was self-limiting in the temperature range 100–250 °C, and the growth per cycle decreased linearly withmore » increasing temperature from ~0.45 Å/cycle at 100 °C to ~0.1 Å/cycle at 250 °C. The AlSx films were amorphous in this temperature range. We conducted electrochemical testing to evaluate the ALD AlS x as a potential anode material for lithium-ion batteries (LIBs). Finally, the ALD AlS x exhibited reliable cyclability over 60 discharge–charge cycles with a sustainable discharge capacity of 640 mAh/g at a current density of 100 mA/g in the voltage window of 0.6–3.5 V.« less

Nanoscale semiconductor Pb1-xSnxSe (x = 0.2) thin films synthesized by electrochemical atomic layer deposition

NASA Astrophysics Data System (ADS)

Lin, Shaoxiong; Zhang, Xin; Shi, Xuezhao; Wei, Jinping; Lu, Daban; Zhang, Yuzhen; Kou, Huanhuan; Wang, Chunming

2011-04-01

In this paper the fabrication and characterization of IV-VI semiconductor Pb1-xSnxSe (x = 0.2) thin films on gold substrate by electrochemical atomic layer deposition (EC-ALD) method at room temperature are reported. Cyclic voltammetry (CV) is used to determine approximate deposition potentials for each element. The amperometric I-t technique is used to fabricate the semiconductor alloy. The elements are deposited in the following sequence: (Se/Pb/Se/Pb/Se/Pb/Se/Pb/Se/Sn …), each period is formed using four ALD cycles of PbSe followed by one cycle of SnSe. Then the deposition manner above is cyclic repeated till a satisfactory film with expected thickness of Pb1-xSnxSe is obtained. The morphology of the deposit is observed by field emission scanning electron microscopy (FE-SEM). X-ray diffraction (XRD) pattern is used to study its crystalline structure; X-ray photoelectron spectroscopy (XPS) of the deposit indicates an approximate ratio 1.0:0.8:0.2 of Se, Pb and Sn, as the expected stoichiometry for the deposit. Open-circuit potential (OCP) studies indicate a good p-type property, and the good optical activity makes it suitable for fabricating a photoelectric switch.

Electrochemical cells and methods of manufacturing the same

DOEpatents

Bazzarella, Ricardo; Slocum, Alexander H; Doherty, Tristan; Cross, III, James C

2015-11-03

Electrochemical cells and methods of making electrochemical cells are described herein. In some embodiments, an apparatus includes a multi-layer sheet for encasing an electrode material for an electrochemical cell. The multi-layer sheet including an outer layer, an intermediate layer that includes a conductive substrate, and an inner layer disposed on a portion of the conductive substrate. The intermediate layer is disposed between the outer layer and the inner layer. The inner layer defines an opening through which a conductive region of the intermediate layer is exposed such that the electrode material can be electrically connected to the conductive region. Thus, the intermediate layer can serve as a current collector for the electrochemical cell.

Pulsed-Current Electrochemical Codeposition and Heat Treatment of Ti-Dispersed Ni-Matrix Layers

NASA Astrophysics Data System (ADS)

Janetaisong, Pathompong; Boonyongmaneerat, Yuttanant; Techapiesancharoenkij, Ratchatee

2016-08-01

An electrochemical deposition is a fast and cost-efficient process to produce film or coating. In this research, Ni-Ti electrodeposition is developed by codepositing a Ti-dispersed Ni-matrix layer from a Ni-plating solution suspended with Ti particles. To enhance the coating uniformity and control the atomic composition, the pulsed current was applied to codeposit Ni-Ti layers with varying pulse duty cycles (10 to 100 pct) and frequencies (10 to 100 Hz). The microstructures and compositions of the codeposited layers were analyzed by scanning electron microscopy, X-ray diffraction, and X-ray fluorescent techniques. The pulsed current significantly improved the quality of the Ni-Ti layer as compared to a direct current. The Ni-Ti layers could be electroplated with a controlled composition within 48 to 51 at. pct of Ti. The optimal pulse duty cycle and frequency are 50 pct and 10 Hz, respectively. The standalone Ni-49Ti layers were removed from copper substrates by selective etching method and subsequently heat-treated under Ar-fed atmosphere at 1423 K (1150 °C) for 5 hours. The phase and microstructures of the post-annealed samples exhibit different Ni-Ti intermetallic compounds, including NiTi, Ni3Ti, and NiTi2. Yet, the contamination of TiN and TiO2 was also present in the post-annealed samples.

Fabrication and electrochemical properties of insoluble fullerene-diamine adduct thin-films as buffer layer by alternate immersion process

NASA Astrophysics Data System (ADS)

Saito, Jo; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

2017-01-01

Insoluble fullerene-diamine adduct thin-films consisting of C60 and 1,2-diaminoethane were easily fabricated on an electrode by an alternate immersion process. Formation of the C60-diamine adduct films were confirmed using transmission absorption spectroscopy and atomic force microscopy. An inverted-type organic solar cells were fabricated by using the C60-diamine adduct film as the electron transport layer. The resultant photoelectric conversation performance of the solar cells suggested that photocurrent is generated via the photoexcitation of polythiophene. The result suggests that the present insoluble fullerene-diamine adduct films worked as buffer layer for organic thin-film solar cells.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Electrochemical cells and methods of manufacturing the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bazzarella, Ricardo; Slocum, Alexander H.; Doherty, Tristan

2016-07-26

Electrochemical cells and methods of making electrochemical cells are described herein. In some embodiments, an apparatus includes a multi-layer sheet for encasing an electrode material for an electrochemical cell. The multi-layer sheet including an outer layer, an intermediate layer that includes a conductive substrate, and an inner layer disposed on a portion of the conductive substrate. The intermediate layer is disposed between the outer layer and the inner layer. The inner layer defines an opening through which a conductive region of the intermediate layer is exposed such that the electrode material can be electrically connected to the conductive region. Thus,more » the intermediate layer can serve as a current collector for the electrochemical cell.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ledina, M. A.; Bui, N.; Liang, X.

Germanene is a single layer allotrope of Ge, with a honeycomb structure similar to graphene. This report concerns the electrochemical formation of germanene in a pH 4.5 solution. The studies were performed using in situ Electrochemical Scanning Tunneling Microscopy (EC-STM), voltammetry, coulometry, surface X-ray diffraction (SXRD) and Raman spectroscopy to study germanene electrodeposition on Au(111) terraces. The deposition of Ge is kinetically slow and stops after 2–3 monolayers. EC-STM revealed a honeycomb (HC) structure with a rhombic unit cell, 0.44 ± 0.02 nm on a side, very close to that predicted for germanene in the literature. Ideally the HC structuremore » is a continuous sheet, with six Ge atoms around each hole. However, only small domains, surrounded by defects, of this structure were observed in this study. The small coherence length and multiple rotations domains made direct observation with surface X-ray diffraction difficult. Raman spectroscopy was used to investigate the multi-layer Ge deposits. A peak near 290 cm -1, predicted to correspond to germanene, was observed on one particular area of the sample, while the rest resembled amorphous germanium. Electrochemical studies of germanene showed limited stability when exposed to oxygen.« less

Carbon fiber brush electrode as a novel substrate for atmospheric solids analysis probe (ASAP) mass spectrometry: Electrochemical oxidation of brominated phenols.

PubMed

Skopalová, Jana; Barták, Petr; Bednář, Petr; Tomková, Hana; Ingr, Tomáš; Lorencová, Iveta; Kučerová, Pavla; Papoušek, Roman; Borovcová, Lucie; Lemr, Karel

2018-01-25

A carbon fiber brush electrode (CFBE) was newly designed and used as a substrate for both controlled potential electrolysis and atmospheric solids analysis probe (ASAP) mass spectrometry. Electropolymerized and strongly adsorbed products of electrolysis were directly desorbed and ionized from the electrode surface. Electrochemical properties of the electrode investigated by cyclic voltammetry revealed large electroactive surface area (23 ± 3 cm 2 ) at 1.3 cm long array of carbon fibers with diameter 6-9 μm. Some products of electrochemical oxidation of pentabromophenol and 2,4,6-tribromophenol formed a compact layer on the carbon fibers and were analyzed using ASAP. Eleven new oligomeric products were identified including quinones and biphenoquinones. These compounds were not observed previously in electrolyzed solutions by liquid or gas chromatography/mass spectrometry. The thickness around 58 nm and 45 nm of the oxidation products layers deposited on carbon fibers during electrolysis of pentabromophenol and 2,4,6-tribromophenol, respectively, was estimated from atomic force microscopy analysis and confirmed by scanning electron microscopy with energy-dispersive X-ray spectroscopy measurements. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of Co-incorporated pristine and Fe-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries.

PubMed

Sun, Hua-Bin; Zhang, Lu-Lu; Yang, Xue-Lin; Liang, Gan; Li, Zhen

2016-10-21

Monoclinic Li 3 V 2 (PO 4 ) 3 /C (LVP/C) and Li 3 V 1.95 Fe 0.05 (PO 4 ) 3 /C (LVFP/C) composites were successfully modified by cobalt incorporation. The effects of cobalt incorporation on the structure, morphology and electrochemical performance of the LVP/C and LVFP/C composites were systematically investigated. The results show that most Co exists in the form of CoO and forms a hybrid layer with the carbon coating on the surface of the LVP and LVFP particles; moreover, a small part of Co enters into the LVP or LVFP lattices due to atomic diffusion. Compared with LVP/C and LVFP/C, Co-incorporated samples exhibit better electrochemical performance. In particular, under the common effect of doping and a hybrid layer (carbon and metal oxides) coating, the LVFP/C-Co electrode displays a prominent initial capacity of 124.7 mA h g -1 and a very low capacity fading of ∼0.04% per cycle even after 500 cycles at 20 C. This novel co-modification method with cation doping and a hybrid layer (carbon and metal oxide) coating is a highly effective way to improve the electrochemical performance and has great potential to be easily used to modify other cathode materials with poor electrical conductivity.

Toward Small-Diameter Carbon Nanotubes Synthesized from Captured Carbon Dioxide: Critical Role of Catalyst Coarsening.

PubMed

Douglas, Anna; Carter, Rachel; Li, Mengya; Pint, Cary L

2018-06-06

Small-diameter carbon nanotubes (CNTs) often require increased sophistication and control in synthesis processes, but exhibit improved physical properties and greater economic value over their larger-diameter counterparts. Here, we study mechanisms controlling the electrochemical synthesis of CNTs from the capture and conversion of ambient CO 2 in molten salts and leverage this understanding to achieve the smallest-diameter CNTs ever reported in the literature from sustainable electrochemical synthesis routes, including some few-walled CNTs. Here, Fe catalyst layers are deposited at different thicknesses onto stainless steel to produce cathodes, and atomic layer deposition of Al 2 O 3 is performed on Ni to produce a corrosion-resistant anode. Our findings indicate a correlation between the CNT diameter and Fe metal layer thickness following electrochemical catalyst reduction at the cathode-molten salt interface. Further, catalyst coarsening during long duration synthesis experiments leads to a 2× increase in average diameters from 3 to 60 min durations, with CNTs produced after 3 min exhibiting a tight diameter distribution centered near ∼10 nm. Energy consumption analysis for the conversion of CO 2 into CNTs demonstrates energy input costs much lower than the value of CNTs-a concept that strictly requires and motivates small-diameter CNTs-and is more favorable compared to other costly CO 2 conversion techniques that produce lower-value materials and products.

Ultra-high power capabilities in amorphous FePO4 thin films

NASA Astrophysics Data System (ADS)

Gandrud, Knut B.; Nilsen, Ola; Fjellvåg, Helmer

2016-02-01

Record breaking electrochemical properties of FePO4 have been found through investigation of the thickness dependent electrochemical properties of amorphous thin film electrodes. Atomic layer deposition was used for production of thin films of amorphous FePO4 with highly accurate thickness and topography. Electrochemical characterization of these thin film electrodes revealed that the thinner electrodes behave in a pseudocapacitive manner even at high rates of Li+ de/intercalation, which enabled specific powers above 1 MW kg-1 FePO4 to be obtained with minimal capacity loss. In addition, a self-enhancing kinetic effect was observed during cycling enabling more than 10,000 cycles at current rates approaching that of a supercapacitor (11s charge/discharge). The current findings may open for construction of ultra-high power battery electrodes that combines the energy density of batteries with the power capabilities of supercapacitors.

Integration of graphene onto silicon through electrochemical reduction of graphene oxide layers in non-aqueous medium

NASA Astrophysics Data System (ADS)

Marrani, Andrea Giacomo; Coico, Anna Chiara; Giacco, Daniela; Zanoni, Robertino; Scaramuzzo, Francesca Anna; Schrebler, Ricardo; Dini, Danilo; Bonomo, Matteo; Dalchiele, Enrique A.

2018-07-01

Wafer-scale integration of reduced graphene oxide with H-terminated Si(1 1 1) surfaces has been accomplished by electrochemical reduction of a thin film of graphene oxide deposited onto Si by drop casting. Two reduction methods have been assayed and carried out in an acetonitrile solution. The initial deposit was subjected either to potential cycling in a 0.1 M TBAPF6/CH3CN solution at scan rates values of 20 mV s-1 and 50 mV s-1, or to a potentiostatic polarization at Eλ,c = -3 V for 450 s. The resulting interface has been characterized in its surface composition, morphology and electrochemical behavior by X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy and electrochemical measurements. The results evidence that few-layer graphene deposits on H-Si(1 1 1) were obtained after reduction, and use of organic instead of aqueous medium led to a very limited surface oxidation of the Si substrate and a very low oxygen-to-carbon ratio. The described approach is fast, simple, economic, scalable and straightforward, as one reduction cycle is already effective in promoting the establishment of a graphene-Si interface. It avoids thermal treatments at high temperatures, use of aggressive chemicals and the presence of metal contaminants, and enables preservation of Si(1 1 1) surface from oxidation.

Highly stable Na2/3 (Mn0.54 Ni0.13 Co0.13 )O2 cathode modified by atomic layer deposition for sodium-ion batteries.

PubMed

Kaliyappan, Karthikeyan; Liu, Jian; Lushington, Andrew; Li, Ruying; Sun, Xueliang

2015-08-10

For the first time, atomic layer deposition (ALD) of Al2 O3 was adopted to enhance the cyclic stability of layered P2-type Na2/3 (Mn0.54 Ni0.13 Co0.13 )O2 (MNC) cathodes for use in sodium-ion batteries (SIBs). Discharge capacities of approximately 120, 123, 113, and 105 mA h g(-1) were obtained for the pristine electrode and electrodes coated with 2, 5, and 10 ALD cycles, respectively. All electrodes were cycled at the 1C discharge current rate for voltages between 2 and 4.5 V in 1 M NaClO4 electrolyte. Among the electrodes tested, the Al2 O3 coating from 2 ALD cycles (MNC-2) exhibited the best electrochemical stability and rate capability, whereas the electrode coated by 10 ALD cycles (MNC-10) displayed the highest columbic efficiency (CE), which exceeded 97 % after 100 cycles. The enhanced electrochemical stability observed for ALD-coated electrodes could be a result of the protection effects and high band-gap energy (Eg =9.00 eV) of the Al2 O3 coating layer. Additionally, the metal-oxide coating provides structural stability against mechanical stresses occurring during the cycling process. The capacity, cyclic stability, and rate performance achieved for the MNC electrode coated with 2 ALD cycles of Al2 O3 reveal the best results for SIBs. This study provides a promising route toward increasing the stability and CE of electrode materials for SIB application. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

NASA Astrophysics Data System (ADS)

Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

2000-03-01

The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the oxides on the Zr and Zry-2 samples which presumably originates from the electrolyte.

Monolayer atomic crystal molecular superlattices.

PubMed

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A; Huang, Yu; Duan, Xiangfeng

2018-03-07

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 10 7 , along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Monolayer atomic crystal molecular superlattices

NASA Astrophysics Data System (ADS)

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O.; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A., III; Huang, Yu; Duan, Xiangfeng

2018-03-01

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

PubMed

Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

2014-10-31

It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Low cost iodine intercalated graphene for fuel cells electrodes

NASA Astrophysics Data System (ADS)

Marinoiu, Adriana; Raceanu, Mircea; Carcadea, Elena; Varlam, Mihai; Stefanescu, Ioan

2017-12-01

On the theoretical predictions, we report the synthesis of iodine intercalated graphene for proton exchange membrane fuel cells (PEMFCs) applications. The structure and morphology of the samples were characterized by X-ray photoelectron spectroscopy (XPS) analysis, specific surface area by BET method, Raman investigations. The presence of elemental iodine in the form of triiodide and pentaiodide was validated, suggesting that iodine was trapped between graphene layers, leading to interactions with C atoms. The electrochemical performances of iodinated graphenes were tested and compared with a typical PEMFC configuration, containing different Pt/C loading (0.4 and 0.2 mg cm-2). If iodinated graphene is included as microporous layer, the electrochemical performances of the fuel cell are higher in terms of power density than the typical fuel cell. Iodine-doped graphenes have been successfully obtained by simple and cost effective synthetic strategy and demonstrated new insights for designing of a high performance metal-free ORR catalyst by a scalable technique.

Preparation and characterization of ultraflat Pt facets by atom-height-resolved differential optical microscopy

NASA Astrophysics Data System (ADS)

Azhagurajan, M.; Wen, R.; Kim, Y. G.; Itoh, T.; Sashikata, K.; Itaya, K.

2015-01-01

We recently demonstrated that improvements to our technique, laser confocal microscopy with differential interference microscopy (LCM-DIM), has rendered it fully capable of resolving monatomic steps with heights of ca. 0.25 nm on Au(111) and Pd(111) surfaces, even as low as 0.14 nm on Si(100), in aqueous solution. In this paper, we describe in detail a method to prepare and characterize, via atomic-layer-resolved LCM-DIM, ultraflat Pt(111) and Pt(100) facets over a wide surface area. The preparation of ultraflat surfaces is important in the characterization at the atomic scale of electrochemical processes under reaction conditions. To showcase the elegance of LCM-DIM, the anodic dissolution of Pt in aqueous HCl is briefly recounted.

Effects of water plasma immersion ion implantation on surface electrochemical behavior of NiTi shape memory alloys in simulated body fluids

NASA Astrophysics Data System (ADS)

Liu, X. M.; Wu, S. L.; Chu, Paul K.; Chung, C. Y.; Chu, C. L.; Yeung, K. W. K.; Lu, W. W.; Cheung, K. M. C.; Luk, K. D. K.

2007-01-01

Water plasma immersion ion implantation (PIII) was conducted on orthopedic NiTi shape memory alloy to enhance the surface electrochemical characteristics. The surface composition of the NiTi alloy before and after H 2O-PIII was determined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was utilized to determine the roughness and morphology of the NiTi samples. Potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) were carried out to investigate the surface electrochemical behavior of the control and H 2O-PIII NiTi samples in simulated body fluids (SBF) at 37 °C as well as the mechanism. The H 2O-PIII NiTi sample showed a higher breakdown potential ( Eb) than the control sample. Based on the AFM results, two different physical models with related equivalent electrical circuits were obtained to fit the EIS data and explain the surface electrochemical behavior of NiTi in SBF. The simulation results demonstrate that the higher resistance of the oxide layer produced by H 2O-PIII is primarily responsible for the improvement in the surface corrosion resistance.

Beyond graphene: Electrochemical sensors and biosensors for biomarkers detection.

PubMed

Bollella, Paolo; Fusco, Giovanni; Tortolini, Cristina; Sanzò, Gabriella; Favero, Gabriele; Gorton, Lo; Antiochia, Riccarda

2017-03-15

Graphene's success has stimulated great interest and research in the synthesis and characterization of graphene-like 2D materials, single and few-atom-thick layers of van der Waals materials, which show fascinating and technologically useful properties. This review presents an overview of recent electrochemical sensors and biosensors based on graphene and on graphene-like 2D materials for biomarkers detection. Initially, we will outline different electrochemical sensors and biosensors based on chemically derived graphene, including graphene oxide and reduced graphene oxide, properly functionalized for improved performances and we will discuss the various strategies to prepare graphene modified electrodes. Successively, we present electrochemical sensors and biosensors based on graphene-like 2D materials, such as boron nitride (BN), graphite-carbon nitride (g-C 3 N 4 ), transition metal dichalcogenides (TMDs), transition metal oxides and graphane, outlining how the new modified 2D nanomaterials will improve the electrochemical performances. Finally, we will compare the results obtained with different sensors and biosensors for the detection of important biomarkers such as glucose, hydrogen peroxide and cancer biomarkers and highlight the advantages and disadvantages of the use of graphene and graphene-like 2D materials in different sensing platforms. Copyright © 2016 Elsevier B.V. All rights reserved.

Preparation of electrochemically active silicon nanotubes in highly ordered arrays

PubMed Central

Grünzel, Tobias; Lee, Young Joo; Kuepper, Karsten

2013-01-01

Summary Silicon as the negative electrode material of lithium ion batteries has a very large capacity, the exploitation of which is impeded by the volume changes taking place upon electrochemical cycling. A Si electrode displaying a controlled porosity could circumvent the difficulty. In this perspective, we present a preparative method that yields ordered arrays of electrochemically competent silicon nanotubes. The method is based on the atomic layer deposition of silicon dioxide onto the pore walls of an anodic alumina template, followed by a thermal reduction with lithium vapor. This thermal reduction is quantitative, homogeneous over macroscopic samples, and it yields amorphous silicon and lithium oxide, at the exclusion of any lithium silicides. The reaction is characterized by spectroscopic ellipsometry for thin silica films, and by nuclear magnetic resonance and X-ray photoelectron spectroscopy for nanoporous samples. After removal of the lithium oxide byproduct, the silicon nanotubes can be contacted electrically. In a lithium ion electrolyte, they then display the electrochemical waves also observed for other bulk or nanostructured silicon systems. The method established here paves the way for systematic investigations of how the electrochemical properties (capacity, charge/discharge rates, cyclability) of nanoporous silicon negative lithium ion battery electrode materials depend on the geometry. PMID:24205460

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bazzarella, Ricardo; Slocum, Alexander H.; Doherty, Tristan

Electrochemical cells and methods of making electrochemical cells are described herein. In some embodiments, an apparatus includes a multi-layer sheet for encasing an electrode material for an electrochemical cell. The multi-layer sheet including an outer layer, an intermediate layer that includes a conductive substrate, and an inner layer disposed on a portion of the conductive substrate. The intermediate layer is disposed between the outer layer and the inner layer. The inner layer defines an opening through which a conductive region of the intermediate layer is exposed such that the electrode material can be electrically connected to the conductive region. Thus,more » the intermediate layer can serve as a current collector for the electrochemical cell.« less

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

DOE PAGES

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.; ...

2018-03-30

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

Platinum Electrodeposition at Unsupported Electrochemically Reduced Nanographene Oxide for Enhanced Ammonia Oxidation

PubMed Central

2015-01-01

The electrochemical reduction of highly oxidized unsupported graphene oxide nanosheets and its platinum electrodeposition was done by the rotating disk slurry electrode technique. Avoiding the use of a solid electrode, graphene oxide was electrochemically reduced in a slurry solution with a scalable process without the use of a reducing agent. Graphene oxide nanosheets were synthesized from carbon platelet nanofibers to obtain highly hydrophilic layers of less than 250 nm in width. The graphene oxide and electrochemically reduced graphene oxide/Pt (erGOx/Pt) hybrid materials were characterized through different spectroscopy and microscopy techniques. Pt nanoparticles with 100 facets, clusters, and atoms at erGOx were identified by high resolution transmission electron microscopy (HRTEM). Cyclic voltammetry was used to characterize the electrocatalytic activity of the highly dispersed erGOx/Pt hybrid material toward the oxidation of ammonia, which showed a 5-fold current density increase when compared with commercially available Vulcan/Pt 20%. This is in agreement with having Pt (100) facets present in the HRTEM images of the erGOx/Pt material. PMID:24417177

Novel multi-layered 1-D nanostructure exhibiting the theoretical capacity of silicon for a super-enhanced lithium-ion battery

NASA Astrophysics Data System (ADS)

Lee, Byoung-Sun; Yang, Ho-Sung; Jung, Heechul; Jeon, Seung-Yeol; Jung, Changhoon; Kim, Sang-Won; Bae, Jihyun; Choong, Chwee-Lin; Im, Jungkyun; Chung, U.-In; Park, Jong-Jin; Yu, Woong-Ryeol

2014-05-01

Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g-1 at 12000 mA g-1) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g-1). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions.Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g-1 at 12000 mA g-1) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g-1). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions. Electronic supplementary information (ESI) available: Simulation details, quantitative measurement of Si content in the nanofibers and ex situ Raman characterization sample preparation procedures are demonstrated. See DOI: 10.1039/c4nr00318g

Structural integrity--Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. Here, our study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. We performed combined X-ray spectroscopy, diffraction and microscopy experiments to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine lengthmore » scale morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. It also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Gramicidin ion channels in a lipid bilayer supported on polyelectrolyte multilayer films: an electrochemical impedance study.

PubMed

Diamanti, Eleftheria; Gutiérrez-Pineda, Eduart; Politakos, Nikolaos; Andreozzi, Patrizia; Rodriguez-Presa, María José; Knoll, Wolfgang; Azzaroni, Omar; Gervasi, Claudio A; Moya, Sergio E

2017-12-06

Supported membranes on polymer cushions are of fundamental interest as models for cell membranes. The use of polyelectrolyte multilayers (PEMs) assembled by the layer by layer (LbL) technique as supports for a bilayer allows for easy integration of the lipid bilayer on surfaces and devices and for nanoscale tunable spacing of the lipid bilayer. Controlling ionic permeability in lipid bilayers supported on PEMs triggers potential applications in sensing and as models for transport phenomena in cell membranes. Lipid bilayers displaying gramicidin channels are fabricated on top of polyallylamine hydrochloride (PAH) and polystyrene sulfonate (PSS) multilayer films, by the assembly of vesicles of phosphatidylcholine and phosphatidylserine, 50 : 50 M/M, carrying gramicidin (GA). Quartz crystal microbalance with dissipation shows that the vesicles with GA fuse into a bilayer. Atomic force microscopy reveals that the presence of GA alters the bilayer topography resulting in depressions in the bilayer of around 70 nm in diameter. Electrochemical impedance spectroscopy (EIS) studies show that supported bilayers carrying GA have smaller resistances than the bilayers without GA. Lipid layers carrying GA display a higher conductance for K + than for Na + and are blocked in the presence of Ca 2+ .

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate.

PubMed

Carino, Emily V; Newman, Daniel J; Connell, Justin G; Kim, Chaerin; Brushett, Fikile R

2017-10-31

Irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6 ) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double-layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6× increase in roughness, in good agreement with the changes in double-layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double-layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. These results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

DOE PAGES

Xu, Yahong; Hu, Enyuan; Yang, Feifei; ...

2016-08-17

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Robust graphene membranes in a silicon carbide frame.

PubMed

Waldmann, Daniel; Butz, Benjamin; Bauer, Sebastian; Englert, Jan M; Jobst, Johannes; Ullmann, Konrad; Fromm, Felix; Ammon, Maximilian; Enzelberger, Michael; Hirsch, Andreas; Maier, Sabine; Schmuki, Patrik; Seyller, Thomas; Spiecker, Erdmann; Weber, Heiko B

2013-05-28

We present a fabrication process for freely suspended membranes consisting of bi- and trilayer graphene grown on silicon carbide. The procedure, involving photoelectrochemical etching, enables the simultaneous fabrication of hundreds of arbitrarily shaped membranes with an area up to 500 μm(2) and a yield of around 90%. Micro-Raman and atomic force microscopy measurements confirm that the graphene layer withstands the electrochemical etching and show that the membranes are virtually unstrained. The process delivers membranes with a cleanliness suited for high-resolution transmission electron microscopy (HRTEM) at atomic scale. The membrane, and its frame, is very robust with respect to thermal cycling above 1000 °C as well as harsh acidic or alkaline treatment.

Core-shell Si@TiO 2 nanosphere anode by atomic layer deposition for Li-ion batteries

DOE PAGES

Dai, Sheng

2016-01-28

Silicon (Si) is regarded as next-generation anode for high-energy lithium-ion batteries (LIBs) due to its high Li storage capacity (4200 mA h g -1). However, the mechanical degradation and resultant capacity fade critically hinder its practical application. In this regard, we demonstrate that nanocoating of Si spheres with a 3 nm titanium dioxide (TiO 2) layer via atomic layer deposition (ALD) can utmostly balance the high conductivity and the good structural stability to improve the cycling stability of Si core material. The resultant sample, Si@TiO 2-3 nm core–shell nanospheres, exhibits the best electrochemical performance of all with a highest initialmore » Coulombic efficiency and specific charge capacity retention after 50 cycles at 0.1C (82.39% and 1580.3 mA h g -1). In addition to making full advantage of the ALD technique, we believe that our strategy and comprehension in coating the electrode and the active material could provide a useful pathway towards enhancing Si anode material itself and community of LIBs.« less

Nano-engineering of three-dimensional core/shell nanotube arrays for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Grote, Fabian; Wen, Liaoyong; Lei, Yong

2014-06-01

Large-scale arrays of core/shell nanostructures are highly desirable to enhance the performance of supercapacitors. Here we demonstrate an innovative template-based fabrication technique with high structural controllability, which is capable of synthesizing well-ordered three-dimensional arrays of SnO2/MnO2 core/shell nanotubes for electrochemical energy storage in supercapacitor applications. The SnO2 core is fabricated by atomic layer deposition and provides a highly electrical conductive matrix. Subsequently a thin MnO2 shell is coated by electrochemical deposition onto the SnO2 core, which guarantees a short ion diffusion length within the shell. The core/shell structure shows an excellent electrochemical performance with a high specific capacitance of 910 F g-1 at 1 A g-1 and a good rate capability of remaining 217 F g-1 at 50 A g-1. These results shall pave the way to realize aqueous based asymmetric supercapacitors with high specific power and high specific energy.

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.

2015-09-01

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminalmore » hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

DOE PAGES

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.; ...

2015-09-01

For the noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The fi ndings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. Moreover, the structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogenmore » bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrodes: A 1000-Fold Current Density Increase.

PubMed

Haschke, Sandra; Pankin, Dmitrii; Petrov, Yuri; Bochmann, Sebastian; Manshina, Alina; Bachmann, Julien

2017-09-22

Nanotubular iron(III) oxide electrodes are optimized for catalytic efficiency in the water oxidation reaction at neutral pH. The nanostructured electrodes are prepared from anodic alumina templates, which are coated with Fe 2 O 3 by atomic layer deposition. Scanning helium ion microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphologies and phases of samples submitted to various treatments. These methods demonstrate the contrasting effects of thermal annealing and electrochemical treatment. The electrochemical performances of the corresponding electrodes under dark conditions are quantified by steady-state electrolysis and electrochemical impedance spectroscopy. A rough and amorphous Fe 2 O 3 with phosphate incorporation is critical for the optimization of the water oxidation reaction. For the ideal pore length of 17 μm, the maximum catalytic turnover is reached with an effective current density of 140 μA cm -2 at an applied overpotential of 0.49 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel hydroxide nanoparticles-reduced graphene oxide nanosheets film: layer-by-layer electrochemical preparation, characterization and rifampicin sensory application.

PubMed

Rastgar, Shokoufeh; Shahrokhian, Saeed

2014-02-01

Electrochemical deposition, as a well-controlled synthesis procedure, has been used for subsequently layer-by-layer preparation of nickel hydroxide nanoparticle-reduced graphene oxide nanosheets (Ni(OH)2-RGO) on a graphene oxide (GO) film pre-cast on a glassy carbon electrode surface. The surface morphology and nature of the nano-hybrid film (Ni(OH)2-RGO) was thoroughly characterized by scanning electron and atomic force microscopy, spectroscopy and electrochemical techniques. The modified electrode appeared as an effective electro-catalytic model for analysis of rifampicin (RIF) by using linear sweep voltammetry (LSV). The prepared modified electrode exhibited a distinctly higher activity for electro-oxidation of RIF than either GO, RGO nanosheets or Ni(OH)2 nanoparticles. Enhancement of peak currents is ascribed to the fast heterogeneous electron transfer kinetics that arise from the synergistic coupling between the excellent properties of RGO nanosheets (such as high density of edge plane sites, subtle electronic characteristics and attractive π-π interaction) and unique properties of metal nanoparticles. Under the optimized analysis conditions, the modified electrode showed two oxidation processes for rifampicin at potentials about 0.08 V (peak I) and 0.69 V (peak II) in buffer solution of pH 7.0 with a wide linear dynamic range of 0.006-10.0 µmol L(-1) and 0.04-10 µmol L(-1) with a detection limit of 4.16 nmol L(-1) and 2.34 nmol L(-1) considering peaks I and II as an analytical signal, respectively. The results proved the efficacy of the fabricated modified electrode for simple, low cost and highly sensitive medicine sensor well suited for the accurate determinations of trace amounts of rifampicin in the pharmaceutical and clinical preparations. © 2013 Elsevier B.V. All rights reserved.

Electrochemical Biosensor Composed of Silver Ion-Mediated dsDNA on Au-Encapsulated Bi2 Se3 Nanoparticles for the Detection of H2 O2 Released from Breast Cancer Cells.

PubMed

Mohammadniaei, Mohsen; Yoon, Jinho; Lee, Taek; Bharate, Bapurao G; Jo, Jinhee; Lee, Donghyun; Choi, Jeong-Woo

2018-04-01

A newly developed electrochemical biosensor composed of a topological insulator (TI) and metallic DNA (mDNA) is fabricated. The bismuth selenide nanoparticle (Bi 2 Se 3 NP) is synthesized and sandwiched between the gold electrode and another Au-deposited thin layer (Bi 2 Se 3 @Au). Then, eight-silver-ion mediated double-stranded DNA (mDNA) is immobilized onto the substrate (Bi 2 Se 3 @Au-mDNA) for the further detection of hydrogen peroxide. The Bi 2 Se 3 NP acts as the electrochemical-signal booster, while unprecedentedly its encapsulation by the Au thin layer keeps the TI surface states protected, improves its electrochemical-signal stability and provides an excellent platform for the subsequent covalent immobilization of the mDNA through Au-thiol interaction. Electrochemical results show that the fabricated biosensor represents much higher Ag + redox current (≈10 times) than those electrodes prepared without Bi 2 Se 3 @Au. The characterization of the Bi 2 Se 3 @Au-mDNA film is confirmed by atomic force microscopy, scanning tunneling microscopy, and cyclic voltammetry. The proposed biosensor shows a dynamic range of 00.10 × 10 -6 m to 27.30 × 10 -6 m, very low detection limit (10 × 10 -9 m), unique current response (1.6 s), sound H 2 O 2 recovery in serum, and substantial capability to classify two breast cancer subtypes (MCF-7 and MDA-MB-231) based on their difference in the H 2 O 2 generation, offering potential applications in the biomedicine and pharmacology fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Accessing the dynamics of end-grafted flexible polymer chains by atomic force-electrochemical microscopy. Theoretical modeling of the approach curves by the elastic bounded diffusion model and Monte Carlo simulations. Evidence for compression-induced lateral chain escape.

PubMed

Abbou, Jeremy; Anne, Agnès; Demaille, Christophe

2006-11-16

The dynamics of a molecular layer of linear poly(ethylene glycol) (PEG) chains of molecular weight 3400, bearing at one end a ferrocene (Fc) label and thiol end-grafted at a low surface coverage onto a gold substrate, is probed using combined atomic force-electrochemical microscopy (AFM-SECM), at the scale of approximately 100 molecules. Force and current approach curves are simultaneously recorded as a force-sensing microelectrode (tip) is inserted within the approximately 10 nm thick, redox labeled, PEG chain layer. Whereas the force approach curve gives access to the structure of the compressed PEG layer, the tip-current, resulting from tip-to-substrate redox cycling of the Fc head of the chain, is controlled by chain dynamics. The elastic bounded diffusion model, which considers the motion of the Fc head as diffusion in a conformational field, complemented by Monte Carlo (MC) simulations, from which the chain conformation can be derived for any degree of confinement, allows the theoretical tip-current approach curve to be calculated. The experimental current approach curve can then be very satisfyingly reproduced by theory, down to a tip-substrate separation of approximately 2 nm, using only one adjustable parameter characterizing the chain dynamics: the effective diffusion coefficient of the chain head. At closer tip-substrate separations, an unpredicted peak is observed in the experimental current approach curve, which is shown to find its origin in a compression-induced escape of the chain from within the narrowing tip-substrate gap. MC simulations provide quantitative support for lateral chain elongation as the escape mechanism.

Lifetime assessment of atomic-layer-deposited Al2O3-Parylene C bilayer coating for neural interfaces using accelerated age testing and electrochemical characterization.

PubMed

Minnikanti, Saugandhika; Diao, Guoqing; Pancrazio, Joseph J; Xie, Xianzong; Rieth, Loren; Solzbacher, Florian; Peixoto, Nathalia

2014-02-01

The lifetime and stability of insulation are critical features for the reliable operation of an implantable neural interface device. A critical factor for an implanted insulation's performance is its barrier properties that limit access of biological fluids to the underlying device or metal electrode. Parylene C is a material that has been used in FDA-approved implantable devices. Considered a biocompatible polymer with barrier properties, it has been used as a substrate, insulation or an encapsulation for neural implant technology. Recently, it has been suggested that a bilayer coating of Parylene C on top of atomic-layer-deposited Al2O3 would provide enhanced barrier properties. Here we report a comprehensive study to examine the mean time to failure of Parylene C and Al2O3-Parylene C coated devices using accelerated lifetime testing. Samples were tested at 60°C for up to 3 months while performing electrochemical measurements to characterize the integrity of the insulation. The mean time to failure for Al2O3-Parylene C was 4.6 times longer than Parylene C coated samples. In addition, based on modeling of the data using electrical circuit equivalents, we show here that there are two main modes of failure. Our results suggest that failure of the insulating layer is due to pore formation or blistering as well as thinning of the coating over time. The enhanced barrier properties of the bilayer Al2O3-Parylene C over Parylene C makes it a promising candidate as an encapsulating neural interface. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Titanium bone implants with superimposed micro/nano-scale porosity and antibacterial capability

NASA Astrophysics Data System (ADS)

Necula, B. S.; Apachitei, I.; Fratila-Apachitei, L. E.; van Langelaan, E. J.; Duszczyk, J.

2013-05-01

This study aimed at producing a multifunctional layer with micro/nano-interconnected porosity and antibacterial capability on a rough macro-porous plasma sprayed titanium surface using the plasma electrolytic oxidation process. The layers were electrochemically formed in electrolytes based on calcium acetate and calcium glycerophosphate salts bearing dispersed Ag nanoparticles. They were characterized with respect to surface morphology and chemical composition using a scanning electron microscope equipped with the energy dispersive spectroscopy and back scattering detectors. Scanning electron microscopy images showed the formation of a micro/nano-scale porous layer, comprised of TiO2 bearing Ca and P species and Ag nanoparticles, following accurately the surface topography of the plasma sprayed titanium coating. The Ca/P atomic ratio was found to be close to that of bone apatite. Ag nanoparticles were incorporated on both on top and inside the porous structure of the TiO2 layer.

Improvement of electrochemical performance of nickel rich LiNi0.6Co0.2Mn0.2O2 cathode active material by ultrathin TiO2 coating.

PubMed

Qin, CanCan; Cao, JiaLi; Chen, Jun; Dai, GaoLe; Wu, TongFu; Chen, Yanbin; Tang, YueFeng; Li, AiDong; Chen, Yanfeng

2016-06-21

LiNi0.6Co0.2Mn0.2O2 cathode material has been surface-modified by coating with ultrathin TiO2via atomic layer deposition (ALD) technology to improve the electrochemical performance of LiNi0.6Co0.2Mn0.2O2 cathodes for lithium ion batteries. Within the cut-off voltage of 2.5-4.3 V, the coated sample delivers an initial discharge capacity of 187.7 mA h g(-1) at 0.1 C and with a capacity retention about 85.9% after 100 cycles at 1 C, which provides a significant improvement in terms of discharge capacity and cyclability, as compared with those of the bare one. Such enhanced electrochemical performance of the coated sample is ascribed to its high-quality ultrathin coating of amorphous TiO2, which can protect the active material from HF attack, withstand the dissolution of metal ions in the electrode and favor the lithium diffusion of oxide as proved by electrochemical impedance spectroscopy (EIS) tests. TiO2 coating via the ALD process provides a potential approach for battery factories to surface-modify Ni-rich electrode materials so as to realize improvements in electrochemical performance.

Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode

PubMed Central

Xie, Jin; Liao, Lei; Gong, Yongji; Li, Yanbin; Shi, Feifei; Pei, Allen; Sun, Jie; Zhang, Rufan; Kong, Biao; Subbaraman, Ram; Christensen, Jake; Cui, Yi

2017-01-01

Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formation during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. The protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte. PMID:29202031

Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jin; Liao, Lei; Gong, Yongji

Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formationmore » during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. In conclusion, the protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte.« less

Atomic Layer Deposition of Pd Nanoparticles on TiO₂ Nanotubes for Ethanol Electrooxidation: Synthesis and Electrochemical Properties.

PubMed

Assaud, Loïc; Brazeau, Nicolas; Barr, Maïssa K S; Hanbücken, Margrit; Ntais, Spyridon; Baranova, Elena A; Santinacci, Lionel

2015-11-11

Palladium nanoparticles are grown on TiO2 nanotubes by atomic layer deposition (ALD), and the resulting three-dimensional nanostructured catalysts are studied for ethanol electrooxidation in alkaline media. The morphology, the crystal structure, and the chemical composition of the Pd particles are fully characterized using scanning and transmission electron microscopies, X-ray diffraction, and X-ray photoelectron spectroscopy. The characterization revealed that the deposition proceeds onto the entire surface of the TiO2 nanotubes leading to the formation of well-defined and highly dispersed Pd nanoparticles. The electrooxidation of ethanol on Pd clusters deposited on TiO2 nanotubes shows not only a direct correlation between the catalytic activity and the particle size but also a steep increase of the response due to the enhancement of the metal-support interaction when the crystal structure of the TiO2 nanotubes is modified by annealing at 450 °C in air.

Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode

DOE PAGES

Xie, Jin; Liao, Lei; Gong, Yongji; ...

2017-11-29

Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formationmore » during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. In conclusion, the protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte.« less

Potential-specific structure at the hematite-electrolyte interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Electroplating and magnetostructural characterization of multisegmented Co54Ni46/Co85Ni15 nanowires from single electrochemical bath in anodic alumina templates

PubMed Central

2013-01-01

Highly hexagonally ordered hard anodic aluminum oxide membranes, which have been modified by a thin cover layer of SiO2 deposited by atomic layer deposition method, were used as templates for the synthesis of electrodeposited magnetic Co-Ni nanowire arrays having diameters of around 180 to 200 nm and made of tens of segments with alternating compositions of Co54Ni46 and Co85Ni15. Each Co-Ni single segment has a mean length of around 290 nm for the Co54Ni46 alloy, whereas the length of the Co85Ni15 segments was around 430 nm. The composition and crystalline structure of each Co-Ni nanowire segment were determined by transmission electron microscopy and selected area electron diffraction techniques. The employed single-bath electrochemical nanowire growth method allows for tuning both the composition and crystalline structure of each individual Co-Ni segment. The room temperature magnetic behavior of the multisegmented Co-Ni nanowire arrays is also studied and correlated with their structural and morphological properties. PMID:23735184

Graphene: corrosion-inhibiting coating.

