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.

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

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.

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.

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.

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.

High speed chalcogenide glass electrochemical metallization cells with various active metals.

PubMed

Hughes, Mark A; Burgess, Alexander; Hinder, Steven; Gholizadeh, A Baset; Craig, Christopher; Hewak, Daniel W

2018-08-03

We fabricated electrochemical metallization cells using a GaLaSO solid electrolyte, an InSnO inactive electrode and active electrodes consisting of various metals (Cu, Ag, Fe, Cu, Mo, Al). Devices with Ag and Cu active metals showed consistent and repeatable resistive switching behaviour, and had a retention of 3 and >43 days, respectively; both had switching speeds of <5 ns. Devices with Cr and Fe active metals displayed incomplete or intermittent resistive switching, and devices with Mo and Al active electrodes displayed no resistive switching ability. Deeper penetration of the active metal into the GaLaSO layer resulted in greater resistive switching ability of the cell. The off-state resistivity was greater for more reactive active metals which may be due to a thicker intermediate layer.

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.

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.

Extending the Diffuse Layer Model of Surface Acidity Behavior: III. Estimating Bound Site Activity Coefficients

EPA Science Inventory

Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in applic...

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

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

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

Planar fuel cell utilizing nail current collectors for increased active surface area

DOEpatents

George, Thomas J.; Meacham, G. B. Kirby

2002-03-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

Planar fuel cell utilizing nail current collectors for increased active surface area

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

George, Thomas J.; Meacham, G.B. Kirby

1999-11-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

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

Electrochemically Active Polyaniline (PANi) Coated Carbon Nanopipes and PANi Nanofibers Containing Composite.

PubMed

Ramana, G Venkata; Kumar, P Sampath; Srikanth, Vadali V S S; Padya, Balaji; Jain, P K

2015-02-01

A composite constituted by carbon nanopipes (CNPs) and polyaniline nanofibers (PANi NFs) is synthesized using in-situ chemical oxidative polymerization. Owing to its electrochemical activity the composite is found to be suitable as a working electrode material in hybrid type supercapacitors. Microstructural and phase analyses of the composite showed that (i) CNP surfaces are coated with PANi and (ii) PANi coated CNPs are distributed among PANi NFs. The composite shows an excellent electrochemical activity and a high specific capacitance of ~224.39 F/g. The electro-chemical activity of the composite is explicated in correlation with crystallinity, intrinsic oxidation state, and doping degree of PANi in the composite. The electro-chemical activity of the composite is also explicated in correlation with BET surface area and ordered meso-porosity pertaining to the composite. Charge/discharge curves indicate that the specific capacitance of the composite is a result of electric double-layer capacitance offered by CNPs and Faradaic pseudo capacitance offered by PANi NFs.

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.

Vapor-Phase Atomic Layer Deposition of Co9S8 and Its Application for Supercapacitors.

PubMed

Li, Hao; Gao, Yuanhong; Shao, Youdong; Su, Yantao; Wang, Xinwei

2015-10-14

Atomic layer deposition (ALD) of cobalt sulfide (Co9S8) is reported. The deposition process uses bis(N,N'-diisopropylacetamidinato)cobalt(II) and H2S as the reactants and is able to produce high-quality Co9S8 films with an ideal layer-by-layer ALD growth behavior. The Co9S8 films can also be conformally deposited into deep narrow trenches with aspect ratio of 10:1, which demonstrates the high promise of this ALD process for conformally coating Co9S8 on high-aspect-ratio 3D nanostructures. As Co9S8 is a highly promising electrochemical active material for energy devices, we further explore its electrochemical performance by depositing Co9S8 on porous nickel foams for supercapacitor electrodes. Benefited from the merits of ALD for making high-quality uniform thin films, the ALD-prepared electrodes exhibit remarkable electrochemical performance, with high specific capacitance, great rate performance, and long-term cyclibility, which highlights the broad and promising applications of this ALD process for energy-related electrochemical devices, as well as for fabricating complex 3D nanodevices in general.

Active hydrogen evolution through lattice distortion in metallic MoTe2

NASA Astrophysics Data System (ADS)

Seok, Jinbong; Lee, Jun-Ho; Cho, Suyeon; Ji, Byungdo; Kim, Hyo Won; Kwon, Min; Kim, Dohyun; Kim, Young-Min; Oh, Sang Ho; Wng Kim, Sung; Lee, Young Hee; Son, Young-Woo; Yang, Heejun

2017-06-01

Engineering surface atoms of transition metal dichalcogenides (TMDs) is a promising way to design catalysts for efficient electrochemical reactions including the hydrogen evolution reaction (HER). However, materials processing based on TMDs, such as vacancy creation or edge exposure, for active HER, has resulted in insufficient atomic-precision lattice homogeneity and a lack of clear understanding of HER over 2D materials. Here, we report a durable and effective HER at atomically defined reaction sites in 2D layered semimetallic MoTe2 with intrinsic turnover frequency (TOF) of 0.14 s-1 at 0 mV overpotential, which cannot be explained by the traditional volcano plot analysis. Unlike former electrochemical catalysts, the rate-determining step of the HER on the semimetallic MoTe2, hydrogen adsorption, drives Peierls-type lattice distortion that, together with a surface charge density wave, unexpectedly enhances the HER. The active HER using unique 2D features of layered TMDs enables an optimal design of electrochemical catalysts and paves the way for a hydrogen economy.

Enabling high areal capacitance in electrochemical double layer capacitors by means of the environmentally friendly starch binder

NASA Astrophysics Data System (ADS)

Varzi, Alberto; Passerini, Stefano

2015-12-01

Potatoes starch (PS), a natural polymer obtainable from non-edible sources, is for the first time evaluated as alternative water-processable binder for Electrochemical Double-Layer Capacitor (EDLC) electrodes. Morphological and electrochemical properties of activated carbon (AC)-based electrodes are investigated and compared to those achieved with the state-of-the-art aqueous binder (CMC, i.e. Na-carboxymethyl cellulose). The obtained results suggest substantial benefits of PS, in particular regarding the electrode fabrication process. As a matter of fact, owing to its amylopectin content (moderately branched polysaccharide), PS displays only minimal shrinkage upon drying, resulting on rather homogeneous electrodes not presenting the dramatic surface cracking observed with CMC. Furthermore, owing to the smaller volume of water required for the processing, much higher active material loading per area unit can be achieved. This is reflected on improvements of up to 60% in terms of areal capacitance.

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« 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.

Unsymmetrical and symmetrical azines toward application in organic photovoltaic

NASA Astrophysics Data System (ADS)

Jarczyk-Jedryka, Anna; Bijak, Katarzyna; Sek, Danuta; Siwy, Mariola; Filapek, Michal; Malecki, Grzegorz; Kula, Slawomir; Lewinska, Gabriela; Nowak, Elzbieta M.; Sanetra, Jerzy; Janeczek, Henryk; Smolarek, Karolina; Mackowski, Sebastian; Schab-Balcerzak, Ewa

2015-01-01

The unsymmetrical and symmetrical azines prepared by condensation of benzophenone hydrazone with (di)aldehydes with thiophene rings were reported in this study The structures of obtained compounds were characterized by FTIR, 1H NMR, and 13C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of azines were investigated. The unsymmetrical azine with bithiophene unit exhibited liquid crystalline properties as was detected by DSC and POM experiments. All compounds are electrochemically active, however, only azines with bithiophene structure undergo reversible reduction process as was found in cyclic and differential pulse voltammetry (CV and DPV) studies. Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). The photovoltaic properties of two azines as active layer in organic solar cells at the configuration ITO/PEDOT:PSS/active layer/Al under an illumination of 1.3 mW/cm2 were studied. Active cell layers blends of poly 3-hekxylthiophene (P3HT) or poly 3-butylthiophene (P3OT) with azines were applied. The device comprising P3HT with symmetrical azine containing bithiophene unit showed the highest value of power conversion efficiency (0.82%). To the best of our knowledge, the azines are very seldom considered as potential compounds in active layer in bulk heterojunction (BHJ) solar cells.

Layered method of electrode for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1991-07-30

A process for fabricating a fuel electrode comprising: slurry dipping to form layers which are structurally graded from all or mostly all stabilized zirconia at a first layer, to an outer most layer of substantially all metal powder, such an nickel. Higher performaance fuel electrodes may be achieved if sinter active stabilized zirconia doped for electronic conductivity is used.

Analysis and Modeling of Boundary Layer Separation Method (BLSM).

PubMed

Pethő, Dóra; Horváth, Géza; Liszi, János; Tóth, Imre; Paor, Dávid

2010-09-01

Nowadays rules of environmental protection strictly regulate pollution material emission into environment. To keep the environmental protection laws recycling is one of the useful methods of waste material treatment. We have developed a new method for the treatment of industrial waste water and named it boundary layer separation method (BLSM). We apply the phenomena that ions can be enriched in the boundary layer of the electrically charged electrode surface compared to the bulk liquid phase. The main point of the method is that the boundary layer at correctly chosen movement velocity can be taken out of the waste water without being damaged, and the ion-enriched boundary layer can be recycled. Electrosorption is a surface phenomenon. It can be used with high efficiency in case of large electrochemically active surface of electrodes. During our research work two high surface area nickel electrodes have been prepared. The value of electrochemically active surface area of electrodes has been estimated. The existence of diffusion part of the double layer has been experimentally approved. The electrical double layer capacity has been determined. Ion transport by boundary layer separation has been introduced. Finally we have tried to estimate the relative significance of physical adsorption and electrosorption.

Novel neural interface for implant electrodes: improving electroactivity of polypyrrole through MWNT incorporation.

PubMed

Green, R A; Williams, C M; Lovell, N H; Poole-Warren, L A

2008-04-01

Multi-walled carbon nanotubes (MWNTs) can be incorporated into conductive polymers to produce superior materials for neural interfaces with high interfacial areas, conductivity and electrochemical stability. This paper explores the addition of MWNTs to polypyrrole (PPy) through two methods, layering and codeposition. Conductivity of PPy doped with polystyrene sulfonate (PSS), a commonly used dopant, was improved by 50% when MWNTs were layered with PPy/PSS. The film electrochemical stability was improved from 38% activity to 66% activity after 400 cycles of oxidation and reduction. Growth inhibition assays indicated that MWNTs are not growth inhibitory. The electroactive polymer-MWNT composites produced demonstrate properties that suggest they are promising candidates for biomedical electrode coatings.

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.

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.

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.

Electrochemical cell having cylindrical electrode elements

DOEpatents

Nelson, Paul A.; Shimotake, Hiroshi

1982-01-01

A secondary, high temperature electrochemical cell especially adapted for lithium alloy negative electrodes, transition metal chalcogenide positive electrodes and alkali metal halide or alkaline earth metal halide electrolyte is disclosed. The cell is held within an elongated cylindrical container in which one of the active materials is filled around the outside surfaces of a plurality of perforate tubular current collectors along the length of the container. Each of the current collector tubes contain a concentric tubular layer of electrically insulative ceramic as an interelectrode separator. The active material of opposite polarity in elongated pin shape is positioned longitudinally within the separator layer. A second electrically conductive tube with perforate walls can be swagged or otherwise bonded to the outer surface of the pin as a current collector and the electrically insulative ceramic layer can be coated or otherwise layered onto the outer surface of this second current collector. Alternatively, the central pin electrode can include an axial core as a current collector.

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide

DOE PAGES

Shadike, Zulipiya; Zhou, Yong -Ning; Chen, Lan -Li; ...

2017-08-30

The intercalation compounds with various electrochemically active or inactive elements in the layered structure have been the subject of increasing interest due to their high capacities, good reversibility, simple structures and ease of synthesis. However, their reversible intercalation/deintercalation redox chemistries in all previous compounds involve a single cationic redox reaction or a cumulative cationic and anionic redox reaction. Here we report an anionic redox only chemistry and structural stabilization of layered sodium chromium sulfide. It is discovered that sulfur in sodium chromium sulfide is electrochemical active undergoing oxidation/reduction of sulfur rather than chromium. Significantly, sodium ions can successfully move outmore » and into without changing its lattice parameter c, which is explained in terms of the occurrence of chromium/sodium vacancy antisite during desodiation and sodiation processes. Here, our present work not only enriches the electrochemistry of layered intercalation compounds, but also extends the scope of investigation on high-capacity electrodes.« less

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide

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

Shadike, Zulipiya; Zhou, Yong -Ning; Chen, Lan -Li

The intercalation compounds with various electrochemically active or inactive elements in the layered structure have been the subject of increasing interest due to their high capacities, good reversibility, simple structures and ease of synthesis. However, their reversible intercalation/deintercalation redox chemistries in all previous compounds involve a single cationic redox reaction or a cumulative cationic and anionic redox reaction. Here we report an anionic redox only chemistry and structural stabilization of layered sodium chromium sulfide. It is discovered that sulfur in sodium chromium sulfide is electrochemical active undergoing oxidation/reduction of sulfur rather than chromium. Significantly, sodium ions can successfully move outmore » and into without changing its lattice parameter c, which is explained in terms of the occurrence of chromium/sodium vacancy antisite during desodiation and sodiation processes. Here, our present work not only enriches the electrochemistry of layered intercalation compounds, but also extends the scope of investigation on high-capacity electrodes.« 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

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.

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

2018-02-01

In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

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.

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.

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.

Electrochromic devices

DOEpatents

Allemand, Pierre M.; Grimes, Randall F.; Ingle, Andrew R.; Cronin, John P.; Kennedy, Steve R.; Agrawal, Anoop; Boulton, Jonathan M.

2001-01-01

An electrochromic device is disclosed having a selective ion transport layer which separates an electrochemically active material from an electrolyte containing a redox active material. The devices are particularly useful as large area architectural and automotive glazings due to there reduced back reaction.

Elucidating anionic oxygen activity in lithium-rich layered oxides

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

Xu, Jing; Sun, Meiling; Qiao, Ruimin

Recent research has explored combining conventional transition metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. For this study, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely differentmore » oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.« less

Elucidating anionic oxygen activity in lithium-rich layered oxides

DOE PAGES

Xu, Jing; Sun, Meiling; Qiao, Ruimin; ...

2018-03-05

Recent research has explored combining conventional transition metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. For this study, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely differentmore » oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.« less

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.

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.

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.

Impedance spectroscopy study of a catechol-modified activated carbon electrode as active material in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Cougnon, C.; Lebègue, E.; Pognon, G.

2015-01-01

Modified activated carbon (Norit S-50) electrodes with electrochemical double layer (EDL) capacitance and redox capacitance contributions to the electric charge storage were tested in 1 M H2SO4 to quantify the benefit and the limitation of the surface redox reactions on the electrochemical performances of the resulting pseudo-capacitive materials. The electrochemical performances of an electrochemically anodized carbon electrode and a catechol-modified carbon electrode, which make use both EDL capacitance of the porous structure of the carbon and redox capacitance, were compared to the performances obtained for the pristine carbon. Nitrogen gas adsorption measurements have been used for studying the impact of the grafting on the BET surface area, pore size distribution, pore volume and average pore diameter. The electrochemical behavior of carbon materials was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The EIS data were discussed by using a complex capacitance model that allows defining the characteristic time constant, the global capacitance and the frequency at which the maximum charge stored is reached. The EIS measurements were achieved at different dc potential values where a redox activity occurs and the evolution of the capacitance and the capacitive relaxation time with the electrode potential are presented. Realistic galvanostatic charge/discharge measurements performed at different current rates corroborate the results obtained by impedance.

Plastic-bonded electrodes for nickel-cadmium accumulators. IV - Some specific problems of the positive active layer

NASA Astrophysics Data System (ADS)

Micka, K.; Mrha, J.; Klapste, B.

1980-06-01

The active layer of plastic-bonded nickel oxide electrodes undergoes expansion during discharging and contraction during charging; the latter however does not fully compensate for the expansion. These volume changes can be made reversible by the action of an external pressure. The electro-chemical behavior of the conductive components, carbon black and graphite, shows more or less severe corrosion during anodic current loading.

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.

Influence of carbon conductive additives on electrochemical double-layer supercapacitor parameters

NASA Astrophysics Data System (ADS)

Kiseleva, E. A.; Zhurilova, M. A.; Kochanova, S. A.; Shkolnikov, E. J.; Tarasenko, A. B.; Zaitseva, O. V.; Uryupina, O. V.; Valyano, G. V.

2018-01-01

Electrochemical double-layer capacitors (EDLC) offer energy storage technology, highly demanded for rapid transition processes in transport and stationary applications, concerned with fast power fluctuations. Rough structure of activated carbon, widely used as electrode material because of its high specific area, leads to poor electrode conductivity. Therefore there is the need for conductive additive to decrease internal resistance and to achieve high specific power and high specific energy. Usually carbon blacks are widely used as conductive additive. In this paper electrodes with different conductive additives—two types of carbon blacks and single-walled carbon nanotubes—were prepared and characterized in organic electrolyte-based EDLC cells. Electrodes are based on original wood derived activated carbon produced by potassium hydroxide high-temperature activation at Joint Institute for High Temperatures RAS. Electrodes were prepared from slurry by cold-rolling. For electrode characterization cyclic voltammetry, impedance spectra analysis, equivalent series resistance measurements and galvanostatic charge-discharge were used.

Simultaneous determination of dopamine and uric acid using layer-by-layer graphene and chitosan assembled multilayer films.

PubMed

Weng, Xuexiang; Cao, Qingxue; Liang, Lixin; Chen, Jianrong; You, Chunping; Ruan, Yongmin; Lin, Hongjun; Wu, Lanju

2013-12-15

Multilayer films containing graphene (Gr) and chitosan (CS) were prepared on glassy carbon electrodes with layer-by-layer (LBL) assembly technique. After being characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM), the electrochemical sensor based on the resulted films was developed to simultaneously determine dopamine (DA) and uric acid (UA). The LBL assembled electrode showed excellent electrocatalytic activity towards the oxidation of DA and UA. In addition, the self-assembly electrode possessed an excellent sensing performance for detection of DA and UA with a linear range from 0.1 μM to 140 µM and from 1.0 µM to 125 µM with the detection limit as low as 0.05 µM and 0.1 µM based on S/N=3, respectively. © 2013 Elsevier B.V. All rights reserved.

Electrochemical cell having an alkali-metal-nitrate electrode

DOEpatents

Roche, M.F.; Preto, S.K.

1982-06-04

A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

Phenomenological Transition of an Aluminum Surface in an Ionic Liquid and Its Beneficial Implementation in Batteries.

PubMed

Shvartsev, B; Gelman, D; Amram, D; Ein-Eli, Y

2015-12-29

Aluminum (Al) electrochemical dissolution in organic nonaqueous media and room temperature ionic liquids (RTILs) is partially hampered by the presence of a native oxide. In this work, Al activation in EMIm(HF)2.3F RTIL is reported. It was confirmed that as a result of the interaction of Al with the RTIL, a new film is formed instead of the pristine oxide layer. Aluminum surface modifications result in a transformation from a passive state to the active behavior of the metal. This was confirmed via the employment of electrochemical methods and characterization by XPS, AFM, and TEM. It was shown that the pristine oxide surface film dissolves in EMIm(HF)2.3F, allowing an Al-O-F layer to be formed instead. This newly built up layer dramatically restricts Al corrosion while enabling high rates of Al anodic dissolution. These beneficial features allow the implementation of Al as an anode in advanced portable power sources, such as aluminum-air batteries.

Preparation of activated carbon hollow fibers from ramie at low temperature for electric double-layer capacitor applications.

PubMed

Du, Xuan; Zhao, Wei; Wang, Yi; Wang, Chengyang; Chen, Mingming; Qi, Tao; Hua, Chao; Ma, Mingguo

2013-12-01

Activated carbon hollow fibers (ACHFs) with high surface area were prepared from inexpensive, renewable ramie fibers (RFs) by a single-step activation method under lower temperature than that of other reports. The effects of activation conditions on the pore structure and turbostratic structure of ACHFs were investigated systematically. The results show that ACHFs surface area decreased but micropore volume and conductivity increased as the increase of activation temperature and activation time. The electrochemical measurements of supercapacitors fabricated from these ACHFs electrodes reveal that the electrochemical properties improved with the enhancing of activation degree. However, too high activation temperature can make the ion diffusion resistance increase. It suggests that pore structure and conductivity are as important as surface area to decide the electrochemical performances of ACHFs electrode materials. A maximum capacity of 287 F g(-1) at 50 mA g(-1) was obtained for the ACHFs electrode prepared under suitable conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical 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.

The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning

NASA Astrophysics Data System (ADS)

Kim, Uk Su; Morita, Noboru; Lee, Deug Woo; Jun, Martin; Park, Jeong Woo

2017-05-01

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.

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.

Solution Processed PEDOT Analogues in Electrochemical Supercapacitors.

PubMed

Österholm, Anna M; Ponder, James F; Kerszulis, Justin A; Reynolds, John R

2016-06-01

We have designed fully soluble ProDOTx-EDOTy copolymers that are electrochemically equivalent to electropolymerized PEDOT without using any surfactants or dispersants. We show that these copolymers can be incorporated as active layers in solution processed thin film supercapacitors to demonstrate capacitance, stability, and voltage similar to the values of those that use electrodeposited PEDOT as the active material with the added advantage of the possibility for large scale, high-throughput processing. These Type I supercapacitors provide exceptional cell voltages (up to 1.6 V), highly symmetrical charge/discharge behavior, promising long-term stability exceeding 50 000 charge/discharge cycles, as well as energy (4-18 Wh/kg) and power densities (0.8-3.3 kW/kg) that are comparable to those of electrochemically synthesized analogues.

Fabrication of SOI structures with buried cavities using Si wafer direct bonding and electrochemical etch-stop

NASA Astrophysics Data System (ADS)

Chung, Gwiy-Sang

2003-10-01

This paper describes the fabrication of SOI structures with buried cavities using SDB and electrochemical etch-stop. These methods are suitable for thick membrane fabrication with accurate thickness, uniformity, and flatness. After a feed-through hole for supplied voltage and buried cavities was formed on a handle Si wafer with p-type, the handle wafer was bonded to an active Si wafer consisting of a p-type substrate with an n-type epitaxial layer corresponding to membrane thickness. The bonded pair was then thinned until electrochemical etch-stop occurred at the pn junction during electrochemical etchback. By using the SDB SOI structure with buried cavities, active membranes, which have a free standing structure with a dimension of 900×900 μm2, were fabricated. It is confirmed that the fabrication process of the SDB SOI structure with buried cavities is a powerful and versatile technology for new MEMS applications.

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.

Kinetics of electrochemical boriding of low carbon steel

NASA Astrophysics Data System (ADS)

Kartal, G.; Eryilmaz, O. L.; Krumdick, G.; Erdemir, A.; Timur, S.

2011-05-01

In this study, the growth kinetics of the boride layers forming on low carbon steel substrates was investigated during electrochemical boriding which was performed at a constant current density of 200 mA/cm 2 in a borax based electrolyte at temperatures ranging from 1123 K to 1273 K for periods of 5-120 min. After boriding, the presence of both FeB and Fe 2B phases were confirmed by the X-ray diffraction method. Cross-sectional microscopy revealed a very dense and thick morphology for both boride phases. Micro hardness testing of the borided steel samples showed a significant increase in the hardness of the borided surfaces (i.e., up to (1700 ± 200) HV), while the hardness of un-borided steel samples was approximately (200 ± 20) HV. Systematic studies over a wide range of boriding time and temperature confirmed that the rate of the boride layer formation is strongly dependent on boriding duration and has a parabolic character. The activation energy of boride layer growth for electrochemical boriding was determined as (172.75 ± 8.6) kJ/mol.

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Flowable Conducting Particle Networks in Redox-Active Electrolytes for Grid Energy Storage

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

Hatzell, K. B.; Boota, M.; Kumbur, E. C.

2015-01-01

This study reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO2+/VO2+ redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage. Charge storage contributionsmore » (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO2+/VO2+ redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s-1) than one based on a non-redox active electrolyte. Furthermore, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

Flowable conducting particle networks in redox-active electrolytes for grid energy storage

DOE PAGES

Hatzell, K. B.; Boota, M.; Kumbur, E. C.; ...

2015-01-09

This paper reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO 2+/VO 2 + redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage.more » Charge storage contributions (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO 2+/VO 2 + redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s -1) than one based on a non-redox active electrolyte. Additionally, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage.

PubMed

Guan, Cao; Wang, John

2016-10-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution-based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed.

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage

PubMed Central

2016-01-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution‐based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed. PMID:27840793

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2012-10-09

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2008-04-01

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

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.

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.

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.

Direct electrochemistry of Shewanella loihica PV-4 on gold nanoparticles-modified boron-doped diamond electrodes fabricated by layer-by-layer technique.

PubMed

Wu, Wenguo; Xie, Ronggang; Bai, Linling; Tang, Zuming; Gu, Zhongze

2012-05-01

Microbial Fuel Cells (MFCs) are robust devices capable of taping biological energy, converting pollutants into electricity through renewable biomass. The fabrication of nanostructured electrodes with good bio- and electrochemical activity, play a profound role in promoting power generation of MFCs. Au nanoparticles (AuNPs)-modified Boron-Doped Diamond (BDD) electrodes are fabricated by layer-by-layer (LBL) self-assembly technique and used for the direct electrochemistry of Shewanella loihica PV-4 in an electrochemical cell. Experimental results show that the peak current densities generated on the Au/PAH multilayer-modified BDD electrodes increased from 1.25 to 2.93 microA/cm(-2) as the layer increased from 0 to 6. Different cell morphologies of S. loihica PV-4 were also observed on the electrodes and the highest density of cells was attached on the (Au/PAH)6/BDD electrode with well-formed three-dimensional nanostructure. The electrochemistry of S. loihica PV-4 was enhanced on the (Au/PAH)4/BDD electrode due to the appropriate amount of AuNPsand thickness of PAH layer.

Humic acids as pseudocapacitive electrolyte additive for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Wasiński, Krzysztof; Walkowiak, Mariusz; Lota, Grzegorz

2014-06-01

Novel electrolyte additive for electrochemical capacitors has been reported. It has been demonstrated for the first time that addition of humic acids (HA) to KOH-based electrolyte significantly increases capacitance of symmetrical capacitors with electrodes made of activated carbon. Specific capacitances determined by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy consistently showed increases for HA concentrations ranging from 2% w/w up to saturated solution with maximum positive effect observed for 5% w/w of the additive. The capacitance increase has been attributed to complex faradaic processes involving oxygen-containing groups of HA molecules. Due to abundant resources, low cost and easy processability the reported solution can find application in electrochemical capacitor technologies.

TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.

PubMed

Tokue, Hiroshi; Oyaizu, Kenichi; Sukegawa, Takashi; Nishide, Hiroyuki

2014-03-26

A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.

Electrochemical properties and electrocatalytic activity of conducting polymer/copper nanoparticles supported on reduced graphene oxide composite

NASA Astrophysics Data System (ADS)

Ehsani, Ali; Jaleh, Babak; Nasrollahzadeh, Mahmoud

2014-07-01

Reduced graphene oxide (rGO) was used to support Cu nanoparticles. As electro-active electrodes for supercapacitors composites of reduced graphene oxide/Cu nanoparticles (rGO/CuNPs) and polytyramine (PT) with good uniformity are prepared by electropolymerization. Composite of rGO/CuNPs-PT was synthesized by cyclic voltammetry (CV) methods and electrochemical properties of film were investigated by using electrochemical techniques. The results show that, the rGO/CuNPs-PT/G has better capacitance performance. This is mainly because of the really large surface area and the better electronic and ionic conductivity of rGO/CuNPs-PT/G, which lead to greater double-layer capacitance and faradic pseudo capacitance. Modified graphite electrodes (rGO/CuNPs-PT/G) were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) were employed. In comparison with a Cu-PT/G (Graphite), rGO/CuNPs-PT/G modified electrode shows a significantly higher response for methanol oxidation. A mechanism based on the electro-chemical generation of Cu(III) active sites and their subsequent consumptions by methanol have been discussed.

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.

Layering and Ordering in Electrochemical Double Layers

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

Liu, Yihua; Kawaguchi, Tomoya; Pierce, Michael S.

Electrochemical double layers (EDL) form at electrified interfaces. While Gouy-Chapman model describes moderately charged EDL, formation of Stern layers was predicted for highly charged EDL. Our results provide structural evidence for a Stern layer of cations, at potentials close to hydrogen evolution in alkali fluoride and chloride electrolytes. Layering was observed by x-ray crystal truncation rods and atomic-scale recoil responses of Pt(111) surface layers. Ordering in the layer is confirmed by glancing-incidence in-plane diffraction measurements.

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

Role of Cobalt Content in Improving the Low-Temperature Performance of Layered Lithium-Rich Cathode Materials for Lithium-Ion Batteries.

PubMed

Kou, Jianwen; Chen, Lai; Su, Yuefeng; Bao, Liying; Wang, Jing; Li, Ning; Li, Weikang; Wang, Meng; Chen, Shi; Wu, Feng

2015-08-19

Layered lithium-rich cathode material, Li1.2Ni0.2-xCo2xMn0.6-xO2 (x = 0-0.05) was successfully synthesized using a sol-gel method, followed by heat treatment. The effects of trace amount of cobalt doping on the structure, morphology, and low-temperature (-20 °C) electrochemical properties of these materials are investigated systematically. X-ray diffraction (XRD) results confirm that the Co has been doped into the Ni/Mn sites in the transition-metal layers without destroying the pristine layered structure. The morphological observations reveal that there are no changes of morphology or particle size after Co doping. The electrochemical performance results indicate that the discharge capacities and operation voltages are drastically lowered along with the decreasing temperature, but their fading rate becomes slower when increasing the Co contents. At -20 °C, the initial discharge capacity of sample with x = 0 could retain only 22.1% (57.3/259.2 mAh g(-1)) of that at 30 °C, while sample with x = 0.05 could maintain 39.4% (111.3/282.2 mAh g(-1)). Activation energy analysis and electrochemical impedance spectroscopy (EIS) results reveal that such an enhancement of low-temperature discharge capacity is originated from the easier interface reduction reaction of Ni(4+) or Co(4+) after doping trace amounts of Co, which decreases the activation energy of the charge transfer process above 3.5 V during discharging.

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.

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).

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Catalytic Graphitization for Preparation of Porous Carbon Material Derived from Bamboo Precursor and Performance as Electrode of Electrical Double-Layer Capacitor

NASA Astrophysics Data System (ADS)

Tsubota, Toshiki; Maguchi, Yuta; Kamimura, Sunao; Ohno, Teruhisa; Yasuoka, Takehiro; Nishida, Haruo

2015-12-01

The combination of addition of Fe (as a catalyst for graphitization) and CO2 activation (a kind of gaseous activation) was applied to prepare a porous carbon material from bamboo powder (a waste product of superheated steam treatment). Regardless of the heat treatment temperature, many macropores were successfully formed after the heating process by removal of Fe compounds. A turbostratic carbon structure was generated in the Fe-added sample heated at 850°C. It was confirmed that the added Fe acted as a template for pore formation. Moreover, it was confirmed that the added Fe acted as a catalyst for graphitization. The resulting electrochemical performance as the electrode of an electrical double-layer capacitor, as demonstrated by cyclic voltammetry, electrochemical impedance spectroscopy, and charge-discharge testing, could be explained based on the graphitization and activation effects. Addition of Fe could affect the electrical properties of carbon material derived from bamboo.

Optimization of Layered Cathode Materials for Lithium-Ion Batteries

PubMed Central

Julien, Christian; Mauger, Alain; Zaghib, Karim; Groult, Henri

2016-01-01

This review presents a survey of the literature on recent progress in lithium-ion batteries, with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar compounds LiMO2, where M stands for a mixture of Ni, Mn, Co elements, and in the family of yLi2MnO3•(1 − y)LiNi½Mn½O2 layered-layered integrated materials. The structural, physical, and chemical properties of these cathode elements are reported and discussed as a function of all the synthesis parameters, which include the choice of the precursors and of the chelating agent, and as a function of the relative concentrations of the M cations and composition y. Their electrochemical properties are also reported and discussed to determine the optimum compositions in order to obtain the best electrochemical performance while maintaining the structural integrity of the electrode lattice during cycling. PMID:28773717

Polypyrrole Actuator Based on Electrospun Microribbons.

PubMed

Beregoi, Mihaela; Evanghelidis, Alexandru; Diculescu, Victor C; Iovu, Horia; Enculescu, Ionut

2017-11-01

The development of soft actuators by using inexpensive raw materials and straightforward fabrication techniques, aiming at creating and developing muscle like micromanipulators, represents an important challenge nowadays. Providing such devices with biomimetic qualities, for example, sensing different external stimuli, adds even more complexity to the task. We developed electroactive polymer-coated microribbons that undergo conformational changes in response to external physical and chemical parameters. These were prepared following three simple steps. During the first step nylon-6/6 microribbons were fabricated by electrospinning. In a second step the microribbons were one side coated with a metallic layer. Finally, a conducting layer of polypyrrole was added by means of electrochemical deposition. Strips of polypyrrole-coated aligned microribbon meshes were tested as actuators responding to current, pH, and temperature. The electrochemical activity of the microstructured actuators was investigated by recording cyclic voltammograms. Chronopontentiograms for specific current, pH, and temperature values were obtained in electrolytes with different compositions. It was shown that, upon variation of the external stimulus, the actuator undergoes conformational changes due to the reduction processes of the polypyrrole layer. The ability of the actuator to hold and release thin wires, and to collect polystyrene microspheres from the bottom of the electrochemical cell, was also investigated.

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Role of additives in formation of solid-electrolyte interfaces on carbon electrodes and their effect on high-voltage stability.

PubMed

Qu, Weiguo; Dorjpalam, Enkhtuvshin; Rajagopalan, Ramakrishnan; Randall, Clive A

2014-04-01

The in situ modification of a lithium hexafluorophosphate-based electrolyte using a molybdenum oxide catalyst and small amount of water (1 vol %) yields hydrolysis products such as mono-, di-, and alkylfluorophosphates. The electrochemical stability of ultrahigh-purity, high-surface-area carbon electrodes derived from polyfurfuryl alcohol was tested using the modified electrolyte. Favorable modification of the solid electrolyte interface (SEI) layer on the activated carbon electrode increased the cyclable electrochemical voltage window (4.8-1.2 V vs. Li/Li(+)). The chemical modification of the SEI layer induced by electrolyte additives was characterized by using X-ray photoelectron spectroscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

Understanding of carbon-based supercapacitors ageing mechanisms by electrochemical and analytical methods

NASA Astrophysics Data System (ADS)

Liu, Yinghui; Soucaze-Guillous, Benoît; Taberna, Pierre-Louis; Simon, Patrice

2017-10-01

In order to shed light on ageing mechanisms of Electrochemical Double Layer Capacitor (EDLC), two kinds of activated carbons are studied in tetraethyl ammonium tetrafluoroborate (Et4NBF4) in acetonitrile. In floating mode, it turns out that two different ageing mechanisms are observed, depending on the activated carbon electrode materials used. On one hand, carbon A exhibits a continuous capacitance and series resistance fall-off; on the other hand, for carbon B, only the series resistance degrades after ageing while the capacitance keeps unchanged. Additional electrochemical characterizations (Electrochemical Impedance Spectroscopy - EIS - and diffusion coefficient calculations) were carried out showing that carbon A's ageing behavior is suspected to be primarily related to the carbon degradation while for carbon B a passivation occurs leading to the formation of a Solid Electrolyte Interphase-Like (SEI-L) film. These hypotheses are supported by TG-IR and Raman spectroscopy analysis. The outcome forms the latter is an increase of carbon defects on carbon A on positive electrode.