PubMed

Prasai, Dhiraj; Tuberquia, Juan Carlos; Harl, Robert R; Jennings, G Kane; Rogers, Bridget R; Bolotin, Kirill I

2012-02-28

We report the use of atomically thin layers of graphene as a protective coating that inhibits corrosion of underlying metals. Here, we employ electrochemical methods to study the corrosion inhibition of copper and nickel by either growing graphene on these metals, or by mechanically transferring multilayer graphene onto them. Cyclic voltammetry measurements reveal that the graphene coating effectively suppresses metal oxidation and oxygen reduction. Electrochemical impedance spectroscopy measurements suggest that while graphene itself is not damaged, the metal under it is corroded at cracks in the graphene film. Finally, we use Tafel analysis to quantify the corrosion rates of samples with and without graphene coatings. These results indicate that copper films coated with graphene grown via chemical vapor deposition are corroded 7 times slower in an aerated Na(2)SO(4) solution as compared to the corrosion rate of bare copper. Tafel analysis reveals that nickel with a multilayer graphene film grown on it corrodes 20 times slower while nickel surfaces coated with four layers of mechanically transferred graphene corrode 4 times slower than bare nickel. These findings establish graphene as the thinnest known corrosion-protecting coating.

Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)

DOE PAGES

Anasori, Babak; Xie, Yu; Beidaghi, Majid; ...

2015-07-24

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. In this paper, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M' 2M"C 2 and M' 2M" 2C 3, where M' and M" are two different early transition metals. In these solids, M' layers sandwich M" carbide layers. By synthesizing Mo 2TiC 2T x, Mo 2Ti 2C 3T x, and Cr 2TiC 2T x (where T is a surface termination), we validated the DFT predictions. Since themore » Mo and Cr atoms are on the outside, they control the 2D flakes’ chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo 2TiC 2T x and Ti 3C 2T x. Finally, this work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.« less

Characterization of stable, electroactive protein cage/synthetic polymer multilayer thin films prepared by layer-by-layer assembly

NASA Astrophysics Data System (ADS)

Uto, Koichiro; Yamamoto, Kazuya; Kishimoto, Naoko; Muraoka, Masahiro; Aoyagi, Takao; Yamashita, Ichiro

2013-04-01

We have fabricated electroactive multilayer thin films containing ferritin protein cages. The multilayer thin films were prepared on a solid substrate by the alternate electrostatic adsorption of (apo)ferritin and poly( N-isopropylacrylamide- co-2-carboxyisopropylacrylamide) (NIPAAm- co-CIPAAm) in pH 3.5 acetate buffer solution. The assembly process was monitored using a quartz crystal microbalance. The (apo)ferritin/poly(NIPAAm- co-CIPAAm) multilayer thin films were then cross-linked using a water-soluble carbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide. The cross-linked films were stable under a variety of conditions. The surface morphology and thickness of the multilayer thin films were characterized by atomic force microscopy, and the ferritin iron cores were observed by scanning electron microscopy to confirm the assembly mechanism. Cyclic voltammetry measurements showed different electrochemical properties for the cross-linked ferritin and apoferritin multilayer thin films, and the effect of stability of the multilayer film on its electrochemical properties was also examined. Our method for constructing multilayer films containing protein cages is expected to be useful in building more complex functional inorganic nanostructures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anasori, Babak; Xie, Yu; Beidaghi, Majid

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. In this paper, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M' 2M"C 2 and M' 2M" 2C 3, where M' and M" are two different early transition metals. In these solids, M' layers sandwich M" carbide layers. By synthesizing Mo 2TiC 2T x, Mo 2Ti 2C 3T x, and Cr 2TiC 2T x (where T is a surface termination), we validated the DFT predictions. Since themore » Mo and Cr atoms are on the outside, they control the 2D flakes’ chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo 2TiC 2T x and Ti 3C 2T x. Finally, this work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.« less

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

PubMed Central

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; Yano, Junko; Hussain, Zahid; Liu, Zhi; Crumlin, Ethan J.

2016-01-01

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. PMID:27576762

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vissers, Daniel R.; Isheim, Dieter; Zhan, Chun

Lithium-ion batteries utilizing 5 V spinel material, LixMn1.5Ni0.5O4 have received considerable interest in recent years for their ability to deliver high energy and power densities. In this paper, we report an atomic scale analysis of the surface layer of a core–shell 5 V spinel structure where a small amount of the manganese lattice sites have been substituted with cobalt in the shell to reach a stoichiometry of LixMn1.18Ni0.55Co0.27O4. Our analyses include electrochemical analysis, atom probe tomography (APT) analysis, kinetic analysis of the interfacial reactions, and high resolution scanning transmission electron microscopy (HR-TEM) analysis. The APT analysis is performed on themore » material before and after long-term cycling at room temperature to provide insights into the atomic scale phenomena within the surface layer of the electrode material. Our APT data reveals a 25–30 nano-meter (nm) region which forms after cycling. From our analyses, we believe that the outer few nanometers of this region stabilizes the 5 V spinel within the chemical environment of the lithium-ion cell such that its structure is not compromised and thereby enables this material to cycle without significant capacity fading.« less

First-Principles Study of Mo Segregation in MoNi(111): Effects of Chemisorbed Atomic Oxygen

PubMed Central

Yu, Yanlin; Xiao, Wei; Wang, Jianwei; Wang, Ligen

2015-01-01

Segregation at metal alloy surfaces is an important issue because many electrochemical and catalytic properties are directly correlated to the surface composition. We have performed density functional theory calculations for Mo segregation in MoNi(111) in the presence of chemisorbed atomic oxygen. In particular, the coverage dependence and possible adsorption-induced segregation phenomena are addressed by investigating segregation energies of the Mo atom in MoNi(111). The theoretical calculated results show that the Mo atom prefers to be embedded in the bulk for the clean MoNi(111), while it segregates to the top-most layer when the oxygen coverage is thicker than 1/9 monolayer (ML). Furthermore, we analyze the densities of states for the clean and oxygen-chemisorbed MoNi(111), and see a strong covalent bonding between Mo d-band states and O p-states. The present study provides valuable insight for exploring practical applications of Ni-based alloys as hydrogen evolution electrodes. PMID:28787811

Atomic resolution of Lithium Ions in LiCoO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao-Horn, Yang; Croguennec, Laurence; Delmas, Claude

2003-03-18

LiCoO2 is the most common lithium storage material for lithium rechargeable batteries, used widely to power portable electronic devices such as laptop computers. Lithium arrangements in the CoO2 framework have a profound effect on the structural stability and electrochemical properties of LixCoO2 (0 < x < 1), however, probing lithium ions has been difficult using traditional X-ray and neutron diffraction techniques. Here we have succeeded in simultaneously resolving columns of cobalt, oxygen, and lithium atoms in layered LiCoO2 battery material using experimental focal series of LiCoO2 images obtained at sub-Angstrom resolution in a mid-voltage transmission electron microscope. Lithium atoms aremore » the smallest and lightest metal atoms, and scatter electrons only very weakly. We believe our observations of lithium to be the first by electron microscopy, and that they show promise to direct visualization of the ordering of lithium and vacancy in LixCoO2.« less

Fabrication of a trimer/single atom tip for gas field ion sources by means of field evaporation without tip heating.

PubMed

Kim, Kwang-Il; Kim, Young Heon; Ogawa, Takashi; Choi, Suji; Cho, Boklae; Ahn, Sang Jung; Park, In-Yong

2018-05-11

A gas field ion source (GFIS) has many advantages that are suitable for ion microscope sources, such as high brightness and a small virtual source size, among others. In order to apply a tip-based GFIS to an ion microscope, it is better to create a trimer/single atom tip (TSAT), where the ion beam must be generated in several atoms of the tip apex. Here, unlike the conventional method which uses tip heating or a reactive gas, we show that the tip surface can be cleaned using only the field evaporation phenomenon and that the TSAT can also be fabricated using an insulating layer containing tungsten oxide, which remains after electrochemical etching. Using this method, we could get TSAT over 90% of yield. Copyright © 2018. Published by Elsevier B.V.

Atomic Layer Deposition of Nickel on ZnO Nanowire Arrays for High-Performance Supercapacitors.

PubMed

Ren, Qing-Hua; Zhang, Yan; Lu, Hong-Liang; Wang, Yong-Ping; Liu, Wen-Jun; Ji, Xin-Ming; Devi, Anjana; Jiang, An-Quan; Zhang, David Wei

2018-01-10

A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g -1 ), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g -1 ). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate

DOE PAGES

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.; ...

2017-09-19

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2010-11-16

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

Multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2010-09-14

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

Atomic-scale understanding of non-stoichiometry effects on the electrochemical performance of Ni-rich cathode materials

NASA Astrophysics Data System (ADS)

Kong, Fantai; Liang, Chaoping; Longo, Roberto C.; Zheng, Yongping; Cho, Kyeongjae

2018-02-01

As the next-generation high energy capacity cathode materials for Li-ion batteries, Ni-rich oxides face the problem of obtaining near-stoichiometric phases due to excessive Ni occupying Li sites. These extra-Ni-defects drastically affect the electrochemical performance. Despite of its importance, the fundamental correlation between such defects and the key electrochemical properties is still poorly understood. In this work, using density-functional-theory, we report a comprehensive study on the effects of non-stoichiometric phases on properties of Ni-rich layered oxides. For instance, extra-Ni-defects trigger charge disproportionation reaction within the system, alleviating the Jahn-Teller distortion of Ni3+ ions, which constitutes an important reason for their low formation energies. Kinetic studies of these defects reveal their immobile nature, creating a "pillar effect" that increases the structural stability. Ab initio molecular dynamics revealed Li depletion regions surrounding extra-Ni-defects, which are ultimate responsible for the arduous Li diffusion and re-intercalation, resulting in poor rate performance and initial capacity loss. Finally, the method with combination of high valence cation doping and ion-exchange synthesis is regarded as the most promising way to obtain stoichiometric oxides. Overall, this work not only deepens our understanding of non-stoichiometric Ni-rich layered oxides, but also enables further optimizations of high energy density cathode materials.

ADHESION AND DE-ADHESION MECHANISMS AT POLYMER/METAL INTERFACES: Mechanistic Understanding Based on In Situ Studies of Buried Interfaces

NASA Astrophysics Data System (ADS)

Grundmeier, G.; Stratmann, M.

2005-08-01

The review highlights the state-of-the-art research regarding the application of modern in situ spectroscopic, microscopic, and electrochemical techniques to improve the understanding of the interaction of organic molecules with metal surfaces. We also consider the chemical and electrochemical processes that lead to a de-adhesion of polymers from metal surfaces. Spectroscopic techniques such as surface-enhanced infrared or Raman spectroscopy provide molecular understanding of organic molecules and water at buried metal surfaces. This information is complementary to adhesion studies by means of atomic force microscopy and de-adhesion studies of polymer layers from metals by means of a scanning Kelvin probe. Adhesion and de-adhesion mechanisms are discussed, especially those involving humid and corrosive environments, which are the predominant and most important for metal/polymer composites in engineering applications.

Atomic-scale electrochemistry on the surface of a manganite

DOE PAGES

Vasudevan, Rama K.; Tselev, Alexander; Baddorf, Arthur P.; ...

2015-04-09

The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La 0.625Ca 0.375MnO 3 grown on (001) SrTiO 3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring themore » tunnelling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.« less

Highly-Stable Li₄Ti₅O12 Anodes Obtained by Atomic-Layer-Deposited Al₂O₃.

PubMed

Yoon, Jae Kook; Nam, Seunghoon; Shim, Hyung Cheoul; Park, Kunwoo; Yoon, Taeho; Park, Hyung Sang; Hyun, Seungmin

2018-05-16

LTO (Li₄Ti₅O 12 ) has been highlighted as anode material for next-generation lithium ion secondary batteries due to advantages such as a high rate capability, excellent cyclic performance, and safety. However, the generation of gases from undesired reactions between the electrode surface and the electrolyte has restricted the application of LTO as a negative electrode in Li-ion batteries in electric vehicles (EVs) and energy storage systems (ESS). As the generation of gases from LTO tends to be accelerated at high temperatures (40⁻60 °C), the thermal stability of LTO should be maintained during battery discharge, especially in EVs. To overcome these technical limitations, a thin layer of Al₂O₃ (~2 nm thickness) was deposited on the LTO electrode surface by atomic layer deposition (ALD), and an electrochemical charge-discharge cycle test was performed at 60 °C. The capacity retention after 500 cycles clearly shows that Al₂O₃-coated LTO outperforms the uncoated one, with a discharge capacity retention of ~98%. TEM and XPS analyses indicate that the surface reactions of Al₂O₃-coated LTO are suppressed, while uncoated LTO undergoes the (111) to (222) phase transformation, as previously reported in the literature.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles

NASA Astrophysics Data System (ADS)

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-12-01

Atomically ordered nickel carbide (Ni3C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni3C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni3C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni3C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles.

PubMed

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-11-22

Atomically ordered nickel carbide (Ni 3 C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni 3 C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni 3 C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni 3 C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

DOE PAGES

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; ...

2016-08-31

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzingmore » the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential.« less

Methods for making a multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2007-05-29

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

Investigation of Corrosion Protection in Oil Mineral Reservoirs by Nanocomposites Used as Coating Layers

NASA Astrophysics Data System (ADS)

Al-Sarraf, Abdulhameed R.; Al-Saaidi, Samer A.

2018-05-01

In this study, a number of nanocomposites were prepared by adding magnesium oxide (MgO) with weight percentages (1, 2 & 3)% to cellulose nitrate and sodium silicate as an intermediate layer and other nanocomposites by adding MgO, coal coke and hybrid (MgO & coal coke with ratio 1:1) with weight percentages (1, 2 & 3)% to epoxy resin as final layer. The identity of the used metal is determined by spectrometer OE thermo. The nature and topography of the surface layers were examined by optical microscope and atomic force microscope (AFM). Mechanical properties are indicated by hardness, wear rate, impact strength and adhesion strength. The efficiency of the layers prepared to inhibit corrosion in the oil mineral reservoirs of the oil products distribution company was studied by electrochemical corrosion test in addition to the chemical corrosion test. The used metal is (St-37) according to (ASTM). It was found that the best intermediate layer (cellulose nitrate+3%MgO) and the final layer is the epoxy resin reinforced by 2% hybrid.

In situ electrochemical high-energy X-ray diffraction using a capillary working electrode cell geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Bedford, Nicholas M.; Jiang, Naisheng

The ability to generate new electrochemically active materials for energy generation and storage with improved properties will likely be derived from an understanding of atomic-scale structure/function relationships during electrochemical events. Here, the design and implementation of a new capillary electrochemical cell designed specifically forin situhigh-energy X-ray diffraction measurements is described. By increasing the amount of electrochemically active material in the X-ray path while implementing low-Zcell materials with anisotropic scattering profiles, an order of magnitude enhancement in diffracted X-ray signal over traditional cell geometries for multiple electrochemically active materials is demonstrated. This signal improvement is crucial for high-energy X-ray diffraction measurementsmore » and subsequent Fourier transformation into atomic pair distribution functions for atomic-scale structural analysis. As an example, clear structural changes in LiCoO 2under reductive and oxidative conditions using the capillary cell are demonstrated, which agree with prior studies. Accurate modeling of the LiCoO 2diffraction data using reverse Monte Carlo simulations further verifies accurate background subtraction and strong signal from the electrochemically active material, enabled by the capillary working electrode geometry.« less

Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact.

PubMed

Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

2018-01-12

Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from 'electrochemical' to 'mechanical', which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

Single-Atom Electrocatalysts.

PubMed

Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong; Du, Dan; Lin, Yuehe

2017-11-06

Recent years have witnessed a dramatic increase in the production of sustainable and renewable energy. However, the electrochemical performances of the various systems are limited, and there is an intensive search for highly efficient electrocatalysts by more rational control over the size, shape, composition, and structure. Of particular interest are the studies on single-atom catalysts (SACs), which have sparked new interests in electrocatalysis because of their high catalytic activity, stability, selectivity, and 100 % atom utilization. In this Review, we introduce innovative syntheses and characterization techniques for SACs, with a focus on their electrochemical applications in the oxygen reduction/evolution reaction, hydrogen evolution reaction, and hydrocarbon conversion reactions for fuel cells (electrooxidation of methanol, ethanol, and formic acid). The electrocatalytic performance is further considered at an atomic level and the underlying mechanisms are discussed. The ultimate goal is the tailoring of single atoms for electrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

2016-03-01

A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

Sputtered Pd as hydrogen storage for a chip-integrated microenergy system.

PubMed

Slavcheva, E; Ganske, G; Schnakenberg, U

2014-01-01

The work presents a research on preparation and physical and electrochemical characterisation of dc magnetron sputtered Pd films envisaged for application as hydrogen storage in a chip-integrated hydrogen microenergy system. The influence of the changes in the sputtering pressure on the surface structure, morphology, and roughness was analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AMF). The electrochemical activity towards hydrogen adsorption/desorption and formation of PdH were investigated in 0.5 M H2SO4 using the methods of cyclic voltammetry and galvanostatic polarisation. The changes in the electrical properties of the films as a function of the sputtering pressure and the level of hydrogenation were evaluated before and immediately after the electrochemical charging tests, using a four-probe technique. The research resulted in establishment of optimal sputter regime, ensuring fully reproducible Pd layers with highly developed surface, moderate porosity, and mechanical stability. Selected samples were integrated as hydrogen storage in a newly developed unitized microenergy system and tested in charging (water electrolysis) and discharging (fuel cell) operative mode at ambient conditions demonstrating a stable recycling performance.

DMSO-Li2O2 Interface in the Rechargeable Li-O2 Battery Cathode: Theoretical and Experimental Perspectives on Stability.

PubMed

Schroeder, Marshall A; Kumar, Nitin; Pearse, Alexander J; Liu, Chanyuan; Lee, Sang Bok; Rubloff, Gary W; Leung, Kevin; Noked, Malachi

2015-06-03

One of the greatest obstacles for the realization of the nonaqueous Li-O2 battery is finding a solvent that is chemically and electrochemically stable under cell operating conditions. Dimethyl sulfoxide (DMSO) is an attractive candidate for rechargeable Li-O2 battery studies; however, there is still significant controversy regarding its stability on the Li-O2 cathode surface. We performed multiple experiments (in situ XPS, FTIR, Raman, and XRD) which assess the stability of the DMSO-Li2O2 interface and report perspectives on previously published studies. Our electrochemical experiments show long-term stable cycling of a DMSO-based operating Li-O2 cell with a platinum@carbon nanotube core-shell cathode fabricated via atomic layer deposition, specifically with >45 cycles of 40 h of discharge per cycle. This work is complemented by density functional theory calculations of DMSO degradation pathways on Li2O2. Both experimental and theoretical evidence strongly suggests that DMSO is chemically and electrochemically stable on the surface of Li2O2 under the reported operating conditions.

Exclusive Ni-N4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO2 Reduction.

PubMed

Li, Xiaogang; Bi, Wentuan; Chen, Minglong; Sun, Yuexiang; Ju, Huanxin; Yan, Wensheng; Zhu, Junfa; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-10-25

Electrochemical reduction of carbon dioxide (CO 2 ) to value-added carbon products is a promising approach to reduce CO 2 levels and mitigate the energy crisis. However, poor product selectivity is still a major obstacle to the development of CO 2 reduction. Here we demonstrate exclusive Ni-N 4 sites through a topo-chemical transformation strategy, bringing unprecedentedly high activity and selectivity for CO 2 reduction. Topo-chemical transformation by carbon layer coating successfully ensures preservation of the Ni-N 4 structure to a maximum extent and avoids the agglomeration of Ni atoms to particles, providing abundant active sites for the catalytic reaction. The Ni-N 4 structure exhibits excellent activity for electrochemical reduction of CO 2 with particularly high selectivity, achieving high faradaic efficiency over 90% for CO in the potential range from -0.5 to -0.9 V and gives a maximum faradaic efficiency of 99% at -0.81 V with a current density of 28.6 mA cm -2 . We anticipate exclusive catalytic sites will shed new light on the design of high-efficiency electrocatalysts for CO 2 reduction.

Atomic Sulfur Anchored on Silicene, Phosphorene, and Borophene for Excellent Cycle Performance of Li-S Batteries.

PubMed

Li, Fen; Zhao, Jijun

2017-12-13

Dissolution of intermediate lithium polysulfides (LiPS) is an inevitable obstacle for the solid sulfur-based cathode in Li-S batteries. For the first time, herein, atomic sulfur is incorporated into silicene, phosphorene, and borophene to intrinsically eliminate the dissolution of LiPS. The small molecular sulfur species are anchored on the silicene surface with stronger Si-S interaction than the P-S and B-S ones. Meanwhile, a high atomic sulfur coverage (63.1 wt %) is achieved in silicene and concomitantly stabilizes the silicene layer. For the S 3 -covered silicene, a high theoretical capacity of 857 mA h g -1 is achieved with slight dissolution of LiPS originated from the loss of interior S atoms that are not directly bound with silicene surface. By realizing the elemental S 2 coverage on silicene with large surface area, the Li + ions can react fast with the S 2 species, leading to a high theoretical capacity of 891 mA h g -1 without dissolution and migration of the intermediate LiPS. Most interestingly, the discharge products of atomic layer of lithium sulfides on silicene surface exhibit completely different behaviors from the traditional discharge products of solid Li 2 S, which can function as effective adsorption and activation sites for the conversion of LiPS from long chain to short chain by accelerated redox reaction. The present study gains some key insights into how the atomic sulfur contributes to the intrinsic shuttle inhibition and offers a feasible way to design the atomic sulfur-based cathode materials of Li-S batteries with better electrochemical performance.

Inverted polymer solar cells with enhanced fill factor by inserting the potassium stearate interfacial modification layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jiangsheng; Faculty of Materials Science and Chemical Engineering, Ningbo University, No. 818 Fenghua Road, Ningbo 315211; Jiu, Tonggang, E-mail: jiutonggang@nimte.ac.cn, E-mail: fangjf@nimte.ac.cn

2016-05-02

A thin potassium stearate (KSt) film combined with an optimized ZnO film was introduced to improve the fill factor (FF) of highly efficient inverted polymer solar cells (PSCs). Atomic force microscopy and contact angle measurements were used to show that the introduction of KSt did not change the morphology of interlayer. On the contrary, it is beneficial for the spread of the active layer on the interlayer. The origin of enhanced FF was systematically studied by the ideal current-voltage model for a single heterojunction solar cell and electrochemical impedance spectroscopy. On the basis of the data analysis, the reduced chargemore » recombination loss was responsible for this improved FF. At last, when KSt was replaced by sodium stearate (NaSt), the similar experiment phenomenon was observed. This indicates that inserting a metallic stearate modified layer is a promising strategy to enhance inverted PSCs performance.« less

Nucleant layer effect on nanocolumnar ZnO films grown by electrodeposition

NASA Astrophysics Data System (ADS)

Tolosa, Maria D. Reyes; Damonte, Laura C.; Brine, Hicham; Bolink, Henk J.; Hernández-Fenollosa, María A.

2013-03-01

Different ZnO nanostructured films were electrochemically grown, using an aqueous solution based on ZnCl2, on three types of transparent conductive oxides grow on commercial ITO (In2O3:Sn)-covered glass substrates: (1) ZnO prepared by spin coating, (2) ZnO prepared by direct current magnetron sputtering, and (3) commercial ITO-covered glass substrates. Although thin, these primary oxide layers play an important role on the properties of the nanostructured films grown on top of them. Additionally, these primary oxide layers prevent direct hole combination when used in optoelectronic devices. Structural and optical characterizations were carried out by scanning electron microscopy, atomic force microscopy, and optical transmission spectroscopy. We show that the properties of the ZnO nanostructured films depend strongly on the type of primary oxide-covered substrate used. Previous studies on different electrodeposition methods for nucleation and growth are considered in the final discussion.

Nucleant layer effect on nanocolumnar ZnO films grown by electrodeposition.

PubMed

Tolosa, Maria D Reyes; Damonte, Laura C; Brine, Hicham; Bolink, Henk J; Hernández-Fenollosa, María A

2013-03-23

Different ZnO nanostructured films were electrochemically grown, using an aqueous solution based on ZnCl2, on three types of transparent conductive oxides grow on commercial ITO (In2O3:Sn)-covered glass substrates: (1) ZnO prepared by spin coating, (2) ZnO prepared by direct current magnetron sputtering, and (3) commercial ITO-covered glass substrates. Although thin, these primary oxide layers play an important role on the properties of the nanostructured films grown on top of them. Additionally, these primary oxide layers prevent direct hole combination when used in optoelectronic devices. Structural and optical characterizations were carried out by scanning electron microscopy, atomic force microscopy, and optical transmission spectroscopy. We show that the properties of the ZnO nanostructured films depend strongly on the type of primary oxide-covered substrate used. Previous studies on different electrodeposition methods for nucleation and growth are considered in the final discussion.

Nucleant layer effect on nanocolumnar ZnO films grown by electrodeposition

PubMed Central

2013-01-01

Different ZnO nanostructured films were electrochemically grown, using an aqueous solution based on ZnCl2, on three types of transparent conductive oxides grow on commercial ITO (In2O3:Sn)-covered glass substrates: (1) ZnO prepared by spin coating, (2) ZnO prepared by direct current magnetron sputtering, and (3) commercial ITO-covered glass substrates. Although thin, these primary oxide layers play an important role on the properties of the nanostructured films grown on top of them. Additionally, these primary oxide layers prevent direct hole combination when used in optoelectronic devices. Structural and optical characterizations were carried out by scanning electron microscopy, atomic force microscopy, and optical transmission spectroscopy. We show that the properties of the ZnO nanostructured films depend strongly on the type of primary oxide-covered substrate used. Previous studies on different electrodeposition methods for nucleation and growth are considered in the final discussion. PMID:23522332

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nehm, F., E-mail: frederik.nehm@iapp.de; Müller-Meskamp, L.; Klumbies, H.

A major failure mechanism is identified in electrical calcium corrosion tests for quality assessment of high-end application moisture barriers. Accelerated calcium corrosion is found at the calcium/electrode junction, leading to an electrical bottleneck. This causes test failure not related to overall calcium loss. The likely cause is a difference in electrochemical potential between the aluminum electrodes and the calcium sensor, resulting in a corrosion element. As a solution, a thin, full-area copper layer is introduced below the calcium, shifting the corrosion element to the calcium/copper junction and inhibiting bottleneck degradation. Using the copper layer improves the level of sensitivity formore » the water vapor transmission rate (WVTR) by over one order of magnitude. Thin-film encapsulated samples with 20 nm of atomic layer deposited alumina barriers this way exhibit WVTRs of 6 × 10{sup −5} g(H{sub 2}O)/m{sup 2}/d at 38 °C, 90% relative humidity.« less

Force microscopy of layering and friction in an ionic liquid

NASA Astrophysics Data System (ADS)

Hoth, Judith; Hausen, Florian; Müser, Martin H.; Bennewitz, Roland

2014-07-01

The mechanical properties of the ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4][FAP]) in confinement between a SiOx and a Au(1 1 1) surface are investigated by means of atomic force microscopy (AFM) under electrochemical control. Up to 12 layers of ion pairs can be detected through force measurements while approaching the tip of the AFM to the surface. The particular shape of the force versus distance curve is explained by a model for the interaction between tip, gold surface and ionic liquid, which assumes an exponentially decaying oscillatory force originating from bulk liquid density correlations. Jumps in the tip-sample distance upon approach correspond to jumps of the compliant force sensor between branches of the oscillatory force curve. Frictional force between the laterally moving tip and the surface is detected only after partial penetration of the last double layer between tip and surface.

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

PubMed Central

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

2016-01-01

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br−) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies. PMID:28344271

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

DOE PAGES

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; ...

2016-01-11

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH 3(CH 2) 15N+(CH 3) 3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na 2S x solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfurmore » reaction products on the cathode surface during the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

Tuning the thickness of electrochemically grafted layers in large area molecular junctions

NASA Astrophysics Data System (ADS)

Fluteau, T.; Bessis, C.; Barraud, C.; Della Rocca, M. L.; Martin, P.; Lacroix, J.-C.; Lafarge, P.

2014-09-01

We have investigated the thickness, the surface roughness, and the transport properties of oligo(1-(2-bisthienyl)benzene) (BTB) thin films grafted on evaporated Au electrodes, thanks to a diazonium-based electro-reduction process. The thickness of the organic film is tuned by varying the number of electrochemical cycles during the growth process. Atomic force microscopy measurements reveal the evolution of the thickness in the range of 2-27 nm. Its variation displays a linear dependence with the number of cycles followed by a saturation attributed to the insulating behavior of the organic films. Both ultrathin (2 nm) and thin (12 and 27 nm) large area BTB-based junctions have then been fabricated using standard CMOS processes and finally electrically characterized. The electronic responses are fully consistent with a tunneling barrier in case of ultrathin BTB film whereas a pronounced rectifying behavior is reported for thicker molecular films.

Direct detection of OTA by impedimetric aptasensor based on modified polypyrrole-dendrimers.

PubMed

Mejri-Omrani, Nawel; Miodek, Anna; Zribi, Becem; Marrakchi, Mouna; Hamdi, Moktar; Marty, Jean-Louis; Korri-Youssoufi, Hafsa

2016-05-12

Ochratoxin A (OTA) is a carcinogenic mycotoxin that contaminates food such as cereals, wine and beer; therefore it represents a risk for human health. Consequently, the allowed concentration of OTA in food is regulated by governmental organizations and its detection is of major agronomical interest. In the current study we report the development of an electrochemical aptasensor able to directly detect trace OTA without any amplification procedure. This aptasensor was constructed by coating the surface of a gold electrode with a film layer of modified polypyrrole (PPy), which was thereafter covalently bound to polyamidoamine dendrimers of the fourth generation (PAMAM G4). Finally, DNA aptamers that specifically binds OTA were covalently bound to the PAMAM G4 providing the aptasensor, which was characterized by using both Atomic Force Microscopy (AFM) and Surface Plasmon Resonance (SPR) techniques. The study of OTA detection by the constructed electrochemical aptasensor was performed using Electrochemical Impedance Spectroscopy (EIS) and revealed that the presence of OTA led to the modification of the electrical properties of the PPy layer. These modifications could be assigned to conformational changes in the folding of the aptamers upon specific binding of OTA. The aptasensor had a dynamic range of up to 5 μg L(-1) of OTA and a detection limit of 2 ng L(-1) of OTA, which is below the OTA concentration allowed in food by the European regulations. The efficient detection of OTA by this electrochemical aptasensor provides an unforeseen platform that could be used for the detection of various small molecules through specific aptamer association. Copyright © 2016 Elsevier B.V. All rights reserved.

Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces

NASA Astrophysics Data System (ADS)

Nellist, Michael R.; Laskowski, Forrest A. L.; Qiu, Jingjing; Hajibabaei, Hamed; Sivula, Kevin; Hamann, Thomas W.; Boettcher, Shannon W.

2018-01-01

Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the "surface" electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.

Nano-Electrochemistry and Nano-Electrografting with an Original Combined AFM-SECM

PubMed Central

Ghorbal, Achraf; Grisotto, Federico; Charlier, Julienne; Palacin, Serge; Goyer, Cédric; Demaille, Christophe; Ben Brahim, Ammar

2013-01-01

This study demonstrates the advantages of the combination between atomic force microscopy and scanning electrochemical microscopy. The combined technique can perform nano-electrochemical measurements onto agarose surface and nano-electrografting of non-conducting polymers onto conducting surfaces. This work was achieved by manufacturing an original Atomic Force Microscopy-Scanning ElectroChemical Microscopy (AFM-SECM) electrode. The capabilities of the AFM-SECM-electrode were tested with the nano-electrografting of vinylic monomers initiated by aryl diazonium salts. Nano-electrochemical and technical processes were thoroughly described, so as to allow experiments reproducing. A plausible explanation of chemical and electrochemical mechanisms, leading to the nano-grafting process, was reported. This combined technique represents the first step towards improved nano-processes for the nano-electrografting. PMID:28348337

Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

NASA Astrophysics Data System (ADS)

Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

2007-03-01

Microporous networks are of interest as electrolyte materials, gas separation membranes and catalytic nanoparticle templates. Here, we create microporous polyelectrolyte networks of tunable pore size and connectivity using the layer-by-layer (LBL) technique. In this method, a film is formed from the alternate adsorption of oppositely charged polyelectrolytes from aqueous solution to create a cohesive thin film. Using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA), LBL thin films of variable composition and charge density were assembled; then, the films were treated in an acidic bath, which ionizes PEI and de-ionizes PAA. This shift in charge density induces morphological rearrangement realized by a microporous network. Depending on the assembly pH and acidic bath pH, we are able to precisely tune the morphology, which is characterized by atomic force microscopy and scanning electron microscopy. To demonstrate the porous nature of the polyelectrolyte multilayer, the pores were filled with non-aqueous electrolyte (i.e. ethylene carbonate, dimethyl carbonate and lithium hexafluorophosphate) and probed with electrochemical impedance spectroscopy. These microporous networks exhibited two time constants, indicative of ions traveling through the liquid-filled pores and ions traveling through the polyelectrolyte matrix.

Electrochemical fluorination of La(2)CuO(4): a mild "chimie douce" route to superconducting oxyfluoride materials.

PubMed

Delville, M H; Barbut, D; Wattiaux, A; Bassat, J M; Ménétrier, M; Labrugère, C; Grenier, J C; Etourneau, J

2009-08-17

The fluorination of La(2)CuO(4) was achieved for the first time under normal conditions of pressure and temperature (1 MPa and 298 K) via electrochemical insertion in organic fluorinated electrolytes and led to lanthanum oxyfluorides of general formula La(2)CuO(4)F(x). Analyses showed that, underneath a very thin layer of LaF(3) (a few atomic layers), fluorine is effectively inserted in the material's structure. The fluorination strongly modifies the lanthanum environment, whereas very little modification is observed on copper, suggesting an insertion in the La(2)O(2) blocks of the structure. In all cases, fluorine insertion breaks the translation symmetry and introduces a long-distance disorder, as shown by electron spin resonance. These results highlight the efficiency of electrochemistry as a new "chimie douce" type fluorination technique for solid-state materials. Performed at room temperature, it additionally does not require any specific experimental care. The choice of the electrolytic medium is crucial with regard to the fluorine insertion rate as well as the material deterioration. Successful application of this technique to the well-known La(2)CuO(4) material provides a basis for further syntheses from other oxides.

Enhanced Electrochemical and Thermal Transport Properties of Graphene/MoS2 Heterostructures for Energy Storage: Insights from Multiscale Modeling.

PubMed

Gong, Feng; Ding, Zhiwei; Fang, Yin; Tong, Chuan-Jia; Xia, Dawei; Lv, Yingying; Wang, Bin; Papavassiliou, Dimitrios V; Liao, Jiaxuan; Wu, Mengqiang

2018-05-02

Graphene has been combined with molybdenum disulfide (MoS 2 ) to ameliorate the poor cycling stability and rate performance of MoS 2 in lithium ion batteries, yet the underlying mechanisms remain less explored. Here, we develop multiscale modeling to investigate the enhanced electrochemical and thermal transport properties of graphene/MoS 2 heterostructures (GM-Hs) with a complex morphology. The calculated electronic structures demonstrate the greatly improved electrical conductivity of GM-Hs compared to MoS 2 . Increasing the graphene layers in GM-Hs not only improves the electrical conductivity but also stabilizes the intercalated Li atoms in GM-Hs. It is also found that GM-Hs with three graphene layers could achieve and maintain a high thermal conductivity of 85.5 W/(m·K) at a large temperature range (100-500 K), nearly 6 times that of pure MoS 2 [∼15 W/(m·K)], which may accelerate the heat conduction from electrodes to the ambient. Our quantitative findings may shed light on the enhanced battery performances of various graphene/transition-metal chalcogenide composites in energy storage devices.

Fundamental Challenges for Modeling Electrochemical Energy Storage Systems at the Atomic Scale.

PubMed

Groß, Axel

2018-04-23

There is a strong need to improve the efficiency of electrochemical energy storage, but progress is hampered by significant technological and scientific challenges. This review describes the potential contribution of atomic-scale modeling to the development of more efficient batteries, with a particular focus on first-principles electronic structure calculations. Numerical and theoretical obstacles are discussed, along with ways to overcome them, and some recent examples are presented illustrating the insights into electrochemical energy storage that can be gained from quantum chemical studies.

Pt-Richcore/Sn-Richsubsurface/Ptskin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction.

PubMed

Rizo, Rubén; Arán-Ais, Rosa M; Padgett, Elliot; Muller, David A; Lázaro, Ma Jesús; Solla-Gullón, José; Feliu, Juan M; Pastor, Elena; Abruña, Héctor D

2018-03-14

Direct ethanol fuel cells are one of the most promising electrochemical energy conversion devices for portable, mobile and stationary power applications. However, more efficient and stable and less expensive electrocatalysts are still required. Interestingly, the electrochemical performance of the electrocatalysts toward the ethanol oxidation reaction can be remarkably enhanced by exploiting the benefits of structural and compositional sensitivity and control. Here, we describe the synthesis, characterization, and electrochemical behavior of cubic Pt-Sn nanoparticles. The electrochemical activity of the cubic Pt-Sn nanoparticles was found to be about three times higher than that obtained with unshaped Pt-Sn nanoparticles and six times higher than that of Pt nanocubes. In addition, stability tests indicated the electrocatalyst preserves its morphology and remains well-dispersed on the carbon support after 5000 potential cycles, while a cubic (pure) Pt catalyst exhibited severe agglomeration of the nanoparticles after a similar stability testing protocol. A detailed analysis of the elemental distribution in the nanoparticles by STEM-EELS indicated that Sn dissolves from the outer part of the shell after potential cycling, forming a ∼0.5 nm Pt skin. This particular atomic composition profile having a Pt-rich core, a Sn-rich subsurface layer, and a Pt-skin surface structure is responsible for the high activity and stability.

Electrochemical DNA sensor for anthrax toxin activator gene atxA-detection of PCR amplicons.

PubMed

Das, Ritu; Goel, Ajay K; Sharma, Mukesh K; Upadhyay, Sanjay

2015-12-15

We report the DNA probe functionalized electrochemical genosensor for the detection of Bacillus anthracis, specific towards the regulatory gene atxA. The DNA sensor is fabricated on electrochemically deposited gold nanoparticle on self assembled layer of (3-Mercaptopropyl) trimethoxysilane (MPTS) on GC electrode. DNA hybridization is monitored by differential pulse voltammogram (DPV). The modified GC electrode is characterized by atomic force microscopy (AFM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) method. We also quantified the DNA probe density on electrode surface by the chronocoulometric method. The detection is specific and selective for atxA gene by DNA probe on the electrode surface. No report is available for the detection of B. anthracis by using atxA an anthrax toxin activator gene. In the light of real and complex sample, we have studied the PCR amplicons of 303, 361 and 568 base pairs by using symmetric and asymmetric PCR approaches. The DNA probe of atxA gene efficiently hybridizes with different base pairs of PCR amplicons. The detection limit is found to be 1.0 pM (S/N ratio=3). The results indicate that the DNA sensor is able to detect synthetic target as well as PCR amplicons of different base pairs. Copyright © 2015 Elsevier B.V. All rights reserved.

Antibacterial inorganic-organic hybrid coatings on stainless steel via consecutive surface-initiated atom transfer radical polymerization for biocorrosion prevention.

PubMed

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2010-05-04

To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.

Analysis of ultraviolet photo-response of ZnO nanostructures prepared by electrodeposition and atomic layer deposition

NASA Astrophysics Data System (ADS)

Makhlouf, Houssin; Karam, Chantal; Lamouchi, Amina; Tingry, Sophie; Miele, Philippe; Habchi, Roland; Chtourou, Radhouane; Bechelany, Mikhael

2018-06-01

In this work, ZnO nanowires (ZnO NWs) and urchin-like ZnO nanowires (U-ZnO NWs) based on self-assembled ordered polystyrene sphere (PS) were successfully prepared by combining atomic layer deposition (ALD) and electrochemical deposition (ECD) processes to build UV photosensors. The photo-response of the prepared samples was investigated and compared. The growth of the nanowires on self-assembled, ordered PS introduces a significant modification on the morphology, crystal orientation and grain size of U-ZnO NWs compared to randomly, vertically aligned ZnO NWs, and therefore improves the photo-response of U-ZnO NWs. The photocurrent may be produced by either a surface or bulk-related process. For ZnO NW-based photosensors, the photocurrent was monitored by a surface related process, whereas, it was mainly governed by a bulk related process for U-ZnO NWs, resulting in a higher and faster photo-response. The study of the rise and decay time constants for both materials showed that these parameters were strikingly sensitive to the optical properties.

Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores.

PubMed

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

NASA Astrophysics Data System (ADS)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

Engendering Long-Term Air and Light Stability of a TiO2-Supported Porphyrinic Dye via Atomic Layer Deposition.

PubMed

Hoffeditz, William L; Son, Ho-Jin; Pellin, Michael J; Farha, Omar K; Hupp, Joseph T

2016-12-21

Organic and porphyrin-based chromophores are prevalent in liquid-junction photovoltaic and photocatalytic solar-cell chemistry; however, their long-term air and light instability may limit their practicality in real world technologies. Here, we describe the protection of a zinc porphyrin dye, adsorbed on nanoparticulate TiO 2 , from air and light degradation by a protective coating of alumina grown with a previously developed post-treatment atomic layer deposition (ALD) technique. The protective Al 2 O 3 ALD layer is deposited using dimethylaluminum isopropoxide as an Al source; in contrast to the ubiquitous ALD precursor trimethylaluminum, dimethylaluminum isopropoxide does not degrade the zinc porphyrin dye, as confirmed by UV-vis measurements. The growth of this protective ALD layer around the dye can be monitored by an in-reactor quartz crystal microbalance (QCM). Furthermore, greater than 80% of porphyrin light absorption is retained over ∼1 month of exposure to air and light when the protective coating is present, whereas almost complete loss of porphyrin absorption is observed in less than 2 days in the absence of the ALD protective layer. Applying the Al 2 O 3 post-treatment technique to the TiO 2 -adsorbed dye allows the dye to remain in electronic contact with both the semiconductor surface and a surrounding electrolyte solution, the combination of which makes this technique promising for numerous other electrochemical photovoltaic and photocatalytic applications, especially those involving the dye-sensitized evolution of oxygen.

Integrated TiN coated porous silicon supercapacitor with large capacitance per foot print

NASA Astrophysics Data System (ADS)

Grigoras, Kestutis; Grönberg, Leif; Ahopelto, Jouni; Prunnila, Mika

2017-05-01

We have fabricated a micro-supercapacitor with porous silicon electrodes coated with TiN by atomic layer deposition technique. The coating provides an efficient surface passivation and high electrical conductivity of the electrodes, resulting in stable and almost ideal electrochemical double layer capacitor behavior with characteristics comparable to the best carbon based micro-supercapacitors. Stability of the supercapacitor is verified by performing 50 000 voltammetry cycles with high capacitance retention obtained. Silicon microfabrication techniques facilitate integration of both supercapacitor electrodes inside the silicon substrate and, in this work, such in-chip supercapacitor is demonstrated. This approach allows realization of very high capacitance per foot print area. The in-chip micro-supercapacitor can be integrated with energy harvesting elements and can be used in wearable and implantable microdevices.

Corrosion Behavior of Zirconium Treated Mild Steel with and Without Organic Coating: a Comparative Study

NASA Astrophysics Data System (ADS)

Ghanbari, Alireza; Attar, Mohammadreza Mohammadzade

2014-10-01

In this study, the anti-corrosion performance of phosphated and zirconium treated mild steel (ZTMS) with and without organic coating was evaluated using AC and DC electrochemical techniques. The topography and morphology of the zirconium treated samples were studied using atomic force microscopy (AFM) and field emission scanning electron microscope (FE-SEM) respectively. The results revealed that the anti-corrosion performance of the phosphate layer was superior to the zirconium conversion layer without an organic coating due to very low thickness and porous nature of the ZTMS. Additionally, the corrosion behavior of the organic coated substrates was substantially different. It was found that the corrosion protection performance of the phosphate steel and ZTMS with an organic coating is in the same order.

Method of depositing epitaxial layers on a substrate

DOEpatents

Goyal, Amit

2003-12-30

An epitaxial article and method for forming the same includes a substrate having a textured surface, and an electrochemically deposited substantially single orientation epitaxial layer disposed on and in contact with the textured surface. The epitaxial article can include an electromagnetically active layer and an epitaxial buffer layer. The electromagnetically active layer and epitaxial buffer layer can also be deposited electrochemically.

XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO2 thin films to produce a new hybrid material coating

NASA Astrophysics Data System (ADS)

Drevet, R.; Dragoé, D.; Barthés-Labrousse, M. G.; Chaussé, A.; Andrieux, M.

2016-10-01

This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO2) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO2 layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

Engineering the surface of LiCoO 2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jin; Zhao, Jie; Liu, Yayuan

Here, developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important, owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles. Here, we deposited chemically inert and ionically conductive LiAlO 2 interfacial layers on LiCoO 2 electrodes using the atomic layer deposition technique. During prolonged cycling at high-voltage, the LiAlO 2 coating not only prevented interfacial reactions between the LiCoO 2 electrode and electrolyte, as confirmed by electrochemical impedance spectroscopy and Raman characterizations, but also allowed lithium ions to freely diffuse into LiCoOmore » 2 without sacrificing the power density. As a result, a capacity value close to 200 mA·h·g –1 was achieved for the LiCoO 2 electrodes with commercial level loading densities, cycled at the cut-off potential of 4.6 V vs. Li +/Li for 50 stable cycles; this represents a 40% capacity gain, compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs. Li +/Li.« less

Engineering the surface of LiCoO 2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries

DOE PAGES

Xie, Jin; Zhao, Jie; Liu, Yayuan; ...

2017-07-25

Here, developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important, owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles. Here, we deposited chemically inert and ionically conductive LiAlO 2 interfacial layers on LiCoO 2 electrodes using the atomic layer deposition technique. During prolonged cycling at high-voltage, the LiAlO 2 coating not only prevented interfacial reactions between the LiCoO 2 electrode and electrolyte, as confirmed by electrochemical impedance spectroscopy and Raman characterizations, but also allowed lithium ions to freely diffuse into LiCoOmore » 2 without sacrificing the power density. As a result, a capacity value close to 200 mA·h·g –1 was achieved for the LiCoO 2 electrodes with commercial level loading densities, cycled at the cut-off potential of 4.6 V vs. Li +/Li for 50 stable cycles; this represents a 40% capacity gain, compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs. Li +/Li.« less

Topics in electrochemical degradation of photovoltaic modules

NASA Technical Reports Server (NTRS)

Mon, G. R.

1984-01-01

Electrochemical degradation of photovoltaic modules was examined. It is found that the extent of electrochemical damage is dependent on the integrated leakage current. The PV electrochemical degradation mechanisms in the two polarities are different: (1) degradation rates in the two polarities are of the same order of magnitude; (2) center tapped grounded arrays are a preferred system configuration to minimize electrochemical degradation. The use of thicker pottant layers and polymer substrate films to reduce equilibrium leakage current values is suggested. A metallized substrate layer, if used, should be isolated from the pottant and the frame by polyester layers, and EVA modules appear to be consistent with 30 year life allocation levels for electrochemical damage. Temperature acceleration factors are well behaved and moderately well understood; humidity acceleration factors vary radically with module construction and materials and require additional research.

Enhanced efficiency and air-stability of NiOX-based perovskite solar cells via PCBM electron transport layer modification with Triton X-100.

PubMed

Lee, Kisu; Ryu, Jaehoon; Yu, Haejun; Yun, Juyoung; Lee, Jungsup; Jang, Jyongsik

2017-11-02

We modified phenyl-C61-butyric acid methyl ester (PCBM) for use as a stable, efficient electron transport layer (ETL) in inverted perovskite solar cells (PSCs). PCBM containing a surfactant Triton X-100 acts as the ETL and NiO X nanocrystals act as a hole transport layer (HTL). Atomic force microscopy and scanning electron microscopy images showed that surfactant-modified PCBM (s-PCBM) forms a high-quality, uniform, and dense ETL on the rough perovskite layer. This layer effectively blocks holes and reduces interfacial recombination. Steady-state photoluminescence and electrochemical impedance spectroscopy analyses confirmed that Triton X-100 improved the electron extraction performance of PCBM. When the s-PCBM ETL was used, the average power conversion efficiency increased from 10.76% to 15.68%. This improvement was primarily caused by the increases in the open-circuit voltage and fill factor. s-PCBM-based PSCs also showed good air-stability, retaining 83.8% of their initial performance after 800 h under ambient conditions.

Facile design and stabilization of a novel one-dimensional silicon-based photonic crystal microcavity

NASA Astrophysics Data System (ADS)

Salem, Mohamed Shaker; Ibrahim, Shaimaa Moustafa; Amin, Mohamed

2017-07-01

A novel silicon-based optical microcavity composed of a defect layer sandwiched between two parallel rugate mirrors is created by the electrochemical anodization of silicon in a hydrofluoric acid-based electrolyte using a precisely controlled current density profile. The profile consists of two sinusoidally modulated current waveforms separated by a fixed current that is applied to produce a defect layer between the mirrors. The spectral response of the rugate-based microcavity is simulated using the transfer matrix method and compared to the conventional Bragg-based microcavity. It is found that the resonance position of both microcavities is unchanged. However, the rugate-based microcavity exhibits a distinct reduction of the sidebands' intensity. Further attenuation of the sidebands' intensity is obtained by creating refractive index matching layers with optimized thickness at the bottom and top of the rugate-based microcavity. In order to stabilize the produced microcavity against natural oxidation, atomic layer deposition of an ultra-thin titanium dioxide layer on the pore wall is carried out followed by thermal annealing. The microcavity resonance position shows an observable sensitivity to the deposition and annealing processes.

Electrochemical Effects of Atomic Layer Deposition on Cathode Materials for Lithium Batteries

NASA Astrophysics Data System (ADS)

Scott, Isaac David

One of the greatest challenges of modern society is to stabilize a consistent energy supply that will meet our growing energy demand while decreasing the use of fossil fuels and the harmful green house gases which they produce. Developing reliable and safe solutions has driven research into exploring alternative energy sources for transportation including fuel cells, hydrogen storage, and lithium-ion batteries (LIBs). For the foreseeable future, though, rechargeable batteries appear to be the most practically viable power source. To deploy LIBs in next-generation vehicles, it is essential to develop electrodes with durability, high energy density, and high power. Unfortunately, the power capability of LIBs is generally hindered by Li+-ion diffusion in micrometer-sized materials and the formation of an insulating solid electrolyte interface (SEI) layer on the surface of the active material. In addition, degradation of the battery material due to chemical and electrochemical reactions with the electrolyte lead to both capacity fade and safety concerns both at room and higher temperatures. The current study focuses on mitigating these issues for high voltage cathode materials by both using nanoscale particles to improve Li+-ion diffusion and using ultrathin nanoscale coatings to protect the battery materials from undesirable side reactions. The electrode material is coated with Al2O3 using atomic layer deposition (ALD), which is a method to grow conformal thin films with atomic thickness (angstrom level control) using sequential, self-limiting surface reactions. First, nano-LiCoO 2 is employed to demonstrate the effectiveness of ALD coatings and demonstrates a profound increase in rate performance (>250% improvement) over generally employed micrometer-sized particles. Second, the cathode materials LiNi 0.8Co0.15Al0.05O2, LiNi0.33Mn 0.33Co0.33O2, LiMn2O4, and LiNi0.5Mn1.5O4 were used to demonstrate the benefits ALD coatings have on thermal runaway. The results show a decrease in exothermic reactions at elevated temperatures (>180 °C) for the coated versus uncoated material. Third, impedance studies were carried out on LiNi0.5Mn1.5O 4 to study the kinetic effects the ALD layer has on battery performance. These studies show that despite Al2O3 being electrically resistive in the bulk; the ultrathin coatings do not impede battery reaction kinetics. Finally, ALD coatings were studied for use in Li-O2 batteries. The results from these studies provide new opportunities for the battery industry to design other novel electrodes that are highly durable, safe, and provide good power performance. It also demonstrates that many of the issues that are detrimental to LIBs may simply be addressed by employing the scalable technique of atomic layer deposition.

Method of bonding an interconnection layer on an electrode of an electrochemical cell

DOEpatents

Pal, U.B.; Isenberg, A.O.; Folser, G.R.

1992-01-14

An electrochemical cell containing an air electrode, contacting electrolyte and electronically conductive interconnection layer, and a fuel electrode, has the interconnection layer attached by: (A) applying a thin, closely packed, discrete layer of LaCrO[sub 3] particles, doped with an element selected from the group consisting of Ca, Sr, Co, Ba, Mg and their mixtures on a portion of the air electrode, and then (B) electrochemical vapor depositing a dense skeletal structure between and around the doped LaCrO[sub 3] particles. 2 figs.

Refined tip preparation by electrochemical etching and ultrahigh vacuum treatment to obtain atomically sharp tips for scanning tunneling microscope and atomic force microscope.

PubMed

Hagedorn, Till; El Ouali, Mehdi; Paul, William; Oliver, David; Miyahara, Yoichi; Grütter, Peter

2011-11-01

A modification of the common electrochemical etching setup is presented. The described method reproducibly yields sharp tungsten tips for usage in the scanning tunneling microscope and tuning fork atomic force microscope. In situ treatment under ultrahigh vacuum (p ≤10(-10) mbar) conditions for cleaning and fine sharpening with minimal blunting is described. The structure of the microscopic apex of these tips is atomically resolved with field ion microscopy and cross checked with field emission. © 2011 American Institute of Physics

Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact

NASA Astrophysics Data System (ADS)

Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

2018-01-01

Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from ‘electrochemical’ to ‘mechanical’, which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

Electrochemical atomic force microscopy: In situ monitoring of electrochemical processes

NASA Astrophysics Data System (ADS)

Reggente, Melania; Passeri, Daniele; Rossi, Marco; Tamburri, Emanuela; Terranova, Maria Letizia

2017-08-01

The in-situ electrodeposition of polyaniline (PANI), one of the most attractive conducting polymers (CP), has been monitored performing electrochemical atomic force microscopy (EC-AFM) experiments. The electropolymerization of PANI on a Pt working electrode has been observed performing cyclic voltammetry experiments and controlling the evolution of current flowing through the electrode surface, together with a standard AFM image. The working principle and the potentialities of this emerging technique are briefly reviewed and factors limiting the studying of the in-situ electrosynthesis of organic compounds discussed.

Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

NASA Astrophysics Data System (ADS)

Travis, Jonathan

The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films is presented as a method for enabling non-conductive, but possibly electrochemically active materials, to be used for electrochemical applications.

Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces.

PubMed

Frechero, M A; Rocci, M; Sánchez-Santolino, G; Kumar, Amit; Salafranca, J; Schmidt, Rainer; Díaz-Guillén, M R; Durá, O J; Rivera-Calzada, A; Mishra, R; Jesse, Stephen; Pantelides, S T; Kalinin, Sergei V; Varela, M; Pennycook, S J; Santamaria, J; Leon, C

2015-12-17

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.

Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces

DOE PAGES

Frechero, M. A.; Rocci, M.; Sanchez-Santolino, G.; ...

2015-12-17

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together withmore » a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. In conclusion, besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.« less

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Fuel cell system with interconnect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goettler, Richard; Liu, Zhien

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Goettler, Richard; Liu, Zhien

2015-08-11

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Goettler, Richard; Liu, Zhien

2015-03-10

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Liu, Zhien; Goettler, Richard

2015-09-29

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Development of an optimized electrochemical process for subsequent coating of 316 stainless steel for stent applications.

PubMed

Haïdopoulos, M; Turgeon, S; Sarra-Bournet, C; Laroche, G; Mantovani, D

2006-07-01

Metallic endovascular stents are used as medical devices to scaffold biological lumen, most often diseased arteries, after balloon angioplasty. They are commonly made of 316L stainless steel or Nitinol, two alloys containing nickel, an element classified as potentially toxic and carcinogenic by the International Agency for Research on Cancer. Although they are largely implanted, the long-term safety of such metallic elements is still controversial, since the corrosion processes may lead to the release of several metallic ions, including nickel ions in diverse oxidation states. To avoid metallic ion release in the body, the strategy behind this work was to develop a process aiming the complete isolation of the stainless steel device from the body fluids by a thin, cohesive and strongly adherent coating of RF-plasma-polymerized fluoropolymer. Nevertheless, prior to the polymer film deposition, an essential aspect was the development of a pre-treatment for the metallic substrate, based on the electrochemical polishing process, aiming the removal of any fragile interlayer, including the native oxide layer and the carbon contaminated layer, in order to obtain a smooth, defect-free surface to optimize the adhesion of the plasma-deposited thin film. In this work, the optimized parameters for electropolishing, such as the duration and the temperature of the electrolysis, and the complementary acid dipping were presented and accurately discussed. Their effects on roughness as well as on the evolution of surface topography were investigated by Atomic Force Microscopy, stylus profilometry and Scanning Electron Microscopy. The modifications induced on the surface atomic concentrations were studied by X-ray Photoelectron Spectroscopy. The improvements in terms of the surface morphology after the pre-treatment were also emphasized, as well as the influence of the original stainless steel surface finish.

Method of bonding an interconnection layer on an electrode of an electrochemical cell

DOEpatents

Pal, Uday B.; Isenberg, Arnold O.; Folser, George R.

1992-01-01

An electrochemical cell containing an air electrode (16), contacting electrolyte and electronically conductive interconnection layer (26), and a fuel electrode, has the interconnection layer (26) attached by: (A) applying a thin, closely packed, discrete layer of LaCrO.sub.3 particles (30), doped with an element selected from the group consisting of Ca, Sr, Co, Ba, Mg and their mixtures on a portion of the air electrode, and then (B) electrochemical vapor depositing a dense skeletal structure (32) between and around the doped LaCrO.sub.3 particles (30).

Sputtered Pd as Hydrogen Storage for a Chip-Integrated Microenergy System

PubMed Central

Slavcheva, E.; Ganske, G.; Schnakenberg, U.

2014-01-01

The work presents a research on preparation and physical and electrochemical characterisation of dc magnetron sputtered Pd films envisaged for application as hydrogen storage in a chip-integrated hydrogen microenergy system. The influence of the changes in the sputtering pressure on the surface structure, morphology, and roughness was analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AMF). The electrochemical activity towards hydrogen adsorption/desorption and formation of PdH were investigated in 0.5 M H2SO4 using the methods of cyclic voltammetry and galvanostatic polarisation. The changes in the electrical properties of the films as a function of the sputtering pressure and the level of hydrogenation were evaluated before and immediately after the electrochemical charging tests, using a four-probe technique. The research resulted in establishment of optimal sputter regime, ensuring fully reproducible Pd layers with highly developed surface, moderate porosity, and mechanical stability. Selected samples were integrated as hydrogen storage in a newly developed unitized microenergy system and tested in charging (water electrolysis) and discharging (fuel cell) operative mode at ambient conditions demonstrating a stable recycling performance. PMID:24516356

Electroconversion of glycerol in alkaline medium: From generation of energy to formation of value-added products

NASA Astrophysics Data System (ADS)

Da Silva, Rodrigo Garcia; Aquino Neto, Sidney; Kokoh, Kouakou Boniface; De Andrade, Adalgisa Rodrigues

2017-05-01

We have investigated the electroconversion of glycerol in alkaline medium using bimetallic M50@Pt50 nanocatalysts (where M = Ru, Sn or Ni) supported on multi-walled carbon nanotubes. The electrocatalysts have been synthesized via an electrostatically oriented co-reduction method in which self-assembly of the positively charged metal species (Sn, Ni and Ru) into the internal catalyst level and of the negatively charged platinum species towards the outer layer afford nanocatalysts with the desired morphology. The physicochemical characterizations have confirmed the atomic ratios, the metal loadings, and the spherical shape of the nanoparticles with average diameter lying between 2 and 3 nm. In terms of electrochemical performance, the Ni@Pt composition displays the highest electrochemically active surface area, the best relation between the peak current and the onset oxidation potential in the presence of glycerol (275 mA mg-1Pt and -492 mV vs. Hg/HgO/OH-), and the most remarkable electrochemical stability in chronoamperometric tests. Long-term experiments to evaluate the oxidation of glycerol and analysis of the products indicate that the different electrocatalysts synthesized herein efficiently perform the electroconversion of glycerol at high rates and generate of value-added products.

One Step Assembly of Thin Films of Carbon Nanotubes on Screen Printed Interface for Electrochemical Aptasensing of Breast Cancer Biomarker.

PubMed

Nawaz, Muhammad Azhar Hayat; Rauf, Sajid; Catanante, Gaelle; Nawaz, Mian Hasnain; Nunes, Gilvanda; Marty, Jean Louis; Hayat, Akhtar

2016-10-06

Thin films of organic moiety functionalized carbon nanotubes (CNTs) from a very well-dispersed aqueous solution were designed on a screen printed transducer surface through a single step directed assembly methodology. Very high density of CNTs was obtained on the screen printed electrode surface, with the formation of a thin and uniform layer on transducer substrate. Functionalized CNTs were characterized by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Brunauer-Emmett- Teller (BET) surface area analyzer methodologies, while CNT coated screen printed transducer platform was analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The proposed methodology makes use of a minimum amount of CNTs and toxic solvents, and is successfully demonstrated to form thin films over macroscopic areas of screen printed carbon transducer surface. The CNT coated screen printed transducer surface was integrated in the fabrication of electrochemical aptasensors for breast cancer biomarker analysis. This CNT coated platform can be applied to immobilize enzymes, antibodies and DNA in the construction of biosensor for a broad spectrum of applications.

One Step Assembly of Thin Films of Carbon Nanotubes on Screen Printed Interface for Electrochemical Aptasensing of Breast Cancer Biomarker

PubMed Central

Nawaz, Muhammad Azhar Hayat; Rauf, Sajid; Catanante, Gaelle; Nawaz, Mian Hasnain; Nunes, Gilvanda; Louis Marty, Jean; Hayat, Akhtar

2016-01-01

Thin films of organic moiety functionalized carbon nanotubes (CNTs) from a very well-dispersed aqueous solution were designed on a screen printed transducer surface through a single step directed assembly methodology. Very high density of CNTs was obtained on the screen printed electrode surface, with the formation of a thin and uniform layer on transducer substrate. Functionalized CNTs were characterized by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Brunauer–Emmett–Teller (BET) surface area analyzer methodologies, while CNT coated screen printed transducer platform was analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The proposed methodology makes use of a minimum amount of CNTs and toxic solvents, and is successfully demonstrated to form thin films over macroscopic areas of screen printed carbon transducer surface. The CNT coated screen printed transducer surface was integrated in the fabrication of electrochemical aptasensors for breast cancer biomarker analysis. This CNT coated platform can be applied to immobilize enzymes, antibodies and DNA in the construction of biosensor for a broad spectrum of applications. PMID:27782067

An electrochemical genosensor for Salmonella typhi on gold nanoparticles-mercaptosilane modified screen printed electrode.

PubMed

Das, Ritu; Sharma, Mukesh K; Rao, Vepa K; Bhattacharya, B K; Garg, Iti; Venkatesh, V; Upadhyay, Sanjay

2014-10-20

In this work, we fabricated a system of integrated self-assembled layer of organosilane 3-mercaptopropyltrimethoxy silane (MPTS) on the screen printed electrode (SPE) and electrochemically deposited gold nanoparticle for Salmonella typhi detection employing Vi gene as a molecular marker. Thiolated DNA probe was immobilized on a gold nanoparticle (AuNP) modified SPE for DNA hybridization assay using methylene blue as redox (electroactive) hybridization indicator, and signal was monitored by differential pulse voltammetry (DPV) method. The modified SPE was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and atomic force microscopy (AFM) method. The DNA biosensor showed excellent performances with high sensitivity and good selectivity. The current response was linear with the target sequence concentrations ranging from 1.0 × 10(-11) to 0.5 × 10(-8)M and the detection limit was found to be 50 (± 2.1)pM. The DNA biosensor showed good discrimination ability to the one-base, two-base and three-base mismatched sequences. The fabricated genosensor could also be regenerated easily and reused for three to four times for further hybridization studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical processes of nucleation and growth of hydroxyapatite on titanium supported by real-time electrochemical atomic force microscopy.

PubMed

Eliaz, Noam; Eliyahu, Moshe

2007-03-01

Recently, interest in electrochemical formation of hydroxyapatite has evolved. In this work, highly crystalline hydroxyapatite is electrodeposited on pure titanium and Ti-6Al-4V alloy. In situ and ex situ imaging, coupled with potentiostatic and potentiodynamic measurements, is conducted by means of electrochemical atomic force microscopy. This allows for a study of the nucleation and growth of hydroxyapatite as well as of its near-atomic structure. Electrodeposition of hydroxyapatite is shown to result from precipitation in solution, following two stages: (1) instantaneous nucleation, two-dimensional growth; (2) progressive nucleation, three-dimensional growth. Although some nucleation occurs already at -842 mV, potentials that are more negative than -1.26 V versus SCE are required for enhanced growth. Mass transport is found to have only secondary effect on the deposition process. The conclusions of this work have implications in optimization of coatings on implants as well as in enhancement of the understanding of bone mineralization in vivo.

Layered Metal Nanoparticle Structures on Electrodes for Sensing, Switchable Controlled Uptake/Release, and Photo-electrochemical Applications.

PubMed

Tel-Vered, Ran; Kahn, Jason S; Willner, Itamar

2016-01-06

Layered metal nanoparticle (NP) assemblies provide highly porous and conductive composites of unique electrical and optical (plasmonic) properties. Two methods to construct layered metal NP matrices are described, and these include the layer-by-layer deposition of NPs, or the electropolymerization of monolayer-functionalized NPs, specifically thioaniline-modified metal NPs. The layered NP composites are used as sensing matrices through the use of electrochemistry or surface plasmon resonance (SPR) as transduction signals. The crosslinking of the metal NP composites with molecular receptors, or the imprinting of molecular recognition sites into the electropolymerized NP matrices lead to selective and chiroselective sensing interfaces. Furthermore, the electrosynthesis of redox-active, imprinted, bis-aniline bridged Au NP composites yields electrochemically triggered "sponges" for the switchable uptake and release of electron-acceptor substrates, and results in conductive surfaces of electrochemically controlled wettability. Also, photosensitizer-relay-crosslinked Au NP composites, or electrochemically polymerized layered semiconductor quantum dot/metal NP matrices on electrodes, are demonstrated as functional nanostructures for photoelectrochemical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

Effect of NaNO3 concentration on anodic electrochemical behavior on the Sb surface in NaOH solution

NASA Astrophysics Data System (ADS)

He, Yun-long; Xu, Rui-dong; He, Shi-wei; Chen, Han-sen; Li, Kuo; Zhu, Yun; Shen, Qing-feng

2018-03-01

The effect of NaNO3 concentration on the anodic electrochemical behavior of antimony in 4 M NaOH solution was investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses. The mechanism of NO 3 - concentration effect on the anodic electrochemical behavior of antimony was proposed, and its availability was confirmed by experimental results. The effect of NaNO3 on the anodic behavior of antimony in NaOH solution can be interpreted as a stepwise formation of different antimony compounds with different NaNO3 concentrations. Metallic antimony is apt to be oxidized into Sb2O3 within the NaNO3 concentration range of 0-0.48 M. NaSbO3 can be found on the antimony surface when the NaNO3 concentration increases gradually. Insoluable NaSbO3 inhibits the anodic oxidation of antimony due to its shielding effect on the mass transport of the reactants and products. Surface morphology and composition were analyzed by X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), and electron dispersion spectroscopy (EDS) analyses. Results indicate that the anodic oxidation layer is composed of Sb2O3, NaSbO3, and Sb. The atomic proportion of antimony in the form of NaSbO3 increases with increasing NaNO3 concentration due to the powerful oxidizing property of NaNO3.

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

PubMed

Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

2018-01-10

Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total Scattering Analysis of Disordered Nanosheet Materials

NASA Astrophysics Data System (ADS)

Metz, Peter C.

Two dimensional materials are of increasing interest as building blocks for functional coatings, catalysts, and electrochemical devices. While increasingly sophisticated processing routes have been designed to obtain high-quality exfoliated nanosheets and controlled, self-assembled mesostructures, structural characterization of these materials remains challenging. This work presents a novel method of analyzing pair distribution function (PDF) data for disordered nanosheet ensembles, where supercell stacking models are used to infer atom correlations over as much as 50 A. Hierarchical models are used to reduce the parameter space of the refined model and help eliminate strongly correlated parameters. Three data sets for restacked nanosheet assemblies with stacking disorder are analyzed using these methods: simulated data for graphene-like layers, experimental data for 1 nm thick perovskite layers, and experimental data for highly defective delta-MnO2 layers. In each case, the sensitivity of the PDF to the real-space distribution of layer positions is demonstrated by exploring the fit residual as a function of stacking vectors. The refined models demonstrate that nanosheets tend towards local interlayer ordering, which is hypothesized to be driven by the electrostatic potential of the layer surfaces. Correctly accounting for interlayer atom correlations permits more accurate refinement of local structural details including local structure perturbations and defect site occupancies. In the delta-MnO2 nanosheet material, the new modeling approach identified 14% Mn vacancies while application of 3D periodic crystalline models to the < 7 A PDF region suggests a 25% vacancy concentration. In contrast, the perovskite nanosheet material is demonstrated to exhibit almost negligible structural relaxation in contrast with the bulk crystalline material from which it is derived.

Atomic layer deposition of TiO2 on nitrogen-doped carbon nanofibers supported Ru nanoparticles for flexible Li-O2 battery: A combined DFT and experimental study

NASA Astrophysics Data System (ADS)

Yang, Jingbo; Mi, Hongwei; Luo, Shan; Li, Yongliang; Zhang, Peixin; Deng, Libo; Sun, Lingna; Ren, Xiangzhong

2017-11-01

Flexible Li-O2 batteries have attracted worldwide research interests and been considered to be potential alternatives for the next-generation flexible devices. Nitrogen-doped carbon nanofibers (N-CNFs) prepared by electrospinning are used as flexible substrate and an amorphous TiO2 layer is coated by atomic layer deposition (ALD) and then decorated with Ru nanoparticles. The Ru/N-CNFs@TiO2 composite is directly used as a free-standing electrode for Li-O2 batteries and the electrode delivers a high specific capacity, improved round-trip efficiency and good cycling ability. The superior electrochemical performance can be attributed to the amorphous TiO2 protecting layer and superior catalytic activity of Ru nanoparticles. Based on density functional theory (DFT) calculations from first principles, the carbon electrode after coating with TiO2 is more stable during discharge/charge process. The analysis of Li2O2 on three different interfaces (Li2O2/N-CNFs, Li2O2/TiO2, and Li2O2/Ru) indicates that the electron transport capacity was higher on Ru and TiO2 compared with N-CNFs, therefore, Li2O2 could be formed and decomposed more easily on the Ru/N-CNFs@TiO2 cathode. This work paves a way to develop the free-standing cathode materials for the future development of high-performance flexible energy storage systems.

Unusual photoelectric behaviors of Mo-doped TiO2 multilayer thin films prepared by RF magnetron co-sputtering: effect of barrier tunneling on internal charge transfer

NASA Astrophysics Data System (ADS)

Yan, B. X.; Luo, S. Y.; Mao, X. G.; Shen, J.; Zhou, Q. F.

2013-01-01

Mo-doped TiO2 multilayer thin films were prepared by RF magnetron co-sputtering. Microstructures, crystallite parameters and the absorption band were investigated with atomic force microscopy, X-ray diffraction and ultraviolet-visible spectroscopy. Internal carrier transport characteristics and the photoelectric property of different layer-assemble modes were examined on an electrochemical workstation under visible light. The result indicates that the double-layer structure with an undoped surface layer demonstrated a red-shifted absorption edge and a much stronger photocurrent compared to the uniformly doped sample, signifying that the electric field implanted at the interface between particles in different layers accelerated internal charge transfer effectively. However, a heavily doped layer implanted at the bottom of the three-layer film merely brought about negative effects on the photoelectric property, mainly because of the Schottky junction existing above the substrate. Nevertheless, this obstacle was successfully eliminated by raising the Mo concentration to 1020 cm-3, where the thickness of the depletion layer fell into the order of angstroms and the tunneling coefficient manifested a dramatic increase. Under this circumstance, the Schottky junction disappeared and the strongest photocurrent was observed in the three-layer film.

Utilization of plasmas for graphene synthesis

NASA Astrophysics Data System (ADS)

Shashurin, Alexey; Keidar, Michael

2013-10-01

Graphene is a one-atom-thick planar sheet of carbon atoms that are densely packed in a honeycomb crystal lattice. Grapheen has tremendous range of potential applications ranging from high-speed transistors to electrochemical energy storage devices and biochemical sensors. Methods of graphene synthesis include mechanical exfoliation, epitaxial growth on SiC, CVD and colloidal suspensions. In this work the utilization of plasmas in synthesis process is considered. Types of carbonaceous structures produced by the anodic arc and regions of their synthesis were studied. Ultimate role of substrate temperature and transformations occurring with various carbonaceous structures generated in plasma discharge were considered. Formation of graphene film on copper substrate was detected at temperatures around the copper melting point. The film was consisted of several layers graphene flakes having typical sizes of about 200 nm. Time required for crystallization of graphene on externally heated substrates was determined. This work was supported by National Science Foundation (NSF Grant No. CBET-1249213).

Lateral electrochemical etching of III-nitride materials for microfabrication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Jung

Conductivity-selective lateral etching of III-nitride materials is described. Methods and structures for making vertical cavity surface emitting lasers with distributed Bragg reflectors via electrochemical etching are described. Layer-selective, lateral electrochemical etching of multi-layer stacks is employed to form semiconductor/air DBR structures adjacent active multiple quantum well regions of the lasers. The electrochemical etching techniques are suitable for high-volume production of lasers and other III-nitride devices, such as lasers, HEMT transistors, power transistors, MEMs structures, and LEDs.

Electrochemical impedance spectroscopy on nanostructured carbon electrodes grown by supersonic cluster beam deposition

NASA Astrophysics Data System (ADS)

Bettini, Luca Giacomo; Bardizza, Giorgio; Podestà, Alessandro; Milani, Paolo; Piseri, Paolo

2013-02-01

Nanostructured porous films of carbon with density of about 0.5 g/cm3 and 200 nm thickness were deposited at room temperature by supersonic cluster beam deposition (SCBD) from carbon clusters formed in the gas phase. Carbon film surface topography, determined by atomic force microscopy, reveals a surface roughness of 16 nm and a granular morphology arising from the low kinetic energy ballistic deposition regime. The material is characterized by a highly disordered carbon structure with predominant sp2 hybridization as evidenced by Raman spectroscopy. The interface properties of nanostructured carbon electrodes were investigated by cyclic voltammetry and electrochemical impedance spectroscopy employing KOH 1 M solution as aqueous electrolyte. An increase of the double layer capacitance is observed when the electrodes are heat treated in air or when a nanostructured nickel layer deposited by SCBD on top of a sputter deposited film of the same metal is employed as a current collector instead of a plain metallic film. This enhancement is consistent with an improved charge injection in the active material and is ascribed to the modification of the electrical contact at the interface between the carbon and the metal current collector. Specific capacitance values up to 120 F/g have been measured for the electrodes with nanostructured metal/carbon interface.

Advanced Cu chemical displacement technique for SiO2-based electrochemical metallization ReRAM application.

PubMed

Chin, Fun-Tat; Lin, Yu-Hsien; You, Hsin-Chiang; Yang, Wen-Luh; Lin, Li-Min; Hsiao, Yu-Ping; Ko, Chum-Min; Chao, Tien-Sheng

2014-01-01

This study investigates an advanced copper (Cu) chemical displacement technique (CDT) with varying the chemical displacement time for fabricating Cu/SiO2-stacked resistive random-access memory (ReRAM). Compared with other Cu deposition methods, this CDT easily controls the interface of the Cu-insulator, the switching layer thickness, and the immunity of the Cu etching process, assisting the 1-transistor-1-ReRAM (1T-1R) structure and system-on-chip integration. The modulated shape of the Cu-SiO2 interface and the thickness of the SiO2 layer obtained by CDT-based Cu deposition on SiO2 were confirmed by scanning electron microscopy and atomic force microscopy. The CDT-fabricated Cu/SiO2-stacked ReRAM exhibited lower operation voltages and more stable data retention characteristics than the control Cu/SiO2-stacked sample. As the Cu CDT processing time increased, the forming and set voltages of the CDT-fabricated Cu/SiO2-stacked ReRAM decreased. Conversely, decreasing the processing time reduced the on-state current and reset voltage while increasing the endurance switching cycle time. Therefore, the switching characteristics were easily modulated by Cu CDT, yielding a high performance electrochemical metallization (ECM)-type ReRAM.

Gold nano particle decorated graphene core first generation PAMAM dendrimer for label free electrochemical DNA hybridization sensing.

PubMed

Jayakumar, K; Rajesh, R; Dharuman, V; Venkatasan, R; Hahn, J H; Pandian, S Karutha

2012-01-15

A novel first generation (G1) poly(amidoamine) dendrimer (PAMAM) with graphene core (GG1PAMAM) was synthesized for the first time. Single layer of GG1PAMAM was immobilized covalently on mercaptopropionic acid (MPA) monolayer on Au transducer. This allows cost effective and easy deposition of single layer graphene on the Au transducer surface than the advanced vacuum techniques used in the literature. Au nano particles (17.5 nm) then decorated the GG1PAMAM and used for electrochemical DNA hybridization sensing. The sensor discriminates selectively and sensitively the complementary double stranded DNA (dsDNA, hybridized), non-complementary DNA (ssDNA, un-hybridized) and single nucleotide polymorphism (SNP) surfaces. Interactions of the MPA, GG1PAMAM and the Au nano particles were characterized by Ultra Violet (UV), Fourier Transform Infrared (FTIR), Raman spectroscopy (RS), Thermo gravimetric analysis (TGA), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Cyclic Voltmetric (CV), Impedance spectroscopy (IS) and Differntial Pulse Voltammetry (DPV) techniques. The sensor showed linear range 1×10(-6) to 1×10(-12) M with lowest detection limit 1 pM which is 1000 times lower than G1PAMAM without graphene core. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of cathodic polarization on coating doxycycline on titanium surfaces.

PubMed

Geißler, Sebastian; Tiainen, Hanna; Haugen, Håvard J

2016-06-01

Cathodic polarization has been reported to enhance the ability of titanium based implant materials to interact with biomolecules by forming titanium hydride at the outermost surface layer. Although this hydride layer has recently been suggested to allow the immobilization of the broad spectrum antibiotic doxycycline on titanium surfaces, the involvement of hydride in binding the biomolecule onto titanium remains poorly understood. To gain better understanding of the influence this immobilization process has on titanium surfaces, mirror-polished commercially pure titanium surfaces were cathodically polarized in the presence of doxycycline and the modified surfaces were thoroughly characterized using atomic force microscopy, electron microscopy, secondary ion mass spectrometry, and angle-resolved X-ray spectroscopy. We demonstrated that no hydride was created during the polarization process. Doxycycline was found to be attached to an oxide layer that was modified during the electrochemical process. A bacterial assay using bioluminescent Staphylococcus epidermidis Xen43 showed the ability of the coating to reduce bacterial colonization and planktonic bacterial growth. Copyright © 2016 Elsevier B.V. All rights reserved.

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE PAGES

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

2018-01-17

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Creation of nanosized holes in graphene planes for improvement of rate capability of lithium-ion batteries

NASA Astrophysics Data System (ADS)

Bulusheva, L. G.; Stolyarova, S. G.; Chuvilin, A. L.; Shubin, Yu V.; Asanov, I. P.; Sorokin, A. M.; Mel'gunov, M. S.; Zhang, Su; Dong, Yue; Chen, Xiaohong; Song, Huaihe; Okotrub, A. V.

2018-04-01

Holes with an average size of 2-5 nm have been created in graphene layers by heating of graphite oxide (GO) in concentrated sulfuric acid followed by annealing in an argon flow. The hot mineral acid acts simultaneously as a defunctionalizing and etching agent, removing a part of oxygen-containing groups and lattice carbon atoms from the layers. Annealing of the holey reduced GO at 800 °C-1000 °C causes a decrease of the content of residual oxygen and the interlayer spacing thus producing thin compact stacks from holey graphene layers. Electrochemical tests of the obtained materials in half-cells showed that the removal of oxygen and creation of basal holes lowers the capacity loss in the first cycle and facilitates intercalation-deintercalation of lithium ions. This was attributed to minimization of electrolyte decomposition reactions, easier desolvation of lithium ions near the hole boundaries and appearance of multiple entrances for the naked ions into graphene stacks.

Surface modifications of hydrogen storage alloy by heavy ion beams with keV to MeV irradiation energies

NASA Astrophysics Data System (ADS)

Abe, Hiroshi; Tokuhira, Shinnosuke; Uchida, Hirohisa; Ohshima, Takeshi

2015-12-01

This study deals with the effect of surface modifications induced from keV to MeV heavy ion beams on the initial reaction rate of a hydrogen storage alloy (AB5) in electrochemical process. The rare earth based alloys like this sample alloy are widely used as a negative electrode of Ni-MH (Nickel-Metal Hydride) battery. We aimed to improve the initial reaction rate of hydrogen absorption by effective induction of defects such as vacancies, dislocations, micro-cracks or by addition of atoms into the surface region of the metal alloys. Since defective layer near the surface can easily be oxidized, the conductive oxide layer is formed on the sample surface by O+ beams irradiation, and the conductive oxide layer might cause the improvement of initial reaction rate of hydriding. This paper demonstrates an effective surface treatment of heavy ion irradiation, which induces catalytic activities of rare earth oxides in the alloy surface.

Atomic layer deposition of ruthenium surface-coating on porous platinum catalysts for high-performance direct ethanol solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Jeong, Heon Jae; Kim, Jun Woo; Jang, Dong Young; Shim, Joon Hyung

2015-09-01

Pt-Ru bi-metallic catalysts are synthesized by atomic layer deposition (ALD) of Ru surface-coating on sputtered Pt mesh. The catalysts are evaluated in direct ethanol solid oxide fuel cells (DESOFCs) in the temperature range of 300-500 °C. Island-growth of the ALD Ru coating is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses. The performance of the DESOFCs is evaluated based on the current-voltage output and electrochemical impedance spectroscopy. Genuine reduction of the polarization impedance, and enhanced power output with improved surface kinetics are achieved with the optimized ALD Ru surface-coating compared to bare Pt. The chemical composition of the Pt/ALD Ru electrode surface after fuel cell operation is analyzed via XPS. Enhanced cell performance is clearly achieved, attributed to the effective Pt/ALD Ru bi-metallic catalysis, including oxidation of Cdbnd O by Ru, and de-protonation of ethanol and cleavage of C-C bonds by Pt, as supported by surface morphology analysis which confirms formation of a large amount of carbon on bare Pt after the ethanol-fuel-cell test.

Atomic Layer Deposition of Al–W–Fluoride on LiCoO 2 Cathodes: Comparison of Particle- and Electrode-Level Coatings

DOE PAGES

Park, Joong Sun; Mane, Anil U.; Elam, Jeffrey W.; ...

2017-07-19

Atomic layer deposition (ALD) of the well-known Al 2O 3 on a LiCoO 2 system is compared with that of a newly developed AlW xF y material. ALD coatings (~1 nm thick) of both materials are shown to be effective in improving cycle life through mitigation of surface-induced capacity losses. However, the behaviors of Al 2O 3 and AlW xF y are shown to be significantly different when coated directly on cathode particles versus deposition on a composite electrode composed of active materials, carbons, and binders. Electrochemical impedance spectroscopy, galvanostatic intermittent titration techniques, and four-point measurements suggest that electron transportmore » is more limited in LiCoO 2 particles coated with Al 2O 3 compared with that in particles coated with AlW xF y. Here, the results show that proper design/choice of coating materials (e.g., AlW xF y) can improve capacity retention without sacrificing electron transport and suggest new avenues for engineering electrode–electrolyte interfaces to enable high-voltage operation of lithium-ion batteries.« less

The effect of zirconium-based surface treatment on the cathodic disbonding resistance of epoxy coated mild steel

NASA Astrophysics Data System (ADS)

Ghanbari, A.; Attar, M. M.

2014-10-01

The effect of zirconium-based surface treatment on the cathodic disbonding resistance and adhesion performance of an epoxy coated mild steel substrate was investigated. The obtained data from pull-off, cathodic disbonding test and electrochemical impedance spectroscopy (EIS) indicated that the zirconium conversion layer significantly improved the adhesion strength and cathodic disbonding resistance of the epoxy coating. This may be attributed to formation of some polar zirconium compounds on the surface and increment of surface roughness, that were evident in the results of field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM), respectively.

Electrochemical impedance spectroscopy investigation on the clinical lifetime of ProTaper rotary file system.

PubMed

Penta, Virgil; Pirvu, Cristian; Demetrescu, Ioana

2014-01-01

The main objective of the current paper is to show that electrochemical impedance spectroscopy (EIS) could be a method for evaluating and predicting of ProTaper rotary file system clinical lifespan. This particular aspect of everyday use of the endodontic files is of great importance in each dental practice and has profound clinical implications. The method used for quantification resides in the electrochemical impedance spectroscopy theory and has in its main focus the characteristics of the surface titanium oxide layer. This electrochemical technique has been adapted successfully to identify the quality of the Ni-Ti files oxide layer. The modification of this protective layer induces changes in corrosion behavior of the alloy modifying the impedance value of the file. In order to assess the method, 14 ProTaper sets utilized on different patients in a dental clinic have been submitted for testing using EIS. The information obtained in regard to the surface oxide layer has offered an indication of use and proves that the said layer evolves with each clinical application. The novelty of this research is related to an electrochemical technique successfully adapted for Ni-Ti file investigation and correlation with surface and clinical aspects.

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Synthesis and application of ion imprinting polymer coated magnetic multi-walled carbon nanotubes for selective adsorption of nickel ion

NASA Astrophysics Data System (ADS)

He, Junnan; Shang, Hongzhou; Zhang, Xing; Sun, Xiaoran

2018-01-01

A novel nickel ion imprinted polymers (IIPs) based on multi-walled carbon nanotubes (MWCNTs) were synthesized inverse emulsion system, using chitosan(CS) and acrylic acid as the functional monomers, Ni (II) as the template, and N' N-methylene bis-acrylamide as the cross-linker. The chemical structure and morphological feature of the IIPs were characterized by scanning electron microscopy (SEM), Thermogravimetry (TG), X-ray diffraction (XRD), and Fourier transform infrared spectrometer (FTIR). The studies indicated that the gel layer was well grafted on the surface of MWCNTs. Studies on the adsorption ability of the IIPs, by atomic absorption spectrophotometry, demonstrated that IIPs possessed excellent adsorption and selective ability towards Ni (II), fitting to pseudo second-order kinetic isotherms and with a maximum capacity of 19.86 mg/g, and selectivity factor of 13.09 and 4.42. The electrochemical performance of ion imprinting carbon paste electrode (CPE/IIPs) was characterized by Cyclic voltammetry (CV). Studies have shown that CPE/IIPs showed excellent electrochemical performance.

Self-assembled nanostructured resistive switching memory devices fabricated by templated bottom-up growth

PubMed Central

Song, Ji-Min; Lee, Jang-Sik

2016-01-01

Metal-oxide-based resistive switching memory device has been studied intensively due to its potential to satisfy the requirements of next-generation memory devices. Active research has been done on the materials and device structures of resistive switching memory devices that meet the requirements of high density, fast switching speed, and reliable data storage. In this study, resistive switching memory devices were fabricated with nano-template-assisted bottom up growth. The electrochemical deposition was adopted to achieve the bottom-up growth of nickel nanodot electrodes. Nickel oxide layer was formed by oxygen plasma treatment of nickel nanodots at low temperature. The structures of fabricated nanoscale memory devices were analyzed with scanning electron microscope and atomic force microscope (AFM). The electrical characteristics of the devices were directly measured using conductive AFM. This work demonstrates the fabrication of resistive switching memory devices using self-assembled nanoscale masks and nanomateirals growth from bottom-up electrochemical deposition. PMID:26739122

Electrochemical de-alloying in two dimensions: role of the local atomic environment

NASA Astrophysics Data System (ADS)

Damian, A.; Maroun, F.; Allongue, P.