Surface structure and electrochemical characteristics of Ti-V-Cr bcc-type solid solution alloys sintered with Ni

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

Tsuji, Yoichiro; Yamamoto, Osamu; Matsuda, Hiromu

2000-07-01

Ti-V-Cr bcc-type solid solution alloys can absorb a large amount of hydrogen and be applied to active materials of the negative electrode in Ni-MH batteries. However, because of the insolubility of Ni into these alloys, the electrochemical characteristics like discharge capacity and cycle life were poor. In order to increase the discharge capacity of hydrogen absorbing alloy electrodes, Ti-V-Cr bcc-type alloy powders were sintered with Ni in order to form Ni contained surface layer on the alloy surface. As sintering temperature rose up, the surface composition changed from TiNi to Ti{sub 2}Ni. TiNi surface layer showed better electrochemical characteristics. Formore » the Ni adding method, Ni electroless plating was preferred because of good adhesion. As a result of optimized conditions, a discharge capacity of 570 mAh/g and an improvement of cycle life were achieved.« less

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

NASA Technical Reports Server (NTRS)

Hagh, Nader; Skandan, Ganesh

2012-01-01

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.

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.

Multilayer Black Phosphorus Exfoliated with the Aid of Sodium Hydroxide: An Improvement in Electrochemical Energy Storage

NASA Astrophysics Data System (ADS)

Liu, Wanying; Zhu, Yabo; Chen, Zhiyan; Lei, Jia; Feng, Peizhong

2018-05-01

We generated multilayer black phosphorus (MBP) as a precipitate in centrifugation under 3000 rpm for 25 min, preceded by liquid exfoliation, in which saturated sodium hydroxide (NaOH(s)) was added as an exfoliation auxiliary. The MBP exfoliated with NaOH(s) was characterized by scanning electron microscope, energy dispersive x-ray detector, x-ray diffraction, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Its electrochemical performance was investigated by cyclic voltammetry, charge/discharge and electrochemical impedance spectroscopy. It was found that the appropriate amount of NaOH(s) can make MBP present a ladder-shaped structure or plackets on the layer edge, which may provide more active sites and channels for charge storage to improve its electrochemical performance. The specific capacitance of MBP samples exfoliated with appropriate amounts of NaOH(s) can quickly enter a relatively stable range of 110-90 F/g after the 75th cycle, and finally stabilize at about 90 F/g after thousands of cycles under the current density of 2 A/g, which demonstrates their good stability in the range of long charge/discharge cycles. MBP exhibits double-layer capacitance properties.

Highly Efficient and Uniform 1 cm2 Perovskite Solar Cells with an Electrochemically Deposited NiOx Hole-Extraction Layer.

PubMed

Park, Ik Jae; Kang, Gyeongho; Park, Min Ah; Kim, Ju Seong; Seo, Se Won; Kim, Dong Hoe; Zhu, Kai; Park, Taiho; Kim, Jin Young

2017-06-22

Given that the highest certified conversion efficiency of the organic-inorganic perovskite solar cell (PSC) already exceeds 22 %, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large-area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large-area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiO x layer prepared by electrochemical deposition is reported as an efficient hole-extraction layer of a p-i-n-type planar PSC with a large active area of >1 cm 2 . It is demonstrated that the increased surface roughness of the NiO x layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiO x , and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiO x layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large-area PSCs. As a result, the p-i-n-type planar PSC with an area of 1.084 cm 2 exhibits a stable conversion efficiency of 17.0 % (19.2 % for 0.1 cm 2 ) without showing hysteresis effects. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Efficient and Uniform 1 cm 2 Perovskite Solar Cells with an Electrochemically Deposited NiO x Hole-Extraction Layer

DOE PAGES

Park, Ik Jae; Kang, Gyeongho; Park, Min Ah; ...

2017-05-10

Here, given that the highest certified conversion efficiency of the organic-inorganic perovskite solar cell (PSC) already exceeds 22%, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large-area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large-area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiO x layer prepared by electrochemical deposition is reported as an efficient hole-extraction layer of a p-i-n-typemore » planar PSC with a large active area of >1 cm 2. It is demonstrated that the increased surface roughness of the NiO x layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiO x, and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiO x layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large-area PSCs. As a result, the p-i-n-type planar PSC with an area of 1.084 cm 2 exhibits a stable conversion efficiency of 17.0% (19.2% for 0.1 cm 2) without showing hysteresis effects.« less

Efficient low-temperature transparent electrocatalytic layers based on graphene oxide nanosheets for dye-sensitized solar cells.

PubMed

Seo, Seon Hee; Jeong, Eun Ji; Han, Joong Tark; Kang, Hyon Chol; Cha, Seung I; Lee, Dong Yoon; Lee, Geon-Woong

2015-05-27

Electrocatalytic materials with a porous structure have been fabricated on glass substrates, via high-temperature fabrication, for application as alternatives to platinum in dye-sensitized solar cells (DSCs). Efficient, nonporous, nanometer-thick electrocatalytic layers based on graphene oxide (GO) nanosheets were prepared on plastic substrates using electrochemical control at low temperatures of ≤100 °C. Single-layer, oxygen-rich GO nanosheets prepared on indium tin oxide (ITO) substrates were electrochemically deoxygenated in acidic medium within a narrow scan range in order to obtain marginally reduced GO at minimum expense of the oxygen groups. The resulting electrochemically reduced GO (E-RGO) had a high density of residual alcohol groups with high electrocatalytic activity toward the positively charged cobalt-complex redox mediators used in DSCs. The ultrathin, alcohol-rich E-RGO layer on ITO-coated poly(ethylene terephthalate) was successfully applied as a lightweight, low-temperature counter electrode with an extremely high optical transmittance of ∼97.7% at 550 nm. A cobalt(II/III)-mediated DSC employing the highly transparent, alcohol-rich E-RGO electrode exhibited a photovoltaic power conversion efficiency of 5.07%. This is superior to that obtained with conventionally reduced GO using hydrazine (3.94%) and even similar to that obtained with platinum (5.10%). This is the first report of a highly transparent planar electrocatalytic layer based on carbonaceous materials fabricated on ITO plastics for application in DSCs.

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.

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.

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.

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%.

Carbon Capsules of Ionic Liquid for Enhanced Performance of Electrochemical Double-Layer Capacitors.

PubMed

Luo, Qinmo; Wei, Peiran; Huang, Qianwen; Gurkan, Burcu; Pentzer, Emily B

2018-05-16

Ion accessibility, large surface area, and complete wetting of a carbonaceous electrode by the electrolyte are crucial for high-performance electrochemical double-layer capacitors. Herein, we report a facile and scalable method to prepare electrode-electrolyte hybrid materials, where an ionic liquid (IL) electrolyte is encapsulated within a shell of reduced graphene oxide (rGO) nanosheets as the active electrode material (called rGO-IL capsules). These structures were templated using a Pickering emulsion consisting of a dispersed phase of 1-methyl-3-butylimidazolium hexafluorophosphate ([bmim][PF 6 ]) and a continuous water phase; graphene oxide nanosheets were used as the surfactant, and interfacial polymerization yielded polyurea that bound the nanosheets together to form the capsule shell. This method prevents the aggregation and restacking of GO nanosheets and allows wetting of the materials by IL. The chemical composition, thermal properties, morphology, and electrochemical behavior of these new hybrid architectures are fully characterized. Specific capacitances of 80 F g -1 at 18 °C and 127 F g -1 at 60 °C were achieved at a scan rate of 10 mV s -1 for symmetric coin cells of rGO-IL capsules. These architected materials have higher capacitance at low temperature (18 °C) across many scan rates (10-500 mV s -1 ) compared with analogous cells with the porous carbon YP-50. These results demonstrate a distinct and important methodology to enhance the performance of electrochemical double-layer capacitors by incorporating electrolyte and carbon material together during synthesis.

PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

PubMed

Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

2011-06-01

The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance. © 2011 American Chemical Society

Multi-Anion Intercalated Layered Double Hydroxide Nanosheet-Assembled Hollow Nanoprisms with Improved Pseudocapacitive and Electrocatalytic Properties.

PubMed

Li, Zhengping; Han, Fangchun; Li, Cheng; Jiao, Xiuling; Chen, Dairong

2018-05-04

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one-step wet-chemical strategy for co-engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo-LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self-templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well-defined NiCo-LDH hollow nanoprisms (HNPs) with multi-anion intercalation. The unique hierarchical nanosheet-assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo-LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo-based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well-defined nanostructures for electrochemical applications and beyond. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical cell

DOEpatents

Redey, L.I.; Vissers, D.R.; Prakash, J.

1994-02-01

An electrochemical cell is described having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm[sup 3]; the cell can be 90% recharged in three hours and can operate at temperatures below 160 C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6[times]10[sup 4] cm[sup 2]/g of Ni. 8 figures.

Electrochemical cell

DOEpatents

Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

1994-01-01

An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

Electrochemical cell

DOEpatents

Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

1996-01-01

An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

Electrochemical cell

DOEpatents

Redey, L.I.; Vissers, D.R.; Prakash, J.

1996-07-16

An electrochemical cell is described having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm{sup 3}; the cell can be 90% recharged in three hours and can operate at temperatures below 160 C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6{times}10{sup 4}cm{sup 2}/g of Ni. 6 figs.

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.

Electrodeposition of catalytic and magnetic gold nanoparticles on dendrimer-carbon nanotube layer-by-layer films.

PubMed

Siqueira, José R; Gabriel, Rayla C; Zucolotto, Valtencir; Silva, Anielle C A; Dantas, Noelio O; Gasparotto, Luiz H S

2012-11-07

Magnetic and catalytic gold nanoparticles were electrodeposited through potential pulse on dendrimer-carbon nanotube layer-by-layer (LbL) films. A plasmon absorption band at about 550 nm revealed the presence of nanoscale gold in the film. The location of the Au nanoparticles in the film was clearly observed by selecting the magnetic force microscopy mode. To our knowledge, this is the first report on the electrochemical synthesis of magnetic Au nanoparticles. In addition to the magnetic properties, the Au nanoparticles also exhibited high catalytic activity towards ethanol and glycerol oxidation in alkaline medium.

Isolating the effect of pore size distribution on electrochemical double-layer capacitance using activated fluid coke

NASA Astrophysics Data System (ADS)

Zuliani, Jocelyn E.; Tong, Shitang; Kirk, Donald W.; Jia, Charles Q.

2015-12-01

Electrochemical double-layer capacitors (EDLCs) use physical ion adsorption in the capacitive electrical double layer of high specific surface area (SSA) materials to store electrical energy. Previous work shows that the SSA-normalized capacitance increases when pore diameters are less than 1 nm. However, there still remains uncertainty about the charge storage mechanism since the enhanced SSA-normalized capacitance is not observed in all microporous materials. In previous studies, the total specific surface area and the chemical composition of the electrode materials were not controlled. The current work is the first reported study that systematically compares the performance of activated carbon prepared from the same raw material, with similar chemical composition and specific surface area, but different pore size distributions. Preparing samples with similar SSAs, but different pores sizes is not straightforward since increasing pore diameters results in decreasing the SSA. This study observes that the microporous activated carbon has a higher SSA-normalized capacitance, 14.1 μF cm-2, compared to the mesoporous material, 12.4 μF cm-2. However, this enhanced SSA-normalized capacitance is only observed above a threshold operating voltage. Therefore, it can be concluded that a minimum applied voltage is required to induce ion adsorption in these sub-nanometer micropores, which increases the capacitance.

(Photo)physical Properties of New Molecular Glasses End-Capped with Thiophene Rings Composed of Diimide and Imine Units

PubMed Central

2014-01-01

New symmetrical arylene bisimide derivatives formed by using electron-donating–electron-accepting systems were synthesized. They consist of a phthalic diimide or naphthalenediimide core and imine linkages and are end-capped with thiophene, bithiophene, and (ethylenedioxy)thiophene units. Moreover, polymers were obtained from a new diamine, N,N′-bis(5-aminonaphthalenyl)naphthalene-1,4,5,8-dicarboximide and 2,5-thiophenedicarboxaldehyde or 2,2′-bithiophene-5,5′-dicarboxaldehyde. The prepared azomethine diimides exhibited glass-forming properties. The obtained compounds emitted blue light with the emission maximum at 470 nm. The value of the absorption coefficient was determined as a function of the photon energy using spectroscopic ellipsometry. All compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry and differential pulse voltammetry (DPV) studies. They exhibited a low electrochemically (DPV) calculated energy band gap (Eg) from 1.14 to 1.70 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels and Eg were additionally calculated theoretically by density functional theory at the B3LYP/6-31G(d,p) level. The photovoltaic properties of two model compounds as the active layer in organic solar cells in the configuration indium tin oxide/poly(3,4-(ethylenedioxy)thiophene):poly(styrenesulfonate)/active layer/Al under an illumination of 1.3 mW/cm2 were studied. The device comprising poly(3-hexylthiophene) with the compound end-capped with bithiophene rings showed the highest value of Voc (above 1 V). The conversion efficiency of the fabricated solar cell was in the range of 0.69–0.90%. PMID:24966893

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

Facile design and synthesis of Li-rich nanoplates cathodes with habit-tuned crystal for lithium ion batteries

NASA Astrophysics Data System (ADS)

Li, Jili; Jia, Tiekun; Liu, Kai; Zhao, Junwei; Chen, Jian; Cao, Chuanbao

2016-11-01

Li-ion batteries with high-energy and high-power density are pursued to apply in the electronic vehicles and renewable energy storage systems. In this work, layered Li-rich transition-metal oxide cathode Li1.2Ni0.2Mn0.6O2 nanoplates with enhanced growth of {010} planes (LNMO-NP) is successfully synthesized through a facile and versatile strategy. Ethylene glycol plays an important role in the formation of LNMO-NP nanoplates with {010} electrochemically active surface planes exposure. As cathode for Li-ion batteries, LNMO-NP demonstrates a high specific discharge capacity of 270.2 mAh g-1 at 0.1 C (1 C = 300 mA g-1) and an excellent rate capability. The good electrochemical performance can be attributed to the nanoplates with the growth of {010} electrochemically active planes which is in favor of Li+ intercalation/deintercalation.

Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells.

PubMed

Kim, Junyoung; Sengodan, Sivaprakash; Kwon, Goeun; Ding, Dong; Shin, Jeeyoung; Liu, Meilin; Kim, Guntae

2014-10-01

We report on an excellent anode-supported H(+) -SOFC material system using a triple conducting (H(+) /O(2-) /e(-) ) oxide (TCO) as a cathode material for H(+) -SOFCs. Generally, mixed ionic (O(2-) ) and electronic conductors (MIECs) have been selected as the cathode material of H(+) -SOFCs. In an H(+) -SOFC system, however, MIEC cathodes limit the electrochemically active sites to the interface between the proton conducting electrolyte and the cathode. New approaches to the tailoring of cathode materials for H(+) -SOFCs should therefore be considered. TCOs can effectively extend the electrochemically active sites from the interface between the cathode and the electrolyte to the entire surface of the cathode. The electrochemical performance of NBSCF/BZCYYb/BZCYYb-NiO shows excellent long term stability for 500 h at 1023 K with high power density of 1.61 W cm(-2) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-discharge of electrochemical capacitors based on soluble or grafted quinone.

PubMed

Shul, Galyna; Bélanger, Daniel

2016-07-28

The self-discharge of hybrid electrochemical capacitors based on the redox activity of electrolyte additives or grafted species to the electrode material is investigated simultaneously for the cell and each individual electrode. Electrochemical capacitors using a redox-active electrolyte consisting in hydroquinone added to the electrolyte solution and a redox-active electrode based on anthraquinone-grafted carbon as a negative electrode are investigated. The results are analyzed by using Conway kinetic models and compared to those of a common electrochemical double layer capacitor. The self-discharge investigation is complemented by charge/discharge cycling and it is shown that processes affecting galvanostatic charge/discharge cycling and the self-discharge rate occurring at each electrode of an electrochemical capacitor are different but related to each other. The electrochemical capacitor containing hydroquinone in the electrolyte exhibits a much quicker self-discharge rate than that using a negative electrode based on grafted anthraquinone with a 50% decay of the cell voltage of the fully charged device in 0.6 and 6 h, respectively. The fast self-discharge of the former is due to the diffusion of benzoquinone molecules (formed at the positive electrode during charging) to the negative electrode, where they are reduced, causing a quick depolarization. The grafting of anthraquinone molecules on the carbon material of the negative electrode led to a much slower self-discharge, which nonetheless occurred, by the reaction of the reduced form of the grafted species with electrolyte species.

Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors

PubMed Central

Rennie, Anthony J. R.; Martins, Vitor L.; Smith, Rachel M.; Hall, Peter J.

2016-01-01

Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs−1) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles. PMID:26911531

Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.

PubMed

Sohail, Manzar; De Marco, Roland; Jarolímová, Zdeňka; Pawlak, Marcin; Bakker, Eric; He, Ning; Latonen, Rose-Marie; Lindfors, Tom; Bobacka, Johan

2015-09-29

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.

Optimizing the Mass-Specific Activity of Bilirubin Oxidase Adlayers through Combined Electrochemical Quartz Crystal Microbalance and Dual Polarization Interferometry Analyses.

PubMed

McArdle, Trevor; McNamara, Thomas P; Fei, Fan; Singh, Kulveer; Blanford, Christopher F

2015-11-18

Two surface analysis techniques, dual polarization interferometry (DPI) and analysis by an electrochemical quartz crystal microbalance with dissipation capability (E-QCM-D), were paired to find the deposition conditions that give the highest and most stable electrocatalytic activity per adsorbed mass of enzyme. Layers were formed by adsorption from buffered solutions of bilirubin oxidase from Myrothecium verrucaria at pH 6.0 to planar surfaces, under high enzyme loading (≥1 mg mL(-1)) for contact periods of up to 2 min. Both unmodified and carboxylate-functionalized gold-coated sensors showed that a deposition solution concentration of 10-25 mg mL(-1) gave the highest activity per mass of adsorbed enzyme with an effective catalytic rate constant (k(cat)) of about 60 s(-1). The densification of adsorbed layers observed by DPI correlated with reduced bioactivity observed by parallel E-QCM-D measurements. Postadsorption changes in thickness and density observed by DPI were incorporated into Kelvin-Voigt models of the QCM-D response. The modeled response matched experimental observations when the adlayer viscosity tripled after adsorption.

3D Microstructure Effects in Ni-YSZ Anodes: Influence of TPB Lengths on the Electrochemical Performance.

PubMed

Pecho, Omar M; Mai, Andreas; Münch, Beat; Hocker, Thomas; Flatt, Robert J; Holzer, Lorenz

2015-10-21

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance ( R pol ). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance . However, the quantitative results also show that there is no simplistic relationship between TPB and R pol . The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and R pol . In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPB active by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPB active , effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer.

Engineered porous silicon counter electrodes for high efficiency dye-sensitized solar cells.

PubMed

Erwin, William R; Oakes, Landon; Chatterjee, Shahana; Zarick, Holly F; Pint, Cary L; Bardhan, Rizia

2014-06-25

In this work, we demonstrate for the first time, the use of porous silicon (P-Si) as counter electrodes in dye-sensitized solar cells (DSSCs) with efficiencies (5.38%) comparable to that achieved with platinum counter electrodes (5.80%). To activate the P-Si for triiodide reduction, few layer carbon passivation is utilized to enable electrochemical stability of the silicon surface. Our results suggest porous silicon as a promising sustainable and manufacturable alternative to rare metals for electrochemical solar cells, following appropriate surface modification.

Self-healing effect of the protective inhibitor-containing coatings on Mg alloys

NASA Astrophysics Data System (ADS)

Gnedenkov, A. S.; Sinebryukhov, S. L.; Mashtalyar, D. V.; Gnedenkov, S. V.

2017-09-01

The method of self-healing coating formation on the surface of magnesium alloys on the base of plasma electrolytic oxidation (PEO) with subsequent impregnation of the obtained layer with inhibitor has been suggested. The protective and electrochemical properties of such coatings have been described. Localised Scanning Electrochemical Methods were used for determining the kinetics and mechanism of the self-healing process. The treatment with the solution containing inhibitor enables us to increase the protective properties of the PEO-coating in 30 times in the corrosion-active environment.

Observing the Electrochemical Oxidation of Co Metal at the Solid/Liquid Interface Using Ambient Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.; ...

2017-08-28

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

High-Capacity, High-Voltage Composite Oxide Cathode Materials

NASA Technical Reports Server (NTRS)

Hagh, Nader M.

2015-01-01

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Electrochemical modelling of QD-phospholipid interactions.

PubMed

Zhang, Shengwen; Chen, Rongjun; Malhotra, Girish; Critchley, Kevin; Vakurov, Alexander; Nelson, Andrew

2014-04-15

The aggregation of quantum dots (QDs) and capping of individual QDs affects their activity towards biomembrane models. Electrochemical methods using a phospholipid layer on mercury (Hg) membrane model have been used to determine the phospholipid monolayer activity of thioglycollic acid (TGA) coated quantum dots (QDs) as an indicator of biomembrane activity. The particles were characterised for size and charge. The activity of the QDs towards dioleoyl phosphatidylcholine (DOPC) monolayers is pH dependent, and is most active at pH 8.2 within the pH range 8.2-6.5 examined in this work. This pH dependent activity is the result of increased particle aggregation coupled to decreasing surface charge emanating from the TGA carboxylic groups employed to stabilize the QD dispersion in aqueous media. Capping the QDs with CdS/ZnS lowers the particles' activity to phospholipid monolayers. Copyright © 2014 Elsevier Inc. All rights reserved.

High-performance super capacitors based on activated anthracite with controlled porosity

NASA Astrophysics Data System (ADS)

Lee, Hyun-Chul; Byamba-Ochir, Narandalai; Shim, Wang-Geun; Balathanigaimani, M. S.; Moon, Hee

2015-02-01

Mongolian anthracite is chemically activated using potassium hydroxide as an activation agent to make activated carbon materials. Prior to the chemical activation, the chemical agent is introduced by two different methods as follows, (1) simple physical mixing, (2) impregnation. The physical properties such as specific surface area, pore volume, pore size distribution, and adsorption energy distribution are measured to assess them as carbon electrode materials for electric double-layer capacitors (EDLC). The surface functional groups and morphology are also characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses respectively. The electrochemical results for the activated carbon electrodes in 3 M sulfuric acid electrolyte solution indicate that the activated Mongolian anthracite has relatively large specific capacitances in the range of 120-238 F g-1 and very high electrochemical stability, as they keep more than 98% of initial capacitances until 1000 charge/discharge cycles.

Individually addressable vertically aligned carbon nanofiber-based electrochemical probes

NASA Astrophysics Data System (ADS)

Guillorn, M. A.; McKnight, T. E.; Melechko, A.; Merkulov, V. I.; Britt, P. F.; Austin, D. W.; Lowndes, D. H.; Simpson, M. L.

2002-03-01

In this paper we present the fabrication and initial testing results of high aspect ratio vertically aligned carbon nanofiber (VACNF)-based electrochemical probes. Electron beam lithography was used to define the catalytic growth sites of the VACNFs. Following catalyst deposition, VACNF were grown using a plasma enhanced chemical vapor deposition process. Photolithography was performed to realize interconnect structures. These probes were passivated with a thin layer of SiO2, which was then removed from the tips of the VACNF, rendering them electrochemically active. We have investigated the functionality of completed devices using cyclic voltammetry (CV) of ruthenium hexammine trichloride, a highly reversible, outer sphere redox system. The faradaic current obtained during CV potential sweeps shows clear oxidation and reduction peaks at magnitudes that correspond well with the geometry of these nanoscale electrochemical probes. Due to the size and the site-specific directed synthesis of the VACNFs, these probes are ideally suited for characterizing electrochemical phenomena with an unprecedented degree of spatial resolution.

Development of a Novel Biosensor Using Cationic Antimicrobial Peptide and Nickel Phthalocyanine Ultrathin Films for Electrochemical Detection of Dopamine

PubMed Central

Zampa, Maysa F.; Araújo, Inês Maria de S.; dos Santos Júnior, José Ribeiro; Zucolotto, Valtencir; Leite, José Roberto de S. A.; Eiras, Carla

2012-01-01

The antimicrobial peptide dermaseptin 01 (DS 01), from the skin secretion of Phyllomedusa hypochondrialis frogs, was immobilized in nanostructured layered films in conjunction with nickel tetrasulfonated phthalocyanines (NiTsPc), widely used in electronic devices, using layer-by-layer technique. The films were used as a biosensor to detect the presence of dopamine (DA), a neurotransmitter associated with diseases such as Alzheimer's and Parkinson's, with detection limits in the order of 10−6 mol L−1. The use of DS 01 in LbL film generated selectivity in the detection of DA despite the presence of ascorbic acid found in biological fluids. This work is the first to report that the antimicrobial peptide and NiTsPc LbL film exhibits electroanalytical activity to DA oxidation. The selectivity in the detection of DA is a fundamental aspect for the development of electrochemical sensors with potential applications in the biomedical and pharmaceutical industries. PMID:22287966

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.

Synthesis and Characterization of Mn3O4 - Graphene Core - Shell Quantum Dots for Electrochemical Pseudocapacitor Applications

NASA Astrophysics Data System (ADS)

Ko, Yohan; Son, Dong Ick

2018-05-01

We report on the in-situ chemical growth of unique core-shell quantum dots (QDs) with single layer graphene on the surfaces of the Mn3O4 QDs and on their structural, optical and electrical properties. The Mn3O4-graphene QDs were synthesized through a simple hydrothermal technique. In order to enhance performance for electrochemical energy storage, we developed core (active material) - shell (conductive material)-type Mn3O4 - graphene QDs as electrode materials by using an aqueous electrolyte (6M KOH). As a result, the performance of electrochemical energy storage exhibit a specific capacitance of 452.72 Fg-1 at a current density of 1 Ag-1.

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.

Binder-induced surface structure evolution effects on Li-ion battery performance

NASA Astrophysics Data System (ADS)

Rezvani, S. J.; Pasqualini, M.; Witkowska, A.; Gunnella, R.; Birrozzi, A.; Minicucci, M.; Rajantie, H.; Copley, M.; Nobili, F.; Di Cicco, A.

2018-03-01

A comparative investigation on binder induced chemical and morphological evolution of Li4Ti5O12 electrodes was performed via X-ray photoemission spectroscopy, scanning electron microscopy, and electrochemical measurements. Composite electrodes were obtained using three different binders (PAA, PVdF, and CMC) with 80:10:10 ratio of active material:carbon:binder. The electrochemical performances of the electrodes, were found to be intimately correlated with the evolution of the microstructure of the electrodes, probed by XPS and SEM analysis. Our analysis shows that the surface chemistry, thickness of the passivation layers and the morphology of the electrodes are strongly dependent on the type of binders that significantly influence the electrochemical properties of the electrodes. These results point to a key role played by binders in optimization of the battery performance and improve our understanding of the previously observed and unexplained electrochemical properties of these electrodes.

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Dziembaj, Roman; Molenda, Marcin

2016-01-01

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material. PMID:28773819

Fuel Cells | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion, Electrochimica Acta (2016) Suppression of Oxygen Reduction Reaction Activity on Pt-Based Electrocatalysts from Ionomer Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction, Journal of the Electrochemical Society

Direct growth of 2D nickel hydroxide nanosheets intercalated with polyoxovanadate anions as a binder-free supercapacitor electrode.

PubMed

Gunjakar, Jayavant L; Inamdar, Akbar I; Hou, Bo; Cha, SeungNam; Pawar, S M; Abu Talha, A A; Chavan, Harish S; Kim, Jongmin; Cho, Sangeun; Lee, Seongwoo; Jo, Yongcheol; Kim, Hyungsang; Im, Hyunsik

2018-05-17

A mesoporous nanoplate network of two-dimensional (2D) layered nickel hydroxide Ni(OH)2 intercalated with polyoxovanadate anions (Ni(OH)2-POV) was built using a chemical solution deposition method. This approach will provide high flexibility for controlling the chemical composition and the pore structure of the resulting Ni(OH)2-POV nanohybrids. The layer-by-layer ordered growth of the Ni(OH)2-POV is demonstrated by powder X-ray diffraction and cross-sectional high-resolution transmission electron microscopy. The random growth of the intercalated Ni(OH)2-POV nanohybrids leads to the formation of an interconnected network morphology with a highly porous stacking structure whose porosity is controlled by changing the ratio of Ni(OH)2 and POV. The lateral size and thickness of the Ni(OH)2-POV nanoplates are ∼400 nm and from ∼5 nm to 7 nm, respectively. The obtained thin films are highly active electrochemical capacitor electrodes with a maximum specific capacity of 1440 F g-1 at a current density of 1 A g-1, and they withstand up to 2000 cycles with a capacity retention of 85%. The superior electrochemical performance of the Ni(OH)2-POV nanohybrids is attributed to the expanded mesoporous surface area and the intercalation of the POV anions. The experimental findings highlight the outstanding electrochemical functionality of the 2D Ni(OH)2-POV nanoplate network that will provide a facile route for the synthesis of low-dimensional hybrid nanomaterials for a highly active supercapacitor electrode.

Recent Advances in Layered Ti3 C2 Tx MXene for Electrochemical Energy Storage.

PubMed

Xiong, Dongbin; Li, Xifei; Bai, Zhimin; Lu, Shigang

2018-04-01

Ti 3 C 2 T x , a typical representative among the emerging family of 2D layered transition metal carbides and/or nitrides referred to as MXenes, has exhibited multiple advantages including metallic conductivity, a plastic layer structure, small band gaps, and the hydrophilic nature of its functionalized surface. As a result, this 2D material is intensively investigated for application in the energy storage field. The composition, morphology and texture, surface chemistry, and structural configuration of Ti 3 C 2 T x directly influence its electrochemical performance, e.g., the use of a well-designed 2D Ti 3 C 2 T x as a rechargeable battery anode has significantly enhanced battery performance by providing more chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier/charge-transport kinetics. Some recent progresses of Ti 3 C 2 T x MXene are achieved in energy storage. This Review summarizes recent advances in the synthesis and electrochemical energy storage applications of Ti 3 C 2 T x MXene including supercapacitors, lithium-ion batteries, sodium-ion batteries, and lithium-sulfur batteries. The current opportunities and future challenges of Ti 3 C 2 T x MXene are addressed for energy-storage devices. This Review seeks to provide a rational and in-depth understanding of the relation between the electrochemical performance and the nanostructural/chemical composition of Ti 3 C 2 T x , which will promote the further development of 2D MXenes in energy-storage applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Density Droplet Microarray of Individually Addressable Electrochemical Cells.

PubMed

Zhang, Huijie; Oellers, Tobias; Feng, Wenqian; Abdulazim, Tarik; Saw, En Ning; Ludwig, Alfred; Levkin, Pavel A; Plumeré, Nicolas

2017-06-06

Microarray technology has shown great potential for various types of high-throughput screening applications. The main read-out methods of most microarray platforms, however, are based on optical techniques, limiting the scope of potential applications of such powerful screening technology. Electrochemical methods possess numerous complementary advantages over optical detection methods, including its label-free nature, capability of quantitative monitoring of various reporter molecules, and the ability to not only detect but also address compositions of individual compartments. However, application of electrochemical methods for the purpose of high-throughput screening remains very limited. In this work, we develop a high-density individually addressable electrochemical droplet microarray (eDMA). The eDMA allows for the detection of redox-active reporter molecules irrespective of their electrochemical reversibility in individual nanoliter-sized droplets. Orthogonal band microelectrodes are arranged to form at their intersections an array of three-electrode systems for precise control of the applied potential, which enables direct read-out of the current related to analyte detection. The band microelectrode array is covered with a layer of permeable porous polymethacrylate functionalized with a highly hydrophobic-hydrophilic pattern, forming spatially separated nanoliter-sized droplets on top of each electrochemical cell. Electrochemical characterization of single droplets demonstrates that the underlying electrode system is accessible to redox-active molecules through the hydrophilic polymeric pattern and that the nonwettable hydrophobic boundaries can spatially separate neighboring cells effectively. The eDMA technology opens the possibility to combine the high-throughput biochemical or living cell screenings using the droplet microarray platform with the sequential electrochemical read-out of individual droplets.

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.

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.

Observation of nanometer-sized electro-active defects in insulating layers by fluorescence microscopy and electrochemistry.

PubMed

Renault, Christophe; Marchuk, Kyle; Ahn, Hyun S; Titus, Eric J; Kim, Jiyeon; Willets, Katherine A; Bard, Allen J

2015-06-02

We report a method to study electro-active defects in passivated electrodes. This method couples fluorescence microscopy and electrochemistry to localize and size electro-active defects. The method was validated by comparison with a scanning probe technique, scanning electrochemical microscopy. We used our method for studying electro-active defects in thin TiO2 layers electrodeposited on 25 μm diameter Pt ultramicroelectrodes (UMEs). The permeability of the TiO2 layer was estimated by measuring the oxidation of ferrocenemethanol at the UME. Blocking of current ranging from 91.4 to 99.8% was achieved. Electro-active defects with an average radius ranging between 9 and 90 nm were observed in these TiO2 blocking layers. The distribution of electro-active defects over the TiO2 layer is highly inhomogeneous and the number of electro-active defect increases for lower degree of current blocking. The interest of the proposed technique is the possibility to quickly (less than 15 min) image samples as large as several hundreds of μm(2) while being able to detect electro-active defects of only a few tens of nm in radius.

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

2014-11-01

In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

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.

Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling.

PubMed

Xie, Jin; Sendek, Austin D; Cubuk, Ekin D; Zhang, Xiaokun; Lu, Zhiyi; Gong, Yongji; Wu, Tong; Shi, Feifei; Liu, Wei; Reed, Evan J; Cui, Yi

2017-07-25

Modern lithium ion batteries are often desired to operate at a wide electrochemical window to maximize energy densities. While pushing the limit of cutoff potentials allows batteries to provide greater energy densities with enhanced specific capacities and higher voltage outputs, it raises key challenges with thermodynamic and kinetic stability in the battery. This is especially true for layered lithium transition-metal oxides, where capacities can improve but stabilities are compromised as wider electrochemical windows are applied. To overcome the above-mentioned challenges, we used atomic layer deposition to develop a LiAlF 4 solid thin film with robust stability and satisfactory ion conductivity, which is superior to commonly used LiF and AlF 3 . With a predicted stable electrochemical window of approximately 2.0 ± 0.9 to 5.7 ± 0.7 V vs Li + /Li for LiAlF 4 , excellent stability was achieved for high Ni content LiNi 0.8 Mn 0.1 Co 0.1 O 2 electrodes with LiAlF 4 interfacial layer at a wide electrochemical window of 2.75-4.50 V vs Li + /Li.

3D Microstructure Effects in Ni-YSZ Anodes: Influence of TPB Lengths on the Electrochemical Performance

PubMed Central

Pecho, Omar M.; Mai, Andreas; Münch, Beat; Hocker, Thomas; Flatt, Robert J.; Holzer, Lorenz

2015-01-01

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance (Rpol). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance. However, the quantitative results also show that there is no simplistic relationship between TPB and Rpol. The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and Rpol. In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPBactive by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPBactive, effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer. PMID:28793624

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.

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.

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.

A self-regenerable soot sensor with a proton-conductive thin electrolyte and a nanostructured platinum sensing electrode.