2016-07-01

We investigate by in situ scanning tunnelling microscopy (STM) the potential dependence of the electrochemical dealloying of NiPd monoatomic layers electrodeposited on Au(111). The dealloying process is achieved by Ni selective dissolution and was studied as a function of NiPd composition: for an alloy with a Ni content >=70%, quasi-complete Ni dissolution is achieved at a potential of -0.9 VMSE whereas for a Ni content <70%, Ni dissolution at the same potential drastically slows down after the removal of small amounts of Ni. The alloy morphology at this ``passivation state'' is characterized by the presence of holes in the alloy monolayer with evidence for the Pd enrichment at the hole edges. These findings are confirmed by Monte Carlo simulations. Further Ni dissolution at passivation was achieved by applying more positive potentials which depend on the alloy composition. These results allowed us to determine the correlation between the Ni dissolution onset potential and the local Pd content.

In situ transmission electron microscopy of lead dendrites and lead ions in aqueous solution.

PubMed

White, Edward R; Singer, Scott B; Augustyn, Veronica; Hubbard, William A; Mecklenburg, Matthew; Dunn, Bruce; Regan, Brian C

2012-07-24

An ideal technique for observing nanoscale assembly would provide atomic-resolution images of both the products and the reactants in real time. Using a transmission electron microscope we image in situ the electrochemical deposition of lead from an aqueous solution of lead(II) nitrate. Both the lead deposits and the local Pb(2+) concentration can be visualized. Depending on the rate of potential change and the potential history, lead deposits on the cathode in a structurally compact layer or in dendrites. In both cases the deposits can be removed and the process repeated. Asperities that persist through many plating and stripping cycles consistently nucleate larger dendrites. Quantitative digital image analysis reveals excellent correlation between changes in the Pb(2+) concentration, the rate of lead deposition, and the current passed by the electrochemical cell. Real-time electron microscopy of dendritic growth dynamics and the associated local ionic concentrations can provide new insight into the functional electrochemistry of batteries and related energy storage technologies.

Surface Modifications of Materials by Electrochemical Methods to Improve the Properties for Industrial and Medical Applications

NASA Astrophysics Data System (ADS)

Benea, Lidia

2018-06-01

There are two applied electrochemical methods in our group in order to obtain advanced functional surfaces on materials: (i) direct electrochemical synthesis by electro-codeposition process and (ii) anodization of materials to form nanoporous oxide layers followed by electrodeposition of hydroxyapatite or other bioactive molecules and compounds into porous film. Electrodeposition is a process of low energy consumption, and therefore very convenient for the surface modification of various types of materials. Electrodeposition is a powerful method compared with other methods, which led her to be adopted and spread rapidly in nanotechnology to obtain nanostructured layers and films. Nanoporous thin oxide layers on titanum alloys as support for hydroxyapatite or other biomolecules electrodeposition in view of biomedical applications could be obtained by electrochemical methods. For surface modification of titanium or titanium alloys to improve the biocompatibility or osseointegration, the two steps must be fulfilled; the first is controlled growth of oxide layer followed by second being biomolecule electrodeposition into nanoporous formed titanium oxide layer.

Copper atomic-scale transistors.

PubMed

Xie, Fangqing; Kavalenka, Maryna N; Röger, Moritz; Albrecht, Daniel; Hölscher, Hendrik; Leuthold, Jürgen; Schimmel, Thomas

2017-01-01

We investigated copper as a working material for metallic atomic-scale transistors and confirmed that copper atomic-scale transistors can be fabricated and operated electrochemically in a copper electrolyte (CuSO 4 + H 2 SO 4 ) in bi-distilled water under ambient conditions with three microelectrodes (source, drain and gate). The electrochemical switching-on potential of the atomic-scale transistor is below 350 mV, and the switching-off potential is between 0 and -170 mV. The switching-on current is above 1 μA, which is compatible with semiconductor transistor devices. Both sign and amplitude of the voltage applied across the source and drain electrodes ( U bias ) influence the switching rate of the transistor and the copper deposition on the electrodes, and correspondingly shift the electrochemical operation potential. The copper atomic-scale transistors can be switched using a function generator without a computer-controlled feedback switching mechanism. The copper atomic-scale transistors, with only one or two atoms at the narrowest constriction, were realized to switch between 0 and 1 G 0 ( G 0 = 2e 2 /h; with e being the electron charge, and h being Planck's constant) or 2 G 0 by the function generator. The switching rate can reach up to 10 Hz. The copper atomic-scale transistor demonstrates volatile/non-volatile dual functionalities. Such an optimal merging of the logic with memory may open a perspective for processor-in-memory and logic-in-memory architectures, using copper as an alternative working material besides silver for fully metallic atomic-scale transistors.

Comparative electrochemical analysis of crystalline and amorphous anodized iron oxide nanotube layers as negative electrode for LIB.

PubMed

Pervez, Syed Atif; Kim, Doohun; Farooq, Umer; Yaqub, Adnan; Choi, Jung-Hee; Lee, You-Jin; Doh, Chil-Hoon

2014-07-23

This work is a comparative study of the electrochemical performance of crystalline and amorphous anodic iron oxide nanotube layers. These nanotube layers were grown directly on top of an iron current collector with a vertical orientation via a simple one-step synthesis. The crystalline structures were obtained by heat treating the as-prepared (amorphous) iron oxide nanotube layers in ambient air environment. A detailed morphological and compositional characterization of the resultant materials was performed via transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and Raman spectroscopy. The XRD patterns were further analyzed using Rietveld refinements to gain in-depth information on their quantitative phase and crystal structures after heat treatment. The results demonstrated that the crystalline iron oxide nanotube layers exhibit better electrochemical properties than the amorphous iron oxide nanotube layers when evaluated in terms of the areal capacity, rate capability, and cycling performance. Such an improved electrochemical response was attributed to the morphology and three-dimensional framework of the crystalline nanotube layers offering short, multidirectional transport lengths, which favor rapid Li(+) ions diffusivity and electron transport.

Porous siliconformation and etching process for use in silicon micromachining

DOEpatents

Guilinger, Terry R.; Kelly, Michael J.; Martin, Jr., Samuel B.; Stevenson, Joel O.; Tsao, Sylvia S.

1991-01-01

A reproducible process for uniformly etching silicon from a series of micromechanical structures used in electrical devices and the like includes providing a micromechanical structure having a silicon layer with defined areas for removal thereon and an electrochemical cell containing an aqueous hydrofluoric acid electrolyte. The micromechanical structure is submerged in the electrochemical cell and the defined areas of the silicon layer thereon are anodically biased by passing a current through the electrochemical cell for a time period sufficient to cause the defined areas of the silicon layer to become porous. The formation of the depth of the porous silicon is regulated by controlling the amount of current passing through the electrochemical cell. The micromechanical structure is then removed from the electrochemical cell and submerged in a hydroxide solution to remove the porous silicon. The process is subsequently repeated for each of the series of micromechanical structures to achieve a reproducibility better than 0.3%.

Band diagram and rate analysis of thin film spinel LiMn 2O 4 formed by electrochemical conversion of ALD-grown MnO

DOE PAGES

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; ...

2016-09-22

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A [Idaho Falls, ID

2008-07-22

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A.

2004-09-07

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Bifunctional sensor of pentachlorophenol and copper ions based on nanostructured hybrid films of humic acid and exfoliated layered double hydroxide via a facile layer-by-layer assembly.

PubMed

Yuan, Shuang; Peng, Dinghua; Hu, Xianluo; Gong, Jingming

2013-06-27

A new, highly sensitive bifunctional electrochemical sensor for the simultaneous determination of pentachlorophenol (PCP) and copper ions (Cu(2+)) has been developed, where organic-inorganic hybrid ultrathin films were fabricated by alternate assembly of humic acid (HA) and exfoliated Mg-Al-layered double hydroxide (LDH) nanosheets onto ITO substrates via a layer-by-layer (LBL) approach. The multilayer films were then characterized by means of UV-vis spectrometry, scanning electron microscopy (SEM), and atomic force microscope (AFM). These films were found to have a relatively smooth surface with almost equal amounts of HA incorporated in each cycle. Its electrochemical performance was systematically investigated. Our results demonstrate that such a newly designed (LDH/HA)n multilayer films, combining the individual properties of HA (dual recognition ability for organic herbicides and metal ions) together with LDH nanosheets (a rigid inorganic matrix), can be applied to the simultaneous analysis of PCP and Cu(II) without interference from each other. The LBL assembled nanoarchitectures were further investigated by X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR), which provides insight for bifunctional sensing behavior. Under the optimized conditions, the detection limit was found to be as low as 0.4 nM PCP, well below the guideline value of PCP in drinking water (3.7 nM) set by the United States Environmental Protection Agency (U.S. EPA), and 2.0 nM Cu(2+), much below the guideline value (2.0 mg L(-1), ~31.2 nM) from the World Health Organization (WHO), respectively. Toward the goal for practical applications, this simple and cost-effective probe was further evaluated by monitoring PCP and Cu(II) in water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Programmable Electrochemical Rectifier Based on a Thin-Layer Cell.

PubMed

Park, Seungjin; Park, Jun Hui; Hwang, Seongpil; Kwak, Juhyoun

2017-06-21

A programmable electrochemical rectifier based on thin-layer electrochemistry is described here. Both the rectification ratio and the response time of the device are programmable by controlling the gap distance of the thin-layer electrochemical cell, which is easily controlled using commercially available beads. One of the electrodes was modified using a ferrocene-terminated self-assembled monolayer to offer unidirectional charge transfers via soluble redox species. The thin-layer configuration provided enhanced mass transport, which was determined by the gap thickness. The device with the smallest gap thickness (∼4 μm) showed an unprecedented, high rectification ratio (up to 160) with a fast response time in a two-terminal configuration using conventional electronics.

Cathodes for secondary electrochemical power-producing cells. [layers of porous substrates impregnated with S alternate with layers containing electrolyte

DOEpatents

Cairns, E.J.; Kyle, M.; Shimotake, H.

1973-02-13

A secondary electrochemical power-producing cell includes an anode containing lithium, an electrolyte containing lithium ions, and a cathode containing sulfur. The cathode comprises plates of a porous substrate material impregnated with sulfur alternating with layers (which may also comprise porous substrate plates) containing electrolyte.

Fundamental studies of glucose oxidase deposition on a Pt electrode.

PubMed

Matsumoto, Norio; Chen, Xiaohong; Wilson, George S

2002-01-15

The direct electrodeposition of glucose oxidase (EC 1.1.3.4) on a platinum electrode was investigated as a means for controlled immobilization. The presence of a nonionic detergent, Triton X-100, was found essential to produce a multilayered deposit. Moreover, to work properly, the detergent must be present above its critical micelle concentration. Under these conditions, a deposit of approximately 50 enzyme layers (480 nm), with surface uniformity of +/-20 nm, was verified using an electrochemical quartz crystal microbalance and by atomic force microscopy. In the absence of detergent, a layer of 25 nm is formed. Contrary to most previous claims, the deposition, which is potential dependent but optimal at 1.3 V versus AgCl/Ag electrode, is not electrophoretically driven, but is instead controlled by a lowering of the pH at the electrode surface due to concomitant oxygen evolution.

Structure of H2Ti3O7 and its evolution during sodium insertion as anode for Na ion batteries.

PubMed

Eguía-Barrio, Aitor; Castillo-Martínez, Elizabeth; Zarrabeitia, Maider; Muñoz-Márquez, Miguel A; Casas-Cabanas, Montse; Rojo, Teófilo

2015-03-14

H2Ti3O7 was prepared as a single phase material by ionic exchange from Na2Ti3O7. The complete ionic exchange was confirmed by (1)H and (23)Na solid state Nuclear Magnetic Resonance (NMR). The atomic positions of H2Ti3O7 were obtained from the Rietveld refinement of powder X-ray diffraction (PXRD) and neutron diffraction experimental data, the latter collected at two different wavelengths to precisely determine the hydrogen atomic positions in the structure. All H(+) cations are hydrogen bonded to two adjacent [Ti3O7](2-) layers leading to the gliding of the layers and lattice centring with respect to the parent Na2Ti3O7. In contrast with a previous report where protons were located in two different positions of H2Ti3O7, 3 types of proton positions were found. Two of the three types of proton are bonded to the only oxygen linked to a single titanium atom forming an H-O-H angle close to that of the water molecule. H2Ti3O7 is able to electrochemically insert Na(+). The electrochemical insertion of sodium into H2Ti3O7 starts with a solid solution regime of the C-centred phase. Then, between 0.6 and 1.2 inserted Na(+) the reaction proceeds through a two phase reaction and a plateau at 1.3 V vs. Na(+)/Na is observed in the voltage-composition curve. The second phase resembles the primitive Na2Ti3O7 cell as detected by in situ PXRD. Upon oxidation, from 0.9 to 2.2 V, the PXRD pattern remains mostly unchanged probably due to H(+) removal instead of Na(+), with the capacity quickly fading upon cycling. Conditioning H2Ti3O7 for two cycles at 0.9-2.2 V before cycling in the 0.05-1.6 V range yields similar specific capacity and better retention than the original Na2Ti3O7 in the same voltage range.

Boron and Nitrogen Codoped Carbon Layers of LiFePO4 Improve the High-Rate Electrochemical Performance for Lithium Ion Batteries.

PubMed

Zhang, Jinli; Nie, Ning; Liu, Yuanyuan; Wang, Jiao; Yu, Feng; Gu, Junjie; Li, Wei

2015-09-16

An evolutionary composite of LiFePO4 with nitrogen and boron codoped carbon layers was prepared by processing hydrothermal-synthesized LiFePO4. This novel codoping method is successfully applied to LiFePO4 for commercial use, and it achieved excellent electrochemical performance. The electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying the LiFePO4/C-B with nitrogen (to synthesis LiFePO4/C-B+N) the undesired nonconducting N-B configurations (190.1 and 397.9 eV) are generated. This decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1) resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (to obtain LiFePO4/C-N+B) not only eliminates the nonconducting N-B impurity, but also promotes the conductive C-N (398.3, 400.3, and 401.1 eV) and C-B (189.5 eV) configurations-this markedly improves the electronic conductivity to 1.36×10(-1) S cm(-1). Meanwhile the positive doping strategy leads to synergistic electrochemical activity distinctly compared with single N- or B-doped materials (even much better than their sum capacity at 20 C). Moreover, due to the electron and hole-type carriers donated by nitrogen and boron atoms, the N+B codoped carbon coating tremendously enhances the electrochemical property: at the rate of 20 C, the codoped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the codoped product based on commercial LiFePO4/C shows a discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N codoped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C changes from 48.1 mAh g(-1) to 40.6 mAh g(-1).

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond.

PubMed

Kaliginedi, Veerabhadrarao; Ozawa, Hiroaki; Kuzume, Akiyoshi; Maharajan, Sivarajakumar; Pobelov, Ilya V; Kwon, Nam Hee; Mohos, Miklos; Broekmann, Peter; Fromm, Katharina M; Haga, Masa-aki; Wandlowski, Thomas

2015-11-14

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge-discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g(-1) at a current density of 10 μA cm(-2) and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

PubMed

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

Electrochemical characteristics of calcium-phosphatized AZ31 magnesium alloy in 0.9 % NaCl solution.

PubMed

Hadzima, Branislav; Mhaede, Mansour; Pastorek, Filip

2014-05-01

Magnesium alloys suffer from their high reactivity in common environments. Protective layers are widely created on the surface of magnesium alloys to improve their corrosion resistance. This article evaluates the influence of a calcium-phosphate layer on the electrochemical characteristics of AZ31 magnesium alloy in 0.9 % NaCl solution. The calcium phosphate (CaP) layer was electrochemically deposited in a solution containing 0.1 M Ca(NO3)2, 0.06 M NH4H2PO4 and 10 ml l(-1) of H2O2. The formed surface layer was composed mainly of brushite [(dicalcium phosphate dihidrate (DCPD)] as proved by energy-dispersive X-ray analysis. The surface morphology was observed by scanning electron microscopy. Immersion test was performed in order to observe degradation of the calcium phosphatized surfaces. The influence of the phosphate layer on the electrochemical characteristics of AZ31, in 0.9 % NaCl solution, was evaluated by potentiodynamic measurements and electrochemical impedance spectroscopy. The obtained results were analysed by the Tafel-extrapolation method and equivalent circuits method. The results showed that the polarization resistance of the DCPD-coated surface is about 25 times higher than that of non-coated surface. The CaP electro-deposition process increased the activation energy of corrosion process.

Effects of growth temperature on the properties of atomic layer deposition grown ZrO2 films

NASA Astrophysics Data System (ADS)

Scarel, G.; Ferrari, S.; Spiga, S.; Wiemer, C.; Tallarida, G.; Fanciulli, M.

2003-07-01

Zirconium dioxide films are grown in 200 atomic layer deposition cycles. Zirconium tetrachloride (ZrCl4) and water (H2O) are used as precursors. A relatively high dielectric constant (κ=22), wide band gap, and conduction band offset (5.8 and 1.4 eV, respectively) indicate that zirconium dioxide is a most promising substitute for silicon dioxide as a dielectric gate in complementary metal-oxide-semiconductor devices. However, crystallization and chlorine ions in the films might affect their electrical properties. These ions are produced during atomic layer deposition in which the ZrCl4 precursor reacts with the growth surface. It is desirable to tune the composition, morphology, and structural properties in order to improve their benefit on the electrical ones. To address this issue it is necessary to properly choose the growth parameters. This work focuses on the effects of the growth temperature Tg. ZrO2 films are grown at different substrate temperatures: 160, 200, 250, and 350 °C. Relevant modification of the film structure with a change in substrate temperature during growth is expected because the density of reactive sites [mainly Si+1-(OH)-1 bonds] decreases with an increase in temperature [Y. B. Kim et al., Electrochem. Solid-State Lett. 3, 346 (2000)]. The amorphous film component, for example, that develops at Si+1-(OH)-1 sites on the starting growth surface, is expected to decrease with an increase in growth temperature. The size and consequences of film property modifications with the growth temperature are investigated in this work using x-ray diffraction and reflectivity, and atomic force microscopy. Time of flight-secondary ion mass spectrometry is used to study contaminant species in the films. From capacitance-voltage (CV) and current-voltage (IV) measurements, respectively, the dielectric constant κZrO2 and the leakage current are studied as a function of the film growth temperature.

Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

PubMed

Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C

2009-11-03

Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

Copper atomic-scale transistors

PubMed Central

Kavalenka, Maryna N; Röger, Moritz; Albrecht, Daniel; Hölscher, Hendrik; Leuthold, Jürgen

2017-01-01

We investigated copper as a working material for metallic atomic-scale transistors and confirmed that copper atomic-scale transistors can be fabricated and operated electrochemically in a copper electrolyte (CuSO4 + H2SO4) in bi-distilled water under ambient conditions with three microelectrodes (source, drain and gate). The electrochemical switching-on potential of the atomic-scale transistor is below 350 mV, and the switching-off potential is between 0 and −170 mV. The switching-on current is above 1 μA, which is compatible with semiconductor transistor devices. Both sign and amplitude of the voltage applied across the source and drain electrodes (U bias) influence the switching rate of the transistor and the copper deposition on the electrodes, and correspondingly shift the electrochemical operation potential. The copper atomic-scale transistors can be switched using a function generator without a computer-controlled feedback switching mechanism. The copper atomic-scale transistors, with only one or two atoms at the narrowest constriction, were realized to switch between 0 and 1G 0 (G 0 = 2e2/h; with e being the electron charge, and h being Planck’s constant) or 2G 0 by the function generator. The switching rate can reach up to 10 Hz. The copper atomic-scale transistor demonstrates volatile/non-volatile dual functionalities. Such an optimal merging of the logic with memory may open a perspective for processor-in-memory and logic-in-memory architectures, using copper as an alternative working material besides silver for fully metallic atomic-scale transistors. PMID:28382242

Chemical etching of stainless steel 301 for improving performance of electrochemical capacitors in aqueous electrolyte

NASA Astrophysics Data System (ADS)

Jeżowski, P.; Nowicki, M.; Grzeszkowiak, M.; Czajka, R.; Béguin, F.

2015-04-01

The main purpose of the study was to increase the surface roughness of stainless steel 301 current collectors by etching, in order to improve the electrochemical performance of electrical double-layer capacitors (EDLC) in 1 mol L-1 lithium sulphate electrolyte. Etching was realized in 1:3:30 (HNO3:HCl:H2O) solution with times varying up to 10 min. For the considered 15 μm thick foil and a mass loss around 0.4 wt.%, pitting was uniform, with diameter of pits ranging from 100 to 300 nm. Atomic force microscopy (AFM) showed an increase of average surface roughness (Ra) from 5 nm for the as-received stainless steel foil to 24 nm for the pitted material. Electrochemical impedance spectroscopy realized on EDLCs with coated electrodes either on as-received or pitted foil in 1 mol L-1 Li2SO4 gave equivalent distributed resistance (EDR) of 8 Ω and 2 Ω, respectively, demonstrating a substantial improvement of collector/electrode interface after pitting. Correlatively, the EDLCs with pitted collector displayed a better charge propagation and low ohmic losses even at relatively high current of 20 A g-1. Hence, chemical pitting of stainless steel current collectors is an appropriate method for optimising the performance of EDLCs in neutral aqueous electrolyte.

Direct electrical control of IgG conformation and functional activity at surfaces

NASA Astrophysics Data System (ADS)

Ghisellini, Paola; Caiazzo, Marialuisa; Alessandrini, Andrea; Eggenhöffner, Roberto; Vassalli, Massimo; Facci, Paolo

2016-11-01

We have devised a supramolecular edifice involving His-tagged protein A and antibodies to yield surface immobilized, uniformly oriented, IgG-type, antibody layers with Fab fragments exposed off an electrode surface. We demonstrate here that we can affect the conformation of IgGs, likely pushing/pulling electrostatically Fab fragments towards/from the electrode surface. A potential difference between electrode and solution acts on IgGs’ charged aminoacids modulating the accessibility of the specific recognition regions of Fab fragments by antigens in solution. Consequently, antibody-antigen affinity is affected by the sign of the applied potential: a positive potential enables an effective capture of antigens; a negative one pulls the fragments towards the electrode, where steric hindrance caused by neighboring molecules largely hampers the capture of antigens. Different experimental techniques (electrochemical quartz crystal microbalance, electrochemical impedance spectroscopy, fluorescence confocal microscopy and electrochemical atomic force spectroscopy) were used to evaluate binding kinetics, surface coverage, effect of the applied electric field on IgGs, and role of charged residues on the phenomenon described. These findings expand the concept of electrical control of biological reactions and can be used to gate electrically specific recognition reactions with impact in biosensors, bioactuators, smart biodevices, nanomedicine, and fundamental studies related to chemical reaction kinetics.

Unexpected Voltage Fade in LMR-NMC Oxides Cycled below the “Activation” Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yan; Bareno, Javier; Bettge, Martin

2015-01-01

A common feature of lithium-excess layered oxides, nominally of composition xLi 2MnO 3•(1-x)LiMO 2 (M = transition metal) is a high-voltage plateau (~4.5 V vs. Li/Li +) in their capacity-voltage profile during the first delithiation cycle. This plateau is believed to result from activation of the Li 2MnO 3 component, which makes additional lithium available for electrochemical cycling. However, oxides cycled beyond this activation plateau are known to display voltage fade which is a continuous reduction in their equilibrium potential. In this article we show that these oxides display gradual voltage fade even on electrochemical cycling in voltage ranges wellmore » below the activation plateau. The average fade is ~0.08 mV-cycle-1 for Li 1.2Ni 0.15Mn 0.55Co 0.1O 2 vs. Li cells after 20 cycles in the 2–4.1 V range at 55°C; a ~54 mV voltage hysteresis, expressed as the difference in average cell voltage between charge and discharge cycles, is also observed. The voltage fade results from a gradual accumulation of local spinel environments in the crystal structure. Some of these spinel sites result from lithium deficiencies during oxide synthesis and are likely to be at the particle surfaces; other sites result from the migration of transition metal atoms in the partially-delithiated LiMO 2 component into the lithium planes during electrochemical cycling. The observed rate of voltage fade depends on a combination of factors that includes the phase equilibrium between the layered and spinel components and the kinetics of transition metal migration.« less

One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

PubMed

Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

2015-05-19

The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

Controllable synthesis of layered Co-Ni hydroxide hierarchical structures for high-performance hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Yuan, Peng; Zhang, Ning; Zhang, Dan; Liu, Tao; Chen, Limiao; Ma, Renzhi; Qiu, Guanzhou; Liu, Xiaohe

2016-01-01

A facile solvothermal method is developed for synthesizing layered Co-Ni hydroxide hierarchical structures by using hexamethylenetetramine (HMT) as alkaline reagent. The electrochemical measurements reveal that the specific capacitances of layered bimetallic (Co-Ni) hydroxides are generally superior to those of layered monometallic (Co, Ni) hydroxides. The as-prepared Co0.5Ni0.5 hydroxide hierarchical structures possesses the highest specific capacitance of 1767 F g-1 at a galvanic current density of 1 A g-1 and an outstanding specific capacitance retention of 87% after 1000 cycles. In comparison with the dispersed nanosheets of Co-Ni hydroxide, layered hydroxide hierarchical structures show much superior electrochemical performance. This study provides a promising method to construct hierarchical structures with controllable transition-metal compositions for enhancing the electrochemical performance in hybrid supercapacitors.

Chemical Composition of Nanoporous Layer Formed by Electrochemical Etching of p-Type GaAs.

PubMed

Bioud, Youcef A; Boucherif, Abderraouf; Belarouci, Ali; Paradis, Etienne; Drouin, Dominique; Arès, Richard

2016-12-01

We have performed a detailed characterization study of electrochemically etched p-type GaAs in a hydrofluoric acid-based electrolyte. The samples were investigated and characterized through cathodoluminescence (CL), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). It was found that after electrochemical etching, the porous layer showed a major decrease in the CL intensity and a change in chemical composition and in the crystalline phase. Contrary to previous reports on p-GaAs porosification, which stated that the formed layer is composed of porous GaAs, we report evidence that the porous layer is in fact mainly constituted of porous As 2 O 3 . Finally, a qualitative model is proposed to explain the porous As 2 O 3 layer formation on p-GaAs substrate.

Atomic Layer Deposition for Improved Electrochemical Stability for Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Riley, Leah Autumn

2011-12-01

The dwindling supply of fossil fuels and the harmful green house gases which they produce have driven research towards developing a reliable and safe solution. Alternative forms of transportation, such as hybrid electric, plug-in hybrid electric and all electric vehicles in turn have recently received vast consumer attention. Lithium ion batteries (LIBs) are seen as the most promising option in HEVs and PHEVs. However, while prevalent in watches, computers and phones, significant improvements in both energy density and rate capability need to be achieved before LIBs are suitable for vehicular applications. Decades of research has yielded a range of anode and cathode materials that exhibit higher capacity and better rate capability than the traditional graphite and LiCoO2 found in commercial batteries. Unfortunately due to material pulverization and electrode/electrolyte interfacial reactions high performance materials are often plagued with poor capacity retention and material degradation. Surprisingly, many of the issues accompanying high performance materials can be suppressed by the application of as little as 8 angstroms of Al 2O3 on the surface. Ultra-thin, conformal, ceramic passivating layers are grown using a thin film technique called Atomic Layer Deposition (ALD). Self-limiting and easily tailored, ALD is a superior coating method compared to the more common wet-chemical methods such as sol-gel. Conformal ALD is applied to commercially common materials (graphite, LiCoO2), as well as high energy density alternatives (MoO3, Li(Ni1/3 Mn1/3Co1/3)O2). It will be shown that the ALD coating protects high surface area state-of-the-art nanoparticles from decomposition and protects electrode surfaces from HF attack and dissolution even up to 5.0 V. In addition to extending overall electrochemical cycling stability, ALD will be shown to minimize hazards and risks, such as thermal runaway, by preventing unwanted side reactions with the organic liquid electrolyte. ALD is a simple, non-toxic and effective method for the implementation of LIBs in high power applications.

Investigating Sodium Storage Mechanisms in Tin Anodes: A Combined Pair Distribution Function Analysis, Density Functional Theory, and Solid-State NMR Approach.

PubMed

Stratford, Joshua M; Mayo, Martin; Allan, Phoebe K; Pecher, Oliver; Borkiewicz, Olaf J; Wiaderek, Kamila M; Chapman, Karena W; Pickard, Chris J; Morris, Andrew J; Grey, Clare P

2017-05-31

The alloying mechanism of high-capacity tin anodes for sodium-ion batteries is investigated using a combined theoretical and experimental approach. Ab initio random structure searching (AIRSS) and high-throughput screening using a species-swap method provide insights into a range of possible sodium-tin structures. These structures are linked to experiments using both average and local structure probes in the form of operando pair distribution function analysis, X-ray diffraction, and 23 Na solid-state nuclear magnetic resonance (ssNMR), along with ex situ 119 Sn ssNMR. Through this approach, we propose structures for the previously unidentified crystalline and amorphous intermediates. The first electrochemical process of sodium insertion into tin results in the conversion of crystalline tin into a layered structure consisting of mixed Na/Sn occupancy sites intercalated between planar hexagonal layers of Sn atoms (approximate stoichiometry NaSn 3 ). Following this, NaSn 2 , which is predicted to be thermodynamically stable by AIRSS, forms; this contains hexagonal layers closely related to NaSn 3 , but has no tin atoms between the layers. NaSn 2 is broken down into an amorphous phase of approximate composition Na 1.2 Sn. Reverse Monte Carlo refinements of an ab initio molecular dynamics model of this phase show that the predominant tin connectivity is chains. Further reaction with sodium results in the formation of structures containing Sn-Sn dumbbells, which interconvert through a solid-solution mechanism. These structures are based upon Na 5-x Sn 2 , with increasing occupancy of one of its sodium sites commensurate with the amount of sodium added. ssNMR results indicate that the final product, Na 15 Sn 4 , can store additional sodium atoms as an off-stoichiometry compound (Na 15+x Sn 4 ) in a manner similar to Li 15 Si 4 .

Investigating Sodium Storage Mechanisms in Tin Anodes: A Combined Pair Distribution Function Analysis, Density Functional Theory, and Solid-State NMR Approach

DOE PAGES

Stratford, Joshua M.; Mayo, Martin; Allan, Phoebe K.; ...

2017-05-04

Here, the alloying mechanism of high-capacity tin anodes for sodium-ion batteries is investigated using a combined theoretical and experimental approach. Ab initio random structure searching (AIRSS) and high-throughput screening using a species-swap method provide insights into a range of possible sodium–tin structures. These structures are linked to experiments using both average and local structure probes in the form of operando pair distribution function analysis, X-ray diffraction, and 23Na solid-state nuclear magnetic resonance (ssNMR), along with ex situ 119Sn ssNMR. Through this approach, we propose structures for the previously unidentified crystalline and amorphous intermediates. The first electrochemical process of sodium insertionmore » into tin results in the conversion of crystalline tin into a layered structure consisting of mixed Na/Sn occupancy sites intercalated between planar hexagonal layers of Sn atoms (approximate stoichiometry NaSn 3). Following this, NaSn 2, which is predicted to be thermodynamically stable by AIRSS, forms; this contains hexagonal layers closely related to NaSn 3, but has no tin atoms between the layers. NaSn 2 is broken down into an amorphous phase of approximate composition Na 1.2Sn. Reverse Monte Carlo refinements of an ab initio molecular dynamics model of this phase show that the predominant tin connectivity is chains. Further reaction with sodium results in the formation of structures containing Sn–Sn dumbbells, which interconvert through a solid-solution mechanism. These structures are based upon Na 5–xSn 2, with increasing occupancy of one of its sodium sites commensurate with the amount of sodium added. ssNMR results indicate that the final product, Na 15Sn 4, can store additional sodium atoms as an off-stoichiometry compound (Na 15+xSn 4) in a manner similar to Li 15Si 4.« less

Investigating Sodium Storage Mechanisms in Tin Anodes: A Combined Pair Distribution Function Analysis, Density Functional Theory, and Solid-State NMR Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stratford, Joshua M.; Mayo, Martin; Allan, Phoebe K.

Here, the alloying mechanism of high-capacity tin anodes for sodium-ion batteries is investigated using a combined theoretical and experimental approach. Ab initio random structure searching (AIRSS) and high-throughput screening using a species-swap method provide insights into a range of possible sodium–tin structures. These structures are linked to experiments using both average and local structure probes in the form of operando pair distribution function analysis, X-ray diffraction, and 23Na solid-state nuclear magnetic resonance (ssNMR), along with ex situ 119Sn ssNMR. Through this approach, we propose structures for the previously unidentified crystalline and amorphous intermediates. The first electrochemical process of sodium insertionmore » into tin results in the conversion of crystalline tin into a layered structure consisting of mixed Na/Sn occupancy sites intercalated between planar hexagonal layers of Sn atoms (approximate stoichiometry NaSn 3). Following this, NaSn 2, which is predicted to be thermodynamically stable by AIRSS, forms; this contains hexagonal layers closely related to NaSn 3, but has no tin atoms between the layers. NaSn 2 is broken down into an amorphous phase of approximate composition Na 1.2Sn. Reverse Monte Carlo refinements of an ab initio molecular dynamics model of this phase show that the predominant tin connectivity is chains. Further reaction with sodium results in the formation of structures containing Sn–Sn dumbbells, which interconvert through a solid-solution mechanism. These structures are based upon Na 5–xSn 2, with increasing occupancy of one of its sodium sites commensurate with the amount of sodium added. ssNMR results indicate that the final product, Na 15Sn 4, can store additional sodium atoms as an off-stoichiometry compound (Na 15+xSn 4) in a manner similar to Li 15Si 4.« less

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-04-03

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-02-20

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Electrochemical behavior of adrenaline at the carbon atom wire modified electrode

NASA Astrophysics Data System (ADS)

Xue, Kuan-Hong; Liu, Jia-Mei; Wei, Ri-Bing; Chen, Shao-Peng

2006-09-01

Electrochemical behavior of adrenaline at an electrode modified by carbon atom wires (CAWs), a new material, was investigated by cyclic voltammetry combined with UV-vis spectrometry, and forced convection method. As to the electrochemical response of redox of adrenaline/adrenalinequinone couple in 0.50 M H 2SO 4, at a nitric acid treated CAW modified electrode, the anodic and cathodic peak potentials Epa and Epc shifted by 87 mV negatively and 139 mV in the positive direction, respectively, and standard heterogeneous rate constant k0 increased by 16 times compared to the corresponding bare electrode, indicating the extraordinary activity of CAWs in electrocatalysis for the process.

Layered transition metal dichalcogenide electrochemistry: journey across the periodic table.

PubMed

Chia, Xinyi; Pumera, Martin

2018-06-08

Studies on layered transition metal dichalcogenides (TMDs), in particular for Group VIB TMDs like MoS2 and WS2, have long reached a crescendo in the realms of electrochemical applications initiated by their remarkable catalytic and electronic properties. One area that garnered considerable attention is the fervent pursuit of layered TMDs as electrocatalysts for hydrogen evolution reaction (HER), driven by global efforts towards reducing carbon footprint and attaining hydrogen economy. This Tutorial Review captures the essence of electrochemistry of different classes of layered TMDs and metal chalcogenides across the period table and showcases their tuneable electrochemical and HER catalytic attributes that are governed by the elemental composition, structure and anisotropy. Of interest to the assiduously studied Group VIB TMDs, we describe the role of elemental constituents and material purity in aspects of surface composition and structure, on their electrochemistry. Across families of layered TMDs in the periodic table, we highlight the apparent trends in their electrochemical and electrocatalytic properties through diligent comparison. Inevitably, these trends vary according to the type of chalcogen or transition metal that constitutes the eventual TMD. Beyond layered TMDs, we discuss the electrochemistry and recent progress in HER electrocatalysis of other layered metal chalcogenides that are overshadowed by the success of Group VIB TMDs. At the pinnacle of the emergent applications of layered TMDs, it is prudent to demystify the intrinsic electrochemical behaviour that originates from the participation of the elemental constitution of transition metal or chalcogen. Moreover, knowledge of the catalytic and electronic properties of the various TMD families and emerging trends across the period or down the group is of paramount importance when introducing or refining their prospective uses. The annotations in this Tutorial Review are envisioned to promote discourse into the catalytic and electrochemical trends of TMDs that is currently absent.

Bragg stack-functionalized counter electrode for solid-state dye-sensitized solar cells.

PubMed

Park, Jung Tae; Prosser, Jacob H; Kim, Dong Jun; Kim, Jong Hak; Lee, Daeyeon

2013-05-01

A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO(2) (om-TiO(2)) and colloidal SiO(2) (col-SiO(2)) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO(2) layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol-gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO(2) layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability of core-shell nanowires in selected model solutions

NASA Astrophysics Data System (ADS)

Kalska-Szostko, B.; Wykowska, U.; Basa, A.; Zambrzycka, E.

2015-03-01

This paper presents the studies of stability of magnetic core-shell nanowires prepared by electrochemical deposition from an acidic solution containing iron in the core and modified surface layer. The obtained nanowires were tested according to their durability in distilled water, 0.01 M citric acid, 0.9% NaCl, and commercial white wine (12% alcohol). The proposed solutions were chosen in such a way as to mimic food related environment due to a possible application of nanowires as additives to, for example, packages. After 1, 2 and 3 weeks wetting in the solutions, nanoparticles were tested by Infrared Spectroscopy, Atomic Absorption Spectroscopy, Transmission Electron Microscopy and X-ray diffraction methods.

Kernel Tuning and Nonuniform Influence on Optical and Electrochemical Gaps of Bimetal Nanoclusters.

PubMed

He, Lizhong; Yuan, Jinyun; Xia, Nan; Liao, Lingwen; Liu, Xu; Gan, Zibao; Wang, Chengming; Yang, Jinlong; Wu, Zhikun

2018-03-14

Fine tuning nanoparticles with atomic precision is exciting and challenging and is critical for tuning the properties, understanding the structure-property correlation and determining the practical applications of nanoparticles. Some ultrasmall thiolated metal nanoparticles (metal nanoclusters) have been shown to be precisely doped, and even the protecting staple metal atom could be precisely reduced. However, the precise addition or reduction of the kernel atom while the other metal atoms in the nanocluster remain the same has not been successful until now, to the best of our knowledge. Here, by carefully selecting the protecting ligand with adequate steric hindrance, we synthesized a novel nanocluster in which the kernel can be regarded as that formed by the addition of two silver atoms to both ends of the Pt@Ag 12 icosohedral kernel of the Ag 24 Pt(SR) 18 (SR: thiolate) nanocluster, as revealed by single crystal X-ray crystallography. Interestingly, compared with the previously reported Ag 24 Pt(SR) 18 nanocluster, the as-obtained novel bimetal nanocluster exhibits a similar absorption but a different electrochemical gap. One possible explanation for this result is that the kernel tuning does not essentially change the electronic structure, but obviously influences the charge on the Pt@Ag 12 kernel, as demonstrated by natural population analysis, thus possibly resulting in the large electrochemical gap difference between the two nanoclusters. This work not only provides a novel strategy to tune metal nanoclusters but also reveals that the kernel change does not necessarily alter the optical and electrochemical gaps in a uniform manner, which has important implications for the structure-property correlation of nanoparticles.

Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

PubMed

Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

2016-11-15

Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k 0 , of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale scanning electrochemical microscopy (SECM) imaging to resolve the electrocatalytic activity of individual electrodeposited NPs within an ensemble sample yielding consistent high k 0 values of ≥2 cm/s for the hydrogen oxidation reaction (HOR) at different NPs. We envision that our advanced electrochemical approaches will enable us to systematically address structure effects on the catalytic activity, thus providing a quantitative guideline for electrocatalysts in energy-related applications.

Electrochemical and spectroelectrochemical behavior of the TCNQ(0/)(-) couple on a glassy carbon electrode. Layer-by-layer nucleation and growth.

PubMed

Gómez, L; Rodríguez-Amaro, R

2006-08-15

On the basis of the electrochemical results obtained for thin films of 7,7,8,8- tetracyanoquinodimethane (TCNQ) on a glassy carbon electrode, the reduction and oxidation of the [TCNQ](0/)(-) couple in KCl aqueous media occurs via a mechanism involving layer-by-layer nucleation and growth. In situ recorded UV-visible spectroelectrochemical data allow two different crystal structures for the oxidized form of TCNQ to be discriminated.

Simultaneous Atomic Absorption Spectrometry for Cadmium and Lead Determination in Wastewater: A Laboratory Exercise

ERIC Educational Resources Information Center

Correia, Paulo R. M.; Oliveira, Pedro V.

2004-01-01

The simultaneous determination of cadmium and lead by multi-element atomic absorption spectrometry with electrochemical atomization is proposed by employing a problem-based approach. The reports indicate that the students assimilated the principles of the simultaneous atomic absorption spectrometry (SIMAAS), the role of the chemical modifier, the…

Inhibitors for magnesium corrosion: Metal organic frameworks

NASA Astrophysics Data System (ADS)

Mesbah, Adel; Juers, Caroline; Lacouture, Françoise; Mathieu, Stéphane; Rocca, Emmanuel; François, Michel; Steinmetz, Jean

2007-03-01

Electrochemical measurements demonstrate that magnesium surfaces can be protected by alkyl carboxylate. In a nearly neutral pH solution of sodium decanoate, the reduced corrosion rate and a passivation behaviour are attributed to the formation of Mg(C 10H 19O 2) 2(H 2O) 3 (Mg(C10) 2) at the magnesium surface whereas heptanoate Mg(C 7H 13O 2) 2(H 2O) 3 (Mg(C7) 2) is not efficient in such media. The crystal structures of the two metal carboxylates Mg(C7) 2 and Mg(C10) 2 are determined by X-ray diffraction. Single crystal data: Mg(C7) 2, P2 1/ a, a = 9.130(5) Å, b = 8.152(5) Å, c = 24.195(5) Å, β = 91.476(5)°, V = 1800.3(15) Å 3, Dx = 1.242 g cm -3, Z = 4. Synchrotron powder data: Mg(C10) 2, P2 1/ a, a = 9.070(3) Å, b = 8.165(1) Å, c = 32.124(1) Å, β = 98.39(1)°, V = 2353.85(8) Å 3, Dx = 1.188 g cm -3, Z = 4. Their layered structures are quite similar and differ mainly by the length of the hydrophobic chains. They consist of two planes of O-octahedra centred by Mg atoms, parallel to (001). The distorted octahedra are constituted by three oxygen atoms from carboxylate groups and by three oxygen atoms coming from water molecules. The layers are connected by hydrogen bonds. The carboxylate chains are located perpendicularly and on both sides of these planes. One carboxylate chain is bridging the Mg atom along [010] while the other is monodendate. The presence of structural water is confirmed by thermal analyses.

Characterization of self-assembled redox polymer and antibody molecules on thiolated gold electrodes.

PubMed

Calvo, E J; Danilowicz, C; Lagier, C M; Manrique, J; Otero, M

2004-05-15

Multilayer immobilization of antibody and redox polymer molecules on a gold electrode was achieved, as a strategy for the potential development of an amperometric immunosensor. The step-by-step assembly of antibiotin IgG on Os(bpy)(2)ClPyCH(2)NH poly(allylamine) redox polymer (PAH-Os) adsorbed on thiolated gold electrodes was proved by quartz crystal microbalance (QCM) and atomic force microscopy (AFM) experiments, confirming the electrochemical evidence. The increase of redox charge during the layer-by-layer deposition demonstrated that charge propagation within the layers is feasible. The multilayer structure proved to be effective for the molecular recognition of horseradish peroxidase-biotin conjugate (HRP-biotin), as confirmed by the QCM measurements and the electrocatalytic reduction current obtained upon H(2)O(2) addition. The catalytic current resulting from PAH-Os mediation was shown to increase with the number of assembled layers. Furthermore, the inventory of IgG molecules on the supramolecular self-assembled structure and the specific and non-specific binding of HRP-biotin conjugate were confirmed by the QCM transient studies, giving information on the kinetics of IgG deposition and HRP-biotin conjugate binding to the IgG.

Development of carbon electrodes for electrochemistry, solid-state electronics and multimodal atomic force microscopy imaging

NASA Astrophysics Data System (ADS)

Morton, Kirstin Claire

Carbon is one of the most remarkable elements due to its wide abundance on Earth and its many allotropes, which include diamond and graphite. Many carbon allotropes are conductive and in recent decades scientists have discovered and synthesized many new forms of carbon, including graphene and carbon nanotubes. The work in this thesis specifically focuses on the fabrication and characterization of pyrolyzed parylene C (PPC), a conductive pyrocarbon, as an electrode material for diodes, as a conductive coating for atomic force microscopy (AFM) probes and as an ultramicroelectrode (UME) for the electrochemical interrogation of cellular systems in vitro. Herein, planar and three-dimensional (3D) PPC electrodes were microscopically, spectroscopically and electrochemically characterized. First, planar PPC films and PPC-coated nanopipettes were utilized to detect a model redox species, Ru(NH3) 6Cl3. Then, free-standing PPC thin films were chemically doped, with hydrazine and concentrated nitric acid, to yield p- and n-type carbon films. Doped PPC thin films were positioned in conjunction with doped silicon to create Schottky and p-n junction diodes for use in an alternating current half-wave rectifier circuit. Pyrolyzed parylene C has found particular merit as a 3D electrode coating of AFM probes. Current sensing-atomic force microscopy imaging in air of nanoscale metallic features was undertaken to demonstrate the electronic imaging applicability of PPC AFM probes. Upon further insulation with parylene C and modification with a focused ion beam, a PPC UME was microfabricated near the AFM probe apex and utilized for electrochemical imaging. Subsequently, scanning electrochemical microscopy-atomic force microscopy imaging was undertaken to electrochemically quantify and image the spatial location of dopamine exocytotic release, elicited mechanically via the AFM probe itself, from differentiated pheochromocytoma 12 cells in vitro.

Operando SXRD of E-ALD deposited sulphides ultra-thin films: Crystallite strain and size

NASA Astrophysics Data System (ADS)

Giaccherini, Andrea; Russo, Francesca; Carlà, Francesco; Guerri, Annalisa; Picca, Rosaria Anna; Cioffi, Nicola; Cinotti, Serena; Montegrossi, Giordano; Passaponti, Maurizio; Di Benedetto, Francesco; Felici, Roberto; Innocenti, Massimo

2018-02-01

Electrochemical Atomic Layer Deposition (E-ALD), exploiting surface limited electrodeposition of atomic layers, can easily grow highly ordered ultra-thin films and 2D structures. Among other compounds CuxZnyS grown by means of E-ALD on Ag(111) has been found particularly suitable for the solar energy conversion due to its band gap (1.61 eV). However its growth seems to be characterized by a micrometric thread-like structure, probably overgrowing a smooth ultra-thin films. On this ground, a SXRD investigation has been performed, to address the open questions about the structure and the growth of CuxZnyS by means of E-ALD. The experiment shows a pseudo single crystal pattern as well as a powder pattern, confirming that part of the sample grows epitaxially on the Ag(111) substrate. The growth of the film was monitored by following the evolution of the Bragg peaks and Debye rings during the E-ALD steps. Breadth and profile analysis of the Bragg peaks lead to a qualitative interpretation of the growth mechanism. This study confirms that Zn lead to the growth of a strained Cu2S-like structure, while the growth of the thread-like structure is probably driven by the release of the stress from the epitaxial phase.

Carbonate scale deactivating the biocathode in a microbial fuel cell

NASA Astrophysics Data System (ADS)

Santini, M.; Marzorati, S.; Fest-Santini, S.; Trasatti, S.; Cristiani, P.

2017-07-01

The development and the following inactivation of a carbon-based biocathode in single chamber and membraneless MFCs was investigated in this work. The electrochemical behavior of the biocathode has been analyzed over time during the MFC life. X-Ray Micro-Computed Tomographies (microCTs) have been carried out at progressive stages, documenting the building over time of a layer of scale deposition becoming thicker and thicker up to the cathode inactivation. The technique provides cross-sectional (tomographic) grayscale images and 3D reconstruction of volumes. Lighter color indicates lower X-ray attenuation (i.e., lower atomic density) thus allowing distinguishing biofilm from inorganic fouling on the basis of the average atomic number Z of each voxel (3D pixel). MicroCT was combined with Scanning Electron Microscopy (SEM) and Energy-Dispersive X-Ray Spectroscopy (EDX) in order to qualitatively recognize chemical species in each different layer of the cathode's section. Results correlated the presence of biofilm and calcium carbonate deposits, prevalently in the inner part of the cathode, with the produced electric current over time. A specific microCT-related software quantified the time-dependent carbonate scale deposition, identifying a correlation between the decreasing performances of the device and the increasing quantity of scale deposition that penetrates the cathode cross section in time.

High-Performance One-Body Core/Shell Nanowire Supercapacitor Enabled by Conformal Growth of Capacitive 2D WS2 Layers.

PubMed

Choudhary, Nitin; Li, Chao; Chung, Hee-Suk; Moore, Julian; Thomas, Jayan; Jung, Yeonwoong

2016-12-27

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have emerged as promising capacitive materials for supercapacitor devices owing to their intrinsically layered structure and large surface areas. Hierarchically integrating 2D TMDs with other functional nanomaterials has recently been pursued to improve electrochemical performances; however, it often suffers from limited cyclic stabilities and capacitance losses due to the poor structural integrity at the interfaces of randomly assembled materials. Here, we report high-performance core/shell nanowire supercapacitors based on an array of one-dimensional (1D) nanowires seamlessly integrated with conformal 2D TMD layers. The 1D and 2D supercapacitor components possess "one-body" geometry with atomically sharp and structurally robust core/shell interfaces, as they were spontaneously converted from identical metal current collectors via sequential oxidation/sulfurization. These hybrid supercapacitors outperform previously developed any stand-alone 2D TMD-based supercapacitors; particularly, exhibiting an exceptional charge-discharge retention over 30,000 cycles owing to their structural robustness, suggesting great potential for unconventional energy storage technologies.

Gas recombination assembly for electrochemical cells

DOEpatents

Levy, Isaac; Charkey, Allen

1989-01-01

An assembly for recombining gases generated in electrochemical cells wherein a catalyst strip is enveloped within a hydrophobic, gas-porous film which, in turn, is encased between gas-porous, metallic layers. The sandwich construction of metallic layers and film is formed into a spiral with a tab for connection to the cell.

Electrochemical Detection in Stacked Paper Networks.

PubMed

Liu, Xiyuan; Lillehoj, Peter B

2015-08-01

Paper-based electrochemical biosensors are a promising technology that enables rapid, quantitative measurements on an inexpensive platform. However, the control of liquids in paper networks is generally limited to a single sample delivery step. Here, we propose a simple method to automate the loading and delivery of liquid samples to sensing electrodes on paper networks by stacking multiple layers of paper. Using these stacked paper devices (SPDs), we demonstrate a unique strategy to fully immerse planar electrodes by aqueous liquids via capillary flow. Amperometric measurements of xanthine oxidase revealed that electrochemical sensors on four-layer SPDs generated detection signals up to 75% higher compared with those on single-layer paper devices. Furthermore, measurements could be performed with minimal user involvement and completed within 30 min. Due to its simplicity, enhanced automation, and capability for quantitative measurements, stacked paper electrochemical biosensors can be useful tools for point-of-care testing in resource-limited settings. © 2015 Society for Laboratory Automation and Screening.

Large energy storage efficiency of the dielectric layer of graphene nanocapacitors.

PubMed

Bezryadin, A; Belkin, A; Ilin, E; Pak, M; Colla, Eugene V; Hubler, A

2017-12-08

Electric capacitors are commonly used in electronic circuits for the short-term storage of small amounts of energy. It is desirable however to use capacitors to store much larger energy amounts to replace rechargeable batteries. Unfortunately existing capacitors cannot store sufficient energy to be able to replace common electrochemical energy storage systems. Here we examine the energy storage capabilities of graphene nanocapacitors, which are tri-layer devices involving an Al film, Al 2 O 3 dielectric layer, and a single layer of carbon atoms, i.e., graphene. This is a purely electronic capacitor and therefore it can function in a wide temperature interval. The capacitor shows a high dielectric breakdown electric field strength, of the order of 1000 kV mm -1 (i.e., 1 GV m -1 ), which is much larger than the table value of the Al 2 O 3 dielectric strength. The corresponding energy density is 10-100 times larger than the energy density of a common electrolytic capacitor. Moreover, we discover that the amount of charge stored in the dielectric layer can be equal or can even exceed the amount of charge stored on the capacitor plates. The dielectric discharge current follows a power-law time dependence. We suggest a model to explain this behavior.

Dimensionally Controlled Lithiation of Chromium Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fister, Tim T.; Hu, Xianyi; Esbenshade, Jennifer

Oxide conversion reactions are an alternative approach for high capacity lithium ion batteries but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. In particular, the morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. Here we use a model electrode with alternating layers of chromium and chromium oxide to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with X-raymore » reflectivity, XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials.« less

Large energy storage efficiency of the dielectric layer of graphene nanocapacitors

NASA Astrophysics Data System (ADS)

Bezryadin, A.; Belkin, A.; Ilin, E.; Pak, M.; Colla, Eugene V.; Hubler, A.

2017-12-01

Electric capacitors are commonly used in electronic circuits for the short-term storage of small amounts of energy. It is desirable however to use capacitors to store much larger energy amounts to replace rechargeable batteries. Unfortunately existing capacitors cannot store sufficient energy to be able to replace common electrochemical energy storage systems. Here we examine the energy storage capabilities of graphene nanocapacitors, which are tri-layer devices involving an Al film, Al2O3 dielectric layer, and a single layer of carbon atoms, i.e., graphene. This is a purely electronic capacitor and therefore it can function in a wide temperature interval. The capacitor shows a high dielectric breakdown electric field strength, of the order of 1000 kV mm-1 (i.e., 1 GV m-1), which is much larger than the table value of the Al2O3 dielectric strength. The corresponding energy density is 10-100 times larger than the energy density of a common electrolytic capacitor. Moreover, we discover that the amount of charge stored in the dielectric layer can be equal or can even exceed the amount of charge stored on the capacitor plates. The dielectric discharge current follows a power-law time dependence. We suggest a model to explain this behavior.

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope.

PubMed

Obermair, Christian; Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a "mechano-electrochemical pen", locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, "write", "read", "delete" and "re-write", were successfully demonstrated on the nanometer scale.

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope

PubMed Central

Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

Summary We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a “mechano-electrochemical pen”, locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, “write”, “read”, “delete” and “re-write”, were successfully demonstrated on the nanometer scale. PMID:23365795

Single crystalline thin films as a novel class of electrocatalysts

DOE PAGES

Snyder, Joshua; Markovic, Nenad; Stamenkovic, Vojislav

2013-01-01

The ubiquitous use of single crystal metal electrodes has garnered invaluable insight into the relationship between surface atomic structure and functional electrochemical properties. But, the sensitivity of their electrochemical response to surface orientation and the amount of precious metal required can limit their use. We present here a generally applicable procedure for producing thin metal films with a large proportion of atomically flat (111) terraces without the use of an epitaxial template. Thermal annealing in a controlled atmosphere induces long-range ordering of magnetron sputtered thin metal films deposited on an amorphous substrate. The ordering transition in these thin metal filmsmore » yields characteristic (111) electrochemical signatures with minimal amount of material and provides an adequate replacement for oriented bulk single crystals. Our procedure can be generalized towards a novel class of practical multimetallic thin film based electrocatalysts with tunable near-surface compositional profile and morphology. Annealing of atomically corrugated sputtered thin film Pt-alloy catalysts yields an atomically smooth structure with highly crystalline, (111)-like ordered and Pt segregated surface that displays superior functional properties, bridging the gap between extended/bulk surfaces and nanoscale systems.« less

Corrosion of NiTi Wires with Cracked Oxide Layer

NASA Astrophysics Data System (ADS)

Racek, Jan; Šittner, Petr; Heller, Luděk; Pilch, Jan; Petrenec, Martin; Sedlák, Petr

2014-07-01

Corrosion behavior of superelastic NiTi shape memory alloy wires with cracked TiO2 surface oxide layers was investigated by electrochemical corrosion tests (Electrochemical Impedance Spectroscopy, Open Circuit Potential, and Potentiodynamic Polarization) on wires bent into U-shapes of various bending radii. Cracks within the oxide on the surface of the bent wires were observed by FIB-SEM and TEM methods. The density and width of the surface oxide cracks dramatically increase with decreasing bending radius. The results of electrochemical experiments consistently show that corrosion properties of NiTi wires with cracked oxide layers (static load keeps the cracks opened) are inferior compared to the corrosion properties of the straight NiTi wires covered by virgin uncracked oxides. Out of the three methods employed, the Electrochemical Impedance Spectroscopy seems to be the most appropriate test for the electrochemical characterization of the cracked oxide layers, since the impedance curves (Nyquist plot) of differently bent NiTi wires can be associated with increasing state of the surface cracking and since the NiTi wires are exposed to similar conditions as the surfaces of NiTi implants in human body. On the other hand, the potentiodynamic polarization test accelerates the corrosion processes and provides clear evidence that the corrosion resistance of bent superelastic NiTi wires degrades with oxide cracking.

Role of nanorods insertion layer in ZnO-based electrochemical metallization memory cell

NASA Astrophysics Data System (ADS)

Mangasa Simanjuntak, Firman; Singh, Pragya; Chandrasekaran, Sridhar; Juanda Lumbantoruan, Franky; Yang, Chih-Chieh; Huang, Chu-Jie; Lin, Chun-Chieh; Tseng, Tseung-Yuen

2017-12-01

An engineering nanorod array in a ZnO-based electrochemical metallization device for nonvolatile memory applications was investigated. A hydrothermally synthesized nanorod layer was inserted into a Cu/ZnO/ITO device structure. Another device was fabricated without nanorods for comparison, and this device demonstrated a diode-like behavior with no switching behavior at a low current compliance (CC). The switching became clear only when the CC was increased to 75 mA. The insertion of a nanorods layer induced switching characteristics at a low operation current and improve the endurance and retention performances. The morphology of the nanorods may control the switching characteristics. A forming-free electrochemical metallization memory device having long switching cycles (>104 cycles) with a sufficient memory window (103 times) for data storage application, good switching stability and sufficient retention was successfully fabricated by adjusting the morphology and defect concentration of the inserted nanorod layer. The nanorod layer not only contributed to inducing resistive switching characteristics but also acted as both a switching layer and a cation diffusion control layer.

The Electrical Double Layer and Its Structure

NASA Astrophysics Data System (ADS)

Stojek, Zbigniew

At any electrode immersed in an electrolyte solution, a specific interfacial region is formed. This region is called the double layer. The electrical properties of such a layer are important, since they significantly affect the electrochemical measurements. In an electrical circuit used to measure the current that flows at a particular working electrode, the double layer can be viewed as a capacitor. Figure I.1.1 depicts this situation where the electrochemical cell is represented by an electrical circuit and capacitor C d corresponds to the differential capacity of the double layer. To obtain a desired potential at the working electrodes, the double-layer capacitor must be first appropriately charged, which means that a capacitive current, not related to the reduction or oxidation of the substrates, flows in the electrical circuit. While this capacitive current carries some information concerning the double layer and its structure, and in some cases can be used for analytical purposes, in general, it interferes with electrochemical investigations. A variety of methods are used in electrochemistry to depress, isolate, or filter the capacitive current.

Modulating the Electrochemical Performances of Layered Cathode Materials for Sodium Ion Batteries through Tuning Coulombic Repulsion between Negatively Charged TMO2 Slabs.

PubMed

Li, Zheng-Yao; Wang, Huibo; Yang, Wenyun; Yang, Jinbo; Zheng, Lirong; Chen, Dongfeng; Sun, Kai; Han, Songbai; Liu, Xiangfeng

2018-01-17

Exploiting advanced layered transition metal oxide cathode materials is of great importance to rechargeable sodium batteries. Layered oxides are composed of negatively charged TMO 2 slabs (TM = transition metal) separated by Na + diffusion layers. Herein, we propose a novel insight, for the first time, to control the electrochemical properties by tuning Coulombic repulsion between negatively charged TMO 2 slabs. Coulombic repulsion can finely tailor the d-spacing of Na ion layers and material structural stability, which can be achieved by employing Na + cations to serve as effective shielding layers between TMO 2 layers. A series of O3-type Na x Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 (x = 1.0, 0.9, 0.8, and 0.7) have been prepared, and Na 0.7 Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 shows the largest Coulombic repulsion between TMO 2 layers, the largest space for Na ion diffusion, the best structural stability, and also the longest Na-O chemical bond with weaker Coulombic attraction, thus leading to the best electrochemical performance. Meanwhile, the thermal stability depends on the Na concentration in pristine materials. Ex situ X-ray absorption (XAS) analysis indicates that Mn, Fe, and Cu ions are all electrochemically active components during insertion and extraction of sodium ion. This study enables some new insights to promote the development of advanced layered Na x TMO 2 materials for rechargeable sodium batteries in the future.

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Electrochemical Behavior Assessment of As-Cast Mg-Y-RE-Zr Alloy in Phosphate Buffer Solutions (X Na3PO4 + Y Na2HPO4) Using Electrochemical Impedance Spectroscopy and Mott-Schottky Techniques

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Asgari, Hamed

2018-05-01

In the present study, electrochemical behavior of as-cast Mg-Y-RE-Zr alloy (RE: rare-earth alloying elements) was investigated using electrochemical tests in phosphate buffer solutions (X Na3PO4 + Y Na2HPO4). X-ray diffraction techniques and Scanning electron microscopy equipped with energy dispersive x-ray spectroscopy were used to investigate the microstructure and phases of the experimental alloy. Different electrochemical tests such as potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis were carried out in order to study the electrochemical behavior of the experimental alloy in phosphate buffer solutions. The PDP curves and EIS measurements indicated that the passive behavior of the as-cast Mg-Y-RE-Zr alloy in phosphate buffer solutions was weakened by an increase in the pH, which is related to formation of an imperfect and less protective passive layer on the alloy surface. The presence of the insoluble zirconium particles along with high number of intermetallic phases of RE elements mainly Mg24Y5 in the magnesium matrix can deteriorate the corrosion performance of the alloy by disrupting the protective passive layer that is formed at pH values over 11. These insoluble zirconium particles embedded in the matrix can detrimentally influence the passivation. The M-S analysis revealed that the formed passive layers on Mg-Y-RE-Zr alloy behaved as an n-type semiconductor. An increase in donor concentration accompanying solutions of higher alkalinity is thought to result in the formation of a less resistive passive layer.

Long-term bilayer encapsulation performance of atomic layer deposited Al₂O₃ and Parylene C for biomedical implantable devices.

PubMed

Xie, Xianzong; Rieth, Loren; Caldwell, Ryan; Diwekar, Mohit; Tathireddy, Prashant; Sharma, Rohit; Solzbacher, Florian

2013-10-01

We present an encapsulation scheme that combines atomic layer deposited (ALD) Al₂O₃ and Parylene C for the encapsulation of implantable devices. The encapsulation performances of combining alumina and Parylene C was compared to individual layers of Parylene C or alumina and the bilayer coating had superior encapsulation properties. The alumina-Parylene coated interdigitated electrodes (IDEs) soaked in PBS for up to nine months at temperatures from 37 to 80 °C for accelerated lifetime testing. For 52-nm alumina and 6-μm Parylene C, leakage current was ∼20 pA at 5 VDC, and the impedance was about 3.5 MΩ at 1 kHz with a phase near -87° from electrochemical impedance spectroscopy for samples soaked at 67 °C for equivalent lifetime of 72 months at 37 °C. The change of impedance during the whole soaking period (up to 70 months of equivalent soaking time at 37 °C) over 1 to 10⁶ Hz was within 5%. The stability of impedance indicated almost no degradation of the encapsulation. Bias voltage effect was studied by continuously applying 5 VDC, and it reduced the lifetime of Parylene coating by ∼75% while it showed no measurable effect on the bilayer coating. Lifetime of encapsulation of IDEs with topography generated by attaching a coil and surface mount device (SMD) capacitor was about half of that of planer IDEs. The stable long-term insulation impedance, low leakage current, and better lifetime under bias voltage and topography made this double-layer encapsulation very promising for chronic implantable devices.

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery

NASA Astrophysics Data System (ADS)

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-05-01

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00465b

Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

NASA Astrophysics Data System (ADS)

Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

2016-03-01

A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wafer-scale fabrication of polymer-based microdevices via injection molding and photolithographic micropatterning protocols.

PubMed

Lee, Dae-Sik; Yang, Haesik; Chung, Kwang-Hyo; Pyo, Hyeon-Bong

2005-08-15

Because of their broad applications in biomedical analysis, integrated, polymer-based microdevices incorporating micropatterned metallic and insulating layers are significant in contemporary research. In this study, micropatterns for temperature sensing and microelectrode sets for electroanalysis have been implemented on an injection-molded thin polymer membrane by employing conventional semiconductor processing techniques (i.e., standard photolithographic methods). Cyclic olefin copolymer (COC) is chosen as the polymer substrate because of its high chemical and thermal stability. A COC 5-in. wafer (1-mm thickness) is manufactured using an injection molding method, in which polymer membranes (approximately 130 microm thick and 3 mm x 6 mm in area) are implemented simultaneously in order to reduce local thermal mass around micropatterned heaters and temperature sensors. The highly polished surface (approximately 4 nm within 40 microm x 40 microm area) of the fabricated COC wafer as well as its good resistance to typical process chemicals makes it possible to use the standard photolithographic and etching protocols on the COC wafer. Gold micropatterns with a minimum 5-microm line width are fabricated for making microheaters, temperature sensors, and microelectrodes. An insulating layer of aluminum oxide (Al2O3) is prepared at a COC-endurable low temperature (approximately 120 degrees C) by using atomic layer deposition and micropatterning for the electrode contacts. The fabricated microdevice for heating and temperature sensing shows improved performance of thermal isolation, and microelectrodes display good electrochemical performances for electrochemical sensors. Thus, this novel 5-in. wafer-level microfabrication method is a simple and cost-effective protocol to prepare polymer substrate and demonstrates good potential for application to highly integrated and miniaturized biomedical devices.

Facet Dependent Disorder in the Pristine High Voltage Lithium-Manganese-Rich Cathode Material

DOE PAGES

Dixit, Hemant M.; Zhou, Wu; Idrobo Tapia, Juan Carlos; ...

2014-11-21

Defects and surface reconstructions are thought to be crucial for the long term stability of high-voltage lithium-manganese-rich cathodes. Unfortunately, many of these defects arise only after electrochemical cycling which occur under harsh conditions making it difficult to fully comprehend the role they play in degrading material performance. Recently, it has been observed that defects are present even in the pristine material. This study, therefore, focuses on examining the nature of the disorder observed in pristine Limore » $$_{1.2}$$Ni$$_{0.175}$$Mn$$_{0.525}$$Co$$_{0.1}$$O$$_2$$ (LNMCO) particles. Using atomic resolution Z-contrast imaging and electron energy-loss spectroscopy measurements we show that there are indeed a significant amount of anti-site defects present in this material; with transition metals substituting on Li metal sites. Furthermore, we find a strong tendency of segregation of these types of defects towards open facets (surfaces perpendicular to the layered arrangement of atoms), rather than closed facets (surfaces parallel to the layered arrangement of atoms). First principles calculations identify anti-site defect pairs of Ni swapping with Li ions as the predominant defect in the material. Furthermore, energetically favorable swapping of Ni on the Mn sites were observed to lead to Mn depletion at open facets. Relatively, low Ni migration barriers also support the notion that Ni are the predominant cause of disorder. These insights suggests that certain facets of the LNMCO particles may be more useful for inhibiting surface reconstruction and improving the stability of these materials through careful consideration of the exposed surface.« less

Method of forming a plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Spengler, Charles J.; Folser, George R.; Vora, Shailesh D.; Kuo, Lewis; Richards, Von L.

1995-01-01

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO.sub.3 particles doped with an element selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by plasma spraying doped LaCrO.sub.3 powder, preferably compensated with chromium as Cr.sub.2 O.sub.3 and/or dopant element, preferably by plasma arc spraying; and, (C) heating the doped and compensated LaCrO.sub.3 layer to about 1100.degree. C. to 1300.degree. C. to provide a dense, substantially gas-tight, substantially hydration-free, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the unselected portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell.

Method of forming a plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Spengler, C.J.; Folser, G.R.; Vora, S.D.; Kuo, L.; Richards, V.L.

1995-06-20

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO{sub 3} particles doped with an element selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by plasma spraying doped LaCrO{sub 3} powder, preferably compensated with chromium as Cr{sub 2}O{sub 3} and/or dopant element, preferably by plasma arc spraying; and, (C) heating the doped and compensated LaCrO{sub 3} layer to about 1100 C to 1300 C to provide a dense, substantially gas-tight, substantially hydration-free, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the unselected portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 6 figs.

Production and Precipitation Hardening of Beta-Type Ti-35Nb-10Cu Alloy Foam for Implant Applications

NASA Astrophysics Data System (ADS)

Mutlu, Ilven; Yeniyol, Sinem; Oktay, Enver

2016-04-01

In this study, beta-type Ti-35Nb-10Cu alloy foams were produced by powder metallurgy method for dental implant applications. 35% Nb was added to stabilize the beta-Ti phase with low Young's modulus. Cu addition enhanced sinterability and gave precipitation hardening capacity to the alloy. Sintered specimens were precipitation hardened in order to enhance the mechanical properties. Electrochemical corrosion behavior of the specimens was examined by electrochemical impedance spectroscopy in artificial saliva. Electrochemical impedance spectroscopy results indicated that the oxide film on the surface of foam is a bi-layer structure consisting of outer porous layer and inner barrier layer. Impedance values of barrier layer were higher than porous layer. Corrosion resistance of specimens decreased at high fluoride concentrations and at low pH of artificial saliva. Corrosion resistance of alloys was slightly decreased with aging. Mechanical properties, microstructure, and surface roughness of the specimens were also examined.

Melanin as an active layer in biosensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piacenti da Silva, Marina, E-mail: marinaness@yahoo.com; Congiu, Mirko, E-mail: congiumat@gmail.com; Oliveira Graeff, Carlos Frederico de, E-mail: graeff@fc.unesp.br

2014-03-15

The development of pH sensors is of great interest due to its extensive application in several areas such as industrial processes, biochemistry and particularly medical diagnostics. In this study, the pH sensing properties of an extended gate field effect transistor (EGFET) based on melanin thin films as active layer are investigated and the physical mechanisms related to the device operation are discussed. Thin films were produced from different melanin precursors on indium tin oxide (ITO) and gold substrates and were investigated by Atomic Force Microscopy and Electrochemical Impedance Spectroscopy. Experiments were performed in the pH range from 2 to 12.more » EGFETs with melanin deposited on ITO and on gold substrates showed sensitivities ranging from 31.3 mV/pH to 48.9 mV/pH, depending on the melanin precursor and the substrate used. The pH detection is associated with specific binding sites in its structure, hydroxyl groups and quinone imine.« less

Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

PubMed

Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

2015-01-01

Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

Layer-by-Layer Assembly of Glucose Oxidase on Carbon Nanotube Modified Electrodes.

PubMed

Suroviec, Alice H

2017-01-01

The use of enzymatically modified electrodes for the detection of glucose or other non-electrochemically active analytes is becoming increasingly common. Direct heterogeneous electron transfer to glucose oxidase has been shown to be kinetically difficult, which is why electron transfer mediators or indirect detection is usually used for monitoring glucose with electrochemical sensors. It has been found, however, that electrodes modified with single or multi-walled carbon nanotubes (CNTs) demonstrate fast heterogeneous electron transfer kinetics as compared to that found for traditional electrodes. Incorporating CNTs into the assembly of electrochemical glucose sensors, therefore, affords the possibility of facile electron transfer to glucose oxidase, and a more direct determination of glucose. This chapter describes the methods used to use CNTs in a layer-by-layer structure along with glucose oxidase to produce an enzymatically modified electrode with high turnover rates, increased stability and shelf-life.

Electrodeposition of hydroxyapatite nanoparticles onto ultra-fine TiO2 nanotube layer by electrochemical reaction in mixed electrolyte.

PubMed

Park, Su-Jung; Jang, Jae-Myung

2011-08-01

Electrochemical depositions of HAp nanoparticles onto Ultra-fine TiO2 nanotube layer were carried out by the electrochemical reaction in mixed electrolyte of 1.6 M (NH4)H2PO4 + 0.8 M NH4F containing 0.15 and 0.25 wt% HAp. The Ca/P ratios of the HAp nanoparticles were evaluated by EDS analysis and their values were 1.53 and 1.66 respectively. The distribution quantity of Ca and P were remained at the middle region of TiO2 nanotube, but the Ti element was mainly stayed at the bottom of barrier layer from the result of line scanning diagram. Especially, adsorbed phosphate ions facilitated nucleation of nanophase calcium phosphate material inside the TiO2 nanotubu layer that resulted in vertical growth of HAp nanoparticles. These surfaces and structures were all effective for biocompatibility from the SBF tests.

Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys

DOEpatents

Ovshinsky, Stanford R.; Fetcenko, Michael A.

1996-01-01

An electrochemical hydrogen storage material comprising: (Base Alloy).sub.a M.sub.b where, Base Alloy is an alloy of Mg and Ni in a ratio of from about 1:2 to about 2:1, preferably 1:1; M represents at least one modifier element chosen from the group consisting of Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, and Ca; b is greater than 0.5, preferably 2.5, atomic percent and less than 30 atomic percent; and a+b=100 atomic percent. Preferably, the at least one modifier is chosen from the group consisting of Co, Mn, Al, Fe, and Cu and the total mass of the at least one modifier element is less than 25 atomic percent of the final composition. Most preferably, the total mass of said at least one modifier element is less than 20 atomic percent of the final composition.

A label-free ultrasensitive electrochemical DNA sensor based on thin-layer MoS2 nanosheets with high electrochemical activity.

PubMed

Wang, Xinxing; Nan, Fuxin; Zhao, Jinlong; Yang, Tao; Ge, Tong; Jiao, Kui

2015-02-15

A label-free and ultrasensitive electrochemical DNA biosensor, based on thin-layer molybdenum disulfide (MoS2) nanosheets sensing platform and differential pulse voltammetry detection, is constructed in this paper. The thin-layer MoS2 nanosheets were prepared via a simple ultrasound exfoliation method from bulk MoS2, which is simpler and no distortion compared with mechanical cleavage and lithium intercalation. Most importantly, this procedure allows the formation of MoS2 with enhanced electrochemical activity. Based on the high electrochemical activity and different affinity toward ssDNA versus dsDNA of the thin-layer MoS2 nanosheets sensing platform, the tlh gene sequence assay can be performed label-freely from 1.0 × 10(-16)M to 1.0 × 10(-10)M with a detection limit of 1.9 × 10(-17)M. Without labeling and the use of amplifiers, the detection method described here not only expands the application of MoS2, but also offers a viable alternative for DNA analysis, which has the priority in sensitivity, simplicity, and costs. Moreover, the proposed sensing platform has good electrocatalytic activity, and can be extended to detect more targets, such as guanine and adenine, which further expands the application of MoS2. Copyright © 2014 Elsevier B.V. All rights reserved.

Materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Simon, Patrice; Gogotsi, Yury

2008-11-01

Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

Materials for electrochemical capacitors.

PubMed

Simon, Patrice; Gogotsi, Yury

2008-11-01

Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

NASA Astrophysics Data System (ADS)

Yang, Hong Bin; Hung, Sung-Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin-Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

2018-02-01

Electrochemical reduction of CO2 to chemical fuel offers a promising strategy for managing the global carbon balance, but presents challenges for chemistry due to the lack of effective electrocatalyst. Here we report atomically dispersed nickel on nitrogenated graphene as an efficient and durable electrocatalyst for CO2 reduction. Based on operando X-ray absorption and photoelectron spectroscopy measurements, the monovalent Ni(i) atomic center with a d9 electronic configuration was identified as the catalytically active site. The single-Ni-atom catalyst exhibits high intrinsic CO2 reduction activity, reaching a specific current of 350 A gcatalyst-1 and turnover frequency of 14,800 h-1 at a mild overpotential of 0.61 V for CO conversion with 97% Faradaic efficiency. The catalyst maintained 98% of its initial activity after 100 h of continuous reaction at CO formation current densities as high as 22 mA cm-2.

Graphene-Composite Carbon Nanofiber-Based Electrodes for Energy Storage Devices

DTIC Science & Technology

2014-04-18

electrochemical supercapacitors . 1. Development of highly conductive graphene composite CNF webs Graphene, a single-atom-thick sheet of sp 2 bonded...electrochemical supercapacitors and evaluated their performance. The capacitance increased with an increase in the amount of MnO2 NWs (duration of the deposition

Electrochemical cell with powdered electrically insulative material as a separator

DOEpatents

Mathers, James P.; Olszanski, Theodore W.; Boquist, Carl W.

1978-01-01

A secondary electrochemical cell includes electrodes separated by a layer of electrically insulative powder. The powder includes refractory materials selected from the oxides and nitrides of metals and metaloids. The powdered refractory material, blended with electrolyte particles, can be compacted in layers with electrode materials to form an integral electrode structure or separately assembled into the cell. The assembled cell is heated to operating temperature leaving porous layers of electrically insulative, refractory particles, containing molten electrolyte between the electrodes.

Method of preparing a powdered, electrically insulative separator for use in an electrochemical cell

DOEpatents

Cooper, Tom O.; Miller, William E.

1978-01-01

A secondary electrochemical cell includes electrodes separated by a layer of electrically insulative powder. The powder includes refractory materials selected from the oxides and nitrides of metals and metaloids. The powdered refractory material, blended with electrolyte particles, is compacted as layers onto an electrode to form an integral electrode structure and assembled into the cell. The assembled cell is heated to its operating temperature leaving porous layers of electrically insulative, refractory particles, containing molten electrolyte between the electrodes.

Screen-printed calcium-birnessite electrodes for water oxidation at neutral pH and an "electrochemical harriman series".

PubMed

Lee, Seung Y; González-Flores, Diego; Ohms, Jonas; Trost, Tim; Dau, Holger; Zaharieva, Ivelina; Kurz, Philipp

2014-12-01

A mild screen-printing method was developed to coat conductive oxide surfaces (here: fluorine-doped tin oxide) with micrometer-thick layers of presynthesized calcium manganese oxide (Ca-birnessite) particles. After optimization steps concerning the printing process and layer thickness, electrodes were obtained that could be used as corrosion-stable water-oxidizing anodes at pH 7 to yield current densities of 1 mA cm(-2) at an overpotential of less than 500 mV. Analyses of the electrode coatings of optimal thickness (≈10 μm) indicated that composition, oxide phase, and morphology of the synthetic Ca-birnessite particles were hardly affected by the screen-printing procedure. However, a more detailed analysis by X-ray absorption spectroscopy revealed small modifications of both the Mn redox state and the structure at the atomic level, which could affect functional properties such as proton conductivity. Furthermore, the versatile new screen-printing method was used for a comparative study of various transition-metal oxides concerning electrochemical water oxidation under "artificial leaf conditions" (neutral pH, fairly low overpotential and current density), for which a general activity ranking of RuO2 >Co3 O4 ≈(Ca)MnOx ≈NiO was observed. Within the group of screened manganese oxides, Ca-birnessite performed better than "Mn-only materials" such as Mn2 O3 and MnO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

PubMed

Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

2012-01-21

Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

Improved Electrochemical Cycling Durability in a Nickel Oxide Double-Layered Film.

PubMed

Hou, Shuai; Zhang, Xiang; Tian, Yanlong; Zhao, Jiupeng; Geng, Hongbin; Qu, Huiying; Zhang, Hangchuan; Zhang, Kun; Wang, Binsheng; Gavrilyuk, Alexander; Li, Yao

2017-11-16

For the first time, a crystalline-amorphous double-layered NiO x film has been prepared by reactive radio frequency magnetron sputtering. This film has exhibited improved electrochemical cycling durability, whereas other electrochromic parameters have been maintained at the required level, namely, a short coloration/bleaching time (0.8 s/1.1 s) and an enhanced transmittance modulation range (62.2 %) at λ=550 nm. Additionally, the double-layered film has shown better reversibility than that of amorphous and crystalline single-layered films. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and pitting corrosion resistance of AISI 4145 steel subjected to massive laser shock peening treatment with different coverage layers

NASA Astrophysics Data System (ADS)

Lu, J. Z.; Han, B.; Cui, C. Y.; Li, C. J.; Luo, K. Y.

2017-02-01

The effects of massive laser shock peening (LSP) treatment with different coverage layers on residual stress, pitting morphologies in a standard corrosive solution and electrochemical corrosion resistance of AISI 4145 steel were investigated by pitting corrosion test, potentiodynamic polarisation test, and SEM observations. Results showed massive LSP treatment can effectively cause an obvious improvement of pitting corrosion resistance of AISI 4145 steel, and increased coverage layer can also gradually improve its corrosion resistance. Massive LSP treatment with multiple layers was shown to influence pitting corrosion behaviour in a standard corrosive solution.

High performance and durability of order-structured cathode catalyst layer based on TiO2@PANI core-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Meng; Yang, Zhaoyi; Wang, Xindong

2017-06-01

In this paper, an order-structured cathode catalyst layer consisting of Pt-TiO2@PANI core-shell nanowire arrays that in situ grown on commercial gas diffusion layer (GDL) are prepared and applied to membrane electrode assembly (MEA) of proton exchange membrane fuel cell (PEMFC). In order to prepare the TiO2@PANI core-shell nanowire arrays with suitable porosity and prominent conductivity, the morphologies of the TiO2 nanoarray and electrochemical polymerization process of aniline are schematically investigated. The MEA with order-structured cathode catalyst layer is assembled in the single cell to evaluate the electrochemical performance and durability of PEMFC. As a result, the PEMFC with order-structured cathode catalyst layer shows higher peak power density (773.54 mW cm-2) than conventional PEMFC (699.30 mW cm-2). Electrochemically active surface area (ECSA) and charge transfer impedance (Rct) are measured before and after accelerated degradation test (ADT), and the corresponding experimental results indicate the novel cathode structure exhibits a better stability with respect to conventional cathode. The enhanced electrochemical performance and durability toward PEMFC can be ascribed to the order-structured cathode nanoarray structure with high specific surface area increases the utilization of catalyst and reduces the tortuosity of transport pathways, and the synergistic effect between TiO2@PANI support and Pt nanoparticles promotes the high efficiency of electrochemical reaction and improves the stability of catalyst. This research provides a facile and controllable method to prepare order-structured membrane electrode with lower Pt loading for PEMFC in the future.

Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments

DOE PAGES

Lopes, Pietro P.; Strmcnik, Dusan; Tripkovic, Dusan; ...

2016-03-07

The development of alternative energy systems for clean production, storage and conversion of energy is strongly dependent on our ability to understand, at atomic-molecular-levels, functional links between activity and stability of electrochemical interfaces. Whereas structure-activity relationships are rapidly evolving, the corresponding structure-stability relationships are still missing. Primarily, this is because there is no adequate experimental approach capable of monitoring in situ stability of well-defined single crystals. Here, by blending the power of Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) connected to a stationary probe to measure in situ and real time dissolution rates of surface atoms (at above 0.4 pg cm-2s-1 levels)more » and a rotating disk electrode method for monitoring simultaneously the kinetic rates of electrochemical reactions in a single unite, it was possible to establish almost “atom-by-atom” the structure-stability-activity relationships for platinum single crystals in both acidic and alkaline environments. Furthermore, we found that the degree of stability is strongly dependent on the coordination of surface atoms (less coordinated yields less stable), the nature of covalent (adsorption of hydroxyl, oxygen atoms and halides species), and non-covalent interactions (interactions between hydrated Li cations and surface oxide), the thermodynamic driving force for Pt complexation (Pt ion speciation in solution) and the nature of the electrochemical reaction (the oxygen reduction/evolution and CO oxidation reactions). Consequently, these findings are opening new opportunities for elucidating key fundamental descriptors that govern both activity and stability trends, that ultimately, will assist to develop real energy conversion and storage systems.« less

Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

PubMed

Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

2015-07-28

The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles.

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials.

PubMed

Acerce, Muharrem; Voiry, Damien; Chhowalla, Manish

2015-04-01

Efficient intercalation of ions in layered materials forms the basis of electrochemical energy storage devices such as batteries and capacitors. Recent research has focused on the exfoliation of layered materials and then restacking the two-dimensional exfoliated nanosheets to form electrodes with enhanced electrochemical response. Here, we show that chemically exfoliated nanosheets of MoS2 containing a high concentration of the metallic 1T phase can electrochemically intercalate ions such as H(+), Li(+), Na(+) and K(+) with extraordinary efficiency and achieve capacitance values ranging from ∼400 to ∼700 F cm(-3) in a variety of aqueous electrolytes. We also demonstrate that this material is suitable for high-voltage (3.5 V) operation in non-aqueous organic electrolytes, showing prime volumetric energy and power density values, coulombic efficiencies in excess of 95%, and stability over 5,000 cycles. As we show by X-ray diffraction analysis, these favourable electrochemical properties of 1T MoS2 layers are mainly a result of their hydrophilicity and high electrical conductivity, as well as the ability of the exfoliated layers to dynamically expand and intercalate the various ions.

Sprayable, Paintable Layer-by-Layer Polyaniline Nanofiber/Graphene Electrodes for Electrochemical Energy Storage

NASA Astrophysics Data System (ADS)

Kwon, Se Ra; Jeon, Ju-Won; Lutkenhus, Jodie

2015-03-01

Sprayable batteries are growing in interest for applications in structural energy storage and power or flexible power. Spray-assisted layer-by-layer (LbL) assembly, in which complementary species are alternately sprayed onto a surface, is particularly amenable toward this application. Here, we report on the fabrication of composite films containing polyaniline nanofibers (PANI NF) and graphene oxide (GO) sheets fabricated via spray-assisted LbL assembly. The resulting films are electrochemical reduced to yield PANI NF/electrochemically reduced graphene (ERGO) electrodes for use as a cathode in non-aqueous energy storage systems. Through the spray-assisted LbL process, the hybrid electrodes could be fabricated 74 times faster than competing dip-assisted LbL assembly. The resulting electrodes are highly porous (0.72 void fraction), and are comprised of 67 wt% PANI NF and 33 wt% ERGO. The sprayed electrodes showed better rate capability, higher specific power, as well as more stable cycle life than dip-assisted LbL electrodes. It is shown here that the spray-assisted LbL approach is well-suited towards the fabrication of paintable electrodes containing polyaniline nanofibers and electrochemically reduced graphene oxide sheets.

A regenerating ultrasensitive electrochemical impedance immunosensor for the detection of adenovirus.

PubMed

Lin, Donghai; Tang, Thompson; Jed Harrison, D; Lee, William E; Jemere, Abebaw B

2015-06-15

We report on the development of a regenerable sensitive immunosensor based on electrochemical impedance spectroscopy for the detection of type 5 adenovirus. The multi-layered immunosensor fabrication involved successive modification steps on gold electrodes: (i) modification with self-assembled layer of 1,6-hexanedithiol to which gold nanoparticles were attached via the distal thiol groups, (ii) formation of self-assembled monolayer of 11-mercaptoundecanoic acid onto the gold nanoparticles, (iii) covalent immobilization of monoclonal anti-adenovirus 5 antibody, with EDC/NHS coupling reaction on the nanoparticles, completing the immunosensor. The immunosensor displayed a very good detection limit of 30 virus particles/ml and a wide linear dynamic range of 10(5). An electrochemical reductive desorption technique was employed to completely desorb the components of the immunosensor surface, then re-assemble the sensing layer and reuse the sensor. On a single electrode, the multi-layered immunosensor could be assembled and disassembled at least 30 times with 87% of the original signal intact. The changes of electrode behavior after each assembly and desorption processes were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. Copyright © 2014 Elsevier B.V. All rights reserved.