PubMed

Lv, Peiling; Ito, Takenori; Oogushi, Akihide; Nakashima, Kensaku; Nagao, Masahiro; Hibino, Takashi

2016-11-18

In recent years, exhaust sensors have become increasingly attractive for use in energy and environmental technologies. Important issues regarding practical applications of these sensors, especially for soot measurements, include the further development of ion-conductive electrolytes and active electrode catalysts for meeting performance and durability requirements. Herein, we design a proton conductor with a high breakdown voltage and a sensing electrode with high sensitivity to electrochemical carbon oxidation, enabling continuous soot monitoring with self-regeneration of the sensor. A Si 0.97 Al 0.03 H x P 2 O 7-δ layer with an excellent balance between proton conductivity and voltage endurance was grown on the surface of a Si 0.97 Al 0.03 O 2-δ substrate by reacting it with liquid H 3 PO 4 at 600 °C. Specific reactivity of the electrochemically formed active oxygen toward soot was accomplished by adding a Pt-impregnated Sn 0.9 In 0.1 H x P 2 O 7-δ catalyst into a Pt sensing electrode. To make the best use of these optimized materials, a unipolar electrochemical device was fabricated by configuring the sensing and counter electrodes on the same surface of the electrolyte layer. The resulting amperometric mode sensor successfully produced a current signal that corresponded to the quantity of soot.

A self-regenerable soot sensor with a proton-conductive thin electrolyte and a nanostructured platinum sensing electrode

PubMed Central

Lv, Peiling; Ito, Takenori; Oogushi, Akihide; Nakashima, Kensaku; Nagao, Masahiro; Hibino, Takashi

2016-01-01

In recent years, exhaust sensors have become increasingly attractive for use in energy and environmental technologies. Important issues regarding practical applications of these sensors, especially for soot measurements, include the further development of ion-conductive electrolytes and active electrode catalysts for meeting performance and durability requirements. Herein, we design a proton conductor with a high breakdown voltage and a sensing electrode with high sensitivity to electrochemical carbon oxidation, enabling continuous soot monitoring with self-regeneration of the sensor. A Si0.97Al0.03HxP2O7-δ layer with an excellent balance between proton conductivity and voltage endurance was grown on the surface of a Si0.97Al0.03O2-δ substrate by reacting it with liquid H3PO4 at 600 °C. Specific reactivity of the electrochemically formed active oxygen toward soot was accomplished by adding a Pt-impregnated Sn0.9In0.1HxP2O7-δ catalyst into a Pt sensing electrode. To make the best use of these optimized materials, a unipolar electrochemical device was fabricated by configuring the sensing and counter electrodes on the same surface of the electrolyte layer. The resulting amperometric mode sensor successfully produced a current signal that corresponded to the quantity of soot. PMID:27857193

A self-regenerable soot sensor with a proton-conductive thin electrolyte and a nanostructured platinum sensing electrode

NASA Astrophysics Data System (ADS)

Lv, Peiling; Ito, Takenori; Oogushi, Akihide; Nakashima, Kensaku; Nagao, Masahiro; Hibino, Takashi

2016-11-01

In recent years, exhaust sensors have become increasingly attractive for use in energy and environmental technologies. Important issues regarding practical applications of these sensors, especially for soot measurements, include the further development of ion-conductive electrolytes and active electrode catalysts for meeting performance and durability requirements. Herein, we design a proton conductor with a high breakdown voltage and a sensing electrode with high sensitivity to electrochemical carbon oxidation, enabling continuous soot monitoring with self-regeneration of the sensor. A Si0.97Al0.03HxP2O7-δ layer with an excellent balance between proton conductivity and voltage endurance was grown on the surface of a Si0.97Al0.03O2-δ substrate by reacting it with liquid H3PO4 at 600 °C. Specific reactivity of the electrochemically formed active oxygen toward soot was accomplished by adding a Pt-impregnated Sn0.9In0.1HxP2O7-δ catalyst into a Pt sensing electrode. To make the best use of these optimized materials, a unipolar electrochemical device was fabricated by configuring the sensing and counter electrodes on the same surface of the electrolyte layer. The resulting amperometric mode sensor successfully produced a current signal that corresponded to the quantity of soot.

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.

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.

Strategies to optimize lithium-ion supercapacitors achieving high-performance: Cathode configurations, lithium loadings on anode, and types of separator

NASA Astrophysics Data System (ADS)

Cao, Wanjun; Li, Yangxing; Fitch, Brian; Shih, Jonathan; Doung, Tien; Zheng, Jim

2014-12-01

The Li-ion capacitor (LIC) is composed of a lithium-doped carbon anode and an activated carbon cathode, which is a half Li-ion battery (LIB) and a half electrochemical double-layer capacitor (EDLC). LICs can achieve much more energy density than EDLC without sacrificing the high power performance advantage of capacitors over batteries. LIC pouch cells were assembled using activated carbon (AC) cathode and hard carbon (HC) + stabilized lithium metal power (SLMP®) anode. Different cathode configurations, various SLMP loadings on HC anode, and two types of separators were investigated to achieve the optimal electrochemical performance of the LIC. Firstly, the cathode binders study suggests that the PTFE binder offers improved energy and power performances for LIC in comparison to PVDF. Secondly, the mass ratio of SLMP to HC is at 1:7 to obtain the optimized electrochemical performance for LIC among all the various studied mass ratios between lithium loading amounts and active anode material. Finally, compared to the separator Celgard PP 3501, cellulose based TF40-30 is proven to be a preferred separator for LIC.

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.

Layer-by-layer self-assembled two-dimensional MXene/layered double hydroxide composites as cathode for alkaline hybrid batteries

NASA Astrophysics Data System (ADS)

Dong, Xiaowan; Zhang, Yadi; Ding, Bing; Hao, Xiaodong; Dou, Hui; Zhang, Xiaogang

2018-06-01

Multifarious layered materials have received extensive concern in the field of energy storage due to their distinctive two-dimensional (2D) structure. However, the natural tendency to be re-superimposed and the inherent disadvantages of a single 2D material significantly limit their performance. In this work, the delaminated Ti3C2Tx (d-Ti3C2Tx)/cobalt-aluminum layered double hydroxide (Ti3C2Tx/CoAl-LDH) composites are prepared by layer-by-layer self-assembly driven by electrostatic interaction. The alternate Ti3C2Tx and CoAl-LDH layers prevent each other from restacking and the obtained Ti3C2Tx/CoAl-LDH heterostructure combine the advantages of high electron conductivity of Ti3C2Tx and high electrochemical activity of CoAl-LDH, thus effectively improving the electrochemical reactivity of electrode materials and accelerating the kinetics of Faraday reaction. As a consequence, as a cathode for alkaline hybrid battery, the Ti3C2Tx/CoAl-LDH electrode exhibits a high specific capacity of 106 mAh g-1 at a current density of 0.5 A g-1 and excellent rate capability (78% at 10 A g-1), with an excellent cycling stability of 90% retention after 5000 cycles at 4 A g-1. This work provides an alternative route to design advanced 2D electrode materials, thus exploiting their full potentials for alkaline hybrid batteries.

Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors.

PubMed

Xiang, Yan; Lu, Shanfu; Jiang, San Ping

2012-11-07

As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).

Pseudocapacitive and hierarchically ordered porous electrode materials supercapacitors

NASA Astrophysics Data System (ADS)

Saruhan, B.; Gönüllü, Y.; Arndt, B.

2013-05-01

Commercially available double layer capacitors store energy in an electrostatic field. This forms in the form of a double layer by charged particles arranged on two electrodes consisting mostly of active carbon. Such double layer capacitors exhibit a low energy density, so that components with large capacity according to large electrode areas are required. Our research focuses on the development of new electrode materials to realize the production of electrical energy storage systems with high energy density and high power density. Metal oxide based electrodes increase the energy density and the capacitance by addition of pseudo capacitance to the static capacitance present by the double layer super-capacitor electrodes. The so-called hybrid asymmetric cell capacitors combine both types of energy storage in a single component. In this work, the production routes followed in our laboratories for synthesis of nano-porous and aligned metal oxide electrodes using the electrochemical and sputter deposition as well as anodization methods will be described. Our characterisation studies concentrate on electrodes having redox metal-oxides (e.g. MnOx and WOx) and hierarchically aligned nano-porous Li-doped TiO2-NTs. The material specific and electrochemical properties achieved with these electrodes will be presented.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

PubMed

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

2015-08-04

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

PubMed Central

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

2015-01-01

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator

PubMed Central

Wu, Guan; Hu, Ying; Liu, Yang; Zhao, Jingjing; Chen, Xueli; Whoehling, Vincent; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Chen, Wei

2015-01-01

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g−1) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m−1) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance. PMID:26028354

Electrochemical behavior of zinc particles with silica based coatings as anode material for zinc air batteries with improved discharge capacity

NASA Astrophysics Data System (ADS)

Schmid, M.; Willert-Porada, M.

2017-05-01

Silica coatings on zinc particles as anode material for alkaline zinc air batteries are expected to reduce early formation of irreversible ZnO passivation layers during discharge by controlling zinc dissolution and precipitation of supersaturated zincates, Zn(OH)42-. Zinc particles were coated with SiO2 (thickness: 15 nm) by chemical solution deposition and with Zn2SiO4 (thickness: 20 nm) by chemical vapor deposition. These coatings formed a Si(OH)4 gel in aqueous KOH and retarded hydrogen evolution by 40%. By treatment in aqueous KOH and drying afterwards, the silica coatings were changed into ZnO-K2O·SiO2 layers. In this work, the electrochemical performance of such coated zinc particles is investigated by different electrochemical methods in order to gain a deeper understanding of the mechanisms of the coatings, which reduce zinc passivation. In particular, zinc utilization and changes in internal resistance are investigated. Moreover, methods for determination of diffusion coefficients, charge carrier numbers and activation energies for electrochemical oxidation are determined. SiO2-coated zinc particles show improved discharge capacity (CVD-coated zinc: 69% zinc utilization, CSD-coated zinc: 62% zinc utilization) as compared to as-received zinc (57% zinc utilization) at C/20 rate, by reducing supersaturation of zincates. Additionally, KOH-modified SiO2-coated zinc particles enhance rechargeability after 100% depth-of-discharge.

Improving cycle life of layered lithium transition metal oxide (LiMO2) based positive electrodes for Li ion batteries by smart selection of the electrochemical charge conditions

NASA Astrophysics Data System (ADS)

Kasnatscheew, Johannes; Evertz, Marco; Streipert, Benjamin; Wagner, Ralf; Nowak, Sascha; Cekic Laskovic, Isidora; Winter, Martin

2017-08-01

Increasing the specific energy of a lithium ion battery and maintaining its cycle life is a predominant goal and major challenge for electrochemical energy storage applications. Focusing on the positive electrode as the specific energy bottleneck, cycle life characteristics of promising layered oxide type active materials (LiMO2) has been thoroughly investigated. Comparing the variety of LiMO2 compositions, it could be shown that the "Ni-rich" (Ni ≥ 60% for M in LiMO2) electrodes expectably revealed best performance compromises between specific energy and cycle life at 20 °C, but only LiNi0.6Mn0.2Co0.2O2 (NMC622) could also maintain sufficient cycle performance at elevated temperatures. Focusing on NMC622, it could be demonstrated that the applied electrochemical conditions (charge capacity, delithiation amount) in the formation cycles significantly influence the subsequent cycling performance. Moreover, the insignificant transition metal dissolution, demonstrated by means of total X-ray fluorescence (TXRF) technique, and unchanged lithiation degree in the discharged state, determined by the measurement of the Li+ content by means of the inductively coupled plasma optical emission spectroscopy (ICP-OES) technique, pointed to a delithiation (charge) hindrance capacity fade mechanism. Considering these insights, thoughtful modifications of the electrochemical charge conditions could significantly prolong the cycle life.

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.

Hydrophobic networked PbO2 electrode for electrochemical oxidation of paracetamol drug and degradation mechanism kinetics.

PubMed

He, Yapeng; Wang, Xue; Huang, Weimin; Chen, Rongling; Zhang, Wenli; Li, Hongdong; Lin, Haibo

2018-02-01

A hydrophobic networked PbO 2 electrode was deposited on mesh titanium substrate and utilized for the electrochemical elimination towards paracetamol drug. Three dimensional growth mechanism of PbO 2 layer provided more loading capacity of active materials and network structure greatly reduced the mass transfer for the electrochemical degradation. The active electrochemical surface area based on voltammetric charge quantity of networked PbO 2 electrode is about 2.1 times for traditional PbO 2 electrode while lower charge transfer resistance (6.78 Ω cm 2 ) could be achieved on networked PbO 2 electrode. The electrochemical incineration kinetics of paracetamol drug followed a pseudo first-order behavior and the corresponding rate constant were 0.354, 0.658 and 0.880 h -1 for traditional, networked PbO 2 and boron doped diamond electrode. Higher electrochemical elimination kinetics could be achieved on networked PbO 2 electrode and the performance can be equal to boron doped diamond electrode in result. Based on the quantification of reactive oxidants (hydroxyl radicals), the utilization rate of hydroxyl radicals could reach as high as 90% on networked PbO 2 electrode. The enhancement of excellent electrochemical oxidation capacity towards paracetamol drug was related to the properties of higher loading capacity, enhanced mass transfer and hydrophobic surface. The possible degradation mechanism and pathway of paracetamol on networked PbO 2 electrode were proposed in details accordingly based on the intermediate products. Copyright © 2017 Elsevier Ltd. All rights reserved.

The improved electrochemical performance of cross-linked 3D graphene nanoribbon monolith electrodes

NASA Astrophysics Data System (ADS)

Vineesh, Thazhe Veettil; Alwarappan, Subbiah; Narayanan, Tharangattu N.

2015-04-01

Technical advancement in the field of ultra-small sensors and devices demands the development of novel micro- or nano-based architectures. Here we report the design and assembly of cross-linked three dimensional graphene nanoribbons (3D GNRs) using solution based covalent binding of individual 2D GNRs and demonstrate its electrochemical application as a 3D electrode. The enhanced performance of 3D GNRs over individual 2D GNRs is established using standard redox probes - [Ru(NH3)6]3+/2+, [Fe(CN)6]3-/4- and important bio-analytes - dopamine and ascorbic acid. 3D GNRs are found to have high double layer capacitance (2482 μF cm-2) and faster electron transfer kinetics; their exceptional electrocatalytic activity towards the oxygen reduction reaction is indicative of their potential over a wide range of electrochemical applications. Moreover, this study opens a new platform for the design of novel point-of-care devices and electrodes for energy devices.Technical advancement in the field of ultra-small sensors and devices demands the development of novel micro- or nano-based architectures. Here we report the design and assembly of cross-linked three dimensional graphene nanoribbons (3D GNRs) using solution based covalent binding of individual 2D GNRs and demonstrate its electrochemical application as a 3D electrode. The enhanced performance of 3D GNRs over individual 2D GNRs is established using standard redox probes - [Ru(NH3)6]3+/2+, [Fe(CN)6]3-/4- and important bio-analytes - dopamine and ascorbic acid. 3D GNRs are found to have high double layer capacitance (2482 μF cm-2) and faster electron transfer kinetics; their exceptional electrocatalytic activity towards the oxygen reduction reaction is indicative of their potential over a wide range of electrochemical applications. Moreover, this study opens a new platform for the design of novel point-of-care devices and electrodes for energy devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07315k

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.

Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene-Sulfur Cathodes in Lithium-Sulfur Batteries.

PubMed

Kim, Jin Won; Ocon, Joey D; Kim, Ho-Sung; Lee, Jaeyoung

2015-09-07

A graphene-based cathode design for lithium-sulfur batteries (LSB) that shows excellent electrochemical performance is proposed. The dual-layered cathode is composed of a sulfur active layer and a polysulfide absorption layer, and both layers are based on vitamin C treated graphene oxide at various degrees of reduction. By controlling the degree of reduction of graphene, the dual-layered cathode can increase sulfur utilization dramatically owing to the uniform formation of nanosized sulfur particles, the chemical bonding of dissolved polysulfides on the oxygen-rich sulfur active layer, and the physisorption of free polysulfides on the absorption layer. This approach enables a LSB with a high specific capacity of over 600 mAh gsulfur (-1) after 100 cycles even under a high current rate of 1C (1675 mA gsulfur (-1) ). An intriguing aspect of our work is the synthesis of a high-performance dual-layered cathode by a green chemistry method, which could be a promising approach to LSBs with high energy and power densities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced electrochemical performance of Li-rich layered cathode materials via chemical activation of Li2MnO3 component and formation of spinel/carbon coating layer

NASA Astrophysics Data System (ADS)

Pang, Shengli; Xu, Kaijie; Wang, Yonggang; Shen, Xiangqian; Wang, Wenzhi; Su, Yanjing; Zhu, Meng; Xi, Xiaoming

2017-10-01

Li-rich layered oxides are promising cathode materials for advanced Li-ion batteries because of their high specific capacity and operating potential. In this work, the Li-rich layered oxide Li1·2Mn0·54Ni0·13Co0·13O2 (LMNC), is modified via a carbonization-reduction process (yielding the corresponding reduced compound denoted LMNC-R). Compared to the pristine oxide, LMNC-R delivers significantly enhanced initial discharge capacity/columbic efficiency, remarkably improved rate performance with an accelerated Li+ diffusion rate, and significantly increased capacity/voltage retention. The specific energy density and energy retention after 100 cycles increase from 378.2 Wh kg-1 and 47.7% for LMNC to 572.0 Wh kg-1 and 71.3%, respectively, for LMNC-R. The enhancement in the electrochemical performance of LMNC-R can be attributed to the synchronous formation of the oxygen non-stoichiometric Li2MnO3-δ component and to the carbon/spinel double coating layer in the material that resulted from the post-treatment process. Thus, the carbonization-reduction modification process can be used to tailor the structural evolution procedure and to suppress the metal ion dissolution of the Li-rich layered oxide during cycling.

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

Effect of acid dopants in biodegradable gel polymer electrolyte and the performance in an electrochemical double layer capacitor

NASA Astrophysics Data System (ADS)

Sudhakar, Y. N.; Selvakumar, M.; Krishna Bhat, D.

2015-09-01

Proton-conducting biodegradable gellan gum gel polymer electrolytes (GPEs) have been prepared using three different dopants, namely ortho-phosphoric (o-H3PO4), sulfuric (H2SO4) and hydrochloric acids (HCl). The GPEs were cross-linked using borax. The polymeric gels were characterized by spectroscopic, thermal, ionic conductivities and dielectric measurements. Proton conductivity was in the range of 5.1 × 10-3 to 3.7 × 10-4 s cm-1 and activation energies were between 0.14 meV and 0.19 meV, at different temperatures. Among the doped acids, the H3PO4 doped GPE exhibited thermal stability at varying temperature. Electrochemical double layer capacitors (EDLCs) were fabricated using activated carbon as electrode material and GPEs. The EDLCs were tested using cyclic voltammetry, ac impedance spectroscopic and galvanostatic charge-discharge techniques. The maximum specific capacitance value was 146 F g-1 at a scan rate of 2 mV s-1. Quite stable values were obtained at a constant current density up to 1000 cycles.

Electric double-layer capacitors with tea waste derived activated carbon electrodes and plastic crystal based flexible gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Suleman, M.; Deraman, M.; Othman, M. A. R.; Omar, R.; Hashim, M. A.; Basri, N. H.; Nor, N. S. M.; Dolah, B. N. M.; Hanappi, M. F. Y. M.; Hamdan, E.; Sazali, N. E. S.; Tajuddin, N. S. M.; Jasni, M. R. M.

2016-08-01

We report a novel configuration of symmetrical electric double-layer capacitors (EDLCs) comprising a plastic crystalline succinonitrile (SN) based flexible polymer gel electrolyte, incorporated with sodium trifluoromethane sulfonate (NaTf) immobilised in a host polymer poly (vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP). The cost-effective activated carbon powder possessing a specific surface area (SSA) of ~ 1700 m2g-1 containing a large proportion of meso-porosity has been derived from tea waste to use as supercapacitor electrodes. The high ionic conductivity (~3.6×10-3 S cm-1 at room temperature) and good electrochemical stability render the gel polymer electrolyte film a suitable candidate for the fabrication of EDLCs. The performance of the EDLCs has been tested by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge-discharge studies. The performance of the EDLC cell is found to be promising in terms of high values of specific capacitance (~270 F g-1), specific energy (~ 36 Wh kg-1), and power density (~ 33 kW kg-1).

Influence of the membrane ion exchange capacity on the catalyst layer of proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Navessin, Titichai

2005-07-01

This work investigated the effect of ion exchange capacity (IEC) of polymer electrolyte membranes (PEM) on the PEM fuel cell cathode catalyst layer. A series of radiation grafted ethylene tetrafluoroethylene-g-polystyrene sulfonic acid (ETFE-g-PSSA) membranes was used to provide a systematic variation of IEC. A method to fabricate gas diffusion electrodes (GDEs) was adapted and custom-made GDEs with known compositions were prepared. Oxygen electrochemistry, mass transport properties, water absorption behaviour and proton conductivity were studied in relation to the IEC. Electrochemical characterization including cyclic voltammetry, electrochemical impedance spectroscopy and linear sweep voltammetry were employed. The agglomerate model for cathodes was adapted and used to extract mass transport parameters from experimental results. Prior to investigation in fuel cell systems, studies were performed in a half-fuel cell, which simplified complicating parameters associated with fuel cell operation. It was found that membranes with higher IEC resulted in a higher active surface area of electrode. In contrast, they exhibited lower oxygen reduction performance. The extracted effective diffusion coefficient of oxygen and O2 solubility in the catalyst layer was used to estimate the extent of flooding, which revealed that ˜67--70% of void space was filled with water. The membrane's IEC regulates the extent of flooding of the cathode, which in turn affects its electrochemical characteristics. The investigation under operating fuel cell conditions revealed an increase in fuel cell performance with increasing IEC---a contradicting trend to that found for the half-fuel cell. This is explained by the interplay of electroosmotic flux and hydraulic counterflux in the membrane which affects water management in the membrane electrode assembly (MEA). The influence was most significant in the cathode catalyst layer, where it affects mass transport and electrochemical characteristics. It was found that the higher IEC facilitated better water management in MEAs. Comparing results obtained with half fuel cell and fuel cell systems revealed insights into the state of hydration and effective use of Pt in the catalyst layer. The two types of measurements provide a convenient approach to study the interplay of different mechanisms of water flux in the membrane.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

Interfacial characterization and supercapacitive properties of polyaniline-Gum arabic nanocomposite/graphene oxide LbL modified electrodes

NASA Astrophysics Data System (ADS)

Oliveira, Rafaela D.; Santos, Cleverson S.; Ferreira, Rodolfo T.; Marciniuk, Gustavo; Marchesi, Luís F.; Garcia, Jarem R.; Vidotti, Marcio; Pessoa, Christiana A.

2017-12-01

In this manuscript, we describe the synthesis and electrochemical characterization of polyaniline-gum arabic nanocomposites and graphene oxide (PANI-GA/GO) modified electrodes with a detailed study concerning their supercapacitive properties. The electrode modification was carried out by using the Layer-by-Layer technique (LbL), where the PANI-GA nanocomposite dispersion was used as polycation and the GO colloidal dispersion as polyanion. The bilayer growth was followed by both UV-vis spectroscopy and cyclic voltammetry, and an increase in the characteristic PANI absorption and in the electrochemical signal was verified, confirming the electrode build up. Galvanostatic charge-discharge curves (GCDC) were performed to evaluate the supercapacitive properties of the modified electrodes, these results showed the dependence of the specific capacitance with the number of bilayers, where values of CS around 15 mF cm-2 (i = 0.1 mA cm-2) were found. Electrochemical impedance spectroscopy confirmed the pseudocapacitive properties of the modified electrodes, showing an increase in the low-frequency capacitance with the number of bilayers. Hereby the (PANI-GA/GO)-LbL electrodes were shown to be good candidates for active materials in supercapacitors.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance.

PubMed

Yilmaz, Gamze; Yam, Kah Meng; Zhang, Chun; Fan, Hong Jin; Ho, Ghim Wei

2017-07-01

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co 9 S 8 ) system. The embedment of metal sulfide species (Co 9 S 8 ) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co 9 S 8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic-organic functional materials for electrochemical applications and beyond. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation on carbon nanocapsules for supercapacitors using a titanium cavity electrode

NASA Astrophysics Data System (ADS)

Wu, Cheng-Yeou; Wu, Pu-Wei; Lin, Pang

We synthesize carbon nanocapsules (CNCs) by a flame combustion method and evaluate their potential as the electrode material for electrochemical double layer capacitor using a titanium cavity electrode (TCE). Identical process is conducted on commercially available carbonaceous materials such as Vulcan XC72R, Black Pearl 2000 (BP2000), multi-walled carbon nanotubes (MWCNTs), and active carbon (AC1100) for comparison purposes. Images from Scanning electron microscope and Transmission electron microscope on the CNCs demonstrate irregular-shaped particles in average size of 10-20 nm with graphene layers on perimeter compassing a hollow core. Electrochemical characterizations including cyclic voltammetry (CV), current reversal chronopotentiometry (CRC), and impedance spectroscopy are carried out in 1N H 2SO 4 to determine the specific capacitance and cycle life time. Among these samples, the BP2000 still delivers the highest specific capacitance in F g -1 but the CNCs demonstrate the largest value in μF cm 2. In addition, the CNCs exhibit impressive life time for 5000 cycles without notable degradation. Consistent results are obtained by CV, CRC, and impedance measurements, validating the TCE as a facile tool to perform reliable electrochemical evaluations.

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.

Colloidal lithography with electrochemical nickel deposition as a unique method for improved silver decorated nanocavities in SERS applications

NASA Astrophysics Data System (ADS)

Petruš, Ondrej; Oriňak, Andrej; Oriňaková, Renáta; Orságová Králová, Zuzana; Múdra, Erika; Kupková, Miriam; Kovaľ, Karol

2017-11-01

Two types of metallised nanocavities (single and hybrid) were fabricated by colloid lithography followed by electrochemical deposition of Ni and subsequently Ag layers. Introductory Ni deposition step iniciates more homogenous decoration of nanocavities with Ag nanoparticles. Silver nanocavity decoration has been so performed with lower nucleation rate and with Ag nanoparticles homogeinity increase. By this, two step Ni and Ag deposition trough polystyrene nanospheres (100, 300, 500, 700, 900 nm), the various Ag surfaces were obtained. Ni layer formation in the first step of deposition enabled more precise controlling of Ag film deposition and thus final Ag surface morphology. Prepared substrates were tested as active surfaces in SERS application. The best SERS signal enhancement was observed at 500 nm Ag nanocavities with normalised thickness Ni layer ∼0.5. Enhancement factor has been established at value 1.078 × 1010; time stability was determined within 13 weeks; charge distribution at nanocavity Ag surfaces as well as reflection spectra were calculated by FDTD method. Newly prepared nanocavity surface can be applied in SERS analysis, predominantly.

Tailor-Made Electrospun Multilayer Composite Polymer Electrolytes for High-Performance Lithium Polymer Batteries.

PubMed

Lim, Du-Hyun; Haridas, Anupriya K; Figerez, Stelbin Peter; Raghavan, Prasanth; Matic, Aleksandar; Ahn, Jou-Hyeon

2018-09-01

A novel tailor-made multilayer composite polymer electrolyte, consisting of two outer layers of electrospun polyacrylonitrile (PAN) and one inner layer of poly(vinyl acetate) (PVAc)/poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) fibrous membrane, was prepared using continuous electrospinning. These membranes, which are made up of fibers with diameters in the nanometer range, were stacked in layers to produce interconnected pores that result in a high porosity. Gel polymer electrolytes (GPEs) were prepared by entrapping a liquid electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate) in the membranes. The composite membranes exhibited a high electrolyte uptake of 450-510%, coupled with an improved room temperature ionic conductivity of up to 4.72 mS cm-1 and a high electrochemical stability of 4.6 V versus Li/Li+. Electrochemical investigations of a composite membrane of PAN-PVAc-PAN, with a LiFePO4 cathode synthesized in-house, showed a high initial discharge capacity of 145 mAh g-1, which corresponds to 85% utilization of the active material, and displayed stable cycle performance.

Protection by Thermal and Chemical Activation with Cerium Salts of the Alloy AA2017 in Aqueous Solutions of NaCl

NASA Astrophysics Data System (ADS)

Bethencourt, Manuel; Botana, Francisco Javier; Cano, María José; González-Rovira, Leandro; Marcos, Mariano; Sánchez-Amaya, José María

2012-01-01

A wide variety of anticorrosive treatments for aluminum alloys that can be employed as "green" alternatives to those based on Cr(VI) are currently under development. This article reports a study of the morphological and anticorrosive characteristics of surface layers formed on the Al-Cu alloy AA2017 by immersion treatment in baths of cerium salt, accelerated by increased temperature and the employment of hydrogen peroxide. Scanning electron microscopy (SEM)/X-ray energy dispersive spectroscopy (XEDS) studies of the samples treated have demonstrated the existence of a heterogeneous layer formed by a film of aluminum oxide/hydroxide on the matrix, and a series of dispersed islands of cerium over the cathodic intermetallics. The protective efficacy has been evaluated using electrochemical techniques, linear polarizations (LP) and electrochemical impedance spectroscopy (EIS), and salt spray tests. The results obtained indicate that the layer provided good resistance to corrosion in media with chlorides, and the method gives a considerable reduction of the time required for the immersion treatments.

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.

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.

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 cell

DOEpatents

Redey, Laszlo I.; Myles, Kevin M.; Vissers, Donald R.; Prakash, Jai

1996-01-01

An electrochemical cell with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated .beta." alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated .beta." alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof.

Microstructure and antibacterial property of in situ TiO(2) nanotube layers/titanium biocomposites.

PubMed

Cui, C X; Gao, X; Qi, Y M; Liu, S J; Sun, J B

2012-04-01

The TiO(2) nanotube layer was in situ synthesized on the surface of pure titanium by the electrochemical anodic oxidation. The diameter of nano- TiO(2) nanotubes was about 70~100 nm. The surface morphology and phase compositions of TiO(2) nanotube layers were observed and analyzed using the scanning electron microscope (SEM). The important processing parameters, including anodizing voltage, reaction time, concentration of electrolyte, were optimized in more detail. The photocatalytic activity of the nano- TiO(2) nanotube layers prepared with optimal conditions was evaluated via the photodegradation of methylthionine in aqueous solution. The antibacterial property of TiO(2) nanotube layers prepared with optimal conditions was evaluated by inoculating Streptococcus mutans on the TiO(2) nanotube layers in vitro. The results showed that TiO(2) nanotube layers/Ti biocomposites had very good antibacterial activity to resist Streptococcus mutans. As a dental implant biomaterial, in situ TiO(2) nanotube layer/Ti biocomposite has better and wider application prospects. Copyright © 2012 Elsevier Ltd. All rights reserved.

The effect of metallic oxide deposition on the electrochemical behaviour of Al-Zn-Mg-Sn alloy in natural tropical seawater

NASA Astrophysics Data System (ADS)

Din Yati, M. S.; Nazree Derman, Mohd; Isa, M. C.; Y Ahmad, M.; Yusoff, N. H. N.; Muhammad, M. M.; Nain, H.

2014-06-01

The potential of aluminium alloys as anode materials in cathodic protection system has been explored and a significant improvement has been achieved. However, for marine application, it is quite difficult to maintain continuous activation process due to passivation behavior of aluminum alloys. Therefore, to choose the best activation mechanism for aluminium alloy in marine environment, it has to be considered from various points such as alloy composition and surface treatment. This paper report the effect of metallic ruthenium oxide (RuO2) deposition on the surface of as-cast Al-Zn-Mg-Sn alloy and to study the effect of its presence on the electrochemical behavior using direct current (DC) electrochemical polarization and current capacity measurement. The morphology and topography of corroded surface were studied by the aid of scanning electron microscope (SEM) and confocal laser scanning microscope (CLSM) respectively. Results from this study showed that the presence of intermetallic compound (Mg2Sn) and also mixed metal oxide compound (Al2O3 and RuO2) on the alloy surface has been very useful in improving electrochemical reaction and charge transfer activities in chloride containing solution. This study also showed that RuO2 catalytic coating applied on the surface of Al-Zn-Mg-Sn alloy has slightly increased the corrosion current density compared to Al-Zn-Mg-Sn without RuO2. The corrosion morphology and topography of corroded surface of Al-Zn-Mg-Sn alloy deposited with RuO2 was found more uniform corrosion attack with the formation of porous and fibrous mud-like crack on outer layer. Based on surface morphology and 3D topographic studies, these features were believed to facilitate ionic species adsorption and diffusion through corrosion product layer at solution-alloy interface. Deposited RuO2 films also was found to increase of current efficiency by more than 10%.

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.

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.

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

NASA Astrophysics Data System (ADS)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

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.

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.

Underpotential deposition-mediated layer-by-layer growth of thin films

DOEpatents

Wang, Jia Xu; Adzic, Radoslav R.

2017-06-27

A method of depositing contiguous, conformal submonolayer-to-multilayer thin films with atomic-level control is described. The process involves electrochemically exchanging a mediating element on a substrate with a noble metal film by alternatingly sweeping potential in forward and reverse directions for a predetermined number of times in an electrochemical cell. By cycling the applied voltage between the bulk deposition potential for the mediating element and the material to be deposited, repeated desorption/adsorption of the mediating element during each potential cycle can be used to precisely control film growth on a layer-by-layer basis.

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.

Surface modification of active material structures in battery electrodes

DOEpatents

Erickson, Michael; Tikhonov, Konstantin

2016-02-02

Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

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.

Metal Oxide Materials and Collector Efficiency in Electrochemical Supercapacitors

DTIC Science & Technology

2010-12-01

However, even if thick tita - nium films and/or nanostructured layers were obtained using these methods, they were composed of non-conducting titanium...following electrochemical reduction in LiClO4/acetonitrile. Table 1 reports the electrochemical parameters and the atomic composition of the tita - nium

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.

Removal of Cu(II) ions from contaminated waters using a conducting microfiltration membrane.

PubMed

Wang, Xueye; Wang, Zhiwei; Chen, Haiqin; Wu, Zhichao

2017-10-05

Efficient removal of toxic metals using low-pressure membrane processes from contaminated waters is an important but challenging task. In the present work, a conducting microfiltration membrane prepared by embedding a stainless steel mesh in the active layer of a polyvinylidene fluoride membrane is developed to remove Cu(II) ions from contaminated waters. Results showed that the conducting membrane had favorable electrochemical properties and stability as cathode. Batch tests showed that Cu(II) removal efficiency increased with the increase of voltages and leveled off with the further enhancement of electric field. The optimal voltages were determined to be 1.0V and 2.0V for the influent Cu(II) concentrations of 5mg/L and 30mg/L, respectively. X-ray photoelectron spectroscopy and X-ray diffraction results demonstrated the presence of Cu(0) and Cu(OH) 2 on the membrane surface. The removal mechanisms involved the intrinsic adsorption of membrane, electrosorption of membrane, adsorption of deposited layer, chemical precipitation of Cu(OH) 2 and deposition of Cu(0) which were aided by electrophoresis and electrochemical oxidation-reduction. Long-term tests showed that the major contributors for Cu(II) removal were the deposition of Cu(0) by electrochemical reduction-oxidation (47.3%±8.5%) and chemical precipitation (41.1%±0.2%), followed by electrosorption, adsorption by the fouling layer and membrane intrinsic sorption. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Nanostructured pseudocapacitive materials decorated 3D graphene foam electrodes for next generation supercapacitors.