Study of oxide surfaces using time of flight positron annihilation induced Auger electron spectroscopy

NASA Astrophysics Data System (ADS)

Nadesalingam, Manori Prasadika

Transition metal oxides (TMOs) exhibit a rich collection of interesting and intriguing properties which can be used for wide variety of applications. In this dissertation, I will discuss the first PAES measurements on vacuum anneal induced changes in the surface layers of Cu2O/Ta, Cu 2O/TCO and oxidized Cu(100) prepared by spray coated, electrochemically deposition and thermal oxidation techniques respectively. PAES measurements on Cu2O/TCO shows that the a very large increase in the intensity of the Cu (M2,3 VV) Auger peak after annealing at 250°C. Similar but significantly smaller changes were observed in the EAES spectra consistent with the fact that PAES is primarily sensitive to the top-most atomic layer due to the fact that the positrons are trapped just outside the surface prior to annihilation while EAES samples several atomic layers. While PAES measurements on oxidized Cu(100) show a large monotonic increase in the intensity of the annihilation induced Cu (M2,3 VV) Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300°C. The intensity then decreases monotonically as the annealing temperature is increase to ˜500°C. These results provide a clear demonstration of the thermal reduction of the copper oxide surface after annealing at 300°C followed by re-oxidation of the copper surface at the higher annealing temperatures presumably due to the diffusion of subsurface oxygen to the surface.

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most successful hydrogen pumping catalysts, comparable to a commercial Pt/C catalyst. Synthesized Pt/C materials were also used as PEMFC catalysts. We found the ALD catalysts with lower platinum loading to be competitive with a commercial fuel cell catalyst, especially when exhibiting similar platinum particle characteristics. The functionalized carbon helped produce smaller and more dispersed platinum particles; however, it encouraged carbon corrosion within an electrode, severing electrical connections and lowering energy production. The most suitable chemistry for competitive Pt/C catalysts was produced by platinum ALD on unmodified carbon using hydrogen as a reactant. ALD is a promising method for fabricating electrocatalysts, which could help fuel cells become an economically viable alternative to fossil fuels.

Electrochemical characterization and control of triple-layer muscles

NASA Astrophysics Data System (ADS)

Otero, Toribio F.; Cortes, Maria T.

2000-06-01

The electrochemical characterization of triple-layers formed by a EPA (Electroactive Polymer)/double-sided tape/EPA, like artificial muscles is described. Those muscles were characterized working under constant potential or under constant current. Due to the electrochemical nature of the electrochemomechanical property, muscles working under constant current produce constant movements, consuming increasing energies at decreasing temperatures, decreasing concentrations of electrolytes or trailing increasing masses. Muscles working at constant potential response with a faster movement if the temperature or the concentration of the electrolyte increase, or if the trailed weight decreases. Specific charges and specific energies were determined for every experimental condition.

Nanomanufacturing of silicon surface with a single atomic layer precision via mechanochemical reactions.

PubMed

Chen, Lei; Wen, Jialin; Zhang, Peng; Yu, Bingjun; Chen, Cheng; Ma, Tianbao; Lu, Xinchun; Kim, Seong H; Qian, Linmao

2018-04-18

Topographic nanomanufacturing with a depth precision down to atomic dimension is of importance for advancement of nanoelectronics with new functionalities. Here we demonstrate a mask-less and chemical-free nanolithography process for regio-specific removal of atomic layers on a single crystalline silicon surface via shear-induced mechanochemical reactions. Since chemical reactions involve only the topmost atomic layer exposed at the interface, the removal of a single atomic layer is possible and the crystalline lattice beneath the processed area remains intact without subsurface structural damages. Molecular dynamics simulations depict the atom-by-atom removal process, where the first atomic layer is removed preferentially through the formation and dissociation of interfacial bridge bonds. Based on the parametric thresholds needed for single atomic layer removal, the critical energy barrier for water-assisted mechanochemical dissociation of Si-Si bonds was determined. The mechanochemical nanolithography method demonstrated here could be extended to nanofabrication of other crystalline materials.

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

PubMed

Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

2016-11-09

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

NASA Astrophysics Data System (ADS)

Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

2014-12-01

Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10-8 S cm-1 at 323 K with ˜0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10-8 S cm-1 at 26 °C (299 K).

Atomic Layer Deposition of Al2O3-Ga2O3 Alloy Coatings for Li[Ni0.5Mn0.3Co0.2]O2 Cathode to Improve Rate Performance in Li-Ion Battery.

PubMed

Laskar, Masihhur R; Jackson, David H K; Guan, Yingxin; Xu, Shenzhen; Fang, Shuyu; Dreibelbis, Mark; Mahanthappa, Mahesh K; Morgan, Dane; Hamers, Robert J; Kuech, Thomas F

2016-04-27

Metal oxide coatings can improve the electrochemical stability of cathodes and hence, their cycle-life in rechargeable batteries. However, such coatings often impose an additional electrical and ionic transport resistance to cathode surfaces leading to poor charge-discharge capacity at high C-rates. Here, a mixed oxide (Al2O3)1-x(Ga2O3)x alloy coating, prepared via atomic layer deposition (ALD), on Li[Ni0.5Mn0.3Co0.2]O2 (NMC) cathodes is developed that has increased electron conductivity and demonstrated an improved rate performance in comparison to uncoated NMC. A "co-pulsing" ALD technique was used which allows intimate and controlled ternary mixing of deposited film to obtain nanometer-thick mixed oxide coatings. Co-pulsing allows for independent control over film composition and thickness in contrast to separate sequential pulsing of the metal sources. (Al2O3)1-x(Ga2O3)x alloy coatings were demonstrated to improve the cycle life of the battery. Cycle tests show that increasing Al-content in alloy coatings increases capacity retention; whereas a mixture of compositions near (Al2O3)0.5(Ga2O3)0.5 was found to produce the optimal rate performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Soumya; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play an essential role in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We present a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This approach incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectricmore » continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Surface morphology and electrochemical studies on polyaniline/CuO nano composites

NASA Astrophysics Data System (ADS)

Ashokkumar, S. P.; Vijeth, H.; Yesappa, L.; Niranjana, M.; Vandana, M.; Basappa, M.; Devendrappa, H.

2018-05-01

An electrochemically synthesized Polyaniline (PANI) and Polyaniline/copper oxide (PCN) nano composite have studied the morphology and electrochemical properties. The composite is characterized by X-ray diffraction (XRD) and surface morphology was studied using FESEM and electrochemical behavior is studied using cyclic voltammetry (CV) technique. The CV curves shows rectangular shaped curve and they have contribution to electrical double layer capacitance (EDCL).

Layered electrode for electrochemical cells

DOEpatents

Swathirajan, Swathy; Mikhail, Youssef M.

2001-01-01

There is provided an electrode structure comprising a current collector sheet and first and second layers of electrode material. Together, the layers improve catalyst utilization and water management.

Graphene-like two-dimensional layered nanomaterials: applications in biosensors and nanomedicine.

PubMed

Yang, Guohai; Zhu, Chengzhou; Du, Dan; Zhu, Junjie; Lin, Yuehe

2015-09-14

The development of nanotechnology provides promising opportunities for various important applications. The recent discovery of atomically-thick two-dimensional (2D) nanomaterials can offer manifold perspectives to construct versatile devices with high-performance to satisfy multiple requirements. Many studies directed at graphene have stimulated renewed interest on graphene-like 2D layered nanomaterials (GLNs). GLNs including boron nitride nanosheets, graphitic-carbon nitride nanosheets and transition metal dichalcogenides (e.g. MoS2 and WS2) have attracted significant interest in numerous research fields from physics and chemistry to biology and engineering, which has led to numerous interdisciplinary advances in nano science. Benefiting from the unique physical and chemical properties (e.g. strong mechanical strength, high surface area, unparalleled thermal conductivity, remarkable biocompatibility and ease of functionalization), these 2D layered nanomaterials have shown great potential in biochemistry and biomedicine. This review summarizes recent advances of GLNs in applications of biosensors and nanomedicine, including electrochemical biosensors, optical biosensors, bioimaging, drug delivery and cancer therapy. Current challenges and future perspectives in these rapidly developing areas are also outlined. It is expected that they will have great practical foundation in biomedical applications with future efforts.

Fabrication of low reflective nanopore-type black Si layer using one-step Ni-assisted chemical etching for Si solar cell application

NASA Astrophysics Data System (ADS)

Takaloo, AshkanVakilipour; Kolahdouz, Mohammadreza; Poursafar, Jafar; Es, Firat; Turan, Rasit; Ki-Joo, Seung

2018-03-01

Nanotextured Si fabricated through metal-assisted chemical etching (MACE) technique exhibits a promising potential for producing antireflective layer for photovoltaic (PV) application. In this study, a novel single-step nickel (Ni) assisted etching technique was applied to produce an antireflective, nonporous Si (black Si) in an aqueous solution containing hydrofluoric acid (HF), hydrogen peroxide (H2O2) and NiSO4 at 40 °C. Field emission scanning electron microscope was used to characterize different morphologies of the textured Si. Optical reflection measurements of samples were carried out to compare the reflectivity of different morphologies. Results indicated that vertical as well as horizontal pores with nanosized diameters were bored in the Si wafer after 1 h treatment in the etching solution containing different molar ratios of H2O2 to HF. Increasing H2O2 concentration in electrochemical etching solution had a considerable influence on the morphology due to higher injection of positive charges from Ni atoms onto the Si surface. Optimized concentration of H2O2 led to formation of an antireflective layer with 2.1% reflectance of incident light.

Graphene-like two-dimensional layered nanomaterials: applications in biosensors and nanomedicine

NASA Astrophysics Data System (ADS)

Yang, Guohai; Zhu, Chengzhou; Du, Dan; Zhu, Junjie; Lin, Yuehe

2015-08-01

The development of nanotechnology provides promising opportunities for various important applications. The recent discovery of atomically-thick two-dimensional (2D) nanomaterials can offer manifold perspectives to construct versatile devices with high-performance to satisfy multiple requirements. Many studies directed at graphene have stimulated renewed interest on graphene-like 2D layered nanomaterials (GLNs). GLNs including boron nitride nanosheets, graphitic-carbon nitride nanosheets and transition metal dichalcogenides (e.g. MoS2 and WS2) have attracted significant interest in numerous research fields from physics and chemistry to biology and engineering, which has led to numerous interdisciplinary advances in nano science. Benefiting from the unique physical and chemical properties (e.g. strong mechanical strength, high surface area, unparalleled thermal conductivity, remarkable biocompatibility and ease of functionalization), these 2D layered nanomaterials have shown great potential in biochemistry and biomedicine. This review summarizes recent advances of GLNs in applications of biosensors and nanomedicine, including electrochemical biosensors, optical biosensors, bioimaging, drug delivery and cancer therapy. Current challenges and future perspectives in these rapidly developing areas are also outlined. It is expected that they will have great practical foundation in biomedical applications with future efforts.

Fabrication of Compositionally and Topographically Complex Robust Tissue Forms by 3D-Electrochemical Compaction of Collagen

PubMed Central

Younesi, Mousa; Islam, Anowarul; Kishore, Vipuil; Panit, Stefi; Akkus, Ozan

2015-01-01

Collagen solutions are phase-transformed to mechanically robust shell structures with curviplanar topographies using electrochemically induced pH gradients. The process enables rapid layer-by-layer deposition of collagen-rich mixtures over the entire field simultaneously to obtain compositionally diverse multilayered structures. In-plane tensile strength and modulus of the electrocompacted collagen sheet samples were 5200 -fold and 2300 -fold greater than that of uncompacted collagen samples. Out of plane compression tests showed 27 -fold and fold increase in compressive stress and 46 -fold increase in compressive modulus compared to uncompacted collagen sheets. Cells proliferated 4.9 times faster, and cellular area spread was 2.7 times greater on compacted collagen sheets. Electrocompaction also resulted in 2.9 times greater focal adhesion area than on regular collagen hydrogel. The reported improvements in the cell-matrix interactions with electrocompaction would serve to expedite the population of electrocompacted collagen scaffolds by cells. The capacity of the method to fabricate nonlinear curved topographies with compositional heterogeneous layers is demonstrated by sequential deposition of collagenhydroxyapatite layer over a collagen layer. The complex curved topography of the nasal structure is replicated by the electrochemical compaction method. The presented electrochemical compaction process is an enabling modality which holds significant promise for reconstruction of a wide spectrum of topographically complex systems such as joint surfaces, craniofacial defects, ears, nose or urogenital forms. PMID:26069162

Novel Electrochemical Raman Spectroscopy Enabled by Water Immersion Objective.

PubMed

Zeng, Zhi-Cong; Hu, Shu; Huang, Sheng-Chao; Zhang, Yue-Jiao; Zhao, Wei-Xing; Li, Jian-Feng; Jiang, Chaoyang; Ren, Bin

2016-10-04

Electrochemical Raman spectroscopy is a powerful molecular level diagnostic technique for in situ investigation of adsorption and reactions on various material surfaces. However, there is still a big room to improve the optical path to meet the increasing request of higher detection sensitivity and spatial resolution. Herein, we proposed a novel electrochemical Raman setup based on a water immersion objective. It dramatically reduces mismatch of the refractive index in the light path. Consequently, significant improvement in detection sensitivity and spatial resolution has been achieved from both Zemax simulation and the experimental results. Furthermore, the thickness of electrolyte layer could be expanded to 2 mm without any influence on the signal collection. Such a thick electrolyte layer allows a much normal electrochemical response during the spectroelectrochemical investigations of the methanol oxidation.

Carbon-Nanotube-Based Electrochemical Double-Layer Capacitor Technologies for Spaceflight Applications

NASA Technical Reports Server (NTRS)

Arepalli, S.; Fireman, H.; Huffman, C.; Maloney, P.; Nikolaev, P.; Yowell, L.; Kim, K.; Kohl, P. A.; Higgins, C. D.; Turano, S. P.

2005-01-01

Electrochemical double-layer capacitors, or supercapacitors, have tremendous potential as high-power energy sources for use in low-weight hybrid systems for space exploration. Electrodes based on single-wall carbon nanotubes (SWCNTs) offer exceptional power and energy performance due to the high surface area, high conductivity, and the ability to functionalize the SWCNTs to optimize capacitor properties. This paper will report on the preparation of electrochemical capacitors incorporating SWCNT electrodes and their performance compared with existing commercial technology. Preliminary results indicate that substantial increases in power and energy density are possible. The effects of nanotube growth and processing methods on electrochemical capacitor performance is also presented. The compatibility of different SWCNTs and electrolytes was studied by varying the type of electrolyte ions that accumulate on the high-surface-area electrodes.

Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

2009-11-01

In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

Preparation of TiO2/boron-doped diamond/Ta multilayer films and use as electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Shi, Chao; Li, Hongji; Li, Cuiping; Li, Mingji; Qu, Changqing; Yang, Baohe

2015-12-01

We report nanostructured TiO2/boron-doped diamond (BDD)/Ta multilayer films and their electrochemical performances as supercapacitor electrodes. The BDD films were grown on Ta substrates using electron-assisted hot filament chemical vapor deposition. Ti metal layers were deposited on the BDD surfaces by radio frequency magnetron sputtering, and nanostructured TiO2/BDD/Ta thin films were prepared by electrochemical etching and thermal annealing. The successful formation of TiO2 and Ta layered nanostructures was demonstrated using scanning electron and transmission electron microscopies. The electrochemical responses of these electrodes were evaluated by examining their use as electrical double-layer capacitors, using cyclic voltammetry, and galvanostatic charge/discharge and impedance measurements. When the TiO2/BDD/Ta film was used as the working electrode with 0.1 M Na2SO4 as the electrolyte, the capacitor had a specific capacitance of 5.23 mF cm-2 at a scan rate of 5 mV s-1 for a B/C ratio of 0.1% w/w. Furthermore, the TiO2/BDD/Ta film had improved electrochemical stability, with a retention of 89.3% after 500 cycles. This electrochemical behavior is attributed to the quality of the BDD, the surface roughness and electrocatalytic activities of the TiO2 layer and Ta nanoporous structures, and the synergies between them. These results show that TiO2/BDD/Ta films are promising as capacitor electrodes for special applications.

Solid oxide electrochemical cell fabrication process

DOEpatents

Dollard, Walter J.; Folser, George R.; Pal, Uday B.; Singhal, Subhash C.

1992-01-01

A method to form an electrochemical cell (12) is characterized by the steps of thermal spraying stabilized zirconia over a doped lanthanum manganite air electrode tube (14) to provide an electrolyte layer (15), coating conductive particles over the electrolyte, pressurizing the outside of the electrolyte layer, feeding halide vapors of yttrium and zirconium to the outside of the electrolyte layer and feeding a source of oxygen to the inside of the electrolyte layer, heating to cause oxygen reaction with the halide vapors to close electrolyte pores if there are any and to form a metal oxide coating on and between the particles and provide a fuel electrode (16).

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOEpatents

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2015-10-27

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

Layered double hydroxide materials coated carbon electrode: New challenge to future electrochemical power devices

NASA Astrophysics Data System (ADS)

Djebbi, Mohamed Amine; Braiek, Mohamed; Namour, Philippe; Ben Haj Amara, Abdesslem; Jaffrezic-Renault, Nicole

2016-11-01

Layered double hydroxides (LDHs) have been widely used in the past years due to their unique physicochemical properties and promising applications in electroanalytical chemistry. The present paper is going to focus exclusively on magnesium-aluminum and zinc-aluminum layered double hydroxides (MgAl & ZnAl LDHs) in order to investigate the property and structure of active cation sites located within the layer structure. The MgAl and ZnAl LDH nanosheets were prepared by the constant pH co-precipitation method and uniformly supported on carbon-based electrode materials to fabricate an LDH electrode. Characterization by powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy revealed the LDH form and well-crystallized materials. Wetting surface properties (hydrophilicity and hydrophobicity) of both prepared LDHs were recorded by contact angle measurement show hydrophilic character and basic property. The electrochemical performance of these hybrid materials was investigated by mainly cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques to identify the oxidation/reduction processes at the electrode/electrolyte interface and the effect of the divalent metal cations in total reactivity. The hierarchy of the modified electrode proves that the electronic conductivity of the bulk material is considerably dependent on the divalent cation and affects the limiting parameter of the overall redox process. However, MgAl LDH shows better performance than ZnAl LDH, due to the presence of magnesium cations in the layers. Following the structural, morphological and electrochemical behavior studies of both synthesized LDHs, the prepared LDH modified electrodes were tested through microbial fuel cell configuration, revealing a remarkable, potential new pathway for high-performance and cost-effective electrode use in electrochemical power devices.

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study

PubMed Central

Jiang, Jin-yang; Wang, Danqian; Chu, Hong-yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-01-01

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed. PMID:28772772

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite.

PubMed

Sevilla, Marta; Ferrero, Guillermo A; Fuertes, Antonio B

2016-11-21

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH 4 ) 2 SO 4 , 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5-1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Conversion of Greenhouse Gas CO2 into Graphene via Molten Salts Electrolysis.

PubMed

Hu, Liwen; Song, Yang; Jiao, Shuqiang; Liu, Yingjun; Ge, Jianbang; Jiao, Handong; Zhu, Jun; Wang, Junxiang; Zhu, Hongmin; Fray, Derek J

2016-03-21

Producing graphene through the electrochemical reduction of CO2 remains a great challenge, which requires precise control of the reaction kinetics, such as diffusivities of multiple ions, solubility of various gases, and the nucleation/growth of carbon on a surface. Here, graphene was successfully created from the greenhouse gas CO2 using molten salts. The results showed that CO2 could be effectively fixed by oxygen ions in CaCl2-NaCl-CaO melts to form carbonate ions, and subsequently electrochemically split into graphene on a stainless steel cathode; O2 gas was produced at the RuO2-TiO2 inert anode. The formation of graphene in this manner can be ascribed to the catalysis of active Fe, Ni, and Cu atoms at the surface of the cathode and the microexplosion effect through evolution of CO in between graphite layers. This finding may lead to a new generation of proceedures for the synthesis of high value-added products from CO2, which may also contribute to the establishment of a low-carbon and sustainable world. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corrosion of aluminium in soft drinks.

PubMed

Seruga, M; Hasenay, D

1996-04-01

The corrosion of aluminium (Al) in several brands of soft drinks (cola- and citrate-based drinks) has been studied, using an electrochemical method, namely potentiodynamic polarization. The results show that the corrosion of Al in soft drinks is a very slow, time-dependent and complex process, strongly influenced by the passivation, complexation and adsorption processes. The corrosion of Al in these drinks occurs principally due to the presence of acids: citric acid in citrate-based drinks and orthophosphoric acid in cola-based drinks. The corrosion rate of Al rose with an increase in the acidity of soft drinks, i.e. with increase of the content of total acids. The corrosion rates are much higher in the cola-based drinks than those in citrate-based drinks, due to the facts that: (1) orthophosphoric acid is more corrosive to Al than is citric acid, (2) a quite different passive oxide layer (with different properties) is formed on Al, depending on whether the drink is cola or citrate based. The method of potentiodynamic polarization was shown as being very suitable for the study of corrosion of Al in soft drinks, especially if it is combined with some non-electrochemical method, e.g. graphite furnace atomic absorption spectrometry (GFAAS).

Sodium alginate: A promising biopolymer for corrosion protection of API X60 high strength carbon steel in saline medium.

PubMed

Obot, I B; Onyeachu, Ikenna B; Kumar, A Madhan

2017-12-15

Sodium alginate (SA), a polysaccharide biopolymer, has been studied as an effective inhibitor against the corrosion of API X60 steel in neutral 3.5% NaCl using gravimetric and electrochemical techniques (OCP, EIS and EFM). The inhibition efficiency of the SA increased with concentration but was lower at higher temperature (70°C). Electrochemical measurements showed that the SA shifted the steel corrosion potential to more positive value and reduced the kinetics of corrosion by forming an adsorbed layer which mitigated the steel surface wetting, based on contact angle measurement. SEM-EDAX was used to confirm the inhibition of SA on API X60 steel surfaces. The SA adsorbs on the steel surface through a physisorption mechanism using its carboxylate oxygen according to UV-vis and ATR-IR measurements, respectively. This phenomena result in decreased localized pitting corrosion of the API X60 steel in 3.5% NaCl solution. Theoretical results using quantum chemical calculations and Monte Carlo simulations provide further atomic level insights into the interaction of SA with steel surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study.

PubMed

Jiang, Jin-Yang; Wang, Danqian; Chu, Hong-Yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-04-14

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed.

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

NASA Astrophysics Data System (ADS)

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. Electronic supplementary information (ESI) available: Fig. S1, AFM image (5 μm × 5 μm) of graphene nanoplate-MnO2 composite obtained at 3 h; Fig. S2, nitrogen adsorption/desorption isotherm of graphene nanoplate-MnO2 composite obtained at 3 h. See DOI: 10.1039/c1nr10229j

Electrochemical fabrication of nanoporous copper films in choline chloride-urea deep eutectic solvent.

PubMed

Zhang, Q B; Abbott, Andrew P; Yang, C

2015-06-14

Nanoporous copper films were fabricated by a facile electrochemical alloying/dealloying process without the need of a template. A deep eutectic solvent made from choline chloride (ChCl) and urea was used with zinc oxide as the metal salt. Cyclic voltammetry was used to characterise the electrochemical reduction of zinc and follow Cu-Zn alloy formation on the copper substrate at elevated temperatures from 353 to 393 K. The alloy formation was confirmed by X-ray diffraction spectra. 3D, open and bicontinuous nanoporous copper films were obtained by in situ electrochemically etching (dealloying) of the zinc component in the Cu-Zn surface alloys at an appropriate potential (-0.4 V vs. Ag). This dealloying process was found to be highly temperature dependent and surface diffusion controlled, which involved the self-assembly of copper atoms at the alloy/electrolyte interface. Additionally, the effects of the deposition parameters, including deposition temperature, current density as well as total charge density on resulting the microstructure were investigated by scanning electron microscopy, and atomic force microscope.

Revisiting the electrochemical impedance spectroscopy of magnesium with online inductively coupled plasma atomic emission spectroscopy.

PubMed

Shkirskiy, Viacheslav; King, Andrew D; Gharbi, Oumaïma; Volovitch, Polina; Scully, John R; Ogle, Kevin; Birbilis, Nick

2015-02-23

The electrochemical impedance of reactive metals such as magnesium is often complicated by an obvious inductive loop with decreasing frequency of the AC polarising signal. The characterisation and ensuing explanation of this phenomenon has been lacking in the literature to date, being either ignored or speculated. Herein, we couple electrochemical impedance spectroscopy (EIS) with online atomic emission spectroelectrochemistry (AESEC) to simultaneously measure Mg-ion concentration and electrochemical impedance spectra during Mg corrosion, in real time. It is revealed that Mg dissolution occurs via Mg(2+) , and that corrosion is activated, as measured by AC frequencies less than approximately 1 Hz approaching DC conditions. The result of this is a higher rate of Mg(2+) dissolution, as the voltage excitation becomes slow enough to enable all Mg(2+) -enabling processes to adjust in real time. The manifestation of this in EIS data is an inductive loop. The rationalisation of such EIS behaviour, as it relates to Mg, is revealed for the first time by using concurrent AESEC. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Differential Electrochemical Conductance Imaging at the Nanoscale.

PubMed

López-Martínez, Montserrat; Artés, Juan Manuel; Sarasso, Veronica; Carminati, Marco; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

2017-09-01

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic-scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current-potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Natural graphene microsheets/sulfur as Li-S battery cathode towards >99% coulombic efficiency of long cycles

NASA Astrophysics Data System (ADS)

Zhang, Yan; Duan, Xiaoyong; Wang, Jie; Wang, Congwei; Wang, Junying; Wang, Jianlong; Wang, Junzhong

2018-02-01

Lithium-sulfur battery receives intense attention owing to its high theoretical energy density. However, poor electrical conductivity of sulfur and poor cycle stability of the battery hinder its application. Here, we report that graphene microsheets prepared from microcrystalline graphite minerals by an electrochemical & mechanical approach work as a special conductive support to load sulfur as the cathode of lithium-sulfur battery. The graphene microsheets have the features of excellent conductivity and low defect, small sheet sizes of <1 μm2 and ≤6 atomic layers as well as natural silicate residue covered. Li-S batteries of graphene microsheets/S as cathode exhibit long-term cyclability and high coulombic efficiency. At 1 C for 2000 cycles, average coulombic efficiency of 99.7% is reached.

Electrochemical preparation of poly(methylene blue)/graphene nanocomposite thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erçarıkcı, Elif; Dağcı, Kader; Topçu, Ezgi

2014-07-01

Highlights: • Poly(MB)/graphene thin films are prepared by a simple electrochemical approach. • Graphene layers in the film show a broad band in visible region of absorbance spectra. • Morphology of composite films indicates both disordered and ordered regions. • XRD reveals that nanocomposite films include rGO layers after electropolymerization process. • Chemically prepared graphene is better than electrochemically prepared graphene for electrooxidation of nitrite. - Abstract: Poly(methylene blue)/graphene nanocomposite thin films were prepared by electropolymerization of methylene blue in the presence of graphene which have been synthesized by two different methods of a chemical oxidation process and an electrochemicalmore » approach. Synthesized nanocomposite thin films were characterized by using cyclic voltammetry, UV–vis. absorption spectroscopy, powder X-ray diffraction, and scanning tunneling microscopy techniques. Electrocatalytical properties of prepared poly(methylene blue)/graphene nanocomposite films were compared toward electrochemical oxidation of nitrite. Under optimized conditions, electrocatalytical effect of nanocomposite films of chemically prepared graphene through electrochemical oxidation of nitrite was better than that of electrochemically prepared graphene.« less

Effect of Sn addition on the corrosion behavior of Ti-7Cu-Sn cast alloys for biomedical applications.

PubMed

Tsao, L C

2015-01-01

The aim of this study was to investigate the effects of Sn content on the microstructure and corrosion resistance of Ti7CuXSn (x=0-5 wt.%) samples. The corrosion tests were carried out in 0.9 wt.% NaCl solution at 25 °C. The electrochemical corrosion behavior of the Ti7CuXSn alloy samples was evaluated using potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and equivalent circuit analysis. The resulting impedance parameters and polarization curves showed that adding Sn improved the electrochemical corrosion behavior of the Ti7CuXSn alloy. The Ti7CuXSn alloy samples were composed of a dual-layer oxide consisting of an inner barrier layer and an outer porous layer. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemically mediated electrodeposition/electropolymerization to yield a glucose microbiosensor with improved characteristics.

PubMed

Chen, Xiaohong; Matsumoto, Norio; Hu, Yibai; Wilson, George S

2002-01-15

A procedure is described that provides for electrochemically mediated deposition of enzyme and a polymer layer permselective for endogenous electroactive species. Electrodeposition was first employed for the direct immobilization of glucose oxidase to produce a uniform, thin, and compact film on a Pt electrode. Electropolymerization of phenol was then employed to form an anti-interference and protective polyphenol film within the enzyme layer. In addition, a stability-reinforcing membrane derived from (3-aminopropyl)trimethoxysilane was constructed by electrochemically assisted cross-linking. This hybrid film outside the enzyme layer contributed to the improved stability and permselectivity. The resulting glucose sensor was characterized by a short response time (<4 s), high sensitivity (1200 nA/mM x cm2), low interference from endogenous electroactive species, and working lifetime of more than 50 days.

Enhanced corrosion resistance of magnesium alloy by a silane-based solution treatment after an in-situ formation of the Mg(OH)2 layer

NASA Astrophysics Data System (ADS)

Gong, Fubao; Shen, Jun; Gao, Runhua; Xie, Xiong; Luo, Xiong

2016-03-01

A novel organic-inorganic Mg(OH)2/silane surface layer has been developed for corrosion protection of AZ31 magnesium alloy. The results of electrochemical impedance spectroscopy (EIS), the immersion tests, Fourier-transform infrared spectroscopy (FTIR) and sellotape tests showed that the Mg(OH)2/silane-based composite surface layer possessed excellent corrosion resistance and very good adhesion due to the formation of Si-O-Mg bond between Mg(OH)2 layer and silane layer. Electrochemical impedance spectroscopy tests results indicated that for the long-term corrosion protection of AZ31 the increase of the curing temperature improved the impedance of the composited layer when the curing temperature was lower than 130 °С. However, the impedance of the composited layer deceased when the curing temperature was more than 130 °С due to the carbonization of the silane layer.

Atomic scale deposition of Pt around Au nanoparticles to achieve much enhanced electrocatalysis of Pt

DOE PAGES

Xi, Zheng; Lv, Haifeng; Erdosy, Daniel P.; ...

2017-05-07

Here, we report an electrochemical method to deposit atomic scale Pt on a 5 nm Au nanoparticle (NP) surface in N 2-saturated 0.5 M H 2SO 4. Furthermore, Pt is provided by the Pt wire counter electrode via one-step Pt wire oxidation, dissolution, and deposition realized by controlled electrochemical scanning. Scanning from 0.6–1.0 V (vs. RHE) for 10 000 cycles gives Au 98.2Pt 1.8, which serves as an excellent catalyst for the formic acid oxidation reaction, showing 41 times higher specific activity (20.19 mA cm -2) and 25 times higher mass activity (10.80 A mg Pt -1) with much bettermore » CO-tolerance and stability than commercial Pt. This work demonstrates a unique strategy to minimize the use of Pt as a catalyst for electrochemical reactions.« less

Atomic scale deposition of Pt around Au nanoparticles to achieve much enhanced electrocatalysis of Pt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xi, Zheng; Lv, Haifeng; Erdosy, Daniel P.

Here, we report an electrochemical method to deposit atomic scale Pt on a 5 nm Au nanoparticle (NP) surface in N 2-saturated 0.5 M H 2SO 4. Furthermore, Pt is provided by the Pt wire counter electrode via one-step Pt wire oxidation, dissolution, and deposition realized by controlled electrochemical scanning. Scanning from 0.6–1.0 V (vs. RHE) for 10 000 cycles gives Au 98.2Pt 1.8, which serves as an excellent catalyst for the formic acid oxidation reaction, showing 41 times higher specific activity (20.19 mA cm -2) and 25 times higher mass activity (10.80 A mg Pt -1) with much bettermore » CO-tolerance and stability than commercial Pt. This work demonstrates a unique strategy to minimize the use of Pt as a catalyst for electrochemical reactions.« less

Electrocatalysis-induced elasticity modulation in a superionic proton conductor probed by band-excitation atomic force microscopy.

PubMed

Papandrew, A B; Li, Q; Okatan, M B; Jesse, S; Hartnett, C; Kalinin, S V; Vasudevan, R K

2015-12-21

Variable temperature band-excitation atomic force microscopy in conjunction with I-V spectroscopy was used to investigate the crystalline superionic proton conductor CsHSO4 during proton exchange induced by a Pt-coated conductive scanning probe. At a sample temperature of 150 °C and under an applied bias <1 V, reduction currents of up to 1 nA were observed. Simultaneously, we show that the electrochemical reactions are accompanied by a reversible decrease in the elastic modulus of CsHSO4, as seen by a contact resonance shift, and find evidence for superplasticity during scanning. These effects were not observed in the room-temperature phase of CsHSO4 or in the case of catalytically inactive conductive probes, proving the utility of this technique for monitoring electrochemical processes on the nanoscale, as well as the use of local contact stiffness as a sensitive indicator of electrochemical reactions.

Lightweight, durable lead-acid batteries

DOEpatents

Lara-Curzio, Edgar [Lenoir City, TN; An, Ke [Knoxville, TX; Kiggans, Jr., James O.; Dudney, Nancy J [Knoxville, TN; Contescu, Cristian I [Knoxville, TN; Baker, Frederick S [Oak Ridge, TN; Armstrong, Beth L [Clinton, TN

2011-09-13

A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

Lightweight, durable lead-acid batteries

DOEpatents

Lara-Curzio, Edgar; An, Ke; Kiggans, Jr., James O; Dudney, Nancy J; Contescu, Cristian I; Baker, Frederick S; Armstrong, Beth L

2013-05-21

A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

Thermally conductive lithium ion electrodes and batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shevchenko, Elena; Sumant, Anirudha V.; Balandin, Alexander

A thermally conductive electrochemical cell comprises a lithium ion-containing liquid electrolyte contacting a cathode and anode. The cathode and anode are in the form of electroactive sheets separated from each other by a membrane that is permeable to the electrolyte. One or more of the cathode and anode comprises two or more layers of carbon nanotubes, one of which layers includes electrochemically active nanoparticles and/or microparticles disposed therein or deposited on the nanotubes thereof. The majority of the carbon nanotubes in each of the layers are oriented generally parallel to the layers. Optionally, one or more of the layers includesmore » an additional carbon material such as graphene, nanoparticulate diamond, microparticulate diamond, and a combination thereof.« less

Sol-gel derived electrode materials for supercapacitor applications

NASA Astrophysics Data System (ADS)

Lin, Chuan

1998-12-01

Electrochemical capacitors have been receiving increasing interest in recent years for use in energy storage systems because of their high energy and power density and long cycle lifes. Possible applications of electrochemical capacitors include high power pulsed lasers, hybrid power system for electric vehicles, etc. In this dissertation, the preparation of electrode materials for use as electrochemical capacitors has been studied using the sol-gel process. The high surface area electrode materials explored in this work include a synthetic carbon xerogel for use in a double-layer capacitor, a cobalt oxide xerogel for use in a pseudocapacitor, and a carbon-ruthenium xerogel composite, which utilizes both double-layer and faradaic capacitances. The preparation conditions of these materials were investigated in detail to maximize the surface area and optimize the pore size so that more energy could be stored while minimizing mass transfer limitations. The microstructures of the materials were also correlated with their performance as electrochemical capacitors to improve their energy and power densities. Finally, an idealistic mathematical model, including both double-layer and faradaic processes, was developed and solved numerically. This model can be used to perform the parametric studies of an electrochemical capacitor so as to gain a better understanding of how the capacitor works and also how to improve cell operations and electrode materials design.

Development and characterization of an electrochemical sensor for furosemide detection based on electropolymerized molecularly imprinted polymer.

PubMed

Kor, Kamalodin; Zarei, Kobra

2016-01-01

A novel electrochemical sensor based on a molecularly imprinted polymer, poly(o-phenylenediamine) (PoPD), has been developed for selective and sensitive detection of furosemide. The sensor was prepared by incorporating of furosemide as template molecules during the electropolymerization of o-phenylenediamine on a gold electrode. To develop the molecularly imprinted polymer (MIP), the template molecules were removed from the modified electrode's surface by washing it with 0.25 mol L(-1) NaOH solution. The imprinted layer was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). The sensor's preparation conditions including furosemide concentration, the number of CV cycles in the electropolymerization process, extraction solution of the template from the imprinted film, the incubation time and the pH level were optimized. The incubation of the MIP-modified electrode, with respect to furosemide concentration, resulted in a suppression of the K4[Fe(CN)6] oxidation process. Under the optimal experimental conditions, the response of the imprinted sensor was linear in the range of 1.0×10(-7)-7.0×10(-6) mol L(-1) of furosemide. The detection limit was obtained as 7.0×10(-8) mol L(-1) for furosemide by using this sensor. The sensor was successfully used to determine the furosemide amount in the tablet and in human urine samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

A novel electrochemical immunosensor based on Au nanoparticles and horseradish peroxidase signal amplification for ultrasensitive detection of α-fetoprotein.

PubMed

Lu, Dingqiang; Xu, Qiuda; Pang, Guangchang; Lu, Fuping

2018-06-05

An electrochemical double-layer Au nanoparticle membrane immunosensor was developed using an electrochemical biosensing signal amplification system with Au nanoparticles, thionine, chitosan, and horseradish peroxidase, which was fabricated using double self-adsorption of Au nanoparticle sol followed by anti-α-fetoprotein Balb/c mouse monoclonal antibody adsorption. The AuNPs sol was characterized by spectrum scanning and transmission electron microscopy. The immunosensor was characterized by atomic force microscopy, cyclic voltammetry, and alternating-current impedance during each stage of adsorption and assembly. The amperometric I-t curve method was used to measure α-fetoprotein (AFP) diluted in phosphate buffered saline. The result indicated a wide linear range, and the change rate of steady-current before and after immune response had linear correlation within the range 0.1-10 4  pg/mL AFP. The current change rate equation was △I = 5.82334 lgC + 37.01195 (R 2  = 0.9922). The lowest limit of detection was 0.03 pg/mL (S/N = 3), and the reproducibility of the sensor was good. Additionally, the sensor could be stably stored above phosphate buffered saline at 4 °C for more than 24 days. More importantly, the sensor is label-free, reagentless and low fouling, making it capable of assaying AFP in real serum samples without suffering from significant interference or biofouling.

Observation of Electron-Beam-Induced Phase Evolution Mimicking the Effect of the Charge–Discharge Cycle in Li-Rich Layered Cathode Materials Used for Li Ion Batteries

DOE PAGES

Lu, Ping; Yan, Pengfei; Romero, Eric; ...

2015-01-27

Capacity loss, and voltage decrease upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[Li xMn yTM 1-x-y]O 2, TM = Ni, Co or Fe) have recently been attributed to the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li 0.2Ni 0.2Mn 0.6]O 2 (LNMO) particles, which are identical to those reported due to the charge-discharge cycle butmore » are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by electron dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LNMO is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. The observation through this study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

Measurements of stretch lengths of gold mono-atomic wires covered with 1,6-hexanedithiol in 0.1 M NaClO4 with an electrochemical scanning tunneling microscope.

PubMed

Sun, Jian; Akiba, Uichi; Fujihira, Masamichi

2008-09-01

Stretch lengths of pure gold mono-atomic wires have been studied recently with an electrochemical scanning tunneling microscope (STM). Here, we will report a study of stretch lengths of gold mono-atomic wires with and without 1,6-hexanedithiol (HDT) using the STM break-junction method. First, the stretch length was measured as a function of electrode potentials of a bare Au(111) substrate and a gold STM tip in a 0.1 M NaClO4 aqueous solution. Second, a self-assembled monolayer (SAM) was fabricated on an Au(111) substrate by dipping the substrate into a 1 mM HDT ethanol solution. At last, we measured the stretch length of gold mono-atomic wires on a substrate covered with the SAM in place of the bare Au(111) substrate. We compared the electrode potential dependence of the stretch lengths of gold mono-atomic wires covered with and without HDT. We will discuss the effect of the electrode potential on the stretch lengths by taking account of electrocapillarity of gold mono-atomic wires.

The effect of an atomically deposited layer of alumina on NiO in P-type dye-sensitized solar cells.

PubMed

Natu, Gayatri; Huang, Zhongjie; Ji, Zhiqiang; Wu, Yiying

2012-01-10

We present a systematic investigation of the fundamental effects of an atomically deposited alumina (AlO(x)H(y)) onto the NiO films in p-type dye-sensitized solar cells (p-DSCs). With P1 as the sensitizing dye and 0.1 M I(2) and 1.0 M LiI in 3-methoxypropionitrile as the electrolyte, one atomic layer deposition (ALD) cycle of alumina was used to achieve a 74% increase in the overall conversion efficiency of a NiO-based DSC. The open circuit voltage of the cells increased from 0.11 to 0.15 V, and the short circuit current density increased from 0.83 to 0.95 mA/cm(2). Adsorption isotherm studies were performed to show that the amount of dye adsorbed on the NiO-alumina film is slightly lower than the amount adsorbed on the nontreated NiO film. The increased J(sc) was therefore assigned to the increased efficiency of carrier collection at the semiconductor-FTO interface. Our study of the photocurrent onset potentials of NiO and NiO-alumina films with the chopped light measurement technique showed no definitive difference in the onset potential values. However, the DSCs based on NiO-alumina showed a higher recombination resistance value from the electrochemical impedance studies and a higher diode ideality factor from the V(oc) versus ln(light intensity) plots as compared to the DSCs based on untreated NiO. It has thus been established that the increase in V(oc) upon alumina treatment arises due to a higher resistance for electron-hole recombination across NiO surface locally.

Surfactant-assisted electrochemical deposition of α-cobalt hydroxide for supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Ting; Jiang, Hao; Ma, Jan

A N-methylpyrrolidone (NMP) assisted electrochemical deposition route has been developed to realize the synthesis of a dense α-Co(OH) 2 layered structure, which is composed of nanosheets, each with a thickness of 10 nm. The capacitive characteristics of the as-obtained α-Co(OH) 2 are investigated by means of cyclic voltammetry (CV), charge/discharge characterization, and electrochemical impedance spectroscopy (EIS), in 1 M KOH electrolyte. The results indicate that α-Co(OH) 2 prepared in the presence of 20 vol.% NMP has denser and thin layered structure which promotes an increased surface area and a shortened ion diffusion path. The as-prepared α-Co(OH) 2 shows better electrochemical performance with specific capacitance of 651 F g -1 in a potential range of -0.1 to 0.45 V. These findings suggest that the surfactant-assisted electrochemical deposition is a promising process for building densely packed material systems with enhanced properties, for application in supercapacitors.

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

PubMed Central

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

2016-01-01

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE PAGES

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

2016-11-18

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Chemical splitting of multiwalled carbon nanotubes to enhance electrochemical capacitance for supercapacitors

NASA Astrophysics Data System (ADS)

Li, Xinlu; Li, Tongtao; Zhang, Xinlin; Zhong, Qineng; Li, Hongyi; Huang, Jiamu

2014-06-01

Multiwalled carbon nanotubes (MWCNTs) were chemically split and self-assembled to a flexible porous paper made of graphene oxide nanoribbons (GONRs). The morphology and microstructure of the pristine MWCNTs and GONRs were analyzed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy. And the specific surface area and porosity structure were measured by N2 adsorption-desorption. The longitudinally split MWCNTs show an enhancement in specific capacitance from 21 F g-1 to 156 F g-1 compared with the pristine counterpart at 0.1 A g-1 in a 6 M KOH aqueous electrolytes. The electrochemical experiments prove that the chemical splitting of MWCNTs will make inner carbon layers opened and exposed to electrochemical double layers, which can effectively improve the electrochemical capacitance for supercapacitors.