PubMed

Patil, Umakant; Lee, Su Chan; Kulkarni, Sachin; Sohn, Ji Soo; Nam, Min Sik; Han, Suhyun; Jun, Seong Chan

2015-04-28

Nowadays, advancement in performance of proficient multifarious electrode materials lies conclusively at the core of research concerning energy storage devices. To accomplish superior capacitance performance the requirements of high capacity, better cyclic stability and good rate capability can be expected from integration of electrochemical double layer capacitor based carbonaceous materials (high power density) and pseudocapacitive based metal hydroxides/oxides or conducting polymers (high energy density). The envisioned three dimensional (3D) graphene foams are predominantly advantageous to extend potential applicability by offering a large active surface area and a highly conductive continuous porous network for fast charge transfer with decoration of nanosized pseudocapacitive materials. In this article, we review the latest methodologies and performance evaluation for several 3D graphene based metal oxides/hydroxides and conducting polymer electrodes with improved electrochemical properties for next-generation supercapacitors. The most recent research advancements of our and other groups in the field of 3D graphene based electrode materials for supercapacitors are discussed. To assess the studied materials fully, a careful interpretation and rigorous scrutiny of their electrochemical characteristics is essential. Auspiciously, both nano-structuration as well as confinement of metal hydroxides/oxides and conducting polymers onto a conducting porous 3D graphene matrix play a great role in improving the performance of electrodes mainly due to: (i) active material access over large surface area with fast charge transportation; (ii) synergetic effect of electric double layer and pseudocapacitive based charge storing.

NiFe-Layered Double Hydroxide Nanosheet Arrays Supported on Carbon Cloth for Highly Sensitive Detection of Nitrite.

PubMed

Ma, Yue; Wang, Yongchuang; Xie, Donghua; Gu, Yue; Zhang, Haimin; Wang, Guozhong; Zhang, Yunxia; Zhao, Huijun; Wong, Po Keung

2018-02-21

Excessive uptake of nitrite has been proven to be detrimental to the ecological system and human health. Hence, there is a rising requirement for constructing effective electrochemical sensors to precisely monitor the level of nitrite. In this work, NiFe-layered double hydroxide nanosheet arrays (NiFe-LDH NSAs) have been successfully fabricated on a carbon cloth (CC) substrate via a facile one-pot hydrothermal route. By integrating the collective merits of macroporous CC and NiFe-LDH NSAs such as superior electrical conductivity, striking synergistic effect between the dual active components, enlarged electrochemically active surface area, unique three-dimensional hierarchical porous network characteristics, and fast charge transport and ion diffusion, the proposed NiFe-LDH NSAs/CC architecture can be served as a self-supporting sensor toward nitrite detection. As a consequence, the resulting NiFe-LDH NSAs/CC electrode demonstrates superior nitrite sensing characteristics, accompanied by broad linear range (5-1000 μM), quick response rate (ca. 3 s), ultralow detection limit (0.02 μM), and high sensitivity (803.6 μA·mM -1 ·cm -2 ). Meanwhile, the electrochemical sensor possesses timeless stability, good reproducibility, and strong anti-interference feature. Importantly, the resulting sensor can determine nitrite level in tap and lake water with high recoveries, suggesting its feasibility for practical applications. These findings show that the obtained NiFe-LDH NSAs/CC electrode holds great prospect in highly sensitive and specific detection of nitrite.

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.

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

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.

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

Effect of poly(3,4-ethylenedioxythiophene) (PEDOT) in carbon-based composite electrodes for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Lei, Chunhong; Wilson, Peter; Lekakou, Constantina

Electrochemical double layer supercapacitor cells were fabricated and tested using composite electrodes of activated carbon with carbon black and poly(3,4-ethylenedioxythiophene) (PEDOT), and an organic electrolyte 1 M TEABF 4/PC solution. The effect of PEDOT on the performance of the EDLC cells was explored and the cells were characterised by electrochemical impedance spectroscopy (EIS), cyclic voltammetry and galvanostatic charge-discharge. A generalised equivalent circuit model was developed for which numerical simulations were performed to determine the properties and parameters of its components from the EIS data. It was found that the proposed model fitted successfully the data of all tested cells. PEDOT enhanced the electrode and cell capacitance via its pseudo-capacitance effect up to a maximum value for an optimum PEDOT loading and greatly increased the energy density of the cell while the maximum power density has been still maintained at supercapacitor levels. Furthermore, PEDOT replaced PVDF as a binder and harmful solvent release was reduced during electrode processing. Activated carbon-carbon black composite electrodes with PEDOT as binder were found to have specific capacitance superior to that of activated carbon-carbon black electrodes with PVDF binder.

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.

Electrochemical performance of microporous and mesoporous activated carbons in neat and diluted 1-ethyl-3-methylimidazolium tetrafluoroborate

NASA Astrophysics Data System (ADS)

Kumagai, Seiji; Hatomi, Masaki; Tashima, Daisuke

2017-03-01

1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIm·BF4), neat and diluted with propylene carbonate to 1 mol L-1, have been employed as electrolytes of electrical double-layer capacitors (EDLCs). The effects of microporosity and mesoporosity in activated carbon (AC) electrodes on the capacitive and resistive performances upon the use of neat and diluted EMIm·BF4 have been explored. In addition to cyclic voltammetry and galvanostatic charge-discharge tests, electrochemical impedance spectroscopy has been performed employing Kang's equivalent circuit model consisting of three resistances, three constant phase elements, and one bounded Warburg impedance. The overall impedance of the EDLC cell was separated into components of intrinsic resistance, bulk electrolyte, diffusion layer, and Helmholtz layer. The specific capacitance and the equivalent series resistance (ESR) of mesoporous AC were found to be highly dependent on the rate of ionic transfer. Lower cell voltage was identified as being responsible for lower specific capacitance and larger ESR of mesoporous AC, which was similarly seen in the neat and diluted EMIm·BF4, and could be alleviated by increasing the cell voltage. The inferior rate performance and the cell-voltage-dependent performance of mesoporous AC, which were more distinctly observed in the neat EMIm·BF4, could be attributed to the lower mobility of EMIm+ and BF4- in mesopores.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

PubMed

Doubaji, Siham; Philippe, Bertrand; Saadoune, Ismael; Gorgoi, Mihaela; Gustafsson, Torbjorn; Solhy, Abderrahim; Valvo, Mario; Rensmo, Håkan; Edström, Kristina

2016-01-08

The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Electrochemistry of sp(2) Carbon Materials: From Graphite and Graphene to Carbon Nanotubes.

PubMed

Unwin, Patrick R; Güell, Aleix G; Zhang, Guohui

2016-09-20

Carbon materials have a long history of use as electrodes in electrochemistry, from (bio)electroanalysis to applications in energy technologies, such as batteries and fuel cells. With the advent of new forms of nanocarbon, particularly, carbon nanotubes and graphene, carbon electrode materials have taken on even greater significance for electrochemical studies, both in their own right and as components and supports in an array of functional composites. With the increasing prominence of carbon nanomaterials in electrochemistry comes a need to critically evaluate the experimental framework from which a microscopic understanding of electrochemical processes is best developed. This Account advocates the use of emerging electrochemical imaging techniques and confined electrochemical cell formats that have considerable potential to reveal major new perspectives on the intrinsic electrochemical activity of carbon materials, with unprecedented detail and spatial resolution. These techniques allow particular features on a surface to be targeted and models of structure-activity to be developed and tested on a wide range of length scales and time scales. When high resolution electrochemical imaging data are combined with information from other microscopy and spectroscopy techniques applied to the same area of an electrode surface, in a correlative-electrochemical microscopy approach, highly resolved and unambiguous pictures of electrode activity are revealed that provide new views of the electrochemical properties of carbon materials. With a focus on major sp(2) carbon materials, graphite, graphene, and single walled carbon nanotubes (SWNTs), this Account summarizes recent advances that have changed understanding of interfacial electrochemistry at carbon electrodes including: (i) Unequivocal evidence for the high activity of the basal surface of highly oriented pyrolytic graphite (HOPG), which is at least as active as noble metal electrodes (e.g., platinum) for outer-sphere redox processes. (ii) Demonstration of the high activity of basal plane HOPG toward other reactions, with no requirement for catalysis by step edges or defects, as exemplified by studies of proton-coupled electron transfer, redox transformations of adsorbed molecules, surface functionalization via diazonium electrochemistry, and metal electrodeposition. (iii) Rationalization of the complex interplay of different factors that determine electrochemistry at graphene, including the source (mechanical exfoliation from graphite vs chemical vapor deposition), number of graphene layers, edges, electronic structure, redox couple, and electrode history effects. (iv) New methodologies that allow nanoscale electrochemistry of 1D materials (SWNTs) to be related to their electronic characteristics (metallic vs semiconductor SWNTs), size, and quality, with high resolution imaging revealing the high activity of SWNT sidewalls and the importance of defects for some electrocatalytic reactions (e.g., the oxygen reduction reaction). The experimental approaches highlighted for carbon electrodes are generally applicable to other electrode materials and set a new framework and course for the study of electrochemical and interfacial processes.

Electrochemical, Structural and Magnetic Analysis of Electrodeposited CoCu/Cu Multilayers: Influence of Cu Layer Deposition Potential

NASA Astrophysics Data System (ADS)

Tekgül, Atakan; Kockar, Hakan; Kuru, Hilal; Alper, Mürsel; ÜnlÜ, C. Gökhan

2018-03-01

The electrochemical, structural and magnetic properties of CoCu/Cu multilayers electrodeposited at different cathode potentials were investigated from a single bath. The Cu layer deposition potentials were selected as - 0.3, V - 0.4 V, and - 0.5 V with respect to saturated calomel electrode (SCE) while the Co layer deposition potential was constant at - 1.5 V versus SCE. For the electrochemical analysis, the current-time transients were obtained. The amount of noble non-magnetic (Cu) metal materials decreased with the increase of deposition potentials due to anomalous codeposition. Further, current-time transient curves for the Co layer deposition and capacitance were calculated. In the structural analysis, the multilayers were found to be polycrystalline with both Co and Cu layers adopting the face-centered cubic structure. The (111) peak shifts towards higher angle with the increase of the deposition potentials. Also, the lattice parameters of the multilayers decrease from 0.3669 nm to 0.3610 nm with the increase of the deposition potentials from - 0.3 V to - 0.5 V, which corresponds to the bulk values of Cu and Co, respectively. The electrochemical and structural results demonstrate that the amount of Co atoms increased and the Cu atoms decreased in the layers with the increase of deposition potentials due to anomalous codeposition. For magnetic measurements, the saturation magnetizations, M_s obtained from the magnetic curves of the multilayers were obtained as 212 kA/m, 276 kA/m, and 366 kA/m with - 0.3 V, - 0.4 V, and - 0.5 V versus SCE, respectively. It is seen that the M_s values increased with the increase of the deposition potentials confirming the increase of the Co atoms and decrease of the Cu amount. The results of electrochemical and structural analysis show that the deposition potentials of non-magnetic layers plays important role on the amount of magnetic and non-magnetic materials in the layers and thus on the magnetic properties of the multilayers.

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

Preparation of porous carbon sphere from waste sugar solution for electric double-layer capacitor

NASA Astrophysics Data System (ADS)

Hao, Zhi-Qiang; Cao, Jing-Pei; Wu, Yan; Zhao, Xiao-Yan; Zhuang, Qi-Qi; Wang, Xing-Yong; Wei, Xian-Yong

2017-09-01

Waste sugar solution (WSS), which contains abundant 2-keto-L-gulonic acid, is harmful to the environment if discharged directly. For value-added utilization of the waste resource, a novel process is developed for preparation of porous carbon spheres by hydrothermal carbonization (HTC) of WSS followed by KOH activation. Additionally, the possible preparation mechanism of carbon spheres is proposed. The effects of hydrothermal and activation parameters on the properties of the carbon sphere are also investigated. The carbon sphere is applied to electric double-layer capacitor and its electrochemical performance is studied. These results show that the carbon sphere obtained by HTC at 180 °C for 12 h with the WSS/deionized water volume ratio of 2/3 possess the highest specific capacitance under identical activation conditions. The specific capacitance of the carbon spheres can reach 296.1 F g-1 at a current density of 40 mA g-1. Besides, excellent cycle life and good capacitance retention (89.6%) are observed at 1.5 A g-1 after 5000 cycles. This study not only provides a facile and potential method for the WSS treatment, but also achieves the high value-added recycling of WSS for the preparation of porous carbon spheres with superior electrochemical properties.

Evaluation of zinc oxide nano-microtetrapods for biomolecule sensing applications

NASA Astrophysics Data System (ADS)

Zhao, Wei; Zhao, Yichen; Karlsson, Mikael; Wang, Qin; Toprak, Muhammet S.

2015-12-01

Zinc oxide tetrapods (ZnO-Ts) were synthesized by flame transport synthesis using Zn microparticles. This work herein reports a systematical study on the structural, optical and electrochemical properties of the ZnO-Ts. The morphology of the ZnO-Ts was confirmed by scanning electron microscopy (SEM) as joint structures of four nano-microstructured legs, of which the diameter of each leg is 0.7-2.2 μm in average from the tip to the stem. The ZnO-Ts were dispersed in glucose solution to study the luminescence as well as photocatalytic activity in a mimicked biological environment. The photoluminescence (PL) intensity in the ultraviolet (UV) region quenches with linear dependence to increased glucose concentration up to 4 mM. The ZnO-Ts were also attached with glucose oxidase (GOx) and over coated with a thin film of Nafion to form active layers for electrochemical glucose sensing. The attachment of GOx and coating of Nafion were confirmed by infrared spectroscopy (FT-IR). Furthermore, the current response of the active layers based on ZnO-Ts was investigated by cyclic voltammetry (CV) in various glucose concentrations. Stable current response of glucose was detected with linear dependence to glucose concentration up to 12 mM, which confirms the potential of ZnO-Ts for biomolecule sensing applications.

Outstanding features of alginate-based gel electrolyte with ionic liquid for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Soeda, Kazunari; Yamagata, Masaki; Ishikawa, Masashi

2015-04-01

An alginate-based gel electrolyte with an ionic liquid (Alg/IL) is investigated for electric double-layer capacitors (EDLCs) by using physicochemical and electrochemical measurements. The Alg/EMImBF4 (EMImBF4 = 1-ethyl-3-methylimidazolium tetrafluoroborate) gel electrolyte is thermally stable up to 280 °C, where EMImBF4 decomposes. Furthermore, the EDLC with the gel electrolyte can be operated even at high temperature. The cell containing Alg/EMImBF4 is also electrochemically stable even under high voltage (∼3.5 V) operation. Thus, the alginate is a suitable host polymer for the gel electrolyte for EDLCs. According to the result of charge-discharge characteristics, the voltage drop in the charge-discharge curve for the cell with Alg/EMImBF4 gel electrolyte is considerably smaller than that with liquid-phase EMImBF4 electrolyte. To clarify the effect of Alg in contact with the activated carbon electrode, we also prepared an Alg-containing ACFC electrode (Alg + ACFC), and evaluated its EDLC characteristics in liquid EMImBF4. The results prove that the presence of Alg close to the active materials significantly reduces the internal resistance of the EDLC cell, which may be attributed to the high affinity of Alg to activated carbon.

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).

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.

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 photo-assistant electrocatalysis of anodization TiO2 nanotubes via surrounded surface decoration with MoS2 for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Tian, Yuanyuan; Song, Ye; Dou, Meiling; Ji, Jing; Wang, Feng

2018-03-01

A highly ordered TiO2 nanotube array covered with MoS2 is fabricated through a facile anodization of a metallic Ti followed by electrochemical deposition approach. The morphologies characterization of v-TiO2@MoS2 indicate that a whole scale of 1D TiO2nanotube uniformly covered with the MoS2 layer inside and outside, and the pathway inside the TiO2nanotube is kept flow-through. The as-synthesized v-TiO2@MoS2 hybrid exhibits higher efficient and stable visible light activities than that of either pure TiO2 nanotubes or nv-TiO2@MoS2 nanostructures. By electrochemical measurements such as linear sweep voltammetry(LSV) and electrochemical impedance spectroscope (EIS) under light illumination or in dark, we find that the v-TiO2@MoS2hybrid shows markedly enhanced photoelectrochemical performance. Furthermore, we compare the electrocatalytic behavior of v-TiO2@MoS2under illumination in H2SO4/Lactic acid within Na2S/NaSO3 solution. The results show that the photo-assistant electrocatalytic activity in acidic environment is much better than in alkaline environment. The highly directional and orthogonal separation of charge carriers between TiO2 nanotubes and MoS2 layer, together with maximally exposed MoS2 edges, light harvesting and junctions formed between TiO2 and MoS2 is supposed to be mainly responsible for the enhanced photo-assistant electrocatalytic activity of v-TiO2@MoS2.

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

Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation

DOE PAGES

Nicholas W. Brady; Takeuchi, Esther S.; Knehr, K. W.; ...

2016-04-24

Magnetite is a known lithium intercalation material, and the loss of active, nanocrystalline magnetite can be inferred from the open-circuit potential relaxation. Specifically, for current interruption after relatively small amounts of lithium insertion, the potential first increases and then decreases, and the decrease is hypothesized to be due to a formation of a surface layer, which increases the solid-state lithium concentration in the remaining active material. Comparisons of simulation to experiment suggest that the reactions with the electrolyte result in the formation of a thin layer of electrochemically inactive material, which is best described by a nucleation and growth mechanism.more » Simulations are consistent with experimental results observed for 6, 8 and 32-nm crystals. As a result, simulations capture the experimental differences in lithiation behavior between the first and second cycles.« less

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.

Role of Cr 3+ /Cr 6+ redox in chromium-substituted Li 2 MnO 3 ·LiNi 1/2 Mn 1/2 O 2 layered composite cathodes: electrochemistry and voltage fade

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

Lee, Eungje; Park, Joong Sun; Wu, Tianpin

2015-01-01

The substitution of chromium into the composite Li 2MnO 3·LiNi 1/2Mn 1/2O 2cathode dramatically affects the initial electrochemical activation process; however the voltage fade process during cycling persists.

Effect of alkyl branches on the thermal stability of quaternary ammonium cations in organic electrolytes for electrochemical double layer capacitors.

PubMed

Ahn, Yong Nam; Lee, Sung Hoon; Lee, Goo Soo; Kim, Hyunbin

2017-08-02

Quaternary ammoniums are cations having widespread use in organic electrolytes for high performance electrochemical double layer capacitors (EDLCs) due to their various advantages such as high electrochemical stability and inexpensive production cost. However, the decomposition of quaternary ammoniums via Hofmann elimination hinders their applications for EDLCs operating at elevated temperatures. This study systematically investigates the reactivity of four different quaternary ammoniums (tetraethyl-, triethylmethyl-, diethyldimethyl-, and trimethylethyl-ammonium) in EDLC by utilizing density functional theory calculations and Brownian dynamics simulations complemented with molecular dynamics simulations. It is found that ammonium stability reduces upon increasing the number of ethyl branches that have a stronger positive charge than the methyl groups. However, the contribution of the entropy change to the reaction free energy makes trimethylethylammonium less stable than diethyldimethylammonium at room temperature although the former has less ethyl branches than the latter. Trimethylethylammonium becomes the most stable at a high temperature of 488 K above which the activation free energy becomes effectively negligible and thus the number of reactive sites determines the overall stability. The fundamental understanding of the ammonium decompositions through Hofmann elimination demonstrated in this study is expected to contribute to developing new long-life organic electrolyte systems for high-temperature applications.

Spiro-(1,1‧)-bipyrrolidinium tetrafluoroborate salt as high voltage electrolyte for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Yu, Xuewen; Ruan, Dianbo; Wu, Changcheng; Wang, Jing; Shi, Zhiqiang

2014-11-01

A novel quaternary ammonium salt based on spiro-(1,1‧)-bipyrolidinium tetrafluoroborate (SBP-BF4) has been synthesized and dissolved in propylene carbonate (PC) with 1.5 mol L-1 (M) concentration for electric double-layer capacitors (EDLCs). The physic-chemical properties and electrochemical performance of SBP-BF4/PC electrolyte are investigated. Compared with the standard electrolyte 1.5 M TEMA-BF4 in PC, the novel SBP-BF4/PC electrolyte exhibited much better electrochemical performance due to its smaller cation size, lower viscosity and higher conductivity. The specific discharge capacitance of activated carbon electrode based EDLCs using SBP-BF4/PC electrolyte is 120 F g-1, the energy density and power density can reach 31 kW kg-1 and 6938 W kg-1, respectively, when the working voltage is 2.7 V and current density is 50 mA g-1. The withstand voltage of activated carbon based EDLCs with SBP-BF4/PC electrolyte can reach to 3.2 V, where the stable discharge capacitance and energy density are 121 F g-1 and 43 Wh kg-1, respectively.

Influences of internal resistance and specific surface area of electrode materials on characteristics of electric double layer capacitors

NASA Astrophysics Data System (ADS)

Suda, Yoshiyuki; Mizutani, Akitaka; Harigai, Toru; Takikawa, Hirofumi; Ue, Hitoshi; Umeda, Yoshito

2017-01-01

We fabricated electric double layer capacitors (EDLCs) using particulate and fibrous types of carbon nanomaterials with a wide range of specific surface areas and resistivity as an active material. The carbon nanomaterials used in this study are carbon nanoballoons (CNBs), onion-like carbon (OLC), and carbon nanocoils (CNCs). A commercially used activated carbon (AC) combined with a conductive agent was used as a comparison. We compared the EDLC performance using cyclic voltammetry (CV), galvanostatic charge/discharge testing, and electrochemical impedance spectroscopy (EIS). OLC showed a poor EDLC performance, although it has the lowest resistivity among the carbon nanomaterials. CNB, which has a 1/16 lower specific surface area than AC but higher specific surface area than CNC and OLC, had a higher specific capacitance than CNC and OLC. Moreover, at current densities of 1.5 Ag-1 and larger, the specific capacitance of the EDLC using CNB was almost the same as that using AC. Electrochemical impedance spectroscopy of the EDLCs revealed that the CNB and CNC electrodes had a much lower internal resistance than the AC electrode, which correlated with a low capacitance maintenance factor as the current density increased.

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.

Mixed Electronic and Ionic Conductor-Coated Cathode Material for High-Voltage Lithium Ion Battery.

PubMed

Shim, Jae-Hyun; Han, Jung-Min; Lee, Joon-Hyung; Lee, Sanghun

2016-05-18

A lithium ionic conductor, Li1.3Al0.3Ti1.7(PO4)3 (LATP), is introduced as a coating material on the surface of Mg-doped LiCoO2 to improve electrochemical performances for high-voltage (4.5 V) lithium ion batteries. Structure, morphology, elemental distribution, and electrical properties of the materials are thoroughly characterized by SEM, TEM, EELS, EDS, and C-AFM. The coating layer is electrically conductive with the aid of Mg ions which are used as a dopant for the active materials; therefore, this mixed electronic ionic conductor strongly enhances the electrochemical performances of initial capacity, cycling property, and rate capability. The LATP coating layer also demonstrates very promising applicability for 4.4 V prismatic full cells with graphite anode, which correspond to the 4.5 V half-cells with lithium anode. The 2900 mA h full cells show 85% of capacity retention after 500 cycles and more than 60% after 700 cycles.

Tobacco Stem-Based Activated Carbons for High Performance Supercapacitors

NASA Astrophysics Data System (ADS)

Xia, Xiaohong; Liu, Hongbo; Shi, Lei; He, Yuede

2012-09-01

Tobacco stem-based activated carbons (TS-ACs) were prepared by simple KOH activation and their application as electrodes in the electrical double layer capacitor (EDLC) performed successfully. The BET surface area, pore volume, and pore size distribution of the TS-ACs were evaluated based on N2 adsorption isotherms at 77 K. The surface area of the obtained activated carbons varies over a wide range (1472.8-3326.7 m2/g) and the mesoporosity was enhanced significantly as the ratio of KOH to tobacco stem (TS) increased. The electrochemical behaviors of series TS-ACs were characterized by means of galvanostatic charging/discharging, cyclic voltammetry, and impedance spectroscopy. The correlation between electrochemical properties and pore structure was investigated. A high specific capacitance value as 190 F/g at 1 mA/cm2 was obtained in 1 M LiPF6-EC/DMC/DEC electrolyte solution. Furthermore, good performance is also achieved even at high current densities. A development of new use for TS into a valuable energy storage material is explored.

Preparation of capacitor's electrode from sunflower seed shell.

PubMed

Li, Xiao; Xing, Wei; Zhuo, Shuping; Zhou, Jin; Li, Feng; Qiao, Shi-Zhang; Lu, Gao-Qing

2011-01-01

Series of nanoporous carbons are prepared from sunflower seed shell (SSS) by two different strategies and used as electrode material for electrochemical double-layer capacitor (EDLC). The surface area and pore-structure of the nanoporous carbons are characterized intensively using N2 adsorption technique. The results show that the pore-structure of the carbons is closely related to activation temperature and dosage of KOH. Electrochemical measurements show that the carbons made by impregnation-activation process have better capacitive behavior and higher capacitance retention ratio at high drain current than the carbons made by carbonization-activation process, which is due to that there are abundant macroscopic pores and less interior micropore surface in the texture of the former. More importantly, the capacitive performances of these carbons are much better than ordered mesoporous carbons and commercial wood-based active carbon, thus highlighting the success of preparing high performance electrode material for EDLC from SSS. Copyright © 2010 Elsevier Ltd. All rights reserved.

C@SiNW/TiO2 Core-Shell Nanoarrays with Sandwiched Carbon Passivation Layer as High Efficiency Photoelectrode for Water Splitting

PubMed Central

Devarapalli, Rami Reddy; Debgupta, Joyashish; Pillai, Vijayamohanan K.; Shelke, Manjusha V.

2014-01-01

One-dimensional heterostructure nanoarrays are efficiently promising as high performance electrodes for photo electrochemical (PEC) water splitting applications, wherein it is highly desirable for the electrode to have a broad light absorption, efficient charge separation and redox properties as well as defect free surface with high area suitable for fast interfacial charge transfer. We present highly active and unique photoelectrode for solar H2 production, consisting of silicon nanowires (SiNWs)/TiO2 core-shell structures. SiNWs are passivated to reduce defect sites and protected against oxidation in air or water by forming very thin carbon layer sandwiched between SiNW and TiO2 surfaces. This carbon layer decreases recombination rates and also enhances the interfacial charge transfer between the silicon and TiO2. A systematic investigation of the role of SiNW length and TiO2 thickness on photocurrent reveals enhanced photocurrent density up to 5.97 mA/cm2 at 1.0 V vs.NHE by using C@SiNW/TiO2 nanoarrays with photo electrochemical efficiency of 1.17%. PMID:24810865

Fe local structure in Pt-free nitrogen-modified carbon based electrocatalysts: XAFS study

NASA Astrophysics Data System (ADS)

Witkowska, Agnieszka; Giuli, Gabriele; Renzi, Marco; Marzorati, Stefania; Yiming, Wubulikasimu; Nobili, Francesco; Longhi, Mariangela

2016-05-01

The paper presents a new results on the bonding environment (coordination number and geometry) and on oxidation states of Fe in nitrogen-modified Fe/C composites used as Pt-free catalysts for oxygen reduction in Direct Hydrogen Fuel Cells. Starting from glucose or fructose, two catalysts displaying different electrochemical performance were prepared and studied in the form of pristine powder and thin catalytic layer of electrode by Fe K-edge XAFS spectroscopy. The results show how the Fe local structure varies as a function of different synthesis conditions and how changes in the structural properties of the catalysts are related to fuel cell electrochemical performance increase during a cell activation period.

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

DOE PAGES

Fields, Meredith; Hong, Xin; Norskov, Jens K.; ...

2018-06-12

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

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

Fields, Meredith; Hong, Xin; Norskov, Jens K.

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

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.

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.

Electrochemical cell

DOEpatents

Redey, L.I.; Myles, K.M.; Vissers, D.R.; Prakash, J.

1996-07-02

An electrochemical cell is described with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated {beta}{double_prime} alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated {beta}{double_prime} alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof. 8 figs.

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

Alleviation of membrane fouling in a submerged membrane bioreactor with electrochemical oxidation mediated by in-situ free chlorine generation.

PubMed

Chung, Chong Min; Tobino, Tomohiro; Cho, Kangwoo; Yamamoto, Kazuo

2016-06-01

The control of membrane fouling is still the biggest challenge that membrane bioreactor (MBR) for wastewater treatment faces with. In this report, we evince that an in-situ electrochemical free chlorine generation is effective for membrane fouling mitigation. An electrochemical oxidation (EO) apparatus with perforated Ti/IrO2 anodes and Ti/Pt cathodes was integrated into a conventional MBR with microfiltration module (EO-MBR). The membrane fouling characteristics of EO-MBR fed with synthetic wastewater were monitored for about 2 months in comparison to control MBRs. In the EO-MBR at a direct current density of 0.4 mA/cm(2), the frequency of membrane fouling when the trans-membrane pressure (TMP) reached 30 kPa was effectively reduced by 40% under a physical membrane cleaning regime. The evolution patterns of TMP together with hydraulic resistance analysis based on resistance-in-series model indicated that the electrochemically generated active chlorine alleviated the physically irremovable membrane fouling. Further analysis on extracellular polymeric substances (EPS) of sludge cake layer (SCL) revealed significant reductions of protein contents in soluble EPS and fluorescence emission intensities from humic acids and other fluorophores in bound EPS, which in-turn would decrease the hydrophobic accumulation of organic foulants on membrane pores. The chlorine dosage from the EO apparatus was estimated to be 4.7 mg Cl2/g MLVSS/day and the overall physicochemical properties (bio-solids concentration, floc diameter, zeta-potential) as well as the microbial activity in terms of specific oxygen utilization rate and removal efficiency of dissolved organic carbon (>97%) were not affected significantly. A T-RFLP (terminal restriction fragment length polymorphism) analysis suggested noticeable shifts in microbial community both in mixed liquor and sludge cake layer. Consequently, our electrochemical chlorination would be an efficient fouling control strategy in membrane-based water treatment processes where additional electricity consumption and cathodic scale deposition are not of serious concerns. Copyright © 2016 Elsevier Ltd. All rights reserved.

Understanding the effect of an in situ generated and integrated spinel phase on a layered Li-rich cathode material using a non-stoichiometric strategy.

PubMed

Zhang, Jicheng; Gao, Rui; Sun, Limei; Li, Zhengyao; Zhang, Heng; Hu, Zhongbo; Liu, Xiangfeng

2016-09-14

Recently, spinel-layered integrated Li-rich cathode materials have attracted great interest due to the large enhancement of their electrochemical performances. However, the modification mechanism and the effect of the integrated spinel phase on Li-rich layered cathode materials are still not very clear. Herein, we have successfully synthesized the spinel-layered integrated Li-rich cathode material using a facile non-stoichiometric strategy (NS-LNCMO). The rate capability (84 mA h g -1 vs. 28 mA h g -1 , 10 C), cycling stability (92.4% vs. 80.5%, 0.2 C), low temperature electrochemical capability (96.5 mA h g -1 vs. 59 mA h g -1 , -20 °C), initial coulomb efficiency (92% vs. 79%) and voltage fading (2.77 V vs. 3.02 V, 200 cycles@1 C) of spinel-layered integrated Li-rich cathode materials have been significantly improved compared with a pure Li-rich phase cathode. Some new insights into the effect of the integrated spinel phase on a layered Li-rich cathode have been proposed through a comparison of the structure evolution of the integrated and Li-rich only materials before and after cycling. The Li-ion diffusion coefficient of NS-LNCMO has been enlarged by about 3 times and almost does not change even after 100 cycles indicating an enhanced structure stability. The integration of the spinel phase not only enhances the structure stability of the layered Li-rich phase during charging-discharging but also expands the interslab spacing of the Li-ion diffusion layer, and elongates TM-O covalent bond lengths, which lowers the activation barrier of Li + -transportation, and alleviates the structure strain during the cycling procedure.

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.

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)

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

Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides

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

Doyle, Andrew D.; Bajdich, Michal; Vojvodic, Aleksandra

The nature of the electrochemical water splitting activity of layered pure and Fe-doped NiOOH is investigated using density functional theory calculations. We find similar thermodynamics for the oxygen evolution reaction (OER) intermediates between the layers of oxyhydroxides, that is, in the bulk of the materials as on the (001) surface. The effect of interlayer spacing on adsorption energy is affected by both the crystal structure and the level of hydrogenation of the active sites. For the Fe-doped NiOOH, we observe general weakening of binding between the different OER intermediates and the catalyst material. The calculated OER activity depends both onmore » doping and interlayer spacing, and our results are generally congruent with available experimental data. In conclusion, these results suggest that such interlayer “bulk” sites may contribute to measured OER activity for both the pure and Fe-doped NiOOH catalysts.« less

Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides

DOE PAGES

Doyle, Andrew D.; Bajdich, Michal; Vojvodic, Aleksandra

2017-04-07

The nature of the electrochemical water splitting activity of layered pure and Fe-doped NiOOH is investigated using density functional theory calculations. We find similar thermodynamics for the oxygen evolution reaction (OER) intermediates between the layers of oxyhydroxides, that is, in the bulk of the materials as on the (001) surface. The effect of interlayer spacing on adsorption energy is affected by both the crystal structure and the level of hydrogenation of the active sites. For the Fe-doped NiOOH, we observe general weakening of binding between the different OER intermediates and the catalyst material. The calculated OER activity depends both onmore » doping and interlayer spacing, and our results are generally congruent with available experimental data. In conclusion, these results suggest that such interlayer “bulk” sites may contribute to measured OER activity for both the pure and Fe-doped NiOOH catalysts.« less

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.

Hybrid nanomaterial of α-Co(OH)2 nanosheets and few-layer graphene as an enhanced electrode material for supercapacitors.

PubMed

Cheng, J P; Liu, L; Ma, K Y; Wang, X; Li, Q Q; Wu, J S; Liu, F

2017-01-15

Supercapacitor with metal hydroxide nanosheets as electrode can have high capacitance. However, the cycling stability and high rate capacity is low due to the low electrical conductivity. Here, the exfoliated α-Co(OH) 2 nanosheets with high capacitance has been assembled on few-layer graphene with high electric conductivity by a facile yet effective and scalable solution method. Exfoliated hydrotalcite-like α-Co(OH) 2 nanosheets and few-layer graphene suspensions were prepared by a simple ultrasonication in formamide and N-methyl-2-pyrrolidone, respectively. Subsequently, a hybrid was made by self-assembly of α-Co(OH) 2 and few-layer graphene when the two dispersions were mixed at room temperature. The hybrid material provided a high specific capacitance of 567.1F/g at 1A/g, while a better rate capability and better stability were achieved compared to that mad of pristine and single exfoliated α-Co(OH) 2 . When the hybrid nanocomposite was used as a positive electrode and activated carbon was applied as negative electrode to assembly an asymmetric capacitor, an energy density of 21.2Wh/kg at a power density of 0.41kW/kg within a potential of 1.65V was delivered. The high electrochemical performance and facile solution-based synthesis method suggested that the hybrid of exfoliated α-Co(OH) 2 /few-layer graphene could be a potential electrode material for electrochemical capacitor. Copyright © 2016 Elsevier Inc. All rights reserved.

Ferrocene bound poly(vinyl chloride) as ion to electron transducer in electrochemical ion sensors.

PubMed

Pawlak, Marcin; Grygolowicz-Pawlak, Ewa; Bakker, Eric

2010-08-15

We report here on the synthesis of poly(vinyl chloride) (PVC) covalently modified with ferrocene groups (FcPVC) and the electrochemical behavior of the resulting polymeric membranes in view of designing all solid state voltammetric ion sensors. The Huisgen cycloaddition ("click chemistry") was found to be a simple and efficient method for ferrocene attachment. A degree of PVC modification with ferrocene groups between 1.9 and 6.1 mol % was achieved. The chemical modification of the PVC backbone does not significantly affect the ion-selective properties (selectivity, mobility, and solvent casting ability) of potentiometric sensing membranes applying this polymer. Importantly, the presence of such ferrocene groups may eliminate the need for an additional redox-active layer between the membrane and the inner electric contact in all solid state sensor designs. Electrochemical doping of this system was studied in a symmetrical sandwich configuration: glassy carbon electrode |FcPVC| glassy carbon electrode. Prior electrochemical doping from aqueous solution, resulting in a partial oxidation of the ferrocene groups, was confirmed to be necessary for the sandwich configuration to pass current effectively. The results suggest that only approximately 2.3 mol % of the ferrocene groups are electrochemically accessible, likely due to surface confined electrochemical behavior in the polymer. Indeed, cyclic voltammetry of aqueous hexacyanoferrate (III) remains featureless at cathodic potentials (down to -0.5 V). This indicates that the modified membrane is not responsive to redox-active species in the sample solution, making it possible to apply this polymer as a traditional, single membrane. Yet, the redox capacity of the electrode modified with this type of membrane was more than 520 microC considering a 20 mm(2) active electrode area, which appears to be sufficient for numerous practical ion voltammetric applications. The electrode was observed to operate reproducibly, with 1% standard deviation, when applying pulsed amperometric techniques.

Enhanced Kinetics of Electrochemical Hydrogen Uptake and Release by Palladium Powders Modified by Electrochemical Atomic Layer Deposition

DOE PAGES

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

2017-04-28

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

Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution.

PubMed

Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping; Zheng, Yixin; Chan, Ting-Shan; Sheu, Hwo-Shuenn; Cheng, Yuan-Chung; Chen, Hao Ming

2015-08-28

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

Swiss roll nanomembranes with controlled proton diffusion as redox micro-supercapacitors.

PubMed

Ji, Hengxing; Mei, Yongfeng; Schmidt, Oliver G

2010-06-14

We demonstrate a redox Swiss roll micro-supercapacitor by rolling up a multilayered nanomembrane with an electrochemical active layer at either the outer or inner surface for different proton diffusion behaviors. The Swiss roll micro-supercapacitor could achieve high performance (e.g. capacity and life time) in a microscale power source and is helpful for studying charge transfer at the electrolyte/electrode interface.

Graphene-carbon nanotube composite aerogel for selective detection of uric acid

NASA Astrophysics Data System (ADS)

Zhang, Feifei; Tang, Jie; Wang, Zonghua; Qin, Lu-Chang

2013-12-01

Graphene and single-walled carbon nanotube (SWNT) composite aerogel has been prepared by hydrothermal synthesis. The restacking of graphene is effectively reduced by SWNTs inserted in between graphene layers in order to make available more active sites and reactive surface area. Electrochemical experiments show that the graphene-SWNT composite electrode has superior catalytic performance in selective detection of uric acid (UA).

Li Storage of Calcium Niobates for Lithium Ion Batteries.

PubMed

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

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.

Few layer graphene wrapped mixed phase TiO2 nanofiber as a potential electrode material for high performance supercapacitor applications

NASA Astrophysics Data System (ADS)

Thirugnanam, Lavanya; Sundara, Ramaprabhu

2018-06-01

A combination of favorable composition and optimized anatase/rutile mixed-phase TiO2 (MPTNF)/Hydrogen exfoliated graphene (HEG) composite nanofibers (MPTNF/HEG) and anatase/rutile mixed-phase TiO2/reduced graphene oxide (rGO) composite nanofibers (MPTNF/rGO) have been reported to enhance the electrochemical properties for supercapacitor applications. These composite nanofibers have been synthesized by an efficient route of electrospinning together with the help of easy chemical methods. Both the composites exhibit good charge storage capability with enhanced pseudocapacitance and electric double-layer capacitance (EDLC) as confirmed by cyclic voltammetry studies. MPTNF/HEG composite showed maximum specific capacitance of 210.5 F/g at the current density of 1 A/g, which was mainly due to its availability of the more active sites for ions adsorption on a few layers of graphene wrapped TiO2 nanofiber surface. The synergistic effect of anatase/rutile mixed phase with one dimensional nanostructure and the electronic interaction between TiO2 and few layer graphene provided the subsequent improvement of ion adsorption capacity. Also exhibit excellent electrochemical performance to improve the capacitive properties of TiO2 electrode materials which is required for the development of flexible electrodes in energy storage devices and open up new opportunities for high performance supercapacitors.

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

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

Eliminating Voltage Decay of Lithium-Rich Li 1.14Mn 0.54Ni 0.14Co 0.14O 2 Cathodes by Controlling the Electrochemical Process

DOE PAGES

Wei, Z.; Zhu, Y.; Zhang, W.; ...

2015-03-27

Lithium-rich material owns a particularly high capacity owing to the activation of electrochemical inactive Li 2MnO 3 phase. But at the same time, MnO 2 phase formed after Li 2MnO 3 activation confronts a severe problem of converting to spinel phase, and resulting in voltage decay. To our knowledge, this phenomenon is inherent property of layered manganese oxide materials and can hardly be overcome. Based on this, unlike previous reports, herein we design a method for the first time to accelerate the phase transformation by tuning the charge upper-limit voltage at a high value, so the phase transformation process canmore » be finished in a few cycles. Then material structure remains stable while cycling at a low upper-limit voltage. By this novel method voltage decay is eliminated significantly.« less

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells

PubMed Central

Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

2016-01-01

Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF–supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected. PMID:28335275

Methanol-Tolerant Platinum-Palladium Catalyst Supported on Nitrogen-Doped Carbon Nanofiber for High Concentration Direct Methanol Fuel Cells.

PubMed

Kim, Jiyoung; Jang, Jin-Sung; Peck, Dong-Hyun; Lee, Byungrok; Yoon, Seong-Ho; Jung, Doo-Hwan

2016-08-15

Pt-Pd catalyst supported on nitrogen-doped carbon nanofiber (N-CNF) was prepared and evaluated as a cathode electrode of the direct methanol fuel cell (DMFC). The N-CNF, which was directly synthesized by the catalytic chemical vapor deposition from acetonitrile at 640 °C, was verified as having a change of electrochemical surface properties such as oxygen reduction reaction (ORR) activities and the electrochemical double layer compared with common carbon black (CB). To attain the competitive oxygen reduction reaction activity with methanol tolerance, the Pt and Pd metals were supported on the CB or the N-CNF. The physical and electrochemical characteristics of the N-CNF-supported Pt-Pd catalyst were examined and compared with catalyst supported on the CB. In addition, DMFC single cells using these catalysts as the cathode electrode were applied to obtain I-V polarization curves and constant current operating performances with high-concentration methanol as the fuel. Pt-Pd catalysts had obvious ORR activity even in the presence of methanol. The higher power density was obtained at all the methanol concentrations when it applied to the membrane electrode assembly (MEA) of the DMFC. When the N-CNF is used as the catalyst support material, a better performance with high-concentration methanol is expected.

Proton exchange membrane micro fuel cells on 3D porous silicon gas diffusion layers

NASA Astrophysics Data System (ADS)

Kouassi, S.; Gautier, G.; Thery, J.; Desplobain, S.; Borella, M.; Ventura, L.; Laurent, J.-Y.

2012-10-01

Since the 90's, porous silicon has been studied and implemented in many devices, especially in MEMS technology. In this article, we present a new approach to build miniaturized proton exchange membrane micro-fuel cells using porous silicon as a hydrogen diffusion layer. In particular, we propose an innovative process to build micro fuel cells from a “corrugated iron like” 3D structured porous silicon substrates. This structure is able to increase up to 40% the cell area keeping a constant footprint on the silicon wafer. We propose here a process route to perform electrochemically 3D porous gas diffusion layers and to deposit fuel cell active layers on such substrates. The prototype peak power performance was measured to be 90 mW cm-2 in a “breathing configuration” at room temperature. These performances are less than expected if we compare with a reference 2D micro fuel cell. Actually, the active layer deposition processes are not fully optimized but this prototype demonstrates the feasibility of these 3D devices.

Fabrication and characterization of electrochemically prepared bioanode (polyaniline/ferritin/glucose oxidase) for biofuel cell application

NASA Astrophysics Data System (ADS)

ul Haque, Sufia; Inamuddin; Nasar, Abu; Asiri, Abdullah M.

2018-01-01

Porous matrix of polyaniline (PANI) has been electrodeposited along with the entrapment of biocompatible redox mediator ferritin (Frt) and glucose oxidase (GOx) on the surface of glassy carbon (GC) electrode. The characterizations have been carried out by X-ray Diffraction (XRD) and Transmission electron microscopy (TEM). The enhanced electrochemical signal transfer rate from enzyme to the electrode surface was due to the intimate contact of the enzyme with the electrochemically polymerized conducting PANI matrix. The PANI/Frt/GOx modified GC bioanode was used to investigate the electrocatalytic activity as a function of the concentration of glucose in the range of 10-60 mM. It was confirmed by the electrochemical impedance spectroscopy (EIS), the thick deposition of PANI layer becomes more compact due to which the charge transfer resistance of PANI matrix becomes higher. All the electrochemical measurements of the electrode were carried out by using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). CV curves were recorded at different scan rates (20-100 mV/s) at 50 mM of glucose in 0.3 M potassium ferrocyanide. A normalized saturation current density of 22.3 ± 2 mA/cm2 was observed for the oxidation of 50 mM glucose at a scan rate of 100 mV/s.

Interpreting the structural and electrochemical complexity of 0.5Li{sub 2}MnO{sub 3}{lg_bullet}.0.5LiMO{sub 2} electrodes for lithium batteries (M=Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x}, 0{le}x{le}0.5).

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

Kang, S. H.; Kempgens, P.; Greenbaum, S.

2007-01-01

The structural and electrochemical features of layered 0.5Li{sub 2}MnO{sub 3} {center_dot} 0.5LiMO{sub 2} electrodes, in which M = Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x} (0{le} x {le} 0.5), have been studied by powder X-ray diffraction, electrochemical differential-capacity measurements, {sup 7}Li magic-angle-spinning nuclear magnetic resonance, and X-ray absorption near-edge spectroscopy. Li{sub 2}MnO{sub 3}-like regions in the as-prepared samples were observed for all values of x, with transition-metal cation disorder between the LiMO{sub 2} and Li{sub 2}MnO{sub 3} components increasing with cobalt content (i.e., the value of x). The structural disorder and complexity of the electrochemical redox reactions increase when the Li{sub 2}MnO{sub 3}-likemore » regions within the electrode are activated to 4.6 V in lithium cells; interpretations of structural and electrochemical phenomena are provided.« 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.

Flexible strategy for immobilizing redox-active compounds using in situ generation of diazonium salts. Investigations of the blocking and catalytic properties of the layers.

PubMed

Noël, Jean-Marc; Sjöberg, Béatrice; Marsac, Rémi; Zigah, Dodzi; Bergamini, Jean-François; Wang, Aifang; Rigaut, Stéphane; Hapiot, Philippe; Lagrost, Corinne

2009-11-03

A versatile two-step method is developed to covalently immobilize redox-active molecules onto carbon surfaces. First, a robust anchoring platform is grafted onto surfaces by electrochemical reduction of aryl diazonium salts in situ generated. Depending on the nature of the layer termini, -COOH or -NH(2), a further chemical coupling involving ferrocenemethylamine or ferrocene carboxylic acid derivatives leads to the covalent binding of ferrocene centers. The chemical strategy using acyl chloride activation is efficient and flexible, since it can be applied either to surface-reactive end groups or to reactive species in solution. Cyclic voltammetry analyses point to the covalent binding of ferrocene units restricted to the upper layers of the underlying aryl films, while AFM measurements show a lost of compactness of the layers after the chemical attachment of ferrocene centers. The preparation conditions of the anchoring layers were found to determine the interfacial properties of the resulted ferrocenyl-modified electrodes. The ferrocene units promoted effective redox mediation providing that the free redox probes are adequately chosen (i.e., vs size/formal potential) and the underlying layers exhibit strong blocking properties. For anchoring films with weaker blocking effect, the coexistence of two distinct phenomena, redox mediation and ET at pinholes could be evidenced.

Robust Platinum-Based Electrocatalysts for Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Coleman, Eric James

Polymer electrolyte fuel cells (PEMFCs) are energy conversion devices that exploit the energetics of the reaction between hydrogen fuel and O 2 to generate electricity with water as the only byproduct. PEMFCs have attracted substantial attention due to their high conversion efficiency, high energy density, and low carbon footprint. However, PEMFC performance is hindered by the high activation barrier and slow reaction rates at the cathode where O2 undergoes an overall 4-electron reduction to water. The most efficient oxygen reduction reaction (ORR) catalyst materials to date are Pt group metals due to their high catalytic activity and stability in a wide range of operating conditions. Before fuel cells can become economically viable, efforts must be taken to decrease Pt content while maintaining a high level of ORR activity. This work describes the design and synthesis of a Pt-Cu electrocatalyst with ORR activity exceeding that of polycrystalline Pt. Production of this novel catalyst is quite simple and begins with synthesis of a porous Cu substrate, formed by etching Al from a Cu-Al alloy. The porous Cu substrate is then coated with a Pt layer via a spontaneous electrochemical process known as galvanic replacement. The Pt layer enhances the ORR activity (as measured by a rotating ring-disk electrode (RRDE)) and acts as a barrier towards corrosion of the Cu understructure. Growth of the Pt layer can be manipulated by time, temperature, concentration of Pt precursor, and convection rate during galvanic replacement. Data from analytical and electrochemical techniques confirm multiple Pt loadings have been achieved via the galvanic replacement process. The boost in ORR activity for the PtCu catalyst was determined to be a result of its lower affinity towards (site-blocking) OH adsorption. A unique catalyst degradation study explains the mechanism of initial catalyst ORR deactivation for both monometallic and bimetallic Pt-based catalysts. Finally, a rigorous and pioneering examination of how Pt surface passivation affects ORR dynamics is presented.

Characterization and electrochemical application of carbon materials based on poly(phenylene oxide)

NASA Astrophysics Data System (ADS)

Gray, Hunter

Carbon materials possess excellent electrical and surface properties for the next generation of energy storage devices. Polymers provide a carbon rich and tailorable precursor for the production of carbon materials. Therefore, activated carbons were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) via a three step process: thermal oxidation, carbonization, and activation with KOH. The activated carbons are predominately microporous with BET specific surface areas up to 2638 m2/g. Impedance spectroscopy revealed these carbons possess electrical conductivities comparable to commercial carbon blacks and consequently were employed in thin-film composite electrodes in electrochemical double-layer capacitors. Cyclic voltammetry confirmed maximum specific capacitances of 13.23 F/g and 2.848 F/g for aqueous and organic electrolyte systems, respectively. Additionally, carbon nanotubes were synthesized from PPO and other polymers with a nickel catalyst via chemical vapor deposition as revealed by transmission electron microscopy. This is the first report of carbon nanotubes produced from PPO.

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.

Atomic Layer Deposition Alumina-Passivated Silicon Nanowires: Probing the Transition from Electrochemical Double-Layer Capacitor to Electrolytic Capacitor.

PubMed

Gaboriau, Dorian; Boniface, Maxime; Valero, Anthony; Aldakov, Dmitry; Brousse, Thierry; Gentile, Pascal; Sadki, Said

2017-04-19

Silicon nanowires were coated by a 1-5 nm thin alumina layer by atomic layer deposition (ALD) in order to replace poorly reproducible and unstable native silicon oxide by a highly conformal passivating alumina layer. The surface coating enabled probing the behavior of symmetric devices using such electrodes in the EMI-TFSI electrolyte, allowing us to attain a large cell voltage up to 6 V in ionic liquid, together with very high cyclability with less than 4% capacitance fade after 10 6 charge/discharge cycles. These results yielded fruitful insights into the transition between an electrochemical double-layer capacitor behavior and an electrolytic capacitor behavior. Ultimately, thin ALD dielectric coatings can be used to obtain hybrid devices exhibiting large cell voltage and excellent cycle life of dielectric capacitors, while retaining energy and power densities close to the ones displayed by supercapacitors.

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

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

Effect of nano-scale characteristics of graphene on electrochemical performance of activated carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Jasni, M. R. M.; Deraman, M.; Suleman, M.; Hamdan, E.; Sazali, N. E. S.; Nor, N. S. M.; Shamsudin, S. A.

2016-02-01

Graphene with its typical nano-scale characteristic properties has been widely used as an additive in activated carbon electrodes in order to enhance the performance of the electrodes for their use in high performance supercapacitors. Activated carbon monoliths (ACMs) electrodes have been prepared by carbonization and activation of green monoliths (GMs) of pre-carbonized fibers of oil palm empty fruit bunches or self-adhesive carbon grains (SACGs) and SACGs added with 6 wt% of KOH-treated multi-layer graphene. ACMs electrodes have been assembled in symmetrical supercapacitor cells that employed aqueous KOH electrolyte (6 M). The cells have been tested with cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge discharge methods to investigate the effect of graphene addition on the specific capacitance (Csp), specific energy (E), specific power (P), equivalent series resistance (ESR) and response time (τo) of the supercapacitor cells. The results show that the addition of graphene in the GMs change the values of Csp, Emax, Pmax, ESR and τo from (61-96) F/g, 2 Wh/kg, 104 W/kg, 2.6 Ω and 38 s, to the respective values of (110-124) F/g, 3 Wh/kg, 156 W/kg, 3.4 Ω and 63 s. This study demonstrates that the graphene addition in the GMs has a significant effect on the electrochemical behavior of the electrodes.

High frequency reference electrode

DOEpatents

Kronberg, J.W.

1994-05-31

A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or halo' at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes. 4 figs.

High frequency reference electrode

DOEpatents

Kronberg, James W.

1994-01-01

A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or "halo" at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes.

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.

Synthesis and electrochemical performances of amorphous carbon-coated Sn Sb particles as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Zhong; Tian, Wenhuai; Liu, Xiaohe; Yang, Rong; Li, Xingguo

2007-12-01

The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn-Sb alloy and carbon alone. This amorphous carbon-coated Sn-Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.

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.

NiCo2O4 nanosheets in-situ grown on three dimensional porous Ni film current collectors as integrated electrodes for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Tao; Guo, Ying; Zhao, Bo; Yu, Shuhui; Yang, Hai-Peng; Lu, Daniel; Fu, Xian-Zhu; Sun, Rong; Wong, Ching-Ping

2015-07-01

Three dimensional interconnected hierarchical porous Ni films are easily fabricated as effective current collectors through hydrogen bubble template electrochemical deposition. The binder-free integrated electrodes of spinel NiCo2O4 nanosheets directly coated the three dimensional porous Ni films are facilely obtained through successively electrochemical co-deposition of Ni/Co alloy layer then followed by subsequent annealing at 350 °C in air. Compared with NiCo2O4 nanosheets on smooth Ni foil or porous NiO/Ni film electrodes, the porous NiCo2O4/Ni integrated film electrodes for supercapacitors demonstrate remarkably higher area specific capacitance. The porous NiCo2O4/Ni film electrodes also exhibit excellent rate capability and cycling stability. The super electrochemical capacitive performances are attributed to the unique integrated architecture of NiCo2O4 nanosheets in-situ grown on three dimensional continuous hierarchical porous Ni collector collectors, which could provide large electrode-electrolyte interface area, high active sites, low contact resistance between current collector and active materials, fast electron conduction and ion/electrolyte diffusion.

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.

The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Xu, XiaoLong; Qi, CongYu; Hao, ZhenDong; Wang, Hao; Jiu, JinTing; Liu, JingBing; Yan, Hui; Suganuma, Katsuaki

2018-03-01

The requirement of energy-storage equipment needs to develop the lithium ion battery (LIB) with high electrochemical performance. The surface modification of commercial LiFePO4 (LFP) by utilizing zeolitic imidazolate frameworks-8 (ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances. In this work, the carbonized ZIF-8 (CZIF-8) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/CZIF-8 sample. The N2 adsorption and desorption isotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/CZIF-8 cathode-active material delivers a discharge specific capacity of 159.3 mAh g-1 at 0.1C and a discharge specific energy of 141.7 mWh g-1 after 200 cycles at 5.0C (the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity, the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/CZIF-8 cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.[Figure not available: see fulltext.

Engineering of high performance supercapacitor electrode based on Fe-Ni/Fe{sub 2}O{sub 3}-NiO core/shell hybrid nanostructures

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

Singh, Ashutosh K., E-mail: ashuvishen@gmail.com, E-mail: aksingh@bose.res.in; Mandal, Kalyan

The present work reports on fabrication and supercapacitor applications of a core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures (HNs) electrode. The core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures have been fabricated through a two step method (nanowire fabrication and their controlled oxidation). The 1D hybrid nanostructure consists of highly porous shell layer (redox active materials NiO and Fe{sub 2}O{sub 3}) and the conductive core (FeNi nanowire). Thus, the highly porous shell layer allows facile electrolyte diffusion as well as faster redox reaction kinetics; whereas the conductive FeNi nanowire core provides the proficient express way for electrons to travel to the current collector,more » which helps in the superior electrochemical performance. The core/shell Fe-Ni/Fe{sub 2}O{sub 3}-NiO hybrid nanostructures electrode based supercapacitor shows very good electrochemical performances in terms of high specific capacitance nearly 1415 F g{sup −1} at a current density of 2.5 A g{sup −1}, excellent cycling stability and rate capability. The high quality electrochemical performance of core/shell hybrid nanostructures electrode shows its potential as an alternative electrode for forthcoming supercapacitor devices.« less

Electrodeposition of flower-like platinum on electrophoretically grown nitrogen-doped graphene as a highly sensitive electrochemical non-enzymatic biosensor for hydrogen peroxide detection

NASA Astrophysics Data System (ADS)

Tajabadi, M. T.; Sookhakian, M.; Zalnezhad, E.; Yoon, G. H.; Hamouda, A. M. S.; Azarang, Majid; Basirun, W. J.; Alias, Y.

2016-11-01

An efficient non-enzymatic biosensor electrode consisting of nitrogen-doped graphene (N-graphene) and platinum nanoflower (Pt NF) with different N-graphene loadings were fabricated on indium tin oxide (ITO) glass using a simple layer-by-layer electrophoretic and electrochemical sequential deposition approach. N-graphene was synthesized by annealing graphene oxide with urea at 900 °C. The structure and morphology of the as-fabricated non-enzymatic biosensor electrodes were determined using X-ray diffraction, field emission electron microscopy, transmission electron microscopy, Raman and X-ray photoelectron spectra. The as-fabricated Pt NF-N-graphene-modified ITO electrodes with different N-graphene loadings were utilized as a non-enzymatic biosensor electrode for the detection of hydrogen peroxide (H2O2). The behaviors of the hybrid electrodes towards H2O2 reduction were assessed using chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy analysis. The Pt NF-N-graphene-modified ITO electrode with a 0.05 mg ml-1 N-graphene loading exhibited the lowest detection limit, fastest amperometric sensing, a wide linear response range, excellent stability and reproducibility for the non-enzymatic H2O2 detection, due to the synergistic effect between the electrocatalytic activity of the Pt NF and the high conductivity and large surface area of N-graphene.

Electrochemical detection of DNA damage induced by acrylamide and its metabolite at the graphene-ionic liquid-Nafion modified pyrolytic graphite electrode.

PubMed

Qiu, Yanyan; Qu, Xiangjin; Dong, Jing; Ai, Shiyun; Han, Ruixia

2011-06-15

A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA)(n) film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA)(n) was incubated in AA solution or AA+H(2)O(2) solution at 37°C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H(2)O(2), HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV-vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

MIPs-graphene nanoplatelets-MWCNTs modified glassy carbon electrode for the determination of cardiac troponin I.

PubMed

Ma, Ya; Shen, Xiao-Lei; Wang, Hai-Shui; Tao, Jia; Huang, Jian-Zhi; Zeng, Qiang; Wang, Li-Shi

2017-03-01

An electrochemical sensor with high selectivity in addition to sensitivity was developed for the determination of cardiac troponin I (cTnI), based on the modification of cTnI imprinted polymer film on a glassy carbon electrode (GCE). The sensor was fabricated by layer-by-layer assembled graphene nanoplatelets (GS), multiwalled carbon nanotubes (MWCNTs), chitosan (CS), glutaraldehyde (GA) composites, which can increase the electronic transfer rate and the active surface area to capture a larger number of antigenic proteins. MWCNTs/GS based imprinted polymers (MIPs/MWCNTs/GS) were synthesized by means of methacrylic acid (MAA) as the monomer, ethylene glycol dimethacrylate (EGDMA) as the cross linker α,α'-azobisisobutyronitrile (AIBN) as the initiator and cTnI as the template. In comparison with conventional methods, the proposed electrochemical sensor is highly sensitive for cTnI, providing a better linear response range from 0.005 to 60 ng cm -3 and a lower limit of detection (LOD) of 0.0008 ng cm -3 under optimal experimental conditions. In addition, the electrochemical sensor exhibited good specificity, acceptable reproducibility and stability. Moreover, satisfactory results were obtained in real human serum samples, indicating that the developed method has the potential to find application in clinical detection of cTnI as an alternative approach. Copyright © 2016 Elsevier Inc. All rights reserved.

Graphene electrode modified with electrochemically reduced graphene oxide for label-free DNA detection.

PubMed

Li, Bing; Pan, Genhua; Avent, Neil D; Lowry, Roy B; Madgett, Tracey E; Waines, Paul L

2015-10-15

A novel printed graphene electrode modified with electrochemically reduced graphene oxide was developed for the detection of a specific oligonucleotide sequence. The graphene oxide was immobilized onto the surface of a graphene electrode via π-π bonds and electrochemical reduction of graphene oxide was achieved by cyclic voltammetry. A much higher redox current was observed from the reduced graphene oxide-graphene double-layer electrode, a 42% and 36.7% increase, respectively, in comparison with that of a bare printed graphene or reduced graphene oxide electrode. The good electron transfer activity is attributed to a combination of the large number of electroactive sites in reduced graphene oxide and the high conductivity nature of graphene. The probe ssDNA was further immobilized onto the surface of the reduced graphene oxide-graphene double-layer electrode via π-π bonds and then hybridized with its target cDNA. The change of peak current due to the hybridized dsDNA could be used for quantitative sensing of DNA concentration. It has been demonstrated that a linear range from 10(-7)M to 10(-12)M is achievable for the detection of human immunodeficiency virus 1 gene with a detection limit of 1.58 × 10(-13)M as determined by three times standard deviation of zero DNA concentration. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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.

Understanding Inhomogeneous Reactions in Li‐Ion Batteries: Operando Synchrotron X‐Ray Diffraction on Two‐Layer Electrodes

PubMed Central

Villevieille, Claire; Takeuchi, Yoji

2015-01-01

To understand inhomogeneous reactions perpendicular to the current collector in an electrode for batteries, a method combining operando synchrotron X‐ray diffraction and two‐layer electrodes with different porosities is developed. The two layers are built using two different active materials (LiNi0.80Co0.15Al0.05O2 and LiMn2O4), therefore, tracing each diffraction pattern reveals which active material is reacting during the electrochemical measurement in transmission mode. The results demonstrate that the active material close to the separator is obviously more active than that one close to the current collector in the case of low porosity electrodes. This inhomogeneity should be due to the rate‐limitation and especially to low average ionic conductivity of the electrolyte in the porous electrode because the current flows first mainly into the electrode regions close to the separator. The inhomogeneity is found to be mitigated by the adjustment of the electrode density and thus porosity. Hence, the novel operando method reveals a clear inhomogeneous reaction perpendicular to the current collector. PMID:27708998

Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water.

PubMed

Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra; Nørskov, Jens K; Bell, Alexis T

2013-09-11

The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), (0112), and (1014). We find that at low applied potentials, the (1014) surface is the most stable, while the (0112) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the (1014) surface is the most active one as characterized by an overpotential of η = 0.48 V. The high activity of the (1014) surface can be attributed to the observation that the resting state of Co in the active site is Co(3+) during the OER, whereas Co is in the Co(4+) state in the less active surfaces. Lastly, we demonstrate that the overpotential of the (1014) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of Ni(y)Co(1-y)O(x) thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.

Fabrication of Lab-on-Paper Using Porous Au-Paper Electrode: Application to Tumor Marker Electrochemical Immunoassays.

PubMed

Ge, Shenguang; Zhang, Yan; Yan, Mei; Huang, Jiadong; Yu, Jinghua

2017-01-01

A simple, low-cost, and sensitive electrochemical lab-on-paper assay is developed based on a novel gold nanoparticle modified porous paper working electrode for use in point-of-care testing (POCT). Electrochemical methods are introduced for lab-on-paper based on screen-printed paper electrodes. To further improve specificity, performance, and sensitivity for point-of-care testing, a novel porous Au-paper working electrode (Au-PWE) is designed for lab-on-paper using growth of an interconnected Au nanoparticle (NP) layer on the surface of cellulose fibers in order to enhance the conductivity of the paper sample zone and immobilize the primary antibodies (Ab1). With a sandwich-type immunoassay format, Pd-Au bimetallic nanoparticles possessing peroxidase-like activity are used as a matrix to immobilize secondary antibodies (Ab2) for rapid detection of targets. This lab-on-paper based immunodevice is applied to the diagnosis of a cancer biomarker in clinical serum samples.

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

Synthesizing 2D MoS2 Nanofins on carbon nanospheres as catalyst support for Proton Exchange Membrane Fuel Cells.

PubMed

Hu, Yan; Chua, Daniel H C

2016-06-15

Highly dense 2D MoS2 fin-like nanostructures on carbon nanospheres were fabricated and formed the main catalyst support structure in the oxygen reduction reaction (ORR) for polymer electrolyte membrane (PEM) fuel cells. These nanofins were observed growing perpendicular to the carbon nanosphere surface in random orientations and high resolution transmission electron microscope confirmed 2D layers. The PEM fuel cell test showed enhanced electrochemical activity with good stability, generating over 8.5 W.mgPt(-1) as compared to standard carbon black of 7.4 W.mgPt(-1) under normal operating conditions. Electrochemical Impedance Spectroscopy confirmed that the performance improvement is highly due to the excellent water management of the MoS2 lamellar network, which facilitates water retention at low current density and flood prevention at high current density. Reliability test further demonstrated that these nanofins are highly stable in the electrochemical reaction and is an excellent ORR catalyst support.

Synthesizing 2D MoS2 Nanofins on carbon nanospheres as catalyst support for Proton Exchange Membrane Fuel Cells

PubMed Central

Hu, Yan; Chua, Daniel H. C.

2016-01-01

Highly dense 2D MoS2 fin-like nanostructures on carbon nanospheres were fabricated and formed the main catalyst support structure in the oxygen reduction reaction (ORR) for polymer electrolyte membrane (PEM) fuel cells. These nanofins were observed growing perpendicular to the carbon nanosphere surface in random orientations and high resolution transmission electron microscope confirmed 2D layers. The PEM fuel cell test showed enhanced electrochemical activity with good stability, generating over 8.5 W.mgPt−1 as compared to standard carbon black of 7.4 W.mgPt−1 under normal operating conditions. Electrochemical Impedance Spectroscopy confirmed that the performance improvement is highly due to the excellent water management of the MoS2 lamellar network, which facilitates water retention at low current density and flood prevention at high current density. Reliability test further demonstrated that these nanofins are highly stable in the electrochemical reaction and is an excellent ORR catalyst support. PMID:27302135

Overall Water Splitting with Room-Temperature Synthesized NiFe Oxyfluoride Nanoporous Films

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

Liang, Kun; Guo, Limin; Marcus, Kyle

Freestanding and lightweight thin-films were rationally designed to serve as robust electrodes for renewable energy applications. A facile and scalable nanomanufacturing process was developed to fabricate these transformative thin-film electrodes (iron group mixed oxides) that exhibit a nanoporous structure and controllable composition. More specifically, electrodeposition and anodic treatments were employed to produce freestanding and lightweight metal oxides nanoporous layers (NPL). These NPL can be directly used as flexible and additive-free electrodes for renewable energy generation (water splitting) and storage (supercapacitor) applications without requiring binders and current collector and other additives. Significantly enhanced electrochemical performance was achieved due to the uniquemore » merits of the NPL: i) highly porous structure considerably increases the electrode/electrolyte interface, which facilitate electrochemical reactions; ii) NPL substantially increase the number of active sites that are favorable in electrochemical reactions; iii) residual metal network within the NPL forms a conductive framework, drastically improving electrode strength, flexibility and conductivity.« less

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.

Exposing the {010} Planes by Oriented Self-Assembly with Nanosheets To Improve the Electrochemical Performances of Ni-Rich Li[Ni0.8Co0.1Mn0.1]O2 Microspheres.

PubMed

Su, Yuefeng; Chen, Gang; Chen, Lai; Li, Weikang; Zhang, Qiyu; Yang, Zhiru; Lu, Yun; Bao, Liying; Tan, Jing; Chen, Renjie; Chen, Shi; Wu, Feng

2018-02-21

A modified Ni-rich Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 cathode material with exposed {010} planes is successfully synthesized for lithium-ion batteries. The scanning electron microscopy images have demonstrated that by tuning the ammonia concentration during the synthesis of precursors, the primary nanosheets could be successfully stacked along the [001] crystal axis predominantly, self-assembling like multilayers. According to the high-resolution transmission electron microscopy results, such a morphology benefits the growth of the {010} active planes of final layered cathodes during calcination treatment, resulting in the increased area of the exposed {010} active planes, a well-ordered layer structure, and a lower cation mixing disorder. The Li-ion diffusion coefficient has also been improved after the modification based on the results of potentiostatic intermittent titration technique. As a consequence, the modified Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 material exhibits superior initial discharges of 201.6 mA h g -1 at 0.2 C and 185.7 mA h g -1 at 1 C within 2.8-4.3 V (vs Li + /Li), and their capacity retentions after 100 cycles reach 90 and 90.6%, respectively. The capacity at 10 C also increases from 98.3 to 146.5 mA h g -1 after the modification. Our work proposes a novel approach for exposing high-energy {010} active planes of the layered cathode material and again confirms its validity in improving electrochemical properties.

Electrochemical systems configured to harvest heat energy

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

Lee, Seok Woo; Yang, Yuan; Ghasemi, Hadi

Electrochemical systems for harvesting heat energy, and associated electrochemical cells and methods, are generally described. The electrochemical cells can be configured, in certain cases, such that at least a portion of the regeneration of the first electrochemically active material is driven by a change in temperature of the electrochemical cell. The electrochemical cells can be configured to include a first electrochemically active material and a second electrochemically active material, and, in some cases, the absolute value of the difference between the first thermogalvanic coefficient of the first electrochemically active material and the second thermogalvanic coefficient of the second electrochemically activemore » material is at least about 0.5 millivolts/Kelvin.« less

Wearable Fabrics with Self-Branched Bimetallic Layered Double Hydroxide Coaxial Nanostructures for Hybrid Supercapacitors.