Performance of carbon material derived from starch mixed with flame retardant as electrochemical capacitor

NASA Astrophysics Data System (ADS)

Tsubota, Toshiki; Morita, Masaki; Murakami, Naoya; Ohno, Teruhisa

2014-12-01

Carbon materials derived from starch with an added flame retardant, such as melamine polyphosphate, melamine sulfate, guanylurea phosphate, or guanidine phosphate, were synthesized for investigating the performance as the electrode of an electrochemical capacitor. The yield after the heat treatment of the carbonization reaction increased by the addition of these flame retardants up to 800 °C. Although both the specific surface area and electrical resistivity are almost independent of the addition of the flame retardants, the capacitance values are improved with the addition of the flame retardants. The nitrogen atoms derived from the flame retardants are introduced to some extent into the synthesized carbon material. Moreover, the phosphorous atoms or the sulfur atoms derived from the flame retardants are doped into the synthesized carbon material. The method applied in this study, that is, the addition of flame retardants before the carbonization process can be used for the doping of the hetero atom such as N, P and S into the carbon material.

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

2014-03-01

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal preferential structures and symmetries. The relevant statistical techniques including k-means clustering, principal component analysis, and Baesian unmixing are briefly intriduced. This approach is illustrated for several systems, including chemical phase identification, mapping ferroic variants, and probing topological and structural defects, and provides real space view on surface atomic processes. Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences (AK, SJ), a DOE-BES user facility.

A new methodology for the determination of enzyme activity based on carbon nanotubes and glucose oxidase.

PubMed

Yeşiller, Gülden; Sezgintürk, Mustafa Kemal

2015-11-10

In this research, a novel enzyme activity analysis methodology is introduced as a new perspective for this area. The activity of elastase enzyme, which is a digestive enzyme mostly of found in the digestive system of vertebrates, was determined by an electrochemical device composed of carbon nanotubes and a second enzyme, glucose oxidase, which was used as a signal generator enzyme. In this novel methodology, a complex bioactive layer was constructed by using carbon nanotubes, glucose oxidase and a supporting protein, gelatin on a solid, conductive substrate. The activity of elastase was determined by monitoring the hydrolysis rate of elastase enzyme in the bioactive layer. As a result of this hydrolysis of elastase, glucose oxidase was dissociated from the bioactive layer, and following this the electrochemical signal due to glucose oxidase was decreased. The progressive elastase-catalyzed digestion of the bioactive layer containing glucose oxidase decreased the layer's enzymatic efficiency, resulting in a decrease of the glucose oxidation current as a function of the enzyme activity. The ratio of the decrease was correlated to elastase activity level. In this study, optimization experiments of bioactive components and characterization of the resulting new electrochemical device were carried out. A linear calibration range from 0.0303U/mL to 0.0729U/mL of elastase was reported. Real sample analyses were also carried out by the new electrochemical device. Copyright © 2015 Elsevier B.V. All rights reserved.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doe, Robert E.; Downie, Craig M.; Fischer, Christopher

2016-01-19

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Synthesis and electrochemical property of few-layer molybdenum disulfide nanosheets

NASA Astrophysics Data System (ADS)

Fu, Yanjue; Wang, Chunrui; Wang, Linlin; Peng, Xia; Wu, Binhe; Sun, Xingqu; Chen, Xiaoshuang

2016-12-01

Large-scale few-layer MoS2 nanosheets have been fabricated via a simple hydrothermal route using molybdenum powder as precursors. The as-prepared MoS2 samples were characterized by X-ray powder diffraction (XRD) analysis, transmission electron microscopy (TEM), and Raman and photoluminescence (PL) spectral analyses at room temperature. The results confirm that the as-prepared MoS2 displays a sheet-like morphology with a thickness of few (bi- to tri-) layers. Electrochemical measurements showed that the as-prepared few-layer MoS2 exhibited the highest reversible capacity of 1127 mAh g-1 and a stable reversible capacity of 1057 mAh g-1 after 30 cycles.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher

2016-07-26

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Method for improving the durability of ion insertion materials

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Cheong, Hyeonsik M.

2002-01-01

The invention provides a method of protecting an ion insertion material from the degradative effects of a liquid or gel-type electrolyte material by disposing a protective, solid ion conducting, electrically insulating, layer between the ion insertion layer and the liquid or gel-type electrolyte material. The invention further provides liquid or gel-type electrochemical cells having improved durability having a pair of electrodes, a pair of ion insertion layers sandwiched between the pair of electrodes, a pair of solid ion conducting layers sandwiched between the ion insertion layers, and a liquid or gel-type electrolyte material disposed between the solid ion conducting layers, where the solid ion conducting layer minimizes or prevents degradation of the faces of the ion insertion materials facing the liquid or gel-type electrolyte material. Electrochemical cells of this invention having increased durability include secondary lithium batteries and electrochromic devices.

An Electrochemical Experiment Using an Optically Transparent Thin Layer Electrode

ERIC Educational Resources Information Center

DeAngelis, Thomas P.; Heineman, William R.

1976-01-01

Describes a unified experiment in which an optically transparent thin layer electrode is used to illustrate the techniques of thin layer electrochemistry, cyclic voltammetry, controlled potential coulometry, and spectroelectrochemistry. (MLH)

Lithium metal protected by atomic layer deposition metal oxide for high performance anodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Lin; Connell, Justin G.; Nie, Anmin

We present that lithium metal is a highly desirable anode material for lithium batteries due to its extremely high theoretical capacity (3860 mA h g -1), low potential (-3.04 V versus standard hydrogen electrode), and low density (0.534 g cm -3). However, dendrite growth during cycling and low coulombic efficiency, resulting in safety hazards and fast battery fading, are huge barriers to commercialization. Herein, we used atomic layer deposition (ALD) to prepare conformal, ultrathin aluminum oxide coatings on lithium. We investigated the growth mechanism during Al 2O 3 ALD on lithium by in situ quartz crystal microbalance and found largermore » growth than expected during the initial cycles. We also discovered that the ALD Al 2O 3 enhances the wettability of the Li surface towards both carbonate and ether electrolytes, leading to uniform and dense SEI formation and reduced electrolyte consumption during battery operation. Scanning electron microscopy verified that the bare Li surfaces become rough and dendritic after electrochemical cycling, whereas the ALD Al 2O 3 coated Li surfaces remain smooth and uniform. Analysis of the Li surfaces after cycling using X-ray photoelectron spectroscopy and in situ transmission electron microscopy revealed that the ALD Al 2O 3 coating remains intact during electrochemical cycling, and that Li ions diffuse through the coating and deposit on the underlying Li. Coin cell testing demonstrated more than two times longer cycling life for the ALD Al 2O 3 protected Li, and a coulombic efficiency as high as ~98% at a practical current rate of 1 mA cm -2. More significantly, when the electrolyte volume was reduced from 20 to 5 μL, the stabilizing effect of the ALD coating became even more pronounced and the cycling life was around four times longer. Finally, these results indicate that ALD Al 2O 3 coatings are a promising strategy to stabilize Li anodes for high performance energy storage devices such as Li–S batteries.« less

Lithium metal protected by atomic layer deposition metal oxide for high performance anodes

DOE PAGES

Chen, Lin; Connell, Justin G.; Nie, Anmin; ...

2017-05-26

We present that lithium metal is a highly desirable anode material for lithium batteries due to its extremely high theoretical capacity (3860 mA h g -1), low potential (-3.04 V versus standard hydrogen electrode), and low density (0.534 g cm -3). However, dendrite growth during cycling and low coulombic efficiency, resulting in safety hazards and fast battery fading, are huge barriers to commercialization. Herein, we used atomic layer deposition (ALD) to prepare conformal, ultrathin aluminum oxide coatings on lithium. We investigated the growth mechanism during Al 2O 3 ALD on lithium by in situ quartz crystal microbalance and found largermore » growth than expected during the initial cycles. We also discovered that the ALD Al 2O 3 enhances the wettability of the Li surface towards both carbonate and ether electrolytes, leading to uniform and dense SEI formation and reduced electrolyte consumption during battery operation. Scanning electron microscopy verified that the bare Li surfaces become rough and dendritic after electrochemical cycling, whereas the ALD Al 2O 3 coated Li surfaces remain smooth and uniform. Analysis of the Li surfaces after cycling using X-ray photoelectron spectroscopy and in situ transmission electron microscopy revealed that the ALD Al 2O 3 coating remains intact during electrochemical cycling, and that Li ions diffuse through the coating and deposit on the underlying Li. Coin cell testing demonstrated more than two times longer cycling life for the ALD Al 2O 3 protected Li, and a coulombic efficiency as high as ~98% at a practical current rate of 1 mA cm -2. More significantly, when the electrolyte volume was reduced from 20 to 5 μL, the stabilizing effect of the ALD coating became even more pronounced and the cycling life was around four times longer. Finally, these results indicate that ALD Al 2O 3 coatings are a promising strategy to stabilize Li anodes for high performance energy storage devices such as Li–S batteries.« less

Electrochemically Promoted Organic Isomerization Reactions at Polymer Electrolyte Fuel Cell Cathodes

DTIC Science & Technology

2011-01-04

fuel cells ( PEMFCs ) incorporate an ionomer membrane (e.g., Nafion 117) for support of electro- catalytic layers and proton conduction between the...central to PEMFC electrocatalysis. For example, a spin coated Nafion layer on polycrystalline Pt enhances electrocatalysis.7,8 Little is known about...CO Poisoning Effect in PEMFCs Operational at Temperatures up to 200°C. Journal of the Electrochemical Society, 2003. 150(12): p. A1599-A1605. 21

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Ping; Yan, Pengfei; Romero, Eric

Capacity loss, and voltage decrease upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[Li xMn yTM 1-x-y]O 2, TM = Ni, Co or Fe) have recently been attributed to the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li 0.2Ni 0.2Mn 0.6]O 2 (LNMO) particles, which are identical to those reported due to the charge-discharge cycle butmore » are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by electron dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LNMO is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. The observation through this study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Ping; Yan, Pengfei; Romero, Eric

Capacity loss, and voltage fade upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[LixMnyTM1-x-y]O2 , TM = Ni, Co or Fe) have recently been identified to be correlated to the gradual phase transformation, featuring the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5 nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li0.2Ni0.2Mn0.6]O2 (LMR) particles, which are identical to those reported due to the charge-dischargemore » cycle but are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200 kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by energy dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LMR is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. This study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

Interfacial characteristics of propylene carbonate and validation of simulation models for electrochemical applications

NASA Astrophysics Data System (ADS)

You, Xinli

Supercapacitors have occupy an indispensable role in today's energy storage systems due to their high power density and long life. The introduction of car- bon nanotube (CNT) forests as electrode offers the possibility of nano-scale design and high capacitance. We have performed molecular dynamics simulations on a CNT forest-based electrochemical double-layer capacitor (EDLC) and a widely used electrolyte solution (tetra-ethylammonium tetra-fluoroborate in propylene carbonate, TEABF4 /PC). We compare corresponding primitive model and atomically detailed model of TEABF4 /P, emphasizing the significance of ion clustering in electrolytes. The molecular dynamic simulation results suggests that the arrangement of closest neigh- bors leads to the formation of cation-anion chains or rings. Fuoss's discussion of ion-pairing model provides the approximation for a primitive model of 1-1 electrolyte is not broadly satisfactory for both primitive and atomically detailed cases. A more general Poisson statistical assumption is shown to be satisfactory when coordina- tion numbers are low, as is likely to be the case when ion-pairing initiates. We examined the Poisson-based model over a range of concentrations for both models of TEABF4 /P, and the atomically detailed model results identified solvent-separated nearest-neighbor ion-pairs. Large surface areas plays an essential role in nanomaterial properties, which calls for an accurate description of interfaces through modeling. We studied propylene carbonate, a widely used solvent in EDLC systems. PC wets graphite with a contact angle of 31°. The MD simulation model reproduced this contact angle after reduction 40% of the strength of graphite-C atom Lennard-Jones interactions with the solvent. The critical temperature of PC was accurately evaluated by extrapolating the PC liquid-vapor surface tensions. PC molecules tend to lie flat on the PC liquid-vapor surface, and project the propyl carbon toward the vapor phase. Liquid PC simulations also provide basic data for construction of accurate information to assist in device- level modeling of EDLCs. The most serious uncertainty with previous simulations of CNT based EDLCs was definition of the actual composition of the pores. Therefore, direct simulations of filling of CNT forest based electrochemical double-layer capacitors with TEABF4 /P solution was performed. Those calculation characterize the charging and discharg- ing process, including rates of charging responses, the possibility of bubble forma- tion, and kinetic properties with confinement. The mobilities of ions and solvent was investigated through mean square displacement (MSD) and velocity autocorrela- tion functions (VACF). The memory kernel was extracted from VACF by discretized linear-equation solving and a specialized Fourier transform method, results implies the existence of dielectric friction. With the interest in chemical features of EDLCs, a multi-scale theory was de- veloped to embed high resolution ab initio molecular dynamics (AIMD) methods into studies of EDLCs. This theory was based on McMillan-Mayer theory, potential dis- tribution approach, and quasi-chemical theory. The quasi-chemical theory allow us to break-up the free energies into packing, outer-shell and chemical contributions, where the last part can be done by AIMD directly. For the primitive model of TEABF4 /P, Gaussian statistical models are effective for these outer-shell contributions. And the Gaussian approximation is more efficient than the Bennett method in achieving an accurate mean activity coefficient.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Price, Carson

2015-10-01

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.

Self-limited growth of Si on B atomic-layer formed Ge(1 0 0) by ultraclean low-pressure CVD system

NASA Astrophysics Data System (ADS)

Yokogawa, Takashi; Ishibashi, Kiyohisa; Sakuraba, Masao; Murota, Junichi; Inokuchi, Yasuhiro; Kunii, Yasuo; Kurokawa, Harushige

2008-07-01

Utilizing BCl 3 reaction on Ge(1 0 0) and subsequent Si epitaxial growth by SiH 4 reaction at 300 °C, B atomic-layer doping in Si/Ge(1 0 0) heterostructure was investigated. Cl atoms on the B atomic-layer formed Ge(1 0 0) scarcely affect upon the SiH 4 reaction. It is also found that Si atom amount deposited by SiH 4 reaction on Ge(1 0 0) is effectively enhanced by the existence of B atomic layer and the deposition rate tends to decrease at around 2-3 atomic layers which is three times larger than that in the case without B. The results of angle-resolved X-ray photoelectron spectroscopy show that most B atoms are incorporated at the heterointerface between the Si and Ge.

Epitaxial Growth of Rhenium with Sputtering

DTIC Science & Technology

2016-05-06

corresponds to two atomic Re layers , considering that the c-axis lattice constant of the tri- atomic layered hcp Re unit cell is ~4.5 Å. Frequently, two...Å) corresponds to two Re atomic layers since the c-axis lattice constant of hcp Re, which is composed of three Re atomic layers , is ~4.5 Å...The growth starts in a three dimensional mode but transforms into two dimensional mode as the film gets thicker. With a thin (~2 nm) seed layer

Electrochemical performance of Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 cermet anodes with functionally graded structures for intermediate-temperature solid oxide fuel cell fueled with syngas

NASA Astrophysics Data System (ADS)

Miyake, Michihiro; Iwami, Makoto; Takeuchi, Mizue; Nishimoto, Shunsuke; Kameshima, Yoshikazu

2018-06-01

The electrochemical performance of layered Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 (GDC) cermet anodes is investigated for intermediate-temperature solid oxide fuel cells (IT-SOFCs) at 600 °C using humidified (3% H2O) model syngas with a molar ratio of H2/CO = 3/2 as the fuel. From the results obtained, the electrochemical performance of the functionally graded multi-layered anodes is found to be superior to the mono-layered anodes. The test cell with a bi-layered anode consisting of 100 mass% Ni0.8Cu0.2/0 mass% GDC (10M/0E) and 70 mass% Ni0.8Cu0.2/30 mass% GDC (7M/3E) exhibits high power density. The test cell with a tri-layered anode consisting of 10M/0E, 7M/3E, and 50 mass% Ni0.8Cu0.2/50 mass% GDC (5M/5E) exhibits an even higher power density, suggesting that 10M/0E and 5M/5E layers contribute to the current collecting part and active part, respectively.

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery.

PubMed

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-06-07

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.

Fabrication of SrTiO3 Layer on Pt Electrode for Label-Free Capacitive Biosensors

PubMed Central

Carapella, Giovanni; Pilloton, Roberto; Di Matteo, Marisa

2018-01-01

Due to their interesting ferroelectric, conductive and dielectric properties, in recent years, perovskite-structured materials have begun to attract increasing interest in the biosensing field. In this study, a strontium titanate perovskite layer (SrTiO3) has been synthesized on a platinum electrode and exploited for the development of an impedimetric label-free immunosensor for Escherichia coli O157:H7 detection. The electrochemical characterization of the perovskite-modified electrode during the construction of the immunosensor, as well as after the interaction with different E. coli O157:H7 concentrations, showed a reproducible decrease of the total capacitance of the system that was used for the analytical characterization of the immunosensor. Under optimized conditions, the capacitive immunosensor showed a linear relationship from to 1 to 7 log cfu/mL with a low detection limit of 1 log cfu/mL. Moreover, the atomic force microscopy (AFM) technique underlined the increase in roughness of the SrTiO3-modified electrode surface after antibody immobilization, as well as the effective presence of cells with the typical size of E. coli. PMID:29547521

Ferromagnetic resonance in low interacting permalloy nanowire arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raposo, V.; Zazo, M.; Flores, A. G.

2016-04-14

Dipolar interactions on magnetic nanowire arrays have been investigated by various techniques. One of the most powerful techniques is the ferromagnetic resonance spectroscopy, because the resonance field depends directly on the anisotropy field strength and its frequency dependence. In order to evaluate the influence of magnetostatic dipolar interactions among ferromagnetic nanowire arrays, several densely packed hexagonal arrays of NiFe nanowires have been prepared by electrochemical deposition filling self-ordered nanopores of alumina membranes with different pore sizes but keeping the same interpore distance. Nanowires’ diameter was changed from 90 to 160 nm, while the lattice parameter was fixed to 300 nm, which wasmore » achieved by carefully reducing the pore diameter by means of Atomic Layer Deposition of conformal Al{sub 2}O{sub 3} layers on the nanoporous alumina templates. Field and frequency dependence of ferromagnetic resonance have been studied in order to obtain the dispersion diagram which gives information about anisotropy, damping factor, and gyromagnetic ratio. The relationship between resonance frequency and magnetic field can be explained by the roles played by the shape anisotropy and dipolar interactions among the ferromagnetic nanowires.« less

High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong

A two-step method consisting of solid-state microwave irradiation and heat treatment under NH₃ gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g⁻¹), high electrical conductivity (1532S m⁻¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg⁻¹ at a current density of 1 A g⁻¹, and a capacitance of 261 F g⁻¹ was retained at 50 A g⁻¹, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorptionmore » fine-structure spectroscopy evidenced the recover of π-conjugation in the carbon networks with the removal of oxygenated groups and revealed the chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content.« less

High-surface-area nitrogen-doped reduced graphene oxide for electric double-layer capacitors

DOE PAGES

Youn, Hee-Chang; Bak, Seong-Min; Kim, Myeong-Seong; ...

2015-06-08

A two-step method consisting of solid-state microwave irradiation and heat treatment under NH₃ gas was used to prepare nitrogen-doped reduced graphene oxide (N-RGO) with a high specific surface area (1007m²g⁻¹), high electrical conductivity (1532S m⁻¹), and low oxygen content (1.5 wt%) for electric double-layer capacitor applications. The specific capacitance of N-RGO was 291 Fg⁻¹ at a current density of 1 A g⁻¹, and a capacitance of 261 F g⁻¹ was retained at 50 A g⁻¹, indicating a very good rate capability. N-RGO also showed excellent cycling stability, preserving 96% of the initial specific capacitance after 100,000 cycles. Near-edge X-ray absorptionmore » fine-structure spectroscopy evidenced the recover of π-conjugation in the carbon networks with the removal of oxygenated groups and revealed the chemical bonding of the nitrogen atoms in N-RGO. The good electrochemical performance of N-RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content.« less

Fuel cell system with interconnect

DOEpatents

Liu, Zhien; Goettler, Richard

2016-12-20

The present invention includes an integrated planar, series connected fuel cell system having electrochemical cells electrically connected via interconnects, wherein the anodes of the electrochemical cells are protected against Ni loss and migration via an engineered porous anode barrier layer.

Electrochemical Visualization of Intracellular Hydrogen Peroxide at Single Cells.

PubMed

He, Ruiqin; Tang, Huifen; Jiang, Dechen; Chen, Hong-yuan

2016-02-16

In this Letter, the electrochemical visualization of hydrogen peroxide inside one cell was achieved first using a comprehensive Au-luminol-microelectrode and electrochemiluminescence. The capillary with a tip opening of 1-2 μm was filled with the mixture of chitosan and luminol, which was coated with the thin layers of polyvinyl chloride/nitrophenyloctyl ether (PVC/NPOE) and gold as the microelectrode. Upon contact with the aqueous hydrogen peroxide, hydrogen peroxide and luminol in contact with the gold layer were oxidized under the positive potential resulting in luminescence for the imaging. Due to the small diameter of the electrode, the microelectrode tip was inserted into one cell and the bright luminescence observed at the tip confirmed the visualization of intracellular hydrogen peroxide. The further coupling of oxidase on the electrode surface could open the field in the electrochemical imaging of intracellular biomolecules at single cells, which benefited the single cell electrochemical detection.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO 2/Ni/Electrolyte Interfaces

DOE PAGES

Lichterman, Michael F.; Richter, Matthias H.; Hu, Shu; ...

2015-12-05

The electrical and spectroscopic properties of the TiO 2/Ni protection layer system, which enables stabilization of otherwise corroding photoanodes, have been investigated in contact with electrolyte solutions by scanning-probe microscopy, electrochemistry and in-situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Specifically, the energy-band relations of the p +-Si/ALD-TiO 2/Ni interface have been determined for a selected range of Ni thicknesses. AP-XPS measurements using tender X-rays were performed in a three-electrode electrochemical arrangement under potentiostatic control to obtain information from the semiconductor near-surface region, the electrochemical double layer (ECDL) and the electrolyte beyond the ECDL. The degree of conductivity depended on themore » chemical state of the Ni on the TiO 2 surface. At low loadings of Ni, the Ni was present primarily as an oxide layer and the samples were not conductive, although the TiO 2 XPS core levels nonetheless displayed behavior indicative of a metal-electrolyte junction. In contrast, as the Ni thickness increased, the Ni phase was primarily metallic and the electrochemical behavior became highly conductive, with the AP-XPS data indicative of a metal-electrolyte junction. Electrochemical and microtopographical methods have been employed to better define the nature of the TiO 2/Ni electrodes and to contextualize the AP-XPS results.« less

Recent progress in layered double hydroxide based materials for electrochemical capacitors: design, synthesis and performance.

PubMed

Zhao, Mingming; Zhao, Qunxing; Li, Bing; Xue, Huaiguo; Pang, Huan; Chen, Changyun

2017-10-19

As representative two-dimensional (2D) materials, layered double hydroxides (LDHs) have received increasing attention in electrochemical energy storage and conversion because of the facile tunability between their composition and morphology. The high dispersion of active species in layered arrays, the simple exfoliation into monolayer nanosheets and chemical modification offer the LDHs an opportunity as active electrode materials in electrochemical capacitors (ECs). LDHs are favourable in providing large specific surface areas, good transport features as well as attractive physicochemical properties. In this review, our purpose is to provide a detailed summary of recent developments in the synthesis and electrochemical performance of the LDHs. Their composites with carbon (carbon quantum dots, carbon black, carbon nanotubes/nanofibers, graphene/graphene oxides), metals (nickel, platinum, silver), metal oxides (TiO 2 , Co 3 O 4 , CuO, MnO 2 , Fe 3 O 4 ), metal sulfides/phosphides (CoS, NiCo 2 S 4 , NiP), MOFs (MOF derivatives) and polymers (PEDOT:PSS, PPy (polypyrrole), P(NIPAM-co-SPMA) and PET) are also discussed in this review. The relationship between structures and electrochemical properties as well as the associated charge-storage mechanisms is discussed. Moreover, challenges and prospects of the LDHs for high-performance ECs are presented. This review sheds light on the sustainable development of ECs with LDH based electrode materials.

Electrochemical Deposition of Conformal and Functional Layers on High Aspect Ratio Silicon Micro/Nanowires.

PubMed

Ozel, Tuncay; Zhang, Benjamin A; Gao, Ruixuan; Day, Robert W; Lieber, Charles M; Nocera, Daniel G

2017-07-12

Development of new synthetic methods for the modification of nanostructures has accelerated materials design advances to furnish complex architectures. Structures based on one-dimensional (1D) silicon (Si) structures synthesized using top-down and bottom-up methods are especially prominent for diverse applications in chemistry, physics, and medicine. Yet further elaboration of these structures with distinct metal-based and polymeric materials, which could open up new opportunities, has been difficult. We present a general electrochemical method for the deposition of conformal layers of various materials onto high aspect ratio Si micro- and nanowire arrays. The electrochemical deposition of a library of coaxial layers comprising metals, metal oxides, and organic/inorganic semiconductors demonstrate the materials generality of the synthesis technique. Depositions may be performed on wire arrays with varying diameter (70 nm to 4 μm), pitch (5 μ to 15 μ), aspect ratio (4:1 to 75:1), shape (cylindrical, conical, hourglass), resistivity (0.001-0.01 to 1-10 ohm/cm 2 ), and substrate orientation. Anisotropic physical etching of wires with one or more coaxial shells yields 1D structures with exposed tips that can be further site-specifically modified by an electrochemical deposition approach. The electrochemical deposition methodology described herein features a wafer-scale synthesis platform for the preparation of multifunctional nanoscale devices based on a 1D Si substrate.

First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technology with high energy density and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. In this paper, we performed first principles calculations to evaluate the thermodynamics of the interfaces between solid electrolyte and electrode materials and to identify the chemical and electrochemical stabilities of these interfaces. Our computation results revealmore » that many solid electrolyte–electrode interfaces have limited chemical and electrochemical stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochemical performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chemical and electrochemical stability of heterogeneous solid interfaces. Finally, the enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.« less

Graphene hydrogels deposited in nickel foams for high-rate electrochemical capacitors.

PubMed

Chen, Ji; Sheng, Kaixuan; Luo, Peihui; Li, Chun; Shi, Gaoquan

2012-08-28

Graphene hydrogel/nickel foam composite electrodes for high-rate electrochemical capacitors are produced by reduction of an aqueous dispersion of graphene oxide in a nickel foam (upper half of figure). The micropores of the hydrogel are exposed to the electrolyte so that ions can enter and form electrochemical double-layers. The nickel framework shortens the distances of charge transfer. Therefore, the electrochemical capacitor exhibits highrate performance (see plots). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regulating the electrical behaviors of 2D inorganic nanomaterials for energy applications.

PubMed

Feng, Feng; Wu, Junchi; Wu, Changzheng; Xie, Yi

2015-02-11

Recent years have witnessed great developments in inorganic 2D nanomaterials for their unique dimensional confinement and diverse electronic energy bands. Precisely regulating their intrinsic electrical behaviors would bring superior electrical conductivity, rendering 2D nanomaterials ideal candidates for active materials in electrochemical applications when combined with the excellent reaction activity from the inorganic lattice. This Concept focuses on highly conducting inorganic 2D nanomaterials, including intrinsic metallic 2D nanomaterials and artificial highly conductive 2D nanomaterials. The intrinsic metallicity of 2D nanomaterials is derived from their closely packed atomic structures that ensure maximum overlapping of electron orbitals, while artificial highly conductive 2D nanomaterials could be achieved by designed methodologies of surface modification, intralayer ion doping, and lattice strain, in which atomic-scale structural modulation plays a vital role in realizing conducting behaviors. Benefiting from fast electron transfer, high reaction activity, as well as large surface areas arising from the 2D inorganic lattice, highly conducting 2D nanomaterials open up prospects for enhancing performance in electrochemical catalysis and electrochemical capacitors. Conductive 2D inorganic nanomaterials promise higher efficiency for electrochemical applications of energy conversion and storage. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct observation of nanowire growth and decomposition.

PubMed

Rackauskas, Simas; Shandakov, Sergey D; Jiang, Hua; Wagner, Jakob B; Nasibulin, Albert G

2017-09-26

Fundamental concepts of the crystal formation suggest that the growth and decomposition are determined by simultaneous embedding and removal of the atoms. Apparently, by changing the crystal formation conditions one can switch the regimes from the growth to decomposition. To the best of our knowledge, so far this has been only postulated, but never observed at the atomic level. By means of in situ environmental transmission electron microscopy we monitored and examined the atomic layer transformation at the conditions of the crystal growth and its decomposition using CuO nanowires selected as a model object. The atomic layer growth/decomposition was studied by varying an O 2 partial pressure. Three distinct regimes of the atomic layer evolution were experimentally observed: growth, transition and decomposition. The transition regime, at which atomic layer growth/decomposition switch takes place, is characterised by random nucleation of the atomic layers on the growing {111} surface. The decomposition starts on the side of the nanowire by removing the atomic layers without altering the overall crystal structure, which besides the fundamental importance offers new possibilities for the nanowire manipulation. Understanding of the crystal growth kinetics and nucleation at the atomic level is essential for the precise control of 1D crystal formation.

Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine

NASA Astrophysics Data System (ADS)

Li, Meixia; Zhu, Jun E.; Zhang, Lili; Chen, Xu; Zhang, Huimin; Zhang, Fazhi; Xu, Sailong; Evans, David G.

2011-10-01

Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach.Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach. Electronic supplementary information (ESI) available: Fig. S1 showing 2D fast Fourier transform (FFT) image of NiAl-LDH phase in NiAl-LDH/G composites, and Fig. S2 showing CV curve of the pristine G modified electrode. See DOI: 10.1039/c1nr10592b.

Submicron patterned metal hole etching

DOEpatents

McCarthy, Anthony M.; Contolini, Robert J.; Liberman, Vladimir; Morse, Jeffrey

2000-01-01

A wet chemical process for etching submicron patterned holes in thin metal layers using electrochemical etching with the aid of a wetting agent. In this process, the processed wafer to be etched is immersed in a wetting agent, such as methanol, for a few seconds prior to inserting the processed wafer into an electrochemical etching setup, with the wafer maintained horizontal during transfer to maintain a film of methanol covering the patterned areas. The electrochemical etching setup includes a tube which seals the edges of the wafer preventing loss of the methanol. An electrolyte composed of 4:1 water: sulfuric is poured into the tube and the electrolyte replaces the wetting agent in the patterned holes. A working electrode is attached to a metal layer of the wafer, with reference and counter electrodes inserted in the electrolyte with all electrodes connected to a potentiostat. A single pulse on the counter electrode, such as a 100 ms pulse at +10.2 volts, is used to excite the electrochemical circuit and perform the etch. The process produces uniform etching of the patterned holes in the metal layers, such as chromium and molybdenum of the wafer without adversely effecting the patterned mask.

Gel electrolytes and electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleischmann, Sven; Bunte, Christine; Mikhaylik, Yuriy V.

Gel electrolytes, especially gel electrolytes for electrochemical cells, are generally described. In some embodiments, the gel electrolyte layers comprise components a) to c). Component a) may be at least one layer of at least one polymer comprising polymerized units of: a1) at least one monomer containing an ethylenically unsaturated unit and an amido group and a2) at least one crosslinker. Component b) may be at least one conducting salt and component c) may be at least one solvent. Electrodes may comprise the components a), d) and e), wherein component a) may be at least one layer of at least onemore » polymer as described herein. Component d) may be at least one electroactive layer and component e) may be at least one ceramic layer. Furthermore, electrochemical cells comprising component a) which may be at least one layer of at least one polymer as described herein, are also provided.« less

Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopymore » (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.« less

Correlation of surface site formation to nanoisland growth in the electrochemical roughening of Pt(111)

NASA Astrophysics Data System (ADS)

Jacobse, Leon; Huang, Yi-Fan; Koper, Marc T. M.; Rost, Marcel J.

2018-03-01

Platinum plays a central role in a variety of electrochemical devices and its practical use depends on the prevention of electrode degradation. However, understanding the underlying atomic processes under conditions of repeated oxidation and reduction inducing irreversible surface structure changes has proved challenging. Here, we examine the correlation between the evolution of the electrochemical signal of Pt(111) and its surface roughening by simultaneously performing cyclic voltammetry and in situ electrochemical scanning tunnelling microscopy (EC-STM). We identify a `nucleation and early growth' regime of nanoisland formation, and a `late growth' regime after island coalescence, which continues up to at least 170 cycles. The correlation analysis shows that each step site that is created in the `late growth' regime contributes equally strongly to both the electrochemical and the roughness evolution. In contrast, in the `nucleation and early growth' regime, created step sites contribute to the roughness, but not to the electrochemical signal.

Electrochemical Carbonitriding of 316L Stainless Steel in Molten Salt System

NASA Astrophysics Data System (ADS)

Ren, Yanjie; Xiao, Bo; Chen, Yaqing; Chen, Jian; Chen, Jianlin

This paper reports an electrochemical route for carbonitriding 316L stainless steel in molten salts. Carbonitriding process was accomplished in molten alkaline chloride (LiCl/KCl) with the addition of KNO2 at 480∘C using a three-electrode system in which a carbon sheet was the counter electrode. The carbonitriding layer of 316L stainless steel obtained by potentiostatic electrolysis was analyzed by several physical techniques. The results showed that a compact layer with a thickness of about 7μm formed after the treatment. According to X-ray diffraction analysis, chromium nitride and carbide formed on the surface of carbonitriding layer. The microhardness of the carbonitriding layer is HV 336, as compared to HV 265 for the substrate.

Influence of the Surface Layer on the Electrochemical Deposition of Metals and Semiconductors into Mesoporous Silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chubenko, E. B., E-mail: eugene.chubenko@gmail.com; Redko, S. V.; Sherstnyov, A. I.

2016-03-15

The influence of the surface layer on the process of the electrochemical deposition of metals and semiconductors into porous silicon is studied. It is shown that the surface layer differs in structure and electrical characteristics from the host porous silicon bulk. It is established that a decrease in the conductivity of silicon crystallites that form the surface layer of porous silicon has a positive effect on the process of the filling of porous silicon with metals and semiconductors. This is demonstrated by the example of nickel and zinc oxide. The effect can be used for the formation of nanocomposite materialsmore » on the basis of porous silicon and nanostructures with a high aspect ratio.« less

Performance enhancement of polymer electrolyte membrane fuel cells by dual-layered membrane electrode assembly structures with carbon nanotubes.

PubMed

Jung, Dong-Won; Kim, Jun-Ho; Kim, Se-Hoon; Kim, Jun-Bom; Oh, Eun-Suok

2013-05-01

The effect of dual-layered membrane electrode assemblies (d-MEAs) on the performance of a polymer electrolyte membrane fuel cell (PEMFC) was investigated using the following characterization techniques: single cell performance test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). It has been shown that the PEMFC with d-MEAs has better cell performance than that with typical mono-layered MEAs (m-MEAs). In particular, the d-MEA whose inner layer is composed of multi-walled carbon nanotubes (MWCNTs) showed the best fuel cell performance. This is due to the fact that the d-MEAs with MWCNTs have the highest electrochemical surface area and the lowest activation polarization, as observed from the CV and EIS test.

Effect of Elastic Strain Fluctuation on Atomic Layer Growth of Epitaxial Silicide in Si Nanowires by Point Contact Reactions.

PubMed

Chou, Yi-Chia; Tang, Wei; Chiou, Chien-Jyun; Chen, Kai; Minor, Andrew M; Tu, K N

2015-06-10

Effects of strain impact a range of applications involving mobility change in field-effect-transistors. We report the effect of strain fluctuation on epitaxial growth of NiSi2 in a Si nanowire via point contact and atomic layer reactions, and we discuss the thermodynamic, kinetic, and mechanical implications. The generation and relaxation of strain shown by in situ TEM is periodic and in synchronization with the atomic layer reaction. The Si lattice at the epitaxial interface is under tensile strain, which enables a high solubility of supersaturated interstitial Ni atoms for homogeneous nucleation of an epitaxial atomic layer of the disilicide phase. The tensile strain is reduced locally during the incubation period of nucleation by the dissolution of supersaturated Ni atoms in the Si lattice but the strained-Si state returns once the atomic layer epitaxial growth of NiSi2 occurs by consuming the supersaturated Ni.

Atomic-Layer-Deposited Transparent Electrodes for Silicon Heterojunction Solar Cells

DOE PAGES

Demaurex, Benedicte; Seif, Johannes P.; Smit, Sjoerd; ...

2014-11-01

We examine damage-free transparent-electrode deposition to fabricate high-efficiency amorphous silicon/crystalline silicon heterojunction solar cells. Such solar cells usually feature sputtered transparent electrodes, the deposition of which may damage the layers underneath. Using atomic layer deposition, we insert thin protective films between the amorphous silicon layers and sputtered contacts and investigate their effect on device operation. We find that a 20-nm-thick protective layer suffices to preserve, unchanged, the amorphous silicon layers beneath. Insertion of such protective atomic-layer-deposited layers yields slightly higher internal voltages at low carrier injection levels. However, we identify the presence of a silicon oxide layer, formed during processing,more » between the amorphous silicon and the atomic-layer-deposited transparent electrode that acts as a barrier, impeding hole and electron collection.« less

Structure, Electronic Properties, and Electrochemical Behavior of a Boron-Doped Diamond/Quartz Optically Transparent Electrode.

PubMed

Wächter, Naihara; Munson, Catherine; Jarošová, Romana; Berkun, Isil; Hogan, Timothy; Rocha-Filho, Romeu C; Swain, Greg M

2016-10-26

The morphology, microstructure, chemistry, electronic properties, and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz were evaluated. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements, offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments. We report on the characterization of a BDD OTE by atomic force microscopy, optical spectroscopy, Raman spectroscopic mapping, alternating-current Hall effect measurements, X-ray photoelectron spectroscopy, and electrochemical methods. The results reported herein provide the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE and the electrode's electrochemical activity.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2013-10-22

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2015-04-28

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2014-09-16

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Time-Resolved Chemical Mapping in Light-Emitting Electrochemical Cells.

PubMed

Jafari, Mohammad Javad; Liu, Jiang; Engquist, Isak; Ederth, Thomas

2017-01-25

An understanding of the doping and ion distributions in light-emitting electrochemical cells (LECs) is required to approach a realistic conduction model which can precisely explain the electrochemical reactions, p-n junction formation, and ion dynamics in the active layer and to provide relevant information about LECs for systematic improvement of function and manufacture. Here, Fourier-transform infrared (FTIR) microscopy is used to monitor anion density profile and polymer structure in situ and for time-resolved mapping of electrochemical doping in an LEC under bias. The results are in very good agreement with the electrochemical doping model with respect to ion redistribution and formation of a dynamic p-n junction in the active layer. We also physically slow ions by decreasing the working temperature and study frozen-junction formation and immobilization of ions in a fixed-junction LEC device by FTIR imaging. The obtained results show irreversibility of the ion redistribution and polymer doping in a fixed-junction device. In addition, we demonstrate that infrared microscopy is a useful tool for in situ characterization of electroactive organic materials.

Sensitive electrochemical detection of dopamine with a DNA/graphene bi-layer modified carbon ionic liquid electrode.

PubMed

Wang, Xiaofeng; You, Zheng; Sha, Hailiang; Cheng, Yong; Zhu, Huanhuan; Sun, Wei

2014-10-01

A DNA and graphene (GR) bi-layer modified carbon ionic liquid electrode (CILE) was fabricated by an electrodeposition method. GR nanosheets were electrodeposited on the surface of CILE at the potential of -1.3 V and then DNA was further deposited at the potential of +0.5 V on GR modified CILE. Electrochemical performances of the fabricated DNA/GR/CILE were carefully investigated. Then electrochemical behaviors of dopamine (DA) on the modified electrode were studied with the calculated electrochemical parameters. Under the optimized conditions, a linear relationship between the oxidation peak current and the concentration of DA was obtained in the range from 0.1 μmol/L to 1.0 mmol/L with a detection limit of 0.027 μmol/L (3σ). The modified electrode exhibited excellent reproducibility, repeatability, stability, validation and robustness for the electrochemical detection of DA. The proposed method was further applied to the DA injection solution and human urine samples determination with satisfactory results. Copyright © 2014 Elsevier B.V. All rights reserved.

Mitigating leaks in membranes

DOEpatents

Karnik, Rohit N.; Bose, Suman; Boutilier, Michael S.H.; Hadjiconstantinou, Nicolas G.; Jain, Tarun Kumar; O'Hern, Sean C.; Laoui, Tahar; Atieh, Muataz A.; Jang, Doojoon

2018-02-27

Two-dimensional material based filters, their method of manufacture, and their use are disclosed. In one embodiment, a membrane may include an active layer including a plurality of defects and a deposited material associated with the plurality of defects may reduce flow therethrough. Additionally, a majority of the active layer may be free from the material. In another embodiment, a membrane may include a porous substrate and an atomic layer deposited material disposed on a surface of the porous substrate. The atomic layer deposited material may be less hydrophilic than the porous substrate and an atomically thin active layer may be disposed on the atomic layer deposited material.

Tribocorrosion Failure Mechanism of TiN/SiOx Duplex Coating Deposited on AISI304 Stainless Steel.

PubMed

Chen, Qiang; Xie, Zhiwen; Chen, Tian; Gong, Feng

2016-11-26

TiN/SiO x duplex coatings were synthesized on AISI304 stainless steel by plasma immersion ion implantation and deposition (PIIID) followed by radio frequency magnetron sputtering (RFMS). The microstructure and tribocorrosion failure behaviors of the duplex coatings were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, reciprocating-sliding tribometer, and electrochemical tests. The as-deposited duplex coating had a two-layered columnar growth structure consisting of face-centered cubic TiN and amorphous SiO x . Sliding tests showed that the TiN interlayer had good adhesion with the substrate, but the SiO x layer suffered from severe delamination failure. Friction force induced a number of micro-cracks in the coating, which provided channels for the diffusion of NaCl solution. The tribocorrosion test showed that the duplex coating exhibited a lower wear-performance in NaCl solution than in ambient atmosphere. Multi-scale chloride ion corrosion occurred simultaneously and substantially degraded the bonding strength of the columnar crystals or neighboring layers. Force-corrosion synergy damage eventually led to multi-degradation failure of the duplex coating. The presented results provide a comprehensive understanding of the tribocorrosion failure mechanism in coatings with duplex architecture.

Carbon Textile Decorated with Pseudocapacitive VC/Vx Oy for High-Performance Flexible Supercapacitors.