PubMed

Nagaraju, Goli; Chandra Sekhar, S; Krishna Bharat, L; Yu, Jae Su

2017-11-28

We report a flexible battery-type electrode based on binder-free nickel cobalt layered double hydroxide nanosheets adhered to nickel cobalt layered double hydroxide nanoflake arrays on nickel fabric (NC LDH NFAs@NSs/Ni fabric) using facile and eco-friendly synthesis methods. Herein, we utilized discarded polyester fabric as a cost-effective substrate for in situ electroless deposition of Ni, which exhibited good flexibility, light weight, and high conductivity. Subsequently, the vertically aligned NC LDH NFAs were grown on Ni fabric by means of a hot-air oven-based method, and fluffy-like NC LDH NS branches are further decorated on NC LDH NFAs by a simple electrochemical deposition method. The as-prepared core-shell-like nanoarchitectures improve the specific surface area and electrochemical activity, which provides the ideal pathways for electrolyte diffusion and charge transportation. When the electrochemical performance was tested in 1 M KOH aqueous solution, the core-shell-like NC LDH NFAs@NSs/Ni fabric electrode liberated a maximum areal capacity of 536.96 μAh/cm 2 at a current density of 2 mA/cm 2 and excellent rate capability of 78.3% at 30 mA/cm 2 (420.5 μAh/cm 2 ) with a good cycling stability. Moreover, a fabric-based hybrid supercapacitor (SC) was assembled, which achieves a stable operational potential window of 1.6 V, a large areal capacitance of 1147.23 mF/cm 2 at 3 mA/cm 2 , and a high energy density of 0.392 mWh/cm 2 at a power density of 2.353 mW/cm 2 . Utilizing such high energy storage abilities and flexible properties, the fabricated hybrid SC operated the wearable digital watch and electric motor fan for real-time applications.

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.

Cephradine as corrosion inhibitor for copper in 0.9% NaCl solution

NASA Astrophysics Data System (ADS)

Tasić, Žaklina Z.; Petrović Mihajlović, Marija B.; Radovanović, Milan B.; Simonović, Ana T.; Antonijević, Milan M.

2018-05-01

The effect of (6R,7R)-7-[[(2R)-2-amino-2-cyclohexa-1,4-dien-1-ylacetyl]amino]-3-methyl-8-oxo-5-thia-1-azobicyclo[4.2.0]oct-2-ene-2-carboxylic acid (cephradine) on corrosion behavior of copper in 0.9% NaCl solution was investigated. The electrochemical methods including the open circuit potential measurements, potentiodynamic polarization and electrochemical impedance spectroscopy measurements, scanning electron microscopy with energy dispersive X-ray spectroscopy and quantum chemical calculations were used for this investigation. According to the results obtained by potentiodynamic polarization, cephradine acts as mixed type inhibitor. Also, the results obtained by electrochemical impedance spectroscopy indicate that cephradine provides good copper protection in 0.9% NaCl solution. The inhibition efficiency of cephradine increases with increasing its concentration. The scanning electron microscopy with energy dispersive X-ray spectroscopy confirms that a protective layer is formed on the copper surface due to the adsorption of cephradine on the active sites on the copper surface. Adsorption of cephradine in 0.9% NaCl solution follows the Langmuir adsorption isotherm. Quantum chemical calculations are in agreement with results obtained by electrochemical measurements.

Electrochemical aptasensor based on the dual-amplification of G-quadruplex horseradish peroxidase-mimicking DNAzyme and blocking reagent-horseradish peroxidase.

PubMed

Yuan, Yali; Gou, Xuxu; Yuan, Ruo; Chai, Yaqin; Zhuo, Ying; Mao, Li; Gan, Xianxue

2011-06-15

A simple electrochemical aptasensor for sensitive detection of thrombin was fabricated with G-quadruplex horseradish peroxidase-mimicking DNAzyme (hemin/G-quadruplex system) and blocking reagent-horseradish peroxidase as dual signal-amplification scheme. Gold nanoparticles (nano-Au) were firstly electrodeposited onto single wall nanotube (SWNT)-graphene modified electrode surface for the immobilization of electrochemical probe of nickel hexacyanoferrates nanoparticles (NiHCFNPs). Subsequently, another nano-Au layer was electrodeposited for further immobilization of thrombin aptamer (TBA), which later formed hemin/G-quadruplex system with hemin. Horseradish peroxidases (HRP) then served as blocking reagent to block possible remaining active sites and avoided the non-specific adsorption. In the presence of thrombin, the TBA binded to thrombin and the hemin released from the hemin/G-quadruplex electrocatalytic structure, increasing steric hindrance of the aptasensor and decomposing hemin/G-quadruplex electrocatalytic structure, which finally decreased the electrocatalytic efficiency of aptasensor toward H(2)O(2) in the presence of NiHCFNPs with a decreased electrochemical signal. On the basis of the synergistic amplifying action, a detection limit as low as 2 pM for thrombin was obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

Activity of vancomycin release from bioinspired coatings of hydroxyapatite or TiO2 nanotubes.

PubMed

Ionita, Daniela; Bajenaru-Georgescu, Daniela; Totea, Georgeta; Mazare, Anca; Schmuki, Patrik; Demetrescu, Ioana

2017-01-30

Herein we investigate the efficiency of various biomimetic coatings for localized drug delivery, using vancomycin as key therapeutic drug, which is a widely used antibiotic for the treatment of strong infections caused by positive Gram bacteria. We evaluate classical hydroxyapatite and biomimetic hydroxyapatite-collagen coatings obtained by electrochemical deposition as well as TiO 2 nanotubes arrays obtained by electrochemical anodization. Surface morphology, compositional and structural data confirm the incorporation of vancomycin into the layers and drug release profiles for vancomycin evaluate their release ability. Namely, hydroxyapatite coatings lead to a ≈92% vancomycin release after 30h and hydroxyapatite-collagen to 85%, while the TiO 2 nanotubes layers lead to 78% release. The antibacterial effect of such drug loaded coatings is evaluated against S. aureus (Gram-positive bacteria). Our study shows that the vancomycin incorporated hydroxyapatite coatings lead to a faster release, while the nanotubular coatings may lead to longer time release and additionally both types of coatings ensure a good antibacterial inhibition. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

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.

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.

Core-shell iron oxide-layered double hydroxide: High electrochemical sensing performance of H2O2 biomarker in live cancer cells with plasma therapeutics.

PubMed

Asif, Muhammad; Liu, Hongwei; Aziz, Ayesha; Wang, Haitao; Wang, Zhengyun; Ajmal, Muhammad; Xiao, Fei; Liu, Hongfang

2017-11-15

In this work, we develop a new type of multifunctional core-shell nanomaterial by controllable integration of CuAl layered double hydroxides (LDHs) over the surface of iron oxides (Fe 3 O 4 ) nanospheres (NSs) to fabricate (Fe 3 O 4 @CuAl NSs) hybrid material with interior tunability of LDH phase and explore its practical application in ultrasensitive detection of emerging biomarker, i.e., H 2 O 2 as cancer diagnostic probe. In addition, atmospheric pressure plasmas (APPs) have also been used as potential therapeutic approach for cancer treatment. Due to the synergistic combination of p-type semiconductive channels of LDHs with multi-functional properties, unique morphology and abundant surface active sites, the Fe 3 O 4 @CuAl NSs modified electrode exhibited attractive electrocatalytic activity towards H 2 O 2 reduction. Under the optimized conditions, the proposed biosensor demonstrated striking electrochemical sensing performances to H 2 O 2 including linear range as broad as 8 orders of magnitude, low real detection limit of 1nM (S/N = 3), high sensitivity, good reproducibility and long-term stability. Arising from the superb efficiency, the electrochemical biosensor has been used for in vitro determination of H 2 O 2 concentrations in human urine and serum samples prior to and following the intake of coffee, and real-time monitoring of H 2 O 2 efflux from different cancer cell lines in normal state and after plasma treatment. We believe that this novel nano-platform of structurally integrated core-shell nanohybrid materials combined with APPs will enhance diagnostic as well as therapeutic window for cancer diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Self-Assembled Carbon-Polyoxometalate Composites for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Genovese, Matthew

The development of high performance yet cost effective energy storage devices is critical for enabling the growth of important emerging sectors from the internet of things to grid integration of renewable energy. Material costs are by far the largest contributor to the overall cost of energy storage devices and thus research into cost effective energy storage materials will play an important role in developing technology to meet real world storage demands. In this thesis, low cost high performance composite electrode materials for supercapacitors (SCs) have been developed through the surface modification of electrochemically double layer capacitive (EDLC) carbon substrates with pseudocapacitive Polyoxometalates (POMs). Significant fundamental contributions have been made to the understanding of all components of the composite electrode including the POM active layer, cation linker, and carbon substrate. The interaction of different POM chemistries in solution has been studied to elucidate the novel ways in which these molecules combine and the mechanism underlying this combination. A more thorough understanding regarding the cation linker's role in electrode fabrication has been developed through examining the linker properties which most strongly affect electrode performance. The development of porosity in biomass derived carbon materials has also been examined leading to important insights regarding the effect of substrate porosity on POM modification and electrochemical properties. These fundamental contributions enabled the design and performance optimization of POM-carbon composite SC electrodes. Understanding how POMs combine in solution, allowed for the development of mixed POM molecular coatings with tunable electrochemical properties. These molecular coatings were used to modify low cost biomass derived carbon substrates that had been structurally optimized to accommodate POM molecules. The resulting electrode composites utilizing low cost materials fabricated through simple scalable techniques demonstrated (i) high capacitance (361 F g-1), (ii) close to ideal pseudocapacitive behavior, (iii) stable cycling, and (iv) good rate performance.

Electric Pulse Discharge Activated Carbon Supercapacitors for Transportation Application

NASA Astrophysics Data System (ADS)

Nayak, Subhadarshi; Agrawal, Jyoti

2012-03-01

ScienceTomorrow is developing a high-speed, low-cost process for synthesizing high-porosity electrodes for electrochemical double-layer capacitors. Four types of coal (lignite, subbituminous, bituminous, and anthracite) were used as precursor materials for spark discharge activation with multiscale porous structure. The final porosity and pore distribution depended, among other factors, on precursor type. The high gas content in low-grade carbon resulted in mechanical disintegration, whereas high capacitance was attained in higher-grade coal. The properties, including capacitance, mechanical robustness, and internal conductivity, were excellent when the cost is taken into consideration.

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.

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.

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.

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.

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

Few layered vanadyl phosphate nano sheets-MWCNT hybrid as an electrode material for supercapacitor application

NASA Astrophysics Data System (ADS)

Dutta, Shibsankar; De, Sukanta

2016-05-01

It have been already seen that 2-dimensional nano materials are the suitable choice for the supercapacitor application due to their large specific surface area, electrochemical active sites, micromechanical flexibility, expedite ion migration channel properties. Free standing hybrid films of functionalized MWCNT (- COOH group) and α-Vanadyl phosphates (VOPO42H2O) are prepared by vacuum filtering. The surface morphology and microstructure of the samples are studied by transmission electron microscope, field emission scanning electron microscope, XRD, Electrochemical properties of hybrid films have been investigated systematically in 1M Na2SO4 aqueous electrolyte. The hybrid material exhibits a high specific capacitance 236 F/g with high energy density of 65.6 Wh/Kg and a power density of 1476 W/Kg.

Electrochromic Behaviors of Water-Soluble Polyaniline with Covalently Bonded Acetyl Ferrocene

NASA Astrophysics Data System (ADS)

Xiong, Shanxin; Wang, Ru; Li, Shuaishuai; Wu, Bohua; Chu, Jia; Wang, Xiaoqin; Zhang, Runlan; Gong, Ming

2018-04-01

A novel ferrocene-containing hybrid electrochromic material was synthesized via copolymerization of aniline with p-phenylenediamine functionalized acetyl ferrocene in the presence of poly (styrene sulfonate) dopant in an aqueous medium, and neat polyaniline (PANI) was prepared for comparison. The polymerization characteristics and the structure of the copolymer were systematically studied by Fourier-transform infrared, meanwhile, their electrochromic properties and electrochemical behaviors were tested by UV-vis spectra, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). It was found that the strong covalent bond and large conjugated system between PANI and ferrocene enhance the electron transfer rate and electron delocalization in the ferrocene-polyaniline (Fc-PANI) hybrid. In particular, the electrochromic device with Fc-PANI as the active layer shows significant enhancement in optical contrast over the PANI-based device.

Interphase evolution at two promising electrode materials for Li-ion batteries: LiFePO4 and LiNi1/2 Mn1/2O2.

PubMed

Dupré, Nicolas; Cuisinier, Marine; Martin, Jean-Frederic; Guyomard, Dominique

2014-07-21

The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and characterization of anode catalyst layers with structural variations for DMFC

NASA Astrophysics Data System (ADS)

Wang, Dazhi; Shi, Peng; Zhou, Peng; Mao, Qing; Liang, Junsheng; Wang, Suli; Li, Yang; Ren, Tongqun; Sun, Gongquan

2018-04-01

In this work, the electrohydrodynamic jet (E-Jet) Layer-by-Layer (LbL) deposition technique was employed to produce anode catalyst layer (CL) structure for direct methanol fuel cells (DMFC). The CLs with different thickness and porosity were fabricated with the control of the E-Jet deposition parameters. Then, the deposited anode CLs with structural variations were assembled to membrane electrode assemblies (MEAs). The results showed that the anode CL with higher porosity contributed higher dispersed catalyst, which further induced greater electrochemical active surface area (ESA) and higher performance. At optimized working condition the anode CL with high-dispersed catalyst of was produced using the E-Jet LbL deposition technique. It was observed that the peak power density is 72.8 mW cm‑2 for the cell having a porosity of 0.63, which has an increase of about 33% after modification of the CL structure.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

PubMed

Song, Taeseup; Cheng, Huanyu; Choi, Heechae; Lee, Jin-Hyon; Han, Hyungkyu; Lee, Dong Hyun; Yoo, Dong Su; Kwon, Moon-Seok; Choi, Jae-Man; Doo, Seok Gwang; Chang, Hyuk; Xiao, Jianliang; Huang, Yonggang; Park, Won Il; Chung, Yong-Chae; Kim, Hansu; Rogers, John A; Paik, Ungyu

2012-01-24

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries. © 2011 American Chemical Society

Method for ultra-fast boriding

DOEpatents

Erdemir, Ali; Sista, Vivekanand; Kahvecioglu, Ozgenur; Eryilmaz, Osman Levent

2017-01-31

An article of manufacture and method of forming a borided material. An electrochemical cell is used to process a substrate to deposit a plurality of borided layers on the substrate. The plurality of layers are co-deposited such that a refractory metal boride layer is disposed on a substrate and a rare earth metal boride conforming layer is disposed on the refractory metal boride layer.

Layer-by-layer multienzyme assembly for highly sensitive electrochemical immunoassay based on tyramine signal amplification strategy.

PubMed

Zhou, Jun; Tang, Juan; Chen, Guonan; Tang, Dianping

2014-04-15

A new sandwich-type electrochemical immunosensor based on nanosilver-doped bovine serum albumin microspheres (Ag@BSA) with a high ratio of horseradish peroxidase (HRP) and detection antibody was developed for quantitative monitoring of biomarkers (carcinoembryonic antigen, CEA, used in this case) by coupling enzymatic biocatalytic precipitation with tyramine signal amplification strategy on capture antibody-modified glassy carbon electrode. Two immunosensing protocols (with and without tyramine signal amplification) were also investigated for the detection of CEA and improved analytical features were acquired with tyramine signal amplification strategy. With the labeling method, the performance and factors influencing the electrochemical immunoassay were studied and evaluated in detail. Under the optimal conditions, the electrochemical immunosensor exhibited a wide dynamic range of 0.005-80 ng mL(-1) toward CEA standards with a low detection limit of 5.0 pg mL(-1). Intra- and inter-assay coefficients of variation were below 11%. No significant differences at the 0.05 significance level were encountered in the analysis of 6 clinical serum specimens and 6 spiked new-born cattle serum samples between the electrochemical immunoassay and the commercialized electrochemiluminescent immunoassay method for the detection of CEA. © 2013 Published by Elsevier B.V.

The role of lipopolysaccharide on the electrochemical behavior of titanium.

PubMed

Barão, V A; Mathew, M T; Assunção, W G; Yuan, J C; Wimmer, M A; Sukotjo, C

2011-05-01

Lipopolysaccharide (LPS) may induce peri-implantitis and implant failure. However, the role of LPS in titanium (Ti) electrochemical behavior remains unknown. We hypothesized that LPS in saliva with different pHs affects Ti corrosion properties. Thirty-six Ti discs (15 mm × 3 mm) were divided into 12 groups according to saliva pH (3, 6.5, and 9) and Escherichia coli LPS concentration (0, 0.15, 15, and 150 µg/mL). Electrochemical tests, such as open circuit potential, potentiodynamic, and electrochemical impedance spectroscopy, were conducted in a controlled environment. Data were evaluated by Pearson correlation and regression analysis (α = 0.05). LPS and pH affected Ti corrosive behavior. In general, lower pH and higher LPS concentration accelerated Ti corrosion. In the control group, the increase of pH significantly reduced the corrosion rate and increased the capacitance of the double layer. In LPS groups, the decrease of pH significantly increased the corrosion rate of Ti. LPS negatively influenced Ti corrosion behavior. C(dl), capacitance of double layer; E(corr), corrosion potential; EIS, electrochemical impedance spectroscopy; I(corr), corrosion current density; I(pass), passivation current density; LPS, lipopolysaccharide; OCP, open circuit potential; R(p), polarization resistance; Ti, titanium.

Probing the characteristics of casein as green binder for non-aqueous electrochemical double layer capacitors' electrodes

NASA Astrophysics Data System (ADS)

Varzi, Alberto; Raccichini, Rinaldo; Marinaro, Mario; Wohlfahrt-Mehrens, Margret; Passerini, Stefano

2016-09-01

Casein from bovine milk is evaluated in this work as binding agent for electrochemical double layer capacitors (EDLCs) electrodes. It is demonstrated that casein provides excellent adhesion strength to the current collector (1187 kPa compared to 51 kPa achieved with PVdF), thus leading to mechanically stable electrodes. At the same time, it offers high thermal stability (above 200 °C) and electrochemical stability in organic electrolytes. Apparently though, the casein-based electrodes offer lower electronic conductivity than those based on other state-of-the-art binders, which can limit the rate performance of the resulting EDLC. In the attempt of improving the electrochemical performance, it is found that the application of a pressing step can solve this issue, leading to excellent rate capability (up to 84% capacitance retention at 50 mA cm-2) and cycling stability (96.8% after 10,000 cycles at 10 mA cm-2) in both PC- and ACN-based electrolytes. Although the adhesive power casein is known since ancient times, this report presents the first proof of concept of its employment in electrochemical power sources.

Graphene decorated microelectrodes for simultaneous detection of ascorbic, dopamine, and folic acids by means of chemical vapor deposition

NASA Astrophysics Data System (ADS)

Namdar, N.; Hassanpour Amiri, M.; Dehghan Nayeri, F.; Gholizadeh, A.; Mohajerzadeh, S.

2015-09-01

In this paper, high quality and large area graphene layers were synthesized using thermal chemical vapour deposition on copper foil substrates. We use graphene incorporated electrodes to measure simultaneously ascorbic acid, dopamine and folic acid. Cyclic voltammetry and differential pulse voltammetry methods were used to evaluate electrochemical behaviour of the grown graphene layers. The graphene-modified electrode shows large electrochemical potential difference compared to bare gold electrodes with higher current responses. Also our fabricated electrodes configuration can be used easily for microfluidic analysis.

Facile Fabrication of 3D Layer-by-layer Graphene-gold Nanorod Hybrid Architecture for Hydrogen Peroxide Based Electrochemical Biosensor

DTIC Science & Technology

2015-01-01

measurement techniques such as radioisotope tracing, NMR spectroscopy, and microfluorometry assay [12,25,18]. In recent years, electrochemical biosensors...control number. 1. REPORT DATE 2015 2. REPORT TYPE 3. DATES COVERED 00-00-2015 to 00-00-2015 4. TITLE AND SUBTITLE Facile Fabrication of 3D...Claussen, S. Jedlicka, J.L. Rickus, D.M. Porterfield, J. Neurosci. Methods 189 (2010) 14–22. [17] E.S. McLamore, J. Shi, D. Jaroch, J.C. Claussen, A

Recent developments in the layer-by-layer assembly of polyaniline and carbon nanomaterials for energy storage and sensing applications. From synthetic aspects to structural and functional characterization

NASA Astrophysics Data System (ADS)

Marmisollé, Waldemar A.; Azzaroni, Omar

2016-05-01

The construction of hybrid polymer-inorganic nanoarchitectures for electrochemical purposes based on the layer-by-layer assembly of conducting polymers and carbon nanomaterials has become increasingly popular over the last decade. This explosion of interest is primarily related to the increasing mastery in the design of supramolecular constructs using simple wet chemical approaches. Concomitantly, this continuous research activity paved the way to the rapid development of nanocomposites or ``nanoblends'' readily integrable into energy storage and sensing devices. In this sense, the layer-by-layer (LbL) assembly technique has allowed us to access three-dimensional (3D) multicomponent carbon-based network nanoarchitectures displaying addressable electrical, electrochemical and transport properties in which conducting polymers, such as polyaniline, and carbon nanomaterials, such as carbon nanotubes or nanographene, play unique roles without disrupting their inherent functions - complementary entities coexisting in harmony. Over the last few years the level of functional sophistication reached by LbL-assembled carbon-based 3D network nanoarchitectures, and the level of knowledge related to how to design, fabricate and optimize the properties of these 3D nanoconstructs have advanced enormously. This feature article presents and discusses not only the recent advances but also the emerging challenges in complex hybrid nanoarchitectures that result from the layer-by-layer assembly of polyaniline, a quintessential conducting polymer, and diverse carbon nanomaterials. This is a rapidly developing research area, and this work attempts to provide an overview of the diverse 3D network nanoarchitectures prepared up to now. The importance of materials processing and LbL integration is explored within each section and while the overall emphasis is on energy storage and sensing applications, the most widely-used synthetic strategies and characterization methods for ``nanoblend'' formation and performance evaluation are also presented.

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

PubMed

Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek; Nakai, Izumi; Komaba, Shinichi

2011-03-30

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

Fabricating porous silicon carbide

NASA Technical Reports Server (NTRS)

Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

1994-01-01

The formation of porous SiC occurs under electrochemical anodization. A sample of SiC is contacted electrically with nickel and placed into an electrochemical cell which cell includes a counter electrode and a reference electrode. The sample is encapsulated so that only a bare semiconductor surface is exposed. The electrochemical cell is filled with an HF electrolyte which dissolves the SiC electrochemically. A potential is applied to the semiconductor and UV light illuminates the surface of the semiconductor. By controlling the light intensity, the potential and the doping level, a porous layer is formed in the semiconductor and thus one produces porous SiC.

Iodine encapsulation in CNTs and its application for electrochemical capacitor

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

Taniguchi, Y.; Ishii, Y.; Al-zubaidi, A.

2016-07-06

We report the experimental results for new type electrochemical capacitor using iodine redox reaction in single-walled carbon nanotubes (SWCNTs). It was found that the energy density of the present redox capacitor using SWCNTs is almost three times larger than that of the normal electric double layer capacitor.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

Achieving high capacity and rate capability in layered lithium transition metal oxide cathodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ahn, Juhyeon; Susanto, Dieky; Noh, Jae-Kyo; Ali, Ghulam; Cho, Byung Won; Chung, Kyung Yoon; Kim, Jong Hak; Oh, Si Hyoung

2017-08-01

In this study, we target to find a new composition for a layered mixed metal oxide, which has a high structural stability and a good electrochemical performance. Our strategy is to alter the transition metal composition focusing on the relative amounts of redox active Ni and Co to the inactive Mn, based on highly-stabilized LiNi1/3Co1/3Mn1/3O2. X-ray absorption near-edge structure and X-ray diffraction analyses show that the degree of cation disorder decreases on increasing the ratio of Ni and Co to Mn, by the presence of Ni3+, suggesting that slightly higher Ni and Co contents lead to improved structural stability. Electrochemical studies demonstrate that LiNi0.4Co0.4Mn0.2O2 cathodes exhibit considerable improvements in both the reversible capacity and the rate capabilities at a voltage range of 2.5-4.6 V. In situ XRD measurements reveal that LiNi0.4Co0.4Mn0.2O2 maintains a single-phase and undergoes lesser structural variations compared to controlled compositions during a delithiation process up to 4.6 V, while achieving a high reversible capacity over 200 mAh g-1. As a result, LiNi0.4Co0.4Mn0.2O2 experiences fewer structural degradations during electrochemical cycling, which explains the excellent long-term cycling performance.

Electrochemical Measurement of Atmospheric Corrosion

NASA Technical Reports Server (NTRS)

DeArmond, Anna H.; Davis, Dennis D.; Beeson, Harold D.

1999-01-01

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

Electrochemical corrosion, wear and cell behavior of ZrO2/TiO2 alloyed layer on Ti-6Al-4V.

PubMed

Li, Jianfang; He, Xiaojing; Zhang, Guannan; Hang, Ruiqiang; Huang, Xiaobo; Tang, Bin; Zhang, Xiangyu

2018-06-01

Ti-6Al-4V (TC4) has received increasing attention as biomaterial but also raised concerns about the long-term safety of releasing of metal ions and poor wear resistance. In this work, an ZrO 2 /TiO 2 alloyed layer was prepared on TC4 by plasma surface alloying with Zr and subsequently annealed in the air for improved corrosion and wear resistant. To assess the corrosion performance of the alloyed layer, the specimens were measured by open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid solution. The result shows that the ZrO 2 /TiO 2 alloyed layer exhibits strikingly high polarization resistance, wide passive region and very low current density, indicating the excellent corrosion resistance. The layer also displays significant improvement of wear resistance. Furthermore, the alloyed layer restricts cell adhesion and spreading. We infer that the ZrO 2 /TiO 2 alloyed layer might be potentially useful implanted devices such as biosensors, bioelectronics or drug delivery devices. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Sodium-ion supercapacitors based on nanoporous pyroproteins containing redox-active heteroatoms

NASA Astrophysics Data System (ADS)

Cho, Se Youn; Yoon, Hyeon Ji; Kim, Na Rae; Yun, Young Soo; Jin, Hyoung-Joon

2016-10-01

Nanostructured carbon-based materials fabricated via simple methods from renewable bio-resources have great potential in rechargeable energy storage systems. In this study, nanoporous pyroproteins containing a large amount of redox-active heteroatoms (H-NPs) were fabricated from silk fibroin by an in situ carbonization/activation method. The H-NPs have a large surface area of ∼3050 m2 g-1, which is mainly comprised of nanometer-scale pores. Also, these H-NPs have oxygen and nitrogen heteroatoms of 17.4 wt% and 2.9 wt%, respectively. Synergistic sodium ion storage behaviors originate from electrochemical double layer capacitance and pseudocapacitance, leading to very high electrochemical performances of H-NPs in aqueous and non-aqueous electrolyte systems. Sodium-ion supercapacitors (NISs) based on commercial graphite//H-NPs show a high specific power of ∼1900 W kg-1 at ∼77 Wh kg-1. Also, NISs based on commercial hard carbon//H-NPs exhibit a high specific energy of ∼217 Wh kg-1 at ∼42 W kg-1. In addition, outstanding cycling performances over 30,000 cycles are achieved for symmetric NISs.

Ultra-high-performance core–shell structured Ru@Pt/C catalyst prepared by a facile pulse electrochemical deposition method

DOE PAGES

Chen, Dan; Li, Yuexia; Liao, Shijun; ...

2015-08-03

Core–shell structured catalysts, made by placing either a monolayer or a thin layer of a noble metal on relatively cheap core-metal nanoparticles, are fascinating and promising fuel cell catalysts due to their high utilization of noble metals. Here, we report our development of a core–shell structured catalyst, Ru@Pt/C, generated by a novel and facile pulse electrochemical deposition (PED) approach. We demonstrate that compared with a commercial Pt/C catalyst, this novel catalyst achieves over four times higher mass activity towards the anodic oxidation of methanol, and 3.6 times higher mass activity towards the cathodic reduction of oxygen. Importantly, we find thatmore » the intrinsic activity of Pt in this Ru@Pt/C catalyst is doubled due to the formation of the core–shell structure. The catalyst also shows superior stability: even after 2000 scans, it still retains up to 90% of the peak current. As a result, our findings demonstrate that this novel PED approach is a promising method for preparing high-performance core–shell catalysts for fuel cell applications.« less

Preparation and electrochemical characterization of polyaniline/activated carbon composites as an electrode material for supercapacitors.

PubMed

Oh, Misoon; Kim, Seok

2012-01-01

Polyaniline (PANI)/activated carbon (AC) composites were prepared by a chemical oxidation polymerization. To find an optimum ratio between PANI and AC which shows superior electrochemical properties, the preparation was carried out in changing the amount of added aniline monomers. The morphology of prepared composites was investigated by scanning electron microscopy (SEM) and transmission electron microscope (TEM). The structural and thermal properties were investigated by Fourier transform infrared spectra (FT-IR) and thermal gravimetric analysis (TGA), respectively. The electrochemical properties were characterized by cyclic voltammetry (CV). Composites showed a summation of capacitances that consisted of two origins. One is double-layer capacitance by ACs and the other is faradic capacitance by redox reaction of PANI. Fiber-like PANIs are coated on the surface of ACs and they contribute to the large surface for redox reaction. The vacancy among fibers provided the better diffusion and accessibility of ion. High capacitances of composites were originated from the network structure having vacancy made by PANI fibers. It was found that the composite prepared with 5 ml of aniline monomer and 0.25 g of AC showed the highest capacitance. Capacitance of 771 F/g was obtained at a scan rate of 5 mV/s.

A review of electrolyte materials and compositions for electrochemical supercapacitors.

PubMed

Zhong, Cheng; Deng, Yida; Hu, Wenbin; Qiao, Jinli; Zhang, Lei; Zhang, Jiujun

2015-11-07

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

High power density supercapacitors based on the carbon dioxide activated D-glucose derived carbon electrodes and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid

NASA Astrophysics Data System (ADS)

Tooming, T.; Thomberg, T.; Kurig, H.; Jänes, A.; Lust, E.

2015-04-01

The electrochemical impedance spectroscopy, cyclic voltammetry, constant current charge/discharge and the constant power discharge methods have been applied to establish the electrochemical characteristics of the electrical double-layer capacitor (EDLC) consisting of the 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) ionic liquid and microporous carbon electrodes. Microporous carbon material used for preparation of electrodes (GDAC - glucose derived activated carbon), has been synthesised from D-(+)-glucose by the hydrothermal carbonization method, including subsequent pyrolysis, carbon dioxide activation and surface cleaning step with hydrogen. The Brunauer-Emmett-Teller specific surface area (SBET = 1540 m2 g-1), specific surface area calculated using the non-local density functional theory in conjunction with stable adsorption integral equation using splines (SAIEUS) model SSAIEUS = 1820 m2 g-1, micropore surface area (Smicro = 1535 m2 g-1), total pore volume (Vtot = 0.695 cm3 g-1) and the pore size distribution were obtained from the N2 sorption data. The SBET, Smicro and Vtot values have been correlated with the electrochemical characteristics strongly dependent on the carbon activation conditions applied for EDLCs. Wide region of ideal polarizability (ΔV ≤ 3.2 V), very short charging/discharging time constant (2.7 s), and high specific series capacitance (158 F g-1) have been calculated for the optimized carbon material GDAC-10h (activation of GDAC with CO2 during 10 h) in EMImBF4 demonstrating that this system can be used for completing the EDLC with high energy- and power densities.

Stacked multilayers of alternating reduced graphene oxide and carbon nanotubes for planar supercapacitors

NASA Astrophysics Data System (ADS)

Moon, Geon Dae; Joo, Ji Bong; Yin, Yadong

2013-11-01

A simple layer-by-layer approach has been developed for constructing 2D planar supercapacitors of multi-stacked reduced graphene oxide and carbon nanotubes. This sandwiched 2D architecture enables the full utilization of the maximum active surface area of rGO nanosheets by using a CNT layer as a porous physical spacer to enhance the permeation of a gel electrolyte inside the structure and reduce the agglomeration of rGO nanosheets along the vertical direction. As a result, the stacked multilayers of rGO and CNTs are capable of offering higher output voltage and current production.A simple layer-by-layer approach has been developed for constructing 2D planar supercapacitors of multi-stacked reduced graphene oxide and carbon nanotubes. This sandwiched 2D architecture enables the full utilization of the maximum active surface area of rGO nanosheets by using a CNT layer as a porous physical spacer to enhance the permeation of a gel electrolyte inside the structure and reduce the agglomeration of rGO nanosheets along the vertical direction. As a result, the stacked multilayers of rGO and CNTs are capable of offering higher output voltage and current production. Electronic supplementary information (ESI) available: Experimental details, SEM and TEM images and additional electrochemical data. See DOI: 10.1039/c3nr04339h

Real-time monitoring of enzyme activity in a mesoporous silicon double layer

PubMed Central

Orosco, Manuel M.; Pacholski, Claudia; Sailor, Michael J.

2009-01-01

A double layer mesoporous silicon with different pore sizes functions as a nano-reactor that can isolate, filter and quantify the kinetics of enzyme reactions in real-time by optical reflectivity. This tiny reactor may be used to rapidly characterize a variety of isolated enzymes in a label-free manner. Activity of certain protease enzymes is often an indicator of disease states such as cancer1,2, stroke2, and neurodegeneracy3, and thus, there is a need for rapid assays that can characterize the kinetics and substrate specificity of enzymatic reactions. Nanostructured membranes can efficiently separate biomolecules4 but coupling a sensitive detection method remains difficult. Here we report a single mesoporous nano-reactor that can isolate and quantify in real-time the reaction products of proteases. The reactor consists of two layers of porous films electrochemically prepared from crystalline silicon. The upper layer with large pore sizes traps the protease enzymes and acts as the reactor while the lower layer with smaller pore sizes excludes the large proteins and captures the reaction products. Infiltration of the digested fragments into the lower layer produces a measurable change in optical reflectivity and this allows label-free quantification of enzyme kinetics in real-time within a volume of approximately 5 nanoliters. PMID:19350037

New Method for Super Hydrophobic Treatment of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells Using Electrochemical Reduction of Diazonium Salts.

PubMed

Thomas, Yohann R J; Benayad, Anass; Schroder, Maxime; Morin, Arnaud; Pauchet, Joël

2015-07-15

The purpose of this article is to report a new method for the surface functionalization of commercially available gas diffusion layers (GDLs) by the electrochemical reduction of diazonium salt containing hydrophobic functional groups. The method results in superhydrophobic GDLs, over a large area, without pore blocking. An X-ray photoelectron spectroscopy study based on core level spectra and chemical mapping has demonstrated the successful grafting route, resulting in a homogeneous distribution of the covalently bonded hydrophobic molecules on the surface of the GDL fibers. The result was corroborated by contact angle measurement, showing similar hydrophobicity between the grafted and PTFE-modified GDLs. The electrochemically modified GDLs were tested in proton exchange membrane fuel cells under automotive, wet, and dry conditions and demonstrated improved performance over traditional GDLs.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

1996-01-01

The invention comprises 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-x-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. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) 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 (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) 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.

Fullerene C60 coated silicon nanowires as anode materials for lithium secondary batteries.

PubMed

Arie, Arenst Andreas; Lee, Joong Kee

2012-04-01

A Fullerene C60 film was introduced as a coating layer for silicon nanowires (Si NWs) by a plasma assisted thermal evaporation technique. The morphology and structural characteristics of the materials were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM observations showed that the shape of the nanowire structure was maintained after the C60 coating and the XPS analysis confirmed the presence of the carbon coating layer. The electrochemical characteristics of C60 coated Si NWs as anode materials were examined by charge-discharge tests and electrochemical impedance measurements. With the C60 film coating, Si NW electrodes exhibited a higher initial coulombic efficiency of 77% and a higher specific capacity of 2020 mA h g(-1) after the 30th cycle at a current density of 100 microA cm(-2) with cut-off voltage between 0-1.5 V. These improved electrochemical characteristics are attributed to the presence of the C60 coating layer which suppresses side reaction with the electrolyte and maintains the structural integrity of the Si NW electrodes during cycle tests.

Polarized emission from light-emitting electrochemical cells using uniaxially oriented polymer thin films of poly(9,9-dioctylfluorene-co-bithiophene)

NASA Astrophysics Data System (ADS)

Miyazaki, Masumi; Sakanoue, Tomo; Takenobu, Taishi

2018-03-01

Uniaxially oriented poly(9,9-dioctylfluorene-co-bithiophene) (F8T2) films were prepared on rubbed polyimide substrates and applied to emitting layers of light-emitting electrochemical cells (LECs). The layered structure of the uniaxially oriented F8T2 film and ionic liquid electrolytes enabled us to demonstrate LEC operations with high anisotropic characteristics both in emission and charge transport. Polarized electroluminescence (EL) from electrochemically induced p-n junctions in the uniaxially oriented F8T2 was obtained. The dichroic ratios of EL were the same as those of photoluminescence, suggesting that the doping process into the oriented F8T2 did not interrupt the polymer ordering. This indicates the usefulness of the layered structure of the polymer/electrolyte for the fabrication of LECs based on highly oriented polymer films. In addition, uniaxially oriented F8T2 was found to show reduced threshold energy in optically pumped amplified spontaneous emission. These demonstrations suggest the advantage of uniaxially oriented polymer-based LECs for potential application in future electrically pumped lasers.

Effects of Additives on Electrochemical Growth of Cu Film on Co/SiO2/Si Substrate by Alternating Underpotential Deposition of Pb and Surface-Limited Redox Replacement by Cu

NASA Astrophysics Data System (ADS)

Fang, J. S.; Lin, L. Y.; Wu, C. L.; Cheng, Y. L.; Chen, G. S.

2017-11-01

The effects of additives to an acidic electrolyte for electrochemical deposition of copper film to prevent corrosion of the Co/SiO2/Si substrate have been investigated. A sacrificial Pb layer was formed by underpotential deposition (UPD), then a Cu layer was prepared using surface-limited redox replacement (SLRR) to exchange the UPD-Pb layer in an acidic copper electrolyte with trisodium citrate, sodium perchlorate, and ethylenediamine as additives. The additives significantly affected the replacement of UPD-Pb by Cu and prevented galvanic corrosion of the Co/SiO2/Si substrate in the acidic Cu electrolyte. The results showed that both sodium perchlorate and ethylenediamine reduced the corrosion of the Co substrate and resulted in Cu film with low electrical resistivity. However, residual Pb was present in the Cu film when using trisodium citrate, as the citrate ions slowed copper displacement. The proposed sequential UPD-Pb and SLRR-Cu growth method may enable electrochemical deposition for fabrication of Cu interconnects on Co substrate from acidic Cu electrolyte.

Optical polarimetry: Instrumentation and applications; Proceedings of the Seminar, San Diego, Calif., August 23, 24, 1977

NASA Technical Reports Server (NTRS)

Azzam, R. M. A. (Editor); Coffeen, D. L.

1977-01-01

Instrumentation used in optical polarimetry is discussed with reference to high-resolution spectropolarimetry, an orbiter cloud photopolarimeter, X-ray polarimeters, and the design of a self-nulling ellipsometer. Consideration is given to surface and thin-film ellipsometry noting studies of electrochemical surface layers, surface anisotropy, polish layers on infrared window materials, and anodic films. Papers on biological, chemical, and physical polarimetry are presented including birefringence in biological materials, vibrational optical activity, and the optical determination of the thermodynamic phase diagram of a metamagnet. Remote sensing is discussed in terms of polarization imagery, the optical polarimetry of particulate surfaces, and techniques and applications of elliptical polarimetry in astronomy and atmospheric studies.

Copper/carbon coated lithium sodium titanate as advanced anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Kaiqiang; Lin, Xiaoting; Shao, Lianyi; Shui, Miao; Long, Nengbing; Ren, Yuanlong; Shu, Jie

2014-08-01

Core-shell Li2Na2Ti6O14@Cu/C is prepared by a preliminary formation of Li2Na2Ti6O14 by solid state reaction and a following coating process with Cu/C layer by thermal decomposition. The amorphous Cu/C coating layer reveals a thickness of 5 nm on the surface of Li2Na2Ti6O14, which improves the electronic conductivity and charge transfer rate of active materials. As a result, Li2Na2Ti6O14@Cu/C shows lower electrochemical polarization and quicker kinetic behavior compared to bare Li2Na2Ti6O14. Cycled at 50 mA g-1, Li2Na2Ti6O14@Cu/C can deliver a reversible capacity of 120.3 mAh g-1 after 50 cycles, which is much higher than the value of 96.8 mAh g-1 obtained by Li2Na2Ti6O14. Even kept at 400 mA g-1, a reversible lithium storage capacity of 76.3 mAh g-1 can be delivered by Li2Na2Ti6O14@Cu/C. The improved electrochemical properties of Li2Na2Ti6O14 are attributed to the electronic conductive Cu/C coating layer on the surface.

Conformal spinel/layered heterostructures of Co3O4 shells grown on single-crystal Li-rich nanoplates for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Xin, Yue; Lan, Xiwei; Chang, Peng; Huang, Yaqun; Wang, Libin; Hu, Xianluo

2018-07-01

Lithium-rich layered materials have received much attention because of their high specific capacity and high energy density. Unfortunately, they suffer from irreversible capacity loss, low initial Coulombic efficiency and poor cyclability. Here we report a facile co-precipitation method to synthesize uniform single-crystal Li-rich Li[Li0.2Mn0.54Ni0.13Co0.13]O2 nanoplates without using any template. Subsequently, a Co3O4 shell is in situ grown on the Li-rich nanoplates through a hydrothermal method, leading to spinel/layered heterostructures. The electrode made of conformal heterostructured Li-rich/Co3O4 nanoplates delivers a high discharge capacity of 296 mA h g-1 at 0.1 C with an initial Coulombic efficiency of 84%. The capacity retention reaches 83.2% with a discharge capacity of 223 mA h g-1 after 160 cycles at 0.2 C during the potential window ranging from 2.0 to 4.8 V. The enhanced electrochemical performance of the resulting Li-rich/Co3O4 nanoplates benefits from the unique conformal heterostructure as well as the electrochemically active LixCoOy generated between the reaction of Co3O4 shells and the extracted Li2O during charging/discharging processes.

Synthesis, electrochemical investigation and structural analysis of doped Li[Ni0.6Mn0.2Co0.2-xMx]O2 (x = 0, 0.05; M = Al, Fe, Sn) cathode materials

NASA Astrophysics Data System (ADS)

Eilers-Rethwisch, Matthias; Winter, Martin; Schappacher, Falko Mark

2018-05-01

Layered Ni-rich Li[Ni0.6Mn0.2Co0.2-xMx]O2 cathode materials (x = 0, 0.05; M = Al, Fe, Sn) are synthesized via a co-precipitation synthesis route and the effect of dopants on the structure and electrochemical performance is investigated. All synthesized materials show a well-defined layered structure of the hexagonal α-NaFeO2 phase investigated by X-ray diffraction (XRD). Undoped LiNi0.6Mn0.2Co0.2O2 exhibits a discharge capacity of 170 mAh g-1 in Li-metal 2032 coin-type cells. Doped materials reach lower capacities between 145 mAh g-1 for Al and 160 mAh g-1 for Sn. However, all doped materials prolong the cycle life by up to 20%. Changes of the lattice parameter before and after delithiation yield information about structural stability. A smaller repulsion of the transition metal layer during delithiation in the Sn-doped material leads to a smaller expansion of the unit cell, which results in enhanced structural stability of the material. The improved structural stability of Sn-doped NMC cathode active material is proven by thermal investigations with the help of Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA).

High-Capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers

PubMed Central

Razaq, Aamir; Nyström, Gustav; Strømme, Maria; Mihranyan, Albert; Nyholm, Leif

2011-01-01

Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg−1, were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30–50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m2 g−1) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)6, (dT)20, and (dT)40 DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules. PMID:22195031

Ultrafast electrochemical preparation of graphene/CoS nanosheet counter electrodes for efficient dye-sensitized solar cells

DOE PAGES

Zhu, Chongyang; Zhu, Yimei; Min, Huihua; ...

2015-10-05

Utilizing inexpensive, high-efficiency counter electrodes (CEs) to replace the traditional platinum counterparts in dye-sensitized solar cells (DSSCs) is worthwhile. In this paper, we detail how we synchronously prepared composite CEs of CoS nanosheet arrays and reduced graphene oxide (rGO) layers for the first time via a low temperature, ultrafast one-step electrochemical strategy. With this approach, the whole fabrication process of the composite CEs was only a small percentage of the average time (~15 hours) using other methods. The DSSC assembled with the rGO–CoS composite CE achieved an enhanced power conversion efficiency (PCE) of 8.34%, which is dramatically higher than 6.27%more » of pure CoS CE-based DSSC and even exceeds 7.50% of Pt CE-based DSSC. The outstanding PCE breakthrough is undoubtedly attributed to the enhancement in electrocatalytic ability of the rGO–CoS composite CE due to the incorporation of highly conducting rGO layers and the GO layers-induced growth of CoS nanosheet arrays with higher density and larger surface area. Therefore, lower charge-transfer resistance and higher exchange current density can be achieved as corroborated by the electrochemical impedance spectra (EIS) and Tafel polarization curves (TPCs). As a result, further experiments also proved that the electrochemical strategy exhibited its universality of fabricating other graphene-enhanced chalcogenide functional composite films.« less

Multilayer poly(3,4-ethylenedioxythiophene)-dexamethasone and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate-carbon nanotubes coatings on glassy carbon microelectrode arrays for controlled drug release.

PubMed

Castagnola, Elisa; Carli, Stefano; Vomero, Maria; Scarpellini, Alice; Prato, Mirko; Goshi, Noah; Fadiga, Luciano; Kassegne, Sam; Ricci, Davide

2017-07-13

The authors present an electrochemically controlled, drug releasing neural interface composed of a glassy carbon (GC) microelectrode array combined with a multilayer poly(3,4-ethylenedioxythiophene) (PEDOT) coating. The system integrates the high stability of the GC electrode substrate, ideal for electrical stimulation and electrochemical detection of neurotransmitters, with the on-demand drug-releasing capabilities of PEDOT-dexamethasone compound, through a mechanically stable interlayer of PEDOT-polystyrene sulfonate (PSS)-carbon nanotubes (CNT). The authors demonstrate that such interlayer improves both the mechanical and electrochemical properties of the neural interface, when compared with a single PEDOT-dexamethasone coating. Moreover, the multilayer coating is able to withstand 10 × 10 6 biphasic pulses and delamination test with negligible change to the impedance spectra. Cross-section scanning electron microscopy images support that the PEDOT-PSS-CNT interlayer significantly improves the adhesion between the GC substrate and PEDOT-dexamethasone coating, showing no discontinuities between the three well-interconnected layers. Furthermore, the multilayer coating has superior electrochemical properties, in terms of impedance and charge transfer capabilities as compared to a single layer of either PEDOT coating or the GC substrate alone. The authors verified the drug releasing capabilities of the PEDOT-dexamethasone layer when integrated into the multilayer interface through repeated stimulation protocols in vitro, and found a pharmacologically relevant release of dexamethasone.

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.

High-performance, polymer-based direct cellular interfaces for electrical stimulation and recording

NASA Astrophysics Data System (ADS)

Kim, Seong-Min; Kim, Nara; Kim, Youngseok; Baik, Min-Seo; Yoo, Minsu; Kim, Dongyoon; Lee, Won-June; Kang, Dong-Hee; Kim, Sohee; Lee, Kwanghee; Yoon, Myung-Han

2018-04-01

Due to the trade-off between their electrical/electrochemical performance and underwater stability, realizing polymer-based, high-performance direct cellular interfaces for electrical stimulation and recording has been very challenging. Herein, we developed transparent and conductive direct cellular interfaces based on a water-stable, high-performance poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) film via solvent-assisted crystallization. The crystallized PEDOT:PSS on a polyethylene terephthalate (PET) substrate exhibited excellent electrical/electrochemical/optical characteristics, long-term underwater stability without film dissolution/delamination, and good viability for primarily cultured cardiomyocytes and neurons over several weeks. Furthermore, the highly crystallized, nanofibrillar PEDOT:PSS networks enabled dramatically enlarged surface areas and electrochemical activities, which were successfully employed to modulate cardiomyocyte beating via direct electrical stimulation. Finally, the high-performance PEDOT:PSS layer was seamlessly incorporated into transparent microelectrode arrays for efficient, real-time recording of cardiomyocyte action potentials with a high signal fidelity. All these results demonstrate the strong potential of crystallized PEDOT:PSS as a crucial component for a variety of versatile bioelectronic interfaces.

Electrochemical Analysis of Conducting Polymer Thin Films

PubMed Central

Vyas, Ritesh N.; Wang, Bin

2010-01-01

Polyelectrolyte multilayers built via the layer-by-layer (LbL) method has been one of the most promising systems in the field of materials science. Layered structures can be constructed by the adsorption of various polyelectrolyte species onto the surface of a solid or liquid material by means of electrostatic interaction. The thickness of the adsorbed layers can be tuned precisely in the nanometer range. Stable, semiconducting thin films are interesting research subjects. We use a conducting polymer, poly(p-phenylene vinylene) (PPV), in the preparation of a stable thin film via the LbL method. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize the ionic conductivity of the PPV multilayer films. The ionic conductivity of the films has been found to be dependent on the polymerization temperature. The film conductivity can be fitted to a modified Randle’s circuit. The circuit equivalent calculations are performed to provide the diffusion coefficient values. PMID:20480052

An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile-Based Electrolytes in Lithium Metal Batteries.

PubMed

Trinh, Ngoc Duc; Lepage, David; Aymé-Perrot, David; Badia, Antonella; Dollé, Mickael; Rochefort, Dominic

2018-04-23

The resurgence of the lithium metal battery requires innovations in technology, including the use of non-conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (-3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile-based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF 6 in acetonitrile. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical method of controlling thiolate coverage on a conductive substrate such as gold

NASA Technical Reports Server (NTRS)

Porter, Marc D. (Inventor); Weisshaar, Duane E. (Inventor)

1998-01-01

An electrochemical method for forming a partial monomolecular layer of a predetermined extent of coverage of a thiolate of the formula, XRS--, therein R can be a linear or branched chain hydrocarbon or an aromatic or the like and X can be any compatible end group, e.g., OH, COOH, CH.sub.3 or the like, upon a substrate such as gold, which involves applying in an electrochemical system a constant voltage preselected to yield the desired predetermined extent of coverage.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1979-01-01

Several aspects of the electrolytic evolution of oxygen for use in life support systems are analyzed including kinetic studies of various metal and nonmetal electrode materials, the formation of underpotential films on electrodes, and electrode surface morphology and the use of single crystal metals. In order to investigate the role of surface morphology to electrochemical reactions, a low energy electron diffraction and an Auger electron spectrometer are combined with an electrochemical thin-layer cell allowing initial characterization of the surface, reaction run, and then a comparative surface analysis.

Electrochemical method of controlling thiolate coverage on a conductive substrate such as gold

DOEpatents

Porter, Marc D.; Weisshaar, Duane E.

1998-10-27

An electrochemical method for forming a partial monomolecular layer of a predetermined extent of coverage of a thiolate of the formula, XRS--, therein R can be a linear or branched chain hydrocarbon or an aromatic or the like and X can be any compatible end group, e.g., OH, COOH, CH.sub.3 or the like, upon a substrate such as gold, which involves applying in an electrochemical system a constant voltage preselected to yield the desired predetermined extent of coverage.

Electrochemical method of controlling thiolate coverage on a conductive substrate such as gold

DOEpatents

Porter, Marc D.; Weisshaar, Duane E.

1997-06-03

An electrochemical method for forming a partial monomolecular layer of a predetermined extent of coverage of a thiolate of the formula, XRS.sup.-, wherein R can be a linear or branched chain hydrocarbon or an aromatic or the like and X can be any compatible end group, e.g., OH, COOH, CH.sub.3 or the like, upon a substrate such as gold, which involves applying in an electrochemical system a constant voltage preselected to yield the desired predetermined extent of coverage.

Mn-Based Cathode with Synergetic Layered-Tunnel Hybrid Structures and Their Enhanced Electrochemical Performance in Sodium Ion Batteries.

PubMed

Wu, Zhen-Guo; Li, Jun-Tao; Zhong, Yan-Jun; Guo, Xiao-Dong; Huang, Ling; Zhong, Ben-He; Agyeman, Daniel-Adjei; Lim, Jin-Myoung; Kim, Du-Ho; Cho, Maeng-Hyo; Kang, Yong-Mook

2017-06-28

A synergistic approach for advanced cathode materials is proposed. Sodium manganese oxide with a layered-tunnel hybrid structure was designed, synthesized, and subsequently investigated. The layered-tunnel hybrid structure provides fast Na ion diffusivity and high structural stability thanks to the tunnel phase, enabling high rate capability and greatly improved cycling stability compared to that of the pure P2 layered phase while retaining the high specific capacity of the P2 layered phase. The hybrid structure provided a decent discharge capacity of 133.4 mAh g -1 even at 8 C, which exceeds the reported best rate capability for Mn-based cathodes. It also displayed an impressive cycling stability, maintaining 83.3 mAh g -1 after 700 cycles at 10 C. Theoretical calculation and the potentiostatic intermittent titration technique (PITT) demonstrated that this hybrid structure helps enhance Na ion diffusivity during charge and discharge, attaining, as a result, an unprecendented electrochemical performance.

Electrochemical deposition of layered copper thin films based on the diffusion limited aggregation

PubMed Central

Wei, Chenhuinan; Wu, Guoxing; Yang, Sanjun; Liu, Qiming

2016-01-01

In this work layered copper films with smooth surface were successfully fabricated onto ITO substrate by electrochemical deposition (ECD) and the thickness of the films was nearly 60 nm. The resulting films were characterized by SEM, TEM, AFM, XPS, and XRD. We have investigated the effects of potential and the concentration of additives and found that 2D dendritic-like growth process leaded the formation of films. A suitable growth mechanism based on diffusion limited aggregation (DLA) mechanism for the copper films formation is presented, which are meaningful for further designing homogeneous and functional films. PMID:27734900

Nucleation and growth of thin films of the organic conductor TTF-iodide over glassy carbon. Electrochemical and spectroelectrochemical study.

PubMed

Gómez, L; Rodríguez-Amaro, R

2009-04-21

On the basis of the electrochemical and spectroelectrochemical behavior of thin films of TTF over a glassy carbon electrode in iodide media, a new, more complete mechanism for the electrode processes involved is proposed. The voltammetric and chronoamperometric results for the films can be explained in light of a recently developed nucleation-growth model involving a layer-by-layer mechanism. Also, their in situ UV-vis spectral data expand the available knowledge about the overall mechanism and the nature of the compound formed over the glassy carbon electrode.

Comparative studies on single-layer reduced graphene oxide films obtained by electrochemical reduction and hydrazine vapor reduction

NASA Astrophysics Data System (ADS)

Wang, Zhijuan; Wu, Shixin; Zhang, Juan; Chen, Peng; Yang, Guocheng; Zhou, Xiaozhu; Zhang, Qichun; Yan, Qingyu; Zhang, Hua

2012-02-01

The comparison between two kinds of single-layer reduced graphene oxide (rGO) sheets, obtained by reduction of graphene oxide (GO) with the electrochemical method and hydrazine vapor reduction, referred to as E-rGO and C-rGO, respectively, is systematically studied. Although there is no morphology difference between the E-rGO and C-rGO films adsorbed on solid substrates observed by AFM, the reduction process to obtain the E-rGO and C-rGO films is quite different. In the hydrazine vapor reduction, the nitrogen element is incorporated into the obtained C-rGO film, while no additional element is introduced to the E-rGO film during the electrochemical reduction. Moreover, Raman spectra show that the electrochemical method is more effective than the hydrazine vapor reduction method to reduce the GO films. In addition, E-rGO shows better electrocatalysis towards dopamine than does C-rGO. This study is helpful for researchers to understand these two different reduction methods and choose a suitable one to reduce GO based on their experimental requirements.

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.

Synthesis and electrochemical properties of layered structure Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} cathode material

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

Prathibha, G.; Rosaiah, P.; Reddy, B. Purusottam

Lithium ion (Li-ion) batteries are currently the energy source of choice for cell phones, laptops, and other mobile electronic devices due to their balance of high energy density with high power density compared to other electrochemical energy carriers. In the present study, mixed hydroxide method is used to prepare Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} from the precursors and analyze qualitatively and studied the electrochemical properties. The XRD spectrum exhibited predominant (003) orientation at 2θ =18.39{sup o} corresponding to hexagonal layered structure of R3m symmetry with evaluated lattice parameters are a= 2.84 Å, c= 14.43 Å. Raman measurements were performed tomore » understand the microstructure and vibrational modes of the prepared sample. From the electrochemical (EC) studies an initial discharge capacity of about 140 mAhg{sup −1} with good cyclic stability was observed for the prepared sample in the potential range 0.0 −1.0V in aqueous medium.« less

High-performance flexible electrode based on electrodeposition of polypyrrole/MnO2 on carbon cloth for supercapacitors

NASA Astrophysics Data System (ADS)

Fan, Xingye; Wang, Xiaolei; Li, Ge; Yu, Aiping; Chen, Zhongwei

2016-09-01

A highly flexible electrodes based on electrodeposited MnO2 and polypyrrole composite on carbon cloth is designed and developed by a facile in-situ electrodeposition technique. Such flexible composite electrodes with multiply layered structure possess a high specific capacitance of 325 F g-1 at a current density of 0.2 A g-1, and an excellent rate capability with a capacitance retention of 70% at a high current density of 5.0 A g-1. The superior electrochemical performance is mainly due to the unique electrode with improved ion- and electron-transportation pathways as well as the efficient utilization of active materials and electrode robustness. The excellent electrochemical performance and the low cost property endow this flexible nanocomposite electrode with great promise in applications of flexible supercapacitors.

Few layered vanadyl phosphate nano sheets-MWCNT hybrid as an electrode material for supercapacitor application

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

Dutta, Shibsankar; De, Sukanta, E-mail: sukanta.physics@presiuniv.ac.in

It have been already seen that 2-dimensional nano materials are the suitable choice for the supercapacitor application due to their large specific surface area, electrochemical active sites, micromechanical flexibility, expedite ion migration channel properties. Free standing hybrid films of functionalized MWCNT (– COOH group) and α-Vanadyl phosphates (VOPO{sub 4}2H{sub 2}O) are prepared by vacuum filtering. The surface morphology and microstructure of the samples are studied by transmission electron microscope, field emission scanning electron microscope, XRD, Electrochemical properties of hybrid films have been investigated systematically in 1M Na{sub 2}SO{sub 4} aqueous electrolyte. The hybrid material exhibits a high specific capacitance 236more » F/g with high energy density of 65.6 Wh/Kg and a power density of 1476 W/Kg.« less

Development of a spectro-electrochemical cell for soft X-ray photon-in photon-out spectroscopy

NASA Astrophysics Data System (ADS)

Ishihara, Tomoko; Tokushima, Takashi; Horikawa, Yuka; Kato, Masaru; Yagi, Ichizo

2017-10-01

We developed a spectro-electrochemical cell for X-ray absorption and X-ray emission spectroscopy, which are element-specific methods to study local electronic structures in the soft X-ray region. In the usual electrochemical measurement setup, the electrode is placed in solution, and the surface/interface region of the electrode is not normally accessible by soft X-rays that have low penetration depth in liquids. To realize soft X-ray observation of electrochemical reactions, a 15-nm-thick Pt layer was deposited on a 150-nm-thick film window with an adhesive 3-nm-thick Ti layer for use as both the working electrode and the separator window between vacuum and a sample liquid under atmospheric pressure. The designed three-electrode electrochemical cell consists of a Pt film on a SiC window, a platinized Pt wire, and a commercial Ag|AgCl electrode as the working, counter, and reference electrodes, respectively. The functionality of the cell was tested by cyclic voltammetry and X-ray absorption and emission spectroscopy. As a demonstration, the electroplating of Pb on the Pt/SiC membrane window was measured by X-ray absorption and real-time monitoring of fluorescence intensity at the O 1s excitation.

Organophosphonate biofunctionalization of diamond electrodes.

PubMed

Caterino, R; Csiki, R; Wiesinger, M; Sachsenhauser, M; Stutzmann, M; Garrido, J A; Cattani-Scholz, A; Speranza, Giorgio; Janssens, S D; Haenen, K

2014-08-27

The modification of the diamond surface with organic molecules is a crucial aspect to be considered for any bioapplication of this material. There is great interest in broadening the range of linker molecules that can be covalently bound to the diamond surface. In the case of protein immobilization, the hydropathicity of the surface has a major influence on the protein conformation and, thus, on the functionality of proteins immobilized at surfaces. For electrochemical applications, particular attention has to be devoted to avoid that the charge transfer between the electrode and the redox center embedded in the protein is hindered by a thick insulating linker layer. This paper reports on the grafting of 6-phosphonohexanoic acid on OH-terminated diamond surfaces, serving as linkers to tether electroactive proteins onto diamond surfaces. X-ray photoelectron spectroscopy (XPS) confirms the formation of a stable layer on the surface. The charge transfer between electroactive molecules and the substrate is studied by electrochemical characterization of the redox activity of aminomethylferrocene and cytochrome c covalently bound to the substrate through this linker. Our work demonstrates that OH-terminated diamond functionalized with 6-phosphonohexanoic acid is a suitable platform to interface redox-proteins, which are fundamental building blocks for many bioelectronics applications.

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

Nanoplasmonic sensing of metal-halide complex formation and the electric double layer capacitor.

PubMed

Dahlin, Andreas B; Zahn, Raphael; Vörös, Janos

2012-04-07

Many nanotechnological devices are based on implementing electrochemistry with plasmonic nanostructures, but these systems are challenging to understand. We present a detailed study of the influence of electrochemical potentials on plasmon resonances, in the absence of surface coatings and redox active molecules, by synchronized voltammetry and spectroscopy. The experiments are performed on gold nanodisks and nanohole arrays in thin gold films, which are fabricated by improved methods. New insights are provided by high resolution spectroscopy and variable scan rates. Furthermore, we introduce new analytical models in order to understand the spectral changes quantitatively. In contrast to most previous literature, we find that the plasmonic signal is caused almost entirely by the formation of ionic complexes on the metal surface, most likely gold chloride in this study. The refractometric sensing effect from the ions in the electric double layer can be fully neglected, and the charging of the metal gives a surprisingly small effect for these systems. Our conclusions are consistent for both localized nanoparticle plasmons and propagating surface plasmons. We consider the results in this work especially important in the context of combined electrochemical and optical sensors. This journal is © The Royal Society of Chemistry 2012

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.

Polyamidoamine dendrimers-assisted electrodeposition of gold-platinum bimetallic nanoflowers.

PubMed

Qian, Lei; Yang, Xiurong

2006-08-24

Novel Au-Pt bimetallic flower nanostructures fabricated on a polyamidoamine dendrimers-modified surface by electrodeposition are reported. These polyamidoamine dendrimers were stable, and they assisted the formation of Au-Pt bimetallic nanoflowers during the electrodeposition process. These nanoflowers were characterized by field-emitted scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and electrochemical methods. FE-SEM images showed that the bimetallic nanoflower included two parts: the "light" and the "pale" part. The two parts consisted of many small bimetallic nanoparticles, which was attributed to the progressive nucleation process. Moreover, the "light" part contained more bimetallic nanoparticles. The morphologies of bimetallic nanoflowers depended on the electrodeposition time and potential and the layer number of assembled dendrimers. The average size of nanoflowers increased with the increase in electrodeposition time. The layer number of assembled dendrimers obviously affected the size and morphologies of the "pale" parts of deposited nanoflowers. EDS and XPS indicated that the content of Au element was higher than that of Pt element in the nanoflowers. The bimetallic nanoflowers-modified electrode had electrochemical properties similar to those of bare gold and platinum electrodes. It also exhibited significant electrocatalytic activities toward oxygen reduction.

An aptamer-based biosensing platform for highly sensitive detection of platelet-derived growth factor via enzyme-mediated direct electrochemistry.

PubMed

Deng, Kun; Xiang, Yang; Zhang, Liqun; Chen, Qinghai; Fu, Weiling

2013-01-08

In this work, a new label-free electrochemical aptamer-based sensor (aptasensor) was constructed for detection of platelet-derived growth factor (PDGF) based on the direct electrochemistry of glucose oxidase (GOD). For this proposed aptasensor, poly(diallyldimethylammonium chloride) (PDDA)-protected graphene-gold nanoparticles (P-Gra-GNPs) composite was firstly coated on electrode surface to form the interface with biocompatibility and huge surface area for the adsorption of GOD layer. Subsequently, gold nanoclusters (GNCs) were deposited on the surface of GOD to capture PDGF binding aptamer (PBA). Finally, GOD as a blocking reagent was employed to block the remaining active sites of the GNCs and avoid the nonspecific adsorption. With the direct electron transfer of double layer GOD membranes, the aptasensor showed excellent electrochemical response and the peak current decreased linearly with increasing logarithm of PDGF concentration from 0.005 nM to 60 nM with a relatively low limit of detection of 1.7 pM. The proposed aptasensor exhibited high specificity, good reproducibility and long-term stability, which provided a new promising technique for aptamer-based protein detection. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Electrochemical force microscopy

DOEpatents

Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

2017-01-10

A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

Materials based on carbon-filled porous layers of PVC cyclam derivatives cross-linked with the surfaces of asbestos fabric fibers

NASA Astrophysics Data System (ADS)

Tzivadze, A. Yu.; Fridman, A. Ya.; Morozova, E. M.; Sokolova, N. P.; Voloshchuk, A. M.; Petukhova, G. A.; Bardishev, I. I.; Gorbunov, A. M.; Novikov, A. K.; Polyakova, I. Ya.; Titova, V. N.; Yavich, A. A.; Petrova, N. V.

2016-08-01

The synthesis of bilayer materials with porous upper layers composed of PVC hydroxyethylcyclam derivatives filled with carbon and a layer consisting of hydroxyethylcyclam, cross-linked via Si-O-C groups with the silica chains of a developed surface of asbestos fabric, is described. The aza-crown groups in these materials are bound with aqua complexes of H2SO4 or NaOH. The structure of the materials is examined, their adsorption characteristics are determined, and the rate of motion of H+ or OH- ions in electrochemical bridges is measured, while the formation of H2 and O2 in their cathodic and anodic polarization is determined as a function of voltage. It is shown that the upper layer of these materials is adsorption-active and electronand H+- or OH-- conductive, while the bottom layer is only H+- or OH-- conductive; through it, the upper layer is supplied with the H+ or OH- ions needed for the regeneration of the aqua complexes broken down to H2 and O2 on carbon particles.

Active corrosion protection performance of an epoxy coating applied on the mild steel modified with an eco-friendly sol-gel film impregnated with green corrosion inhibitor loaded nanocontainers

NASA Astrophysics Data System (ADS)

Izadi, M.; Shahrabi, T.; Ramezanzadeh, B.

2018-05-01

In this study the corrosion resistance, active protection, and cathodic disbonding performance of an epoxy coating were improved through surface modification of steel by a hybrid sol-gel system filled with green corrosion inhibitors loaded nanocontainer as intermediate layer on mild steel substrate. The green inhibitor loaded nanocontainers (GIN) were used to induce active inhibition performance in the protective coating system. The corrosion protection performance of the coated panels was investigated by electrochemical impedance spectroscopy (EIS), salt spray, and cathodic disbonding tests. It was observed that the corrosion inhibition performance of the coated mild steel panels was significantly improved by utilization of active multilayer coating system. The inhibitor release from nanocontainers at the epoxy-silane film/steel interface resulted in the anodic and cathodic reactions restriction, leading to the lower coating delamination from the substrate and corrosion products progress. Also, the active inhibition performance of the coating system was approved by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and energy dispersive X-ray (EDS) analysis on the panels with artificial defects. The inhibitive agents were released to the scratch region and blocked the active sites on the metal surface.

Battery and fuel cell electrodes containing stainless steel charging additive

DOEpatents

Zuckerbrod, David; Gibney, Ann

1984-01-01

An electrode for use in electrochemical energy cells is made, comprising a hydrophilic layer and a hydrophobic layer, where the hydrophilic layer comprises a hydrophilic composite which includes: (i) carbon particles; (ii) stainless steel particles; (iii) a nonwetting agent; and (iv) a catalyst, where at least one current collector contacts said composite.

Layer-by-layer composite film of nickel phthalocyanine and montmorillonite clay for synergistic effect on electrochemical detection of dopamine

NASA Astrophysics Data System (ADS)

de Lucena, Nathalia C.; Miyazaki, Celina M.; Shimizu, Flávio M.; Constantino, Carlos J. L.; Ferreira, Marystela

2018-04-01

Dopamine (DA) abnormal levels are related to diseases which makes important the development of fast, reliable, low-cost and sensitive devices for diagnosis and pharmaceutical controls. Nanostructured film composite of sodium montmorillonite clay (Na+MMT) and nickel phthalocyanine (NiTsPc) was self-assembled by layer-by-layer (LbL) technique and applied as electrochemical sensor for DA in the presence of common natural interferents as ascorbic acid (AA) and uric acid (UA). Three different LbL architecture films were investigated: LbL films of clay (PEI/Na+MMT) and phthalocyanine (PEI/NiTsPc) in a bilayer structure with a conventional polyelectrolyte (PEI) and a composite film formed by both materials to verify the synergistic effect in the LbL film in a quadri-layer assembly (PEI/Na+MMT/PEI/NiTsPc). Structural characterization indicated molecular level interactions between the layers forming the LbL films. The ITO/(PEI/Na+MMT/PEI/NiTsPc)10 electrode exhibited a LOD of 1.0 μmol L-1 and linear range 5-150 μmol L-1.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

DOE PAGES

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.; ...

2015-08-10

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

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

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

PubMed

Wetzel, David J; Malone, Marvin A; Haasch, Richard T; Meng, Yifei; Vieker, Henning; Hahn, Nathan T; Gölzhäuser, Armin; Zuo, Jian-Min; Zavadil, Kevin R; Gewirth, Andrew A; Nuzzo, Ralph G

2015-08-26

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

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).

Influence of the charge double layer on solid oxide fuel cell stack behavior

NASA Astrophysics Data System (ADS)

Whiston, Michael M.; Bilec, Melissa M.; Schaefer, Laura A.