PubMed

Van Lam, Do; Shim, Hyung Cheoul; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

2017-11-01

It is demonstrated that, via V 2 O 5 coating by low temperature atomic layer deposition and subsequent pyrolysis, ubiquitous cotton textile can readily turn into high-surface-area carbon textile fully decorated with pseudocapacitive V x O y /VC widely usable as electrodes of high-performance supercapacitor. It is found that carbothermic reduction of V 2 O 5 (C + V 2 O 5 → C' + VC + CO/CO 2 (g)) leads to chemical/mechanical activation of carbon textile, thereby producing high-surface-area conductive carbon textile. In addition, sequential phase transformation and carbide formation (V 2 O 5 → V x O y → VC) occurred by carbothermic reduction trigger decoration of the carbon textile with redox-active V x O y /VC. Thanks to the synergistic effect of electrical double layer and pseudocapacitance, the supercapacitors made of the hybrid carbon textile exhibit far better energy density (over 30-fold increase) with excellent cycling stability than the carbon textile simply undergone pyrolysis. The method can open up a promising and facile way to synthesize hybrid electrode materials for electrochemical energy storages possessing advantages of both electrical double layer and pseudocapacitive material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembly of a thin highly reduced graphene oxide film and its high electrocatalytic activity

NASA Astrophysics Data System (ADS)

Bai, Yan-Feng; Zhang, Yong-Fang; Zhou, An-Wei; Li, Hai-Wai; Zhang, Yu; Luong, John H. T.; Cui, Hui-Fang

2014-10-01

A thin highly reduced graphene oxide (rGO) film was self-assembled at the dimethyl formamide (DMF)-air interface through evaporation-induced water-assisted thin film formation at the pentane-DMF interface, followed by complete evaporation of pentane. The thin film was transferred onto various solid substrates for film characterization and electrochemical sensing. UV-visible spectrometry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemistry techniques were used to characterize the film. An rGO film showing 82.8% of the transmittance at 550 nm corresponds to a few layers of rGO nanosheets. The rGO nanosheets cross-stack with each other, lying approximately in the plane of the film. An rGO film collected on a glassy carbon (GC) electrode exhibited improved electrical conductivity compared to GC, with the electrode charge-transfer resistance (Rct) reduced from 31 Ω to 22 Ω. The as-formed rGO/GC electrode was mechanically very stable, exhibiting significantly enhanced electrocatalytic activity to H2O2 and dopamine. Multiple layers of the rGO films on the GC electrode showed even stronger electrocatalytic activity to dopamine than that of the single rGO film layer. The controllable formation of a stable rGO film on various solid substrates has potential applications for nanoelectronics and sensors/biosensors.

Tailored surface structure of LiFePO4/C nanofibers by phosphidation and their electrochemical superiority for lithium rechargeable batteries.

PubMed

Lee, Yoon Cheol; Han, Dong-Wook; Park, Mihui; Jo, Mi Ru; Kang, Seung Ho; Lee, Ju Kyung; Kang, Yong-Mook

2014-06-25

We offer a brand new strategy for enhancing Li ion transport at the surface of LiFePO4/C nanofibers through noble Li ion conducting pathways built along reduced carbon webs by phosphorus. Pristine LiFePO4/C nanofibers composed of 1-dimensional (1D) LiFePO4 nanofibers with thick carbon coating layers on the surfaces of the nanofibers were prepared by the electrospinning technique. These dense and thick carbon layers prevented not only electrolyte penetration into the inner LiFePO4 nanofibers but also facile Li ion transport at the electrode/electrolyte interface. In contrast, the existing strong interactions between the carbon and oxygen atoms on the surface of the pristine LiFePO4/C nanofibers were weakened or partly broken by the adhesion of phosphorus, thereby improving Li ion migration through the thick carbon layers on the surfaces of the LiFePO4 nanofibers. As a result, the phosphidated LiFePO4/C nanofibers have a higher initial discharge capacity and a greatly improved rate capability when compared with pristine LiFePO4/C nanofibers. Our findings of high Li ion transport induced by phosphidation can be widely applied to other carbon-coated electrode materials.

Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

NASA Astrophysics Data System (ADS)

Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

2014-07-01

Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices.

Layer-by-Layer Motif Architectures: Programmed Electrochemical Syntheses of Multilayer Mesoporous Metallic Films with Uniformly Sized Pores.

PubMed

Jiang, Bo; Li, Cuiling; Qian, Huayu; Hossain, Md Shahriar A; Malgras, Victor; Yamauchi, Yusuke

2017-06-26

Although multilayer films have been extensively reported, most compositions have been limited to non-catalytically active materials (e.g. polymers, proteins, lipids, or nucleic acids). Herein, we report the preparation of binder-free multilayer metallic mesoporous films with sufficient accessibility for high electrocatalytic activity by using a programmed electrochemical strategy. By precisely tuning the deposition potential and duration, multilayer mesoporous architectures consisting of alternating mesoporous Pd layers and mesoporous PdPt layers with controlled layer thicknesses can be synthesized within a single electrolyte, containing polymeric micelles as soft templates. This novel architecture, combining the advantages of bimetallic alloys, multilayer architectures, and mesoporous structures, exhibits high electrocatalytic activity for both the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, Characterization, and Electrochemical Properties of Polyaniline Thin Films

NASA Astrophysics Data System (ADS)

Rami, Soukaina

Conjugated polymers have been used in various applications (battery, supercapacitor, electromagnetic shielding, chemical sensor, biosensor, nanocomposite, light-emitting-diode, electrochromic display etc.) due to their excellent conductivity, electrochemical and optical properties, and low cost. Polyaniline has attracted the researchers from all disciplines of science, engineering, and industry due to its redox properties, environmental stability, conductivity, and optical properties. Moreover, it is a polymer with fast electroactive switching and reversible properties displayed at low potential, which is an important feature in many applications. The thin oriented polyaniline films have been fabricated using self-assembly, Langmuir-Blodgett, in-situ self-assembly, layer-by-layer, and electrochemical technique. The focus of this thesis is to synthesize and characterize polyaniline thin films with and without dyes. Also, the purpose of this thesis is to find the fastest electroactive switching PANI electrode in different electrolytic medium by studying their electrochemical properties. These films were fabricated using two deposition techniques: in-situ self-assembly and electrochemical deposition. The characterization of these films was done using techniques such as Fourier Transform Infrared Spectroscopy (FTIR), UV-spectroscopy, Scanning Electron Microscope (SEM), and X-Ray Diffraction (XRD). FTIR and UV-spectroscopy showed similar results in the structure of the polyaniline films. However, for the dye incorporated films, since there was an addition in the synthesis of the material, peak locations shifted, and new peaks corresponding to these materials appeared. The 1 layer PANI showed compact film morphology, comparing to other PANI films, which displayed a fiber-like structure. Finally, the electrochemical properties of these thin films were studied using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in different scenarios. These scenarios included the study in different acid based electrolytes and different gel based electrolytes. The ultra-thin self-assembled PANI films were shown to have a faster switching time, especially for the 1 layer PANI, whereas the color contrast could be observed for the film containing the dye molecule. Also, HCl based electrolyte gave the best electrochemical reversibility compared to other acids used. For the gelatin and PVA based electrolytes, having the same concentration, the results were similar. Hence, the change in the electrolyte consistencies, from liquid to semi-solid, did not change the electrochemical properties of the films. Finally, in the EIS, it was shown that these PANI thin films exhibit a pseudo-capacitance behavior, and as the film thickness grew, the capacitance increased.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, P.; Vasilow, T.R.; Richards, V.L.

1996-05-14

The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

Layer-by-layer evolution of structure, strain, and activity for the oxygen evolution reaction in graphene-templated Pt monolayers.

PubMed

Abdelhafiz, Ali; Vitale, Adam; Joiner, Corey; Vogel, Eric; Alamgir, Faisal M

2015-03-25

In this study, we explore the dimensional aspect of structure-driven surface properties of metal monolayers grown on a graphene/Au template. Here, surface limited redox replacement (SLRR) is used to provide precise layer-by-layer growth of Pt monolayers on graphene. We find that after a few iterations of SLRR, fully wetted 4-5 monolayer Pt films can be grown on graphene. Incorporating graphene at the Pt-Au interface modifies the growth mechanism, charge transfers, equilibrium interatomic distances, and associated strain of the synthesized Pt monolayers. We find that a single layer of sandwiched graphene is able to induce a 3.5% compressive strain on the Pt adlayer grown on it, and as a result, catalytic activity is increased due to a greater areal density of the Pt layers beyond face-centered-cubic close packing. At the same time, the sandwiched graphene does not obstruct vicinity effects of near-surface electron exchange between the substrate Au and adlayers Pt. X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) techniques are used to examine charge mediation across the Pt-graphene-Au junction and the local atomic arrangement as a function of the Pt adlayer dimension. Cyclic voltammetry (CV) and the oxygen reduction reaction (ORR) are used as probes to examine the electrochemically active area of Pt monolayers and catalyst activity, respectively. Results show that the inserted graphene monolayer results in increased activity for the Pt due to a graphene-induced compressive strain, as well as a higher resistance against loss of the catalytically active Pt surface.

Electrochemical hydride generation for the simultaneous determination of hydride forming elements by inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Castillo, J. R.; Sturgeon, R. E.

2004-04-01

Simultaneous measurements of As, Sb, Se, Sn and Ge were performed by inductively coupled plasma atomic emission spectrometry following their electrochemical hydride generation. An electrochemical hydride generator based on a concentric arrangement with a porous cathode, working in a continuous flow mode was used. The effects of sample flow rate, applied current and electrolytic solution concentration on response were studied and their influence on the mechanisms of hydride generation discussed. Four materials, particulate lead, reticulated vitreous carbon (RVC), silver and amalgamated silver were tested as cathode materials. The best results were achieved with particulate lead and RVC cathodes, wherein generation efficiencies higher than 80% were estimated for most of the analytes. In general, limits of detection between 0.1 and 3.6 ng ml -1 and a precision better than 5% were achieved using a lead cathode. The analysis of a marine sediment reference material (PACS-2, NRC) showed good agreement with the certified values for As and Se.

Molecular Layer Deposition for Surface Modification of Lithium-Ion Battery Electrodes

DOE PAGES

Ban, Chunmei; George, Steven M.

2016-10-21

This review presents the MLD process and its outstanding attributes for electrochemical applications and is inspired by recent successes in applying molecular layer deposition (MLD) to stabilize lithium-ion (Li-ion) electrodes. Furthermore, this review discusses various MLD materials and their implementation in Li-ion electrodes. The rationale behind these emerging uses of MLD is examined to motivate future efforts on the fundamental understanding of interphase chemistry and the development of new materials for enhanced electrochemical performance.

Method of making gas diffusion layers for electrochemical cells

DOEpatents

Frisk, Joseph William; Boand, Wayne Meredith; Larson, James Michael

2002-01-01

A method is provided for making a gas diffusion layer for an electrochemical cell comprising the steps of: a) combining carbon particles and one or more surfactants in a typically aqueous vehicle to make a preliminary composition, typically by high shear mixing; b) adding one or more highly fluorinated polymers to said preliminary composition by low shear mixing to make a coating composition; and c) applying the coating composition to an electrically conductive porous substrate, typically by a low shear coating method.

Chemical shielding properties for BN, BP, AlN, and AlP nanocones: DFT studies

NASA Astrophysics Data System (ADS)

Mirzaei, Mahmoud; Yousefi, Mohammad; Meskinfam, Masoumeh

2012-06-01

The properties of boron nitride (BN), boron phosphide (BP), aluminum nitride (AlN), and aluminum phosphide (AlP) nanocones were investigated by density functional theory (DFT) calculations. The investigated structures were optimized and chemical shielding (CS) properties including isotropic and anisotropic CS parameters were calculated for the atoms of the optimized structures. The magnitudes of CS parameters were observed to be mainly dependent on the bond lengths of considered atoms. The results indicated that the atoms could be divided into atomic layers due to the similarities of their CS properties for the atoms of each layer. The trend means that the atoms of each layer detect almost similar electronic environments. Moreover, the atoms at the apex and mouth of nanocones exhibit different properties with respect to the other atomic layers.

Rational design of new electrolyte materials for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Schütter, Christoph; Husch, Tamara; Viswanathan, Venkatasubramanian; Passerini, Stefano; Balducci, Andrea; Korth, Martin

2016-09-01

The development of new electrolytes is a centerpiece of many strategies to improve electrochemical double layer capacitor (EDLC) devices. We present here a computational screening-based rational design approach to find new electrolyte materials. As an example application, the known chemical space of almost 70 million compounds is investigated in search of electrochemically more stable solvents. Cyano esters are identified as especially promising new compound class. Theoretical predictions are validated with subsequent experimental studies on a selected case. These studies show that based on theoretical predictions only, a previously untested, but very well performing compound class was identified. We thus find that our rational design strategy is indeed able to successfully identify completely new materials with substantially improved properties.

Electrochemical characterization of pulsed layer deposited hydroxyapatite-zirconia layers on Ti-21Nb-15Ta-6Zr alloy for biomedical application

NASA Astrophysics Data System (ADS)

Izquierdo, Javier; Bolat, Georgiana; Cimpoesu, Nicanor; Trinca, Lucia Carmen; Mareci, Daniel; Souto, Ricardo Manuel

2016-11-01

A new titanium base Ti-21Nb-15Ta-6Zr alloy covered with hydroxyapatite-zirconia (HA-ZrO2) by pulsed laser deposition (PLD) technique was characterized regarding its corrosion resistance in simulated physiological Ringer's solution at 37 °C. For the sake of comparison, Ti-6Al-4V standard implant alloy, with and without hydroxyapatite-zirconia coating, was also characterized. Multiscale electrochemical analysis using both conventional averaging electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization, and spatially-resolved microelectrochemical techniques (scanning electrochemical microscopy, SECM) were used to investigate the electrochemical behaviour of the materials. In addition, scanning electron microscopy evidenced that no relevant surface morphology changes occurred on the materials upon immersion in the simulated physiological solution, despite variations in their electrochemical behaviour. Although uncoated metals appear to show better performances during conventional corrosion tests, the response is still quite similar for the HA-ZrO2 coated materials while providing superior resistance towards electron transfer due to the formation of a more dense film on the surface, thus effectively behaving as a passive material. It is believed corrosion of the HA-ZrO2 coated Ti-21Nb-15Ta-6Zr alloy will have negligible effect upon biochemical and cellular events at the bone-implant interface and could facilitate osseointegration.

Science and Emerging Technology of 2D Atomic Layered Materials and Devices

DTIC Science & Technology

2017-09-09

AFRL-AFOSR-JP-TR-2017-0067 Science & Emerging Technology of 2D Atomic Layered Materials and Devices Angel Rubio UNIVERSIDAD DEL PAIS VASCO - EUSKAL...Emerging Technology of 2D Atomic Layered Materials and Devices 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-15-1-0006 5c.  PROGRAM ELEMENT NUMBER...reporting documents for AOARD project 144088, “2D Materials and Devices Beyond Graphene Science & Emerging Technology of 2D Atomic Layered Materials and

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

DOE PAGES

Sugiyama, Issei; Kim, Yunseok; Jesse, Stephen; ...

2014-10-22

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were furthermore » correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. In conclusion, these studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.« less

Partially Oxidized SnS2 Atomic Layers Achieving Efficient Visible-Light-Driven CO2 Reduction.

PubMed

Jiao, Xingchen; Li, Xiaodong; Jin, Xiuyu; Sun, Yongfu; Xu, Jiaqi; Liang, Liang; Ju, Huanxin; Zhu, Junfa; Pan, Yang; Yan, Wensheng; Lin, Yue; Xie, Yi

2017-12-13

Unraveling the role of surface oxide on affecting its native metal disulfide's CO 2 photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS 2 atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS 2 atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g -1 h -1 , roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS 2 atomic layers and the SnS 2 atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO 2 reduction property, paving a new way for obtaining high-efficiency CO 2 photoreduction performances.

An electrochemical immunosensor based on chemical assembly of vertically aligned carbon nanotubes on carbon substrates for direct detection of the pesticide endosulfan in environmental water.

PubMed

Liu, Guozhen; Wang, Shuo; Liu, Jingquan; Song, Dandan

2012-05-01

A glassy carbon substrate was covalently modified with a mixed layer of 4-aminophenyl and phenyl via in situ electrografting of their aryldiazonium salts in acidic solutions. Single-walled carbon nanotubes (SWNTs) were covalently and vertically anchored on the electrode surface via the formation of amide bonds from the reaction between the amines located on the modified substrate and the carboxylic groups at the ends of the nanotubes. Ferrocenedimethylamine (FDMA) was subsequently attached to the ends of SWNTs through amide bonding followed by the attachment of an epitope, i.e., endosulfan hapten to which an antibody would bind. Association or dissociation of the antibody with the sensing interface causes a modulation of the ferrocene electrochemistry. Antibody-complexed electrodes were exposed to samples containing spiked endosulfan (unbound target analyte) in environment water and interrogated using the square wave voltammetry (SWV) technique. The modified sensing surfaces were characterized by atomic force microscopy, XPS, and electrochemistry. The fabricated electrochemical immunosensor can be successfully used for the detection of endosulfan over the range of 0.01-20 ppb by a displacement assay. The lowest detection limit of this immunosensor is 0.01 ppb endosulfan in 50 mM phosphate buffer at pH 7.0.

Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors.

PubMed

Zang, Xining; Shen, Caiwei; Kao, Emmeline; Warren, Roseanne; Zhang, Ruopeng; Teh, Kwok Siong; Zhong, Junwen; Wei, Minsong; Li, Buxuan; Chu, Yao; Sanghadasa, Mohan; Schwartzberg, Adam; Lin, Liwei

2018-02-01

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS 2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g -1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg -1 -the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg -1 with stable operation over 10 000 cycles. A flexible solid-state supercapacitor prepared by transferring the TiS 2 -VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatically Gated Graphene-Zinc Oxide Nanowire Heterojunction.

PubMed

You, Xueqiu; Pak, James Jungho

2015-03-01

This paper presents an electrostatically gated graphene-ZnO nanowire (NW) heterojunction for the purpose of device applications for the first time. A sub-nanometer-thick energy barrier width was formed between a monatomic graphene layer and electrochemically grown ZnO NWs. Because of the narrow energy barrier, electrons can tunnel through the barrier when a voltage is applied across the junction. A near-ohmic current-voltage (I-V) curve was obtained from the graphene-electrochemically grown ZnO NW heterojunction. This near-ohmic contact changed to asymmetric I-V Schottky contact when the samples were exposed to an oxygen environment. It is believed that the adsorbed oxygen atoms or molecules on the ZnO NW surface capture free electrons of the ZnO NWs, thereby creating a depletion region in the ZnO NWs. Consequentially, the electron concentration in the ZnO NWs is dramatically reduced, and the energy barrier width of the graphene-ZnO NW heterojunction increases greatly. This increased energy barrier width reduces the electron tunneling probability, resulting in a typical Schottky contact. By adjusting the back-gate voltage to control the graphene-ZnO NW Schottky energy barrier height, a large modulation on the junction current (on/off ratio of 10(3)) was achieved.

Ultrasensitive electrochemical detection of tumor cells based on multiple layer CdS quantum dots-functionalized polystyrene microspheres and graphene oxide - polyaniline composite.

PubMed

Wang, Jidong; Wang, Xiaoyu; Tang, Hengshan; Gao, Zehua; He, Shengquan; Li, Jian; Han, Shumin

2018-02-15

In this work, a novel ultrasensitive electrochemical biosensor was developed for the detection of K562 cell by a signal amplification strategy based on multiple layer CdS QDs functionalized polystyrene microspheres(PS) as bioprobe and graphene oxide(GO) -polyaniline(PANI) composite as modified materials of capture electrode. Due to electrostatic force of different charge, CdS QDs were decorated on the surface of PS by PDDA (poly(diallyldimethyl-ammonium chloride)) through a layer-by-layer(LBL) assemble technology, in which the structure of multiple layer CdS QDs increased the detection signal intensity. Moreover, GO-PANI composite not only enhanced the electron transfer rate, but also increased tumor cells load ratio. The resulting electrochemical biosensor was used to detect K562 cells with a lower detection limit of 3 cellsmL -1 (S/N = 3) and a wider linear range from 10 to 1.0 × 10 7 cellsmL -1 . This sensor was also used for mannosyl groups on HeLa cells and Hct116 cells, which showed high specificity and sensitivity. This signal amplification strategy would provide a novel approach for detection, diagnosis and treatment for tumor cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

PubMed

Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

2018-05-04

Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Theoretical study for heterojunction surface of NEA GaN photocathode dispensed with Cs activation

NASA Astrophysics Data System (ADS)

Xia, Sihao; Liu, Lei; Wang, Honggang; Wang, Meishan; Kong, Yike

2016-09-01

For the disadvantages of conventional negative electron affinity (NEA) GaN photocathodes activated by Cs or Cs/O, new-type NEA GaN photocathodes with heterojunction surface dispensed with Cs activation are investigated based on first-principle study with density functional theory. Through the growth of an ultrathin n-type GaN cap layer on p-type GaN emission layer, a p-n heterojunction is formed on the surface. According to the calculation results, it is found that Si atoms tend to replace Ga atoms to result in an n-type doped cap layer which contributes to the decreasing of work function. After the growth of n-type GaN cap layer, the atom structure near the p-type emission layer is changed while that away from the surface has no obvious variations. By analyzing the E-Mulliken charge distribution of emission surface with and without cap layer, it is found that the positive charge of Ga and Mg atoms in the emission layer decrease caused by the cap layer, while the negative charge of N atom increases. The conduction band moves downwards after the growth of cap layer. Si atom produces donor levels around the valence band maximum. The absorption coefficient of GaN emission layer decreases and the reflectivity increases caused by n-type GaN cap layer.

Compositional modulated atomic layer stacking and uniaxial magnetocrystalline anisotropy of CoPt alloy sputtered films with close-packed plane orientation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saito, Shin, E-mail: ssaito@ecei.tohoku.ac.jp; Nozawa, Naoki; Hinata, Shintaro

An atomic layer stacking structure in hexagonal close packed (hcp) Co{sub 100−x}Pt{sub x} alloy films with c-plane sheet texture was directly observed by a high-angle annular dark-field imaging scanning transmission electron microscopy. The analysis of sequential and/or compositional atomic layer stacking structure and uniaxial magnetocrystalline anisotropy (K{sub u} = K{sub u1} + K{sub u2}) revealed that (1) integrated intensity of the superlattice diffraction takes the maximum at x = 20 at. % and shows broadening feature against x for the film fabricated under the substrate temperature (T{sub sub}) of 400 °C. (2) Compositional separation structure in atomic layers is formed for the films fabricated under T{sub sub} = 400 °C.more » A sequential alternative stacking of atomic layers with different compositions is hardly formed in the film with x = 50 at. %, whereas easily formed in the film with x = 20 at. %. This peculiar atomic layer stacking structure consists of in-plane-disordered Pt-rich and Pt-poor layers, which is completely different from the so-called atomic site ordered structure. (3) A face centered cubic atomic layer stacking as faults appeared in the host hcp atomic layer stacking exists in accompanies with irregularities for the periodicity of the compositional modulation atomic layers. (4) K{sub u1} takes the maximum of 1.4 × 10{sup 7 }erg/cm{sup 3} at around x = 20 at. %, whereas K{sub u2} takes the maximum of 0.7 × 10{sup 7 }erg/cm{sup 3} at around x = 40 at. %, which results in the maximum of 1.8 × 10{sup 7 }erg/cm{sup 3} of K{sub u} at x = 30 at. % and a shoulder in compositional dependence of K{sub u} in the range of x = 30–60 at. %. Not only compositional separation of atomic layers but also sequential alternative stacking of different compositional layers is quite important to improve essential uniaxial magnetocrystalline anisotropy.« less

Open carbon nanopipettes as resistive-pulse sensors, rectification sensors, and electrochemical nanoprobes.

PubMed

Hu, Keke; Wang, Yixian; Cai, Huijing; Mirkin, Michael V; Gao, Yang; Friedman, Gary; Gogotsi, Yury

2014-09-16

Nanometer-sized glass and quartz pipettes have been widely used as a core of chemical sensors, patch clamps, and scanning probe microscope tips. Many of those applications require the control of the surface charge and chemical state of the inner pipette wall. Both objectives can be attained by coating the inner wall of a quartz pipette with a nanometer-thick layer of carbon. In this letter, we demonstrate the possibility of using open carbon nanopipettes (CNP) produced by chemical vapor deposition as resistive-pulse sensors, rectification sensors, and electrochemical nanoprobes. By applying a potential to the carbon layer, one can change the surface charge and electrical double-layer at the pipette wall, which, in turn, affect the ion current rectification and adsorption/desorption processes essential for resistive-pulse sensors. CNPs can also be used as versatile electrochemical probes such as asymmetric bipolar nanoelectrodes and dual electrodes based on simultaneous recording of the ion current through the pipette and the current produced by oxidation/reduction of molecules at the carbon nanoring.

Ultrafast triggered transient energy storage by atomic layer deposition into porous silicon for integrated transient electronics

NASA Astrophysics Data System (ADS)

Douglas, Anna; Muralidharan, Nitin; Carter, Rachel; Share, Keith; Pint, Cary L.

2016-03-01

Here we demonstrate the first on-chip silicon-integrated rechargeable transient power source based on atomic layer deposition (ALD) coating of vanadium oxide (VOx) into porous silicon. A stable specific capacitance above 20 F g-1 is achieved until the device is triggered with alkaline solutions. Due to the rational design of the active VOx coating enabled by ALD, transience occurs through a rapid disabling step that occurs within seconds, followed by full dissolution of all active materials within 30 minutes of the initial trigger. This work demonstrates how engineered materials for energy storage can provide a basis for next-generation transient systems and highlights porous silicon as a versatile scaffold to integrate transient energy storage into transient electronics.Here we demonstrate the first on-chip silicon-integrated rechargeable transient power source based on atomic layer deposition (ALD) coating of vanadium oxide (VOx) into porous silicon. A stable specific capacitance above 20 F g-1 is achieved until the device is triggered with alkaline solutions. Due to the rational design of the active VOx coating enabled by ALD, transience occurs through a rapid disabling step that occurs within seconds, followed by full dissolution of all active materials within 30 minutes of the initial trigger. This work demonstrates how engineered materials for energy storage can provide a basis for next-generation transient systems and highlights porous silicon as a versatile scaffold to integrate transient energy storage into transient electronics. Electronic supplementary information (ESI) available: (i) Experimental details for ALD and material fabrication, ellipsometry film thickness, preparation of gel electrolyte and separator, details for electrochemical measurements, HRTEM image of VOx coated porous silicon, Raman spectroscopy for VOx as-deposited as well as annealed in air for 1 hour at 450 °C, SEM and transient behavior dissolution tests of uniformly coated VOx on porous silicon, dissolution tests for 0.1 M and 0.01 M NaOH trigger solutions, EIS analysis for VOx coated devices, and EDS compositional analysis of VOx. (ii) Video showing transient behavior of integrated VOx/porous silicon scaffolds. See DOI: 10.1039/c5nr09095d

Studies of electrode structures and dynamics using coherent X-ray scattering and imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, H.; Liu, Y.; Ulvestad, A.

2017-08-01

Electrochemical systems studied in situ with advanced surface X-ray scattering techniques are reviewed. The electrochemical systems covered include interfaces of single-crystals and nanocrystals with respect to surface modification, aqueous dissolution, surface reconstruction, and electrochemical double layers. An emphasis will be given on recent results by coherent X-ray techniques such as X-ray photon correlation spectroscopy, Bragg coherent diffraction imaging, and surface ptychography.

ELLIPSOMETRY OF ELECTROCHEMICAL SURFACE LAYERS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muller, R.H.

1977-06-01

Ellipsometry is concerned with the analysis and interpretation of changes in the state of polarization caused by reflection. The technique has found increasing interest in recent years for the measurement of thin films because it is unusually sensitive, disturbs the object minimally and can be applied to surfaces contained in any optically transparent medium. Film thicknesses amenable to measurement range from fractional monoatomic coverage to microscopic thicknesses. The measurement of changes in the state of polarization of light due to reflection provides an unusually sensitive tool for observing surface layers in any optically transparent environment. A fast, self-compensating ellipsometer hasmore » been used to observe the electrochemical formation of reacted surface layers. The optical effect of mass-transport boundary layers and component imperfections have been taken into account in the interpretation of results.« less

Cell structure for electrochemical devices and method of making same

DOEpatents

Kaun, Thomas D.

2007-03-27

An electrochemical device comprising alternating layers of positive and negative electrodes separated from each other by separator layers. The electrode layers extend beyond the periphery of the separator layers providing superior contact between the electrodes and battery terminals, eliminating the need for welding the electrode to the terminal. Electrical resistance within the battery is decreased and thermal conductivity of the cell is increased allowing for superior heat removal from the battery and increased efficiency. Increased internal pressure within the battery can be alleviated without damaging or removing the battery from service while keeping the contents of the battery sealed off from the atmosphere by a pressure release system. Nonoperative cells within a battery assembly can also be removed from service by shorting the nonoperative cell thus decreasing battery life.

Ultrathin Nickel Hydroxide and Oxide Nanosheets: Synthesis, Characterizations and Excellent Supercapacitor Performances

PubMed Central

Zhu, Youqi; Cao, Chuanbao; Tao, Shi; Chu, Wangsheng; Wu, Ziyu; Li, Yadong

2014-01-01

High-quality ultrathin two-dimensional nanosheets of α-Ni(OH)2 are synthesized at large scale via microwave-assisted liquid-phase growth under low-temperature atmospheric conditions. After heat treatment, non-layered NiO nanosheets are obtained while maintaining their original frame structure. The well-defined and freestanding nanosheets exhibit a micron-sized planar area and ultrathin thickness (<2 nm), suggesting an ultrahigh surface atom ratio with unique surface and electronic structure. The ultrathin 2D nanostructure can make most atoms exposed outside with high activity thus facilitate the surface-dependent electrochemical reaction processes. The ultrathin α-Ni(OH)2 and NiO nanosheets exhibit enhanced supercapacitor performances. Particularly, the α-Ni(OH)2 nanosheets exhibit a maximum specific capacitance of 4172.5 F g−1 at a current density of 1 A g−1. Even at higher rate of 16 A g−1, the specific capacitance is still maintained at 2680 F g−1 with 98.5% retention after 2000 cycles. Even more important, we develop a facile and scalable method to produce high-quality ultrathin transition metal hydroxide and oxide nanosheets and make a possibility in commercial applications. PMID:25168127

The Effects of Different Electrode Types for Obtaining Surface Machining Shape on Shape Memory Alloy Using Electrochemical Machining

NASA Astrophysics Data System (ADS)

Choi, S. G.; Kim, S. H.; Choi, W. K.; Moon, G. C.; Lee, E. S.

2017-06-01

Shape memory alloy (SMA) is important material used for the medicine and aerospace industry due to its characteristics called the shape memory effect, which involves the recovery of deformed alloy to its original state through the application of temperature or stress. Consumers in modern society demand stability in parts. Electrochemical machining is one of the methods for obtained these stabilities in parts requirements. These parts of shape memory alloy require fine patterns in some applications. In order to machine a fine pattern, the electrochemical machining method is suitable. For precision electrochemical machining using different shape electrodes, the current density should be controlled precisely. And electrode shape is required for precise electrochemical machining. It is possible to obtain precise square holes on the SMA if the insulation layer controlled the unnecessary current between electrode and workpiece. If it is adjusting the unnecessary current to obtain the desired shape, it will be a great contribution to the medical industry and the aerospace industry. It is possible to process a desired shape to the shape memory alloy by micro controlling the unnecessary current. In case of the square electrode without insulation layer, it derives inexact square holes due to the unnecessary current. The results using the insulated electrode in only side show precise square holes. The removal rate improved in case of insulated electrode than others because insulation layer concentrate the applied current to the machining zone.

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach.

PubMed

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO(2) composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO(2) nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. This journal is © The Royal Society of Chemistry 2011

Pseudocapacitive Effects of N-Doped Carbon Nanotube Electrodes in Supercapacitors

PubMed Central

Yun, Young Soo; Park, Hyun Ho; Jin, Hyoung-Joon

2012-01-01

Nitrogen- and micropore-containing carbon nanotubes (NMCNTs) were prepared by carbonization of nitrogen-enriched, polymer-coated carbon nanotubes (CNTs), and the electrochemical performances of the NMCNTs with different heteroatom contents were investigated. NMCNTs-700 containing 9.1 wt% nitrogen atoms had a capacitance of 190.8 F/g, which was much higher than that of pristine CNTs (48.4 F/g), despite the similar surface area of the two CNTs, and was also higher than that of activated CNTs (151.7 F/g) with a surface area of 778 m2/g and a nitrogen atom content of 1.2 wt%. These results showed that pseudocapacitive effects play an important role in the electrochemical performance of supercapacitor electrodes.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Sanju, E-mail: sanju.gupta@wku.edu; Price, Carson

2015-10-15

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnectedmore » graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.« less

Room-Temperature Ionic Liquids for Electrochemical Capacitors

NASA Technical Reports Server (NTRS)

Fireman, Heather; Yowell, Leonard; Moloney, Padraig G.; Arepalli, Sivaram; Nikolaev, P.; Huffman, C.; Ready, Jud; Higgins, C.D.; Turano, S. P.; Kohl, P.A.;

Layer-by-layer assembled polyaniline nanofiber/multiwall carbon nanotube thin film electrodes for high-power and high-energy storage applications.

PubMed

Hyder, Md Nasim; Lee, Seung Woo; Cebeci, Fevzi Ç; Schmidt, Daniel J; Shao-Horn, Yang; Hammond, Paula T

2011-11-22

Thin film electrodes of polyaniline (PANi) nanofibers and functionalized multiwall carbon nanotubes (MWNTs) are created by layer-by-layer (LbL) assembly for microbatteries or -electrochemical capacitors. Highly stable cationic PANi nanofibers, synthesized from the rapid aqueous phase polymerization of aniline, are assembled with carboxylic acid functionalized MWNT into LbL films. The pH-dependent surface charge of PANi nanofibers and MWNTs allows the system to behave like weak polyelectrolytes with controllable LbL film thickness and morphology by varying the number of bilayers. The LbL-PANi/MWNT films consist of a nanoscale interpenetrating network structure with well developed nanopores that yield excellent electrochemical performance for energy storage applications. These LbL-PANi/MWNT films in lithium cell can store high volumetric capacitance (~238 ± 32 F/cm(3)) and high volumetric capacity (~210 mAh/cm(3)). In addition, rate-dependent galvanostatic tests show LbL-PANi/MWNT films can deliver both high power and high energy density (~220 Wh/L(electrode) at ~100 kW/L(electrode)) and could be promising positive electrode materials for thin film microbatteries or electrochemical capacitors. © 2011 American Chemical Society

Mechanically delaminated few layered MoS2 nanosheets based high performance wire type solid-state symmetric supercapacitors

NASA Astrophysics Data System (ADS)

Krishnamoorthy, Karthikeyan; Pazhamalai, Parthiban; Veerasubramani, Ganesh Kumar; Kim, Sang Jae

2016-07-01

Two dimensional nanostructures are increasingly used as electrode materials in flexible supercapacitors for portable electronic applications. Herein, we demonstrated a ball milling approach for achieving few layered molybdenum disulfide (MoS2) via exfoliation from their bulk. Physico-chemical characterizations such as X-ray diffraction, field emission scanning electron microscope, and laser Raman analyses confirmed the occurrence of exfoliated MoS2 sheets with few layers from their bulk via ball milling process. MoS2 based wire type solid state supercapacitors (WSCs) are fabricated and examined using cyclic voltammetry (CV), electrochemical impedance spectroscopy, and galvanostatic charge discharge (CD) measurements. The presence of rectangular shaped CV curves and symmetric triangular shaped CD profiles suggested the mechanism of charge storage in MoS2 WSC is due to the formation of electrochemical double layer capacitance. The MoS2 WSC device delivered a specific capacitance of 119 μF cm-1, and energy density of 8.1 nW h cm-1 with better capacitance retention of about 89.36% over 2500 cycles, which ensures the use of the ball milled MoS2 for electrochemical energy storage devices.

Double-shelled silicon anode nanocomposite materials: A facile approach for stabilizing electrochemical performance via interface construction

NASA Astrophysics Data System (ADS)

Du, Lulu; Wen, Zhongsheng; Wang, Guanqin; Yang, Yan-E.

2018-04-01

The rapid capacity fading induced by volumetric changes is the main issue that hinders the widespread application of silicon anode materials. Thus, double-shelled silicon composite materials where lithium silicate was located between an Nb2O5 coating layer and a silicon active core were configured to overcome the chemical compatibility issues related to silicon and oxides. The proposed composites were prepared via a facile co-precipitation method combined with calcination. Transmission electron microscopy and X-ray photoelectron spectroscopy analysis demonstrated that a transition layer of lithium silicate was constructed successfully, which effectively hindered the thermal inter-diffusion between the silicon and oxide coating layers during heat treatment. The electrochemical performance of the double-shelled silicon composites was enhanced dramatically with a retained specific capacity of 1030 mAh g-1 after 200 cycles at a current density of 200 mA g-1 compared with 598 mAh g-1 for a core-shell Si@Nb2O5 composite that lacked the interface. The lithium silicate transition layer was shown to play an important role in maintaining the high electrochemical stability.

Remotely adjustable check-valves with an electrochemical release mechanism for implantable biomedical microsystems.

PubMed

Pan, Tingrui; Baldi, Antonio; Ziaie, Babak

2007-06-01

In this paper, we present two remotely adjustable check-valves with an electrochemical release mechanism for implantable biomedical microsystems. These valves allow one to vary the opening pressure set-point and flow resistance over a period of time. The first design consists of a micromachined check-valve array using a SU-8 polymer structural layer deposited on the top of a gold sacrificial layer. The second design is based on a variable length cantilever beam structure with a gold sacrificial layer. The adjustable cantilever-beam structure is fabricated by gold thermo-compression bond of a thin silicon wafer over a glass substrate. In both designs, the evaporated gold can be electrochemically dissolved using a constant DC current via a telemetry link. In the first design the dissolution simply opens up individual outlets, while in the second design, gold anchors are sequentially dissolved hence increasing the effective length of the cantilever beam (reducing the opening pressure). A current density of 35 mA/cm(2) is used to dissolve the gold sacrificial layers. Both gravity and syringe-pump driven flow are used to characterize the valve performance. A multi-stage fluidic performance (e.g. flow resistance and opening pressure) is clearly demonstrated.

Electrochemical exfoliation of graphite to stage-III graphite bisulfate flakes in low concentration sulfuric acid solution: A novel synthesis route to completely trilayer graphene suspension

NASA Astrophysics Data System (ADS)

Mir, Afkham; Shukla, Anupam

2018-06-01

Graphene produced from electrochemical exfoliation of graphite show a scatter in the number of layers. This scatter is a serious drawback for sensor and opto-electronic applications since the electronic properties of graphene change with number of layers. The scatter in the layer number of graphene is caused by formation of the intermediate graphite intercalation compounds (GIC) of different stage numbers as well as simultaneous cleaving of the GICs in the dispersion-unsuitable aqueous environment. In this work, we show the synthesis of stage-III graphite bisulfate (GB) enriched flakes by electrochemical exfoliation of graphite in low concentration (0.1 M) sulfuric acid from two different routes. We further show that the intercalated bisulfate planes provide sites for selective cleaving of the GB particles to trilayer graphene in DMF, a solvent favorable for graphene dispersion. Morphological characterizations show that while GB particles from one of the routes give graphene with a small scatter in the layer numbers, the other route provides a completely trilayer graphene dispersion. TEM and optical micrographs show graphene flakes have linear dimensions of several micrometers and a low aspect ratio suitable for use in sensor applications.

Synthesis and structure of cesium complexes of nitrilotris(methylenephosphonic) acid [Cs-μ6-NH(CH2PO3)3H4] and [Cs2-μ10-NH(CH2PO3H)3] · H2O

NASA Astrophysics Data System (ADS)

Somov, N. V.; Chausov, F. F.; Zakirov, R. M.

2017-07-01

3D coordination polymers cesium nitrilotris(methylenephosphonate) and dicesium nitrilotris( methylenephosphonate) are synthesized and their crystal structure is determined. In the crystal of [Cs-μ6-NH(CH2PO3)3H4] (space group P, Z = 2), cesium atoms occupy two crystallographically inequivalent positions with c.n. = 10 and c.n. = 14. The phosphonate ligand plays the bridging function; its denticity is nine. The crystal packing consists of alternating layers of Cs atoms in different environments with layers of ligand molecules between them. A ligand is bound to three Cs atoms of one layer and three Cs atoms of another layer. In the crystal of [Cs2-μ10-NH(CH2PO3H)3] · H2O (space group P, Z = 2), the complex has a dimeric structure: the bridging phosphonate ligand coordinates Cs to form a three-dimensional Cs4O6 cluster. The denticity of the ligand is equal to nine; the coordination numbers of cesium atoms are seven and nine. Two-dimensional corrugated layers of Cs4O6 clusters lie in the (002) plane, and layers of ligand molecules are located between them. Each ligand molecule coordinates eight Cs atoms of one layer and two Cs atoms of the neighboring layer.

Nanoscale potentiometry.

PubMed

Bakker, Eric; Pretsch, Ernö

2008-01-01

Potentiometric sensors share unique characteristics that set them apart from other electrochemical sensors. Potentiometric nanoelectrodes have been reported and successfully used for many decades, and we review these developments. Current research chiefly focuses on nanoscale films at the outer or the inner side of the membrane, with outer layers for increasing biocompatibility, expanding the sensor response, or improving the limit of detection (LOD). Inner layers are mainly used for stabilizing the response and eliminating inner aqueous contacts or undesired nanoscale layers of water. We also discuss the ultimate detectability of ions with such sensors and the power of coupling the ultra-low LODs of ion-selective electrodes with nanoparticle labels to give attractive bioassays that can compete with state-of-the-art electrochemical detection.

Unexpected Voltage Fade in LMR-NMC Oxides Cycled below the "Activation" Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Y.; Bareno, J.; Bettge, M.

A common feature of lithium-excess layered oxides, nominally of composition xLi(2)MnO(3)center dot(1-x)LiMO2 (M = transition metal) is a high-voltage plateau (similar to 4.5 V vs. Li/Li+) in their capacity-voltage profile during the first delithiation cycle. This plateau is believed to result from activation of the Li2MnO3 component, which makes additional lithium available for electrochemical cycling. However, oxides cycled beyond this activation plateau are known to display voltage fade which is a continuous reduction in their equilibrium potential. In this article we show that these oxides display gradual voltage fade even on electrochemical cycling in voltage ranges well below the activationmore » plateau. The average fade is similar to 0.08 mV-cycle(-1) for Li(1.2)Ni(0.1)5Mn(0.5)5Co(0.1)O(2) vs. Li cells after 20 cycles in the 2-4.1 V range at 55 degrees C; a similar to 54 mV voltage hysteresis, expressed as the difference in average cell voltage between charge and discharge cycles, is also observed. The voltage fade results from a gradual accumulation of local spinel environments in the crystal structure. Some of these spinel sites result from lithium deficiencies during oxide synthesis and are likely to be at the particle surfaces; other sites result from the migration of transition metal atoms in the partially-delithiated LiMO2 component into the lithium planes during electrochemical cycling. The observed rate of voltage fade depends on a combination of factors that includes the phase equilibrium between the layered and spinel components and the kinetics of transition metal migration. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.« less

Synthesis and characterization of sputtered titanium nitride as a nucleation layer for novel neural electrode coatings

NASA Astrophysics Data System (ADS)

Sait, R. A.; Cross, R. B. M.

2017-12-01

A growing demand for chronically implantable electrodes has led to a search for the most suitable neural electrode interface material. Nobel metals such as platinum (Pt) are inadequate for electrode/neuron interfaces at small scales due to their poor electrochemical properties, low charge injection and high charge density per unit area. Titanium nitride (TiN) has been implemented in neural electrodes application due to its outstanding properties. In this work, TiNx films were deposited by non-reactive radio frequency (RF) magnetron sputtering towards the development of a novel TiN nanowires (NWs) neural interface. Although, there is substantial work on this material, its growth using non-reactive RF magnetron sputtering has not been reported previously and optimised towards the growth of TiN NWs and their use in neural interface applications. The sputtering parameters of RF power and argon (Ar) flow rate were varied in order to investigate their effects on the structural, electrical and electrochemical properties of the TiN films. A dense film morphology was observed in the scanning electron microscopy (SEM) images of TiN thin films showing a columnar structure. The film preferential orientation was changed between (200) and (111) with Ar flow rate due to the variation of the kinetic energy (KE) of the sputtered atoms. The crystallites size obtained were in the range of 13-95 nm. Surface roughness was found to increase from 0.69 to 1.95 nm as Ar flow rate increased. TiNx films showed a good electrical resistivity of 228 μΩ cm. Stoichiometry was found to vary with sputtering conditions in which the nitrogen content was found to deplete from the film at low Ar flow rate. The electrochemical behaviour of TiN films were characterised and the highest capacitance value obtained was 0.416 mF/cm2. From the results, it can be suggested that TiN thin film can be easily optimised to act as a nucleation layer for the growth of nanowires.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.