2015-10-01

While the charge double layer effect has traditionally been characterized as a millisecond phenomenon, longer timescales may be possible under certain operating conditions. This study simulates the dynamic response of a previously developed solid oxide fuel cell (SOFC) stack model that incorporates the charge double layer via an equivalent circuit. The model is simulated under step load changes. Baseline conditions are first defined, followed by consideration of minor and major deviations from the baseline case. This study also investigates the behavior of the SOFC stack with a relatively large double layer capacitance value, as well as operation of the SOFC stack under proportional-integral (PI) control. Results indicate that the presence of the charge double layer influences the SOFC stack's settling time significantly under the following conditions: (i) activation and concentration polarizations are significantly increased, or (ii) a large value of the double layer capacitance is assumed. Under normal (baseline) operation, on the other hand, the charge double layer effect diminishes within milliseconds, as expected. It seems reasonable, then, to neglect the charge double layer under normal operation. However, careful consideration should be given to potential variations in operation or material properties that may give rise to longer electrochemical settling times.

Tribochemical investigation of microelectronic materials

NASA Astrophysics Data System (ADS)

Kulkarni, Milind Sudhakar

To achieve efficient planarization with reduced device dimensions in integrated circuits, a better understanding of the physics, chemistry, and the complex interplay involved in chemical mechanical planarization (CMP) is needed. The CMP process takes place at the interface of the pad and wafer in the presence of the fluid slurry medium. The hardness of Cu is significantly less than the slurry abrasive particles which are usually alumina or silica. It has been accepted that a surface layer can protect the Cu surface from scratching during CMP. Four competing mechanisms in materials removal have been reported: the chemical dissolution of Cu, the mechanical removal through slurry abrasives, the formation of thin layer of Cu oxide and the sweeping surface material by slurry flow. Despite the previous investigation of Cu removal, the electrochemical properties of Cu surface layer is yet to be understood. The motivation of this research was to understand the fundamental aspects of removal mechanisms in terms of electrochemical interactions, chemical dissolution, mechanical wear, and factors affecting planarization. Since one of the major requirements in CMP is to have a high surface finish, i.e., low surface roughness, optimization of the surface finish in reference to various parameters was emphasized. Three approaches were used in this research: in situ measurement of material removal, exploration of the electropotential activation and passivation at the copper surface and modeling of the synergistic electrochemical-mechanical interactions on the copper surface. In this research, copper polishing experiments were conducted using a table top tribometer. A potentiostat was coupled with this tribometer. This combination enabled the evaluation of important variables such as applied pressure, polishing speed, slurry chemistry, pH, materials, and applied DC potential. Experiments were designed to understand the combined and individual effect of electrochemical interactions as well as mechanical impact during polishing. Extensive surface characterization was performed with AFM, SEM, TEM and XPS. An innovative method for direct material removal measurement on the nanometer scale was developed and used. Experimental observations were compared with the theoretically calculated material removal rate values. The synergistic effect of all of the components of the process, which result in a better quality surface finish was quantitatively evaluated for the first time. Impressed potential during CMP proved to be a controlling parameter in the material removal mechanism. Using the experimental results, a model was developed, which provided a practical insight into the CMP process. The research is expected to help with electrochemical material removal in copper planarization with low-k dielectrics.

Photoacoustic spectroscopy and the in situ characterization of the electrochemical interface

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

Vallet, C.E.

1988-01-01

Photoacoustics is a new spectroscopic method which has been used for in situ characterization of the electrochemical interface during the past ten years. The basic principles of the photoacoustic effect and the principal results of the Rosencwaig-Gersho theory are discussed in light of the usefulness of the method in electrochemical studies. Different experimental arrangements suitable for in situ electrode studies are presented. A review of the use to date of photoacoustics in electrochemistry includes studies of electrochromic systems, semiconductor electrodes, passivation layers, and of electrocatalytic mixed oxides. These works demonstrated that, with relatively simple apparatus, it was possible to detectmore » and to characterize very thin layers formed on electrodes. It is still not clear whether in most cases photoacoustic spectroscopy has an overwhelming advantage over well-established optical methods for adsorption measurements; however, all the potentialities of the method have yet to be explored. 73 refs., 6 figs.« less

Effect of Pd Interlayer on Electrochemical Properties of ENIG Surface Finish in 3.5 wt.% NaCl Solution

NASA Astrophysics Data System (ADS)

Nam, N. D.; Bui, Q. V.; Nhan, H. T.; Phuong, D. V.; Bian, M. Z.

2014-09-01

The corrosion resistance of a multilayered (NiP-Pd-Au) coating with various thicknesses of palladium (Pd) interlayer deposited on copper by an electroless method was investigated using electrochemical techniques including potentiodynamic polarization and electrochemical impedance spectroscopy. In addition, the surface finish was examined by x-ray diffraction analysis and scanning electron microscopy, and the contact angle of the liquid-solid interface was recorded. The corrosion resistance of the copper substrate was considerably improved by Pd interlayer addition. Increase of the thickness of the Pd interlayer enhanced the performance of the Cu-NiP-Pd-Au coating due to low porosity, high protective efficiency, high charge-transfer resistance, and contact angle. These are attributed to the diffusion of layers in the Cu-NiP-Pd-Au coating acting as a physical barrier layer, leading to the protection provided by the coating.

Defect physics vis-à-vis electrochemical performance in layered mixed-metal oxide cathode materials

NASA Astrophysics Data System (ADS)

Hoang, Khang; Johannes, Michelle

Layered mixed-metal oxides with different compositions of (Ni,Co,Mn) [NCM] or (Ni,Co,Al) [NCA] have been used in commercial lithium-ion batteries. Yet their defect physics and chemistry is still not well understood, despite having important implications for the electrochemical performance. In this presentation, we report a hybrid density functional study of intrinsic point defects in the compositions LiNi1/3Co1/3Mn1/3O2 (NCM1/3) and LiNi1/3Co1/3Al1/3O2 (NCA1/3) which can also be regarded as model compounds for NCM and NCA. We will discuss defect landscapes in NCM1/3 and NCA1/3 under relevant synthesis conditions with a focus on the formation of metal antisite defects and its implications on the electrochemical properties and ultimately the design of NCM and NCA cathode materials.

Promoting Effect of Layered Titanium Phosphate on the Electrochemical and Photovoltaic Performance of Dye-Sensitized Solar Cells

PubMed Central

2010-01-01

We reported a composite electrolyte prepared by incorporating layered α-titanium phosphate (α-TiP) into an iodide-based electrolyte using 1-ethyl-3-methylimidazolium tetrafluoroborate(EmimBF4) ionic liquid as solvent. The obtained composite electrolyte exhibited excellent electrochemical and photovoltaic properties compared to pure ionic liquid electrolyte. Both the diffusion coefficient of triiodide (I3−) in the electrolyte and the charge-transfer reaction at the electrode/electrolyte interface were improved markedly. The mechanism for the enhanced electrochemical properties of the composite electrolyte was discussed. The highest conversion efficiency of dye-sensitized solar cell (DSSC) was obtained for the composite electrolyte containing 1wt% α-TiP, with an improvement of 58% in the conversion efficiency than the blank one, which offered a broad prospect for the fabrication of stable DSSCs with a high conversion efficiency. PMID:20676195

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

1992-01-01

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Recent advances in polymer supporting layered double hydroxides nanocomposite for electrochemical biosensors

NASA Astrophysics Data System (ADS)

Dhanasekaran, T.; Padmanaban, A.; Gnanamoorthy, G.; Manigandan, R.; Praveen Kumar, S.; Stephen, A.; Narayanan, V.

2018-01-01

In recent years, layered double hydroxides (LDHs) materials having emerging due to their ability of intercalate a variety of anions, either organic or inorganic molecules. The most significance of the LDHs has been found potential applications in catalysis, wastewater treatment, and electrochemical sensors. The Mg-Al LDHs (MAL) and Poly-o-phenylenediamine @ Mg-Al LDHs (P-MAL) was prepared via simple one step hydrothermal method. As prepared material was characterized using many techniques such as, the structural and crystal phase was determined from XRD and Raman analyses. The functional groups were depicted using FT-IR spectroscopy. The optical propertied studied using diffuse reflectance spectroscopy UV-vis spectroscopy and the emission property were analyzed from Photoluminescence spectroscopy. The surface morphology and average particle size was analyzed using FESEM microscopy. The prepared polymer composite material P-MAL was further used for highly sensitive electrochemical detection towards dopamine (DA).

A comparative study of layered transition metal oxide cathodes for application in sodium-ion battery.

PubMed

Hasa, Ivana; Buchholz, Daniel; Passerini, Stefano; Hassoun, Jusef

2015-03-11

Herein, we report a study on P-type layered sodium transition metal-based oxides with a general formula of NaxMO2 (M = Ni, Fe, Mn). We synthesize the materials via coprecipitation followed by annealing in air and rinsing with water, and we examine the electrodes as cathodes for sodium-ion batteries using a propylene carbonate-based electrolyte. We fully investigate the effect of the Ni-to-Fe ratio, annealing temperature, and sodium content on the electrochemical performances of the electrodes. The impact of these parameters on the structural and electrochemical properties of the materials is revealed by X-ray diffraction, scanning electron microscopy, and cyclic voltammetry, respectively. The suitability of this class of P-type materials for sodium battery application is finally demonstrated by cycling tests revealing an excellent electrochemical performance in terms of delivered capacity (i.e., about 200 mAh g(-1)) and charge-discharge efficiency (approaching 100%).

Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

NASA Astrophysics Data System (ADS)

Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

2014-03-01

We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures

NASA Astrophysics Data System (ADS)

Zhang, Yifu; Zheng, Jiqi; Wang, Qiushi; Hu, Tao; Tian, Fuping; Meng, Changgong

2017-03-01

Layer-by-layer V2O5 structures self-assembly by quadrate sheets like "multilayer cake" were successfully synthesized using NH4VO3 as the vanadium sources by a facile hydrothermal route and combination of the calcination. The structure and composition were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectrometer, X-ray powder diffraction, Raman and Fourier transform infrared spectroscopy. The optical properties of the as-obtained V2O5 layer-by-layer structures were investigated by the Ultraviolet-visible spectroscopy and photoluminescence spectrum. The electrochemical properties of the as-obtained V2O5 layer-by-layer structures as electrodes in supercapacitor device were measured by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) both in the aqueous and organic electrolyte. The specific capacitance is 347 F g-1 at 1 A g-1 in organic electrolyte, which is improved by 46% compared with 238 F g-1 in aqueous electrolyte. During the cycle performance, the specific capacitances of V2O5 layer-by-layer structures after 100 cycles are 30% and 82% of the initial discharge capacity in the aqueous and organic electrolyte, respectively, indicating the cycle performance is significantly improved in organic electrolyte. Our results turn out that layer-by-layer V2O5 structures are an ideal material for supercapacitor electrode in the present work.

Optical and electrical nano eco-sensors using alternative deposition of charged layer

NASA Astrophysics Data System (ADS)

Ahmed, Syed Rahin; Hong, Seong Cheol; Lee, Jaebeom

2011-03-01

This review focuses on layer by layer (LBL) assembly-based nano ecological sensor (hereafter, eco-sensor) for pesticide detection, which is one of the most versatile methods. The effects of pesticides on human health and on the environment (air, water, soil, plants, and animals) are of great concern due to their increasing use. We highlight two of the most popular detecting methods, i.e., fluorescence and electrochemical detection of pesticides on an LBL assembly. Fluorescence materials are of great interest among researchers for their sensitivity and reliable detection, and electrochemical processes allow us to investigate synergistic interactions among film components through charge transfer mechanisms in LBL film at the molecular level. Then, we noted some prospective directions for development of different types of sensing systems.

Electrochemical Atomic Layer Epitaxy of Thin Film CdSe

NASA Astrophysics Data System (ADS)

Pham, L.; Kaleida, K.; Happek, U.; Mathe, M. K.; Vaidyanathan, R.; Stickney, J. L.; Radevic, M.

2002-10-01

Electrochemical atomic layer epitaxy (EC-ALE) is a current developmental technique for the fabrication of compound semiconductor thin films. The deposition of elements making up the compound utilizes surface limited reactions where the potential is less than that required for bulk growth. This growth method offers mono-atomic layer control, allowing the deposition of superlattices with sharp interfaces. Here we report on the EC-ALE formation of CdSe thin films on Au and Cu substrates using an automated flow cell system. The band gap was measured using IR absorption and photoconductivity and found to be consistent with the literature value of 1.74 eV at 300K and 1.85 eV at 20K. The stoichiometry of the thin film was confirmed with electron microprobe analysis and x-ray diffraction.

Influence of mill scale and rust layer on the corrosion resistance of low-alloy steel in simulated concrete pore solution

NASA Astrophysics Data System (ADS)

Shi, Jin-jie; Ming, Jing

2017-01-01

Electrochemical impedance spectroscopy, cyclic potentiodynamic polarization measurements, and scanning electron microscopy in conjunction with energy-dispersive X-ray spectroscopy were used to investigate the influence of mill scale and rust layer on the passivation capability and chloride-induced corrosion behaviors of conventional low-carbon (LC) steel and low-alloy (LA) steel in simulated concrete pore solution. The results show that mill scale exerts different influences on the corrosion resistance of both steels at various electrochemical stages. We propose that the high long-term corrosion resistance of LA steel is mainly achieved through the synergistic effect of a gradually formed compact, adherent and well-distributed Cr-enriched inner rust layer and the physical barrier protection effect of mill scale.

A new self-assembled layer-by-layer glucose biosensor based on chitosan biopolymer entrapped enzyme with nitrogen doped graphene.

PubMed

Barsan, Madalina M; David, Melinda; Florescu, Monica; Ţugulea, Laura; Brett, Christopher M A

2014-10-01

The layer-by-layer (LbL) technique has been used for the construction of a new enzyme biosensor. Multilayer films containing glucose oxidase, GOx, and nitrogen-doped graphene (NG) dispersed in the biocompatible positively-charged polymer chitosan (chit(+)(NG+GOx)), together with the negatively charged polymer poly(styrene sulfonate), PSS(-), were assembled by alternately immersing a gold electrode substrate in chit(+)(NG+GOx) and PSS(-) solutions. Gravimetric monitoring during LbL assembly by an electrochemical quartz microbalance enabled investigation of the adsorption mechanism and deposited mass for each monolayer. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the LbL modified electrodes, in order to establish the contribution of each monolayer to the overall electrochemical properties of the biosensor. The importance of NG in the biosensor architecture was evaluated by undertaking a comparative study without NG in the chit layer. The GOx biosensor's analytical properties were evaluated by fixed potential chronoamperometry and compared with similar reported biosensors. The biosensor operates at a low potential of -0.2V vs., Ag/AgCl, exhibiting a high sensitivity of 10.5 μA cm(-2) mM(-1), and a detection limit of 64 μM. This study shows a simple approach in developing new biosensor architectures, combining the advantages of nitrogen-doped graphene with the LbL technique for enzyme immobilization. Copyright © 2014 Elsevier B.V. All rights reserved.

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

PubMed Central

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

Electrochemical Cathodic Polarization, a Simplified Method That Can Modified and Increase the Biological Activity of Titanium Surfaces: A Systematic Review

PubMed Central

2016-01-01

Background The cathodic polarization seems to be an electrochemical method capable of modifying and coat biomolecules on titanium surfaces, improving the surface activity and promoting better biological responses. Objective The aim of the systematic review is to assess the scientific literature to evaluate the cellular response produced by treatment of titanium surfaces by applying the cathodic polarization technique. Data, Sources, and Selection The literature search was performed in several databases including PubMed, Web of Science, Scopus, Science Direct, Scielo and EBSCO Host, until June 2016, with no limits used. Eligibility criteria were used and quality assessment was performed following slightly modified ARRIVE and SYRCLE guidelines for cellular studies and animal research. Results Thirteen studies accomplished the inclusion criteria and were considered in the review. The quality of reporting studies in animal models was low and for the in vitro studies it was high. The in vitro and in vivo results reported that the use of cathodic polarization promoted hydride surfaces, effective deposition, and adhesion of the coated biomolecules. In the experimental groups that used the electrochemical method, cellular viability, proliferation, adhesion, differentiation, or bone growth were better or comparable with the control groups. Conclusions The use of the cathodic polarization method to modify titanium surfaces seems to be an interesting method that could produce active layers and consequently enhance cellular response, in vitro and in vivo animal model studies. PMID:27441840

Alizarin Red S-Confined Layer-By-Layer Films as Redox-Active Coatings on Electrodes for the Voltammetric Determination of L-Dopa

PubMed Central

Takahashi, Shigehiro; Suzuki, Iwao; Sugawara, Tatsuro; Seno, Masaru; Minaki, Daichi; Anzai, Jun-Ichi

2017-01-01

The preparation of redox-active coatings is a key step in fabricating electrochemical biosensors. To this goal, a variety of coating materials have been used in combination with redox-active compounds. In this study, alizarin red S (ARS) was confined in layer-by-layer (LbL) films composed of poly(ethyleneimine) (PEI) and carboxymethylcellulose (CMC) to study the redox properties. A gold (Au) disc electrode coated with PEI/CMC LbL film was immersed in an ARS solution to uptake ARS into the film. ARS was successfully confined in the LbL film through electrostatic interactions. The cyclic voltammogram (CV) of ARS-confined PEI/CMC film-coated electrodes thus prepared exhibited redox waves in the potential range from −0.5 to −0.7 V originating from 9,10-anthraquinone moiety in ARS, demonstrating that ARS preserves its redox activity in the LbL film. An additional oxidation peak appeared around −0.4 V in the CV recorded in the solution containing phenylboronic acid (PBA), due to the formation of a boronate ester of ARS (ARS-PBA) in the film. The oxidation peak current at −0.4 V decreased upon addition of 3,4-dihydroxyphenylalanine (L-dopa) to the solution. Thus, the results suggest a potential use of the ARS-confined PEI/CMC films for constructing voltammetric sensors for L-dopa. PMID:28772942

Nanohybrids from NiCoAl-LDH coupled with carbon for pseudocapacitors: understanding the role of nano-structured carbon

NASA Astrophysics Data System (ADS)

Yu, Chang; Yang, Juan; Zhao, Changtai; Fan, Xiaoming; Wang, Gang; Qiu, Jieshan

2014-02-01

Transition metal layered double hydroxides (LDHs) are one of the great potential electrode materials for pseudocapacitors. However, the aggregation and low conductivity of these metal compounds will constrain electrolyte ion and electron transfer and further affect their electrochemical performances. The nano-structured carbon coupled with the LDH matrix can act as an active component or conducting scaffold to enhance or improve the rate capacity and cycle life. Here, various nano-structured carbon species, including zero-dimensional carbon black (CB), one-dimensional carbon nanotubes (CNTs), two-dimensional reduced graphene oxide (RGO), and CNT/RGO composites were used to couple with the NiCoAl-LDHs to construct LDH-carbon nanohybrid electrodes for pseudocapacitors, and the role of the nanostructured carbon was investigated and discussed in terms of the pore structure of nanohybrids and electrical conductivity. The results show that all of the carbons can be well incorporated into the LDH nanosheets to form homogeneous nanohybrid materials. The pore structure properties and electrical conductivity of nanohybrids have statistically significant effects on the electrochemical performances of the LDH-carbon nanohybrids. Of the electrodes adopted, the nanohybrid electrode consisting of NiCoAl-LDHs, CNTs, and RGO exhibits excellent electrochemical performance with a specific capacitance as high as 1188 F g-1 at a current density of 1 A g-1 due to the synergistic effect of NiCoAl-LDHs, RGO, and CNTs, in which the RGO nanosheets are favorable for high specific surface area while the CNT has a fast electron transport path for enhancing the electrical conductivity of nanohybrids. This will shed a new light on the effect of nano-structured carbon within the electrode matrix on the electrochemical activity and open a new way for the carbon-related electrode configuration/design for supercapacitors, and other energy storage and conversion devices.Transition metal layered double hydroxides (LDHs) are one of the great potential electrode materials for pseudocapacitors. However, the aggregation and low conductivity of these metal compounds will constrain electrolyte ion and electron transfer and further affect their electrochemical performances. The nano-structured carbon coupled with the LDH matrix can act as an active component or conducting scaffold to enhance or improve the rate capacity and cycle life. Here, various nano-structured carbon species, including zero-dimensional carbon black (CB), one-dimensional carbon nanotubes (CNTs), two-dimensional reduced graphene oxide (RGO), and CNT/RGO composites were used to couple with the NiCoAl-LDHs to construct LDH-carbon nanohybrid electrodes for pseudocapacitors, and the role of the nanostructured carbon was investigated and discussed in terms of the pore structure of nanohybrids and electrical conductivity. The results show that all of the carbons can be well incorporated into the LDH nanosheets to form homogeneous nanohybrid materials. The pore structure properties and electrical conductivity of nanohybrids have statistically significant effects on the electrochemical performances of the LDH-carbon nanohybrids. Of the electrodes adopted, the nanohybrid electrode consisting of NiCoAl-LDHs, CNTs, and RGO exhibits excellent electrochemical performance with a specific capacitance as high as 1188 F g-1 at a current density of 1 A g-1 due to the synergistic effect of NiCoAl-LDHs, RGO, and CNTs, in which the RGO nanosheets are favorable for high specific surface area while the CNT has a fast electron transport path for enhancing the electrical conductivity of nanohybrids. This will shed a new light on the effect of nano-structured carbon within the electrode matrix on the electrochemical activity and open a new way for the carbon-related electrode configuration/design for supercapacitors, and other energy storage and conversion devices. Electronic supplementary information available: FE-SEM images, TEM images, TGA curves, nitrogen adsorption/desorption isotherms, and the corresponding pore size distribution as well as the current-voltage (I-V) curves of LDH-carbon nanohybrids. See DOI: 10.1039/c3nr05477b

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

LiNi1/3Co1/3Mn1/3O2 nanoplates with {010} active planes exposing prepared in polyol medium as a high-performance cathode for Li-ion battery.

PubMed

Li, Jili; Yao, Ruimin; Cao, Chuanbao

2014-04-09

As we know, Li(+)-ion transport in layered LiNi1/3Co1/3Mn1/3O2 (NCM) is through two-dimensional channels parallel to the Li(+)-ion layers that are indexed as {010} active planes. In this paper, NCM nanoplates with exposed {010} active facets are synthesized in a polyol medium (ethylene glycol) and characterized by XRD, XPS, SEM, and HR-TEM. In addition, the effects of reaction conditions on the morphologies, structures and electrochemical performances are also evaluated. The results show that more {010} facets can be exposed with the thickness of NCM nanoplates increasing which can lead to more channels for Li(+)-ion migration. However, when the annealing temperatures exceed 900 °C, many new crystal planes grow along the thickness direction covering the {010} facets. In all of the NCM nanoplates obtained at different conditions, the NCM nanoplates calcined at 850 °C for 12 h (NCM-850-12H) display a high initial discharge capacity of 207.6 mAh g(-1) at 0.1 C (1 C = 200 mA g(-1)) between 2.5 and 4.5 V higher than most of NCM materials as cathodes for lithium ion batteries. The discharge capacities of NCM-850-12H are 169.8, 160.5, and 149.3 mAh g(-1) at 2, 5, and 7 C, respectively, illustrating the excellent rate capability. The superior electrochemical performance of NCM-850-12H cathode can be attributed to more {010} active planes exposure.

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.

Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes

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

Britto, Reuben J.; Benck, Jesse D.; Young, James L.

2016-06-02

Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis since MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, andmore » light limited current density) after 60 hours of operation. This represents a five-hundred fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions.« less

Sequential Injection/Electrochemical Immunoassay for Quantifying the Pesticide Metabolite 3, 5, 6-Trichloro-2-Pyridinol

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

Liu, Guodong; Riechers, Shawn L.; Timchalk, Chuck

2005-12-04

An automated and sensitive sequential injection electrochemical immunoassay was developed to monitor a potential insecticide biomarker, 3, 5, 6-trichloro-2-pyridinol. The current method involved a sequential injection analysis (SIA) system equipped with a thin-layer electrochemical flow cell and permanent magnet, which was used to fix 3,5,6-trichloro-2-pyridinol (TCP) antibody coated magnetic beads (TCP-Ab-MBs) in the reaction zone. After competitive immunoreactions among TCP-Ab-MBs, TCP analyte, and horseradish peroxidase (HRP) labeled TCP, a 3, 3?, 5, 5?-tetramethylbenzidine dihydrochloride and hydrogen peroxide (TMB-H2O2) substrate solution was injected to produce an electroactive enzymatic product. The activity of HRP tracers was monitored by a square wave voltammetricmore » scanning electroactive enzymatic product in the thin-layer flow cell. The voltammetric characteristics of the substrate and the enzymatic product were investigated under batch conditions, and the parameters of the immunoassay were optimized in the SIA system. Under the optimal conditions, the system was used to measure as low as 6 ng L-1 (ppt) TCP, which is around 50-fold lower than the value indicated by the manufacturer of the TCP RaPID Assay? kit (0.25 ug/L, colorimetric detection). The performance of the developed immunoassay system was successfully evaluated on tap water and river water samples spiked with TCP. This technique could be readily used for detecting other environmental contaminants by developing specific antibodies against contaminants and is expected to open new opportunities for environmental and biological monitoring.« less

Engineering the Pores of Biomass-Derived Carbon: Insights for Achieving Ultrahigh Stability at High Power in High-Energy Supercapacitors.

PubMed

Thangavel, Ranjith; Kaliyappan, Karthikeyan; Ramasamy, Hari Vignesh; Sun, Xueliang; Lee, Yun-Sung

2017-07-10

Electrochemical supercapacitors with high energy density are promising devices due to their simple construction and long-term cycling performance. The development of a supercapacitor based on electrical double-layer charge storage with high energy density that can preserve its cyclability at higher power presents an ongoing challenge. Herein, we provide insights to achieve a high energy density at high power with an ultrahigh stability in an electrical double-layer capacitor (EDLC) system by using carbon from a biomass precursor (cinnamon sticks) in a sodium ion-based organic electrolyte. Herein, we investigated the dependence of EDLC performance on structural, textural, and functional properties of porous carbon engineered by using various activation agents. The results demonstrate that the performance of EDLCs is not only dependent on their textural properties but also on their structural features and surface functionalities, as is evident from the electrochemical studies. The electrochemical results are highly promising and revealed that the porous carbon with poor textural properties has great potential to deliver high capacitance and outstanding stability over 300 000 cycles compared with porous carbon with good textural properties. A very low capacitance degradation of around 0.066 % per 1000 cycles, along with high energy density (≈71 Wh kg -1 ) and high power density, have been achieved. These results offer a new platform for the application of low-surface-area biomass-derived carbons in the design of highly stable high-energy supercapacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray photoelectron spectroscopy and electrochemical studies of mild steel FeE500 passivation in concrete simulated water

NASA Astrophysics Data System (ADS)

Miserque, F.; Huet, B.; Azou, G.; Bendjaballah, D.; L'Hostis, V.

2006-11-01

In the context of the prediction of the long-term behaviour of reinforced concrete structures involved in the nuclear waste storage, the corrosion mechanisms of steels have to be assessed. When mild steel rebars are embedded in concrete, the chemical environment of the reinforcement is progressively modified, due to the carbonation of the concrete matrix. This modification leads to the variation of iron oxides properties formed at the steel/concrete interface, and the active corrosion can be initiated. The aim of this study is to evaluate the passivation behaviour and to provide insights into the depassivation of mild steel in concrete pore solution. In a young concrete, due to the alkalinity of the interstitial solution, steel reinforcement remains passive. Immersion tests of mild steel substrate in various alkaline solutions (from pH 13 to 10) have been performed. Due to the low thickness of the corrosion layers formed, X-ray photoelectron spectroscopy has been used to characterize them. In the passive domain, the corrosion products are similar for the various solutions. The corrosion layer is composed of a mixture of Fe3+ and Fe2+. A similar approach is used to determine the depassivation mechanism. The effect of various components such as carbonates, sulfates and silicates resulting from the dissolution of minerals of cement during the carbonation process is investigated. In addition to the surface analysis, the evolution of the electrochemical behaviour as function of the solution nature (pH) is evaluated with the help of electrochemical measurements (free corrosion potential, cyclic voltamperometry).

Electrochemical planarization

DOEpatents

Bernhardt, A.F.; Contolini, R.J.

1993-10-26

In a process for fabricating planarized thin film metal interconnects for integrated circuit structures, a planarized metal layer is etched back to the underlying dielectric layer by electropolishing, ion milling or other procedure. Electropolishing reduces processing time from hours to minutes and allows batch processing of multiple wafers. The etched back planarized thin film interconnect is flush with the dielectric layer. 12 figures.

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

Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Lei, Fengcai; Liu, Wei; Sun, Yongfu; Xu, Jiaqi; Liu, Katong; Liang, Liang; Yao, Tao; Pan, Bicai; Wei, Shiqiang; Xie, Yi

2016-09-01

Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin-tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis.

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

PubMed

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

PubMed Central

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-01-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

DOE PAGES

Qiu, Bao; Zhang, Minghao; Wu, Lijun; ...

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high asmore » 301 mAh g –1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g –1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.« 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

System-based approach for an advanced drug delivery platform

NASA Astrophysics Data System (ADS)

Kulinsky, Lawrence; Xu, Han; Tsai, Han-Kuan A.; Madou, Marc

2006-03-01

Present study is looking at the problem of integrating drug delivery microcapsule, a bio-sensor, and a control mechanism into a biomedical drug delivery system. A wide range of medical practices from cancer therapy to gastroenterological treatments can benefit from such novel bio-system. Drug release in our drug delivery system is achieved by electrochemically actuating an array of polymeric valves on a set of drug reservoirs. The valves are bi-layer structures, made in the shape of a flap hinged on one side to a valve seat, and consisting of thin films of evaporated gold and electrochemically deposited polypyrrole (PPy). These thin PPy(DBS) bi-layer flaps cover access holes of underlying chambers micromachined in a silicon substrate. Chromium and polyimide layers are applied to implement "differential adhesion" to obtain a voltage induced deflection of the bilayer away from the drug reservoir. The Cr is an adhesion-promoting layer, which is used to strongly bind the gold layer down to the substrate, whereas the gold adheres weakly to polyimide. Drug actives (dry or wet) were pre-stored in the chambers and their release is achieved upon the application of a small bias (~ 1V). Negative voltage causes cation adsorption and volume change in PPy film. This translates into the bending of the PPy/Au bi-layer actuator and release of the drug from reservoirs. This design of the drug delivery module is miniaturized to the dimensions of 200μm valve diameter. Galvanostatic and potentiostatic PPy deposition methods were compared, and potentiostatic deposition method yields film of more uniform thickness. PPy deposition experiments with various pyrrole and NaDBS concentrations were also performed. Glucose biosensor based on glucose oxidase (GOx) embedded in the PPy matrix during elechtrochemical deposition was manufactured and successfully tested. Multiple-drug pulsatile release and continuous linear release patterns can be implemented by controlling the operation of an array of valves. Varying amounts of drugs, together with more complex controlling strategies would allow creation of more complex drug delivery patterns.

Anticorrosion efficiency of ultrasonically deposited silica coatings on titanium

NASA Astrophysics Data System (ADS)

Ertaş, Fatma Sinem; Kaş, Recep; Mikó, Annamária; Birer, Özgür

2013-07-01

We utilized high intensity ultrasound to prepare coatings of silica and organically modified silica composed of multiple layers of densely packed nanoparticles. Ultrasound was used to collide nanoparticles onto an activated titanium surface with high speed. Large areas could be homogeneously coated by this method. These coatings were characterized by spectroscopy and microscopy methods and the anticorrosion efficiency in NaCl solution was evaluated by electrochemical measurements. The results indicated that the composite coatings provided good quality barrier layer on bare titanium and decreased the anodic corrosion rate. It was found that increase in the organic content of the coating shifted the passivation potential towards more positive direction. The comparison of the impedance results recorded at the corrosion potential pointed out that in each case a good quality barrier layer was formed on the titanium surface. The outstanding corrosion resistance of the composite coatings with only ~200 nm thickness shows that ultrasound assisted deposition can be a competitive method to obtain corrosion protective layers.

Electrochemical Approach for Effective Antifouling and Antimicrobial Surfaces.

PubMed

Gaw, Sheng Long; Sarkar, Sujoy; Nir, Sivan; Schnell, Yafit; Mandler, Daniel; Xu, Zhichuan J; Lee, Pooi See; Reches, Meital

2017-08-09

Biofouling, the adsorption of organisms to a surface, is a major problem today in many areas of our lives. This includes: (i) health, as biofouling on medical device leads to hospital-acquired infections, (ii) water, since the accumulation of organisms on membranes and pipes in desalination systems harms the function of the system, and (iii) energy, due to the heavy load of the organic layer that accumulates on marine vessels and causes a larger consumption of fuel. This paper presents an effective electrochemical approach for generating antifouling and antimicrobial surfaces. Distinct from previously reported antifouling or antimicrobial electrochemical studies, we demonstrate the formation of a hydrogen gas bubble layer through the application of a low-voltage square-waveform pulses to the conductive surface. This electrochemically generated gas bubble layer serves as a separation barrier between the surroundings and the target surface where the adhesion of bacteria can be deterred. Our results indicate that this barrier could effectively reduce the adsorption of bacteria to the surface by 99.5%. We propose that the antimicrobial mechanism correlates with the fundamental of hydrogen evolution reaction (HER). HER leads to an arid environment that does not allow the existence of live bacteria. In addition, we show that this drought condition kills the preadhered bacteria on the surface due to water stress. This work serves as the basis for the exploration of future self-sustainable antifouling techniques such as incorporating it with photocatalytic and photoelectrochemical reactions.

Electrochemical formation of field emitters

DOEpatents

Bernhardt, Anthony F.

1999-01-01

Electrochemical formation of field emitters, particularly useful in the fabrication of flat panel displays. The fabrication involves field emitting points in a gated field emitter structure. Metal field emitters are formed by electroplating and the shape of the formed emitter is controlled by the potential imposed on the gate as well as on a separate counter electrode. This allows sharp emitters to be formed in a more inexpensive and manufacturable process than vacuum deposition processes used at present. The fabrication process involves etching of the gate metal and the dielectric layer down to the resistor layer, and then electroplating the etched area and forming an electroplated emitter point in the etched area.

Corrosion Behavior of Weathering Steel Under Thin Electrolyte Layer at Different Relative Humidity

NASA Astrophysics Data System (ADS)

Xia, Yan; Liu, Pan; Zhang, Jianqing; Cao, Fahe

2018-01-01

The corrosion behavior of weathering steel under thin electrolyte layer (TEL) at different relative humidity (RH) was investigated by cathodic polarization, electrochemical impedance spectroscopy, electrochemical noise, SEM/EDS, XRD and Raman spectroscopy. The results indicate that during the initial stage, the corrosion rate increases as the RH decreases when the initial thickness of TEL is above 100 μm. During the middle and final corrosion stages, the corrosion behavior of weathering steel is influenced by RH, the initial thickness of TEL and corrosion product. The TEL corrosion is divided into three types, and a weathering steel corrosion model under TEL and bulk solution is also proposed.

Layered electrodes for lithium cells and batteries

DOEpatents

Johnson; Christopher S. , Thackeray; Michael M. , Vaughey; John T. , Kahaian; Arthur J. , Kim; Jeom-Soo

2008-04-15

Lithium metal oxide compounds of nominal formula Li.sub.2MO.sub.2, in which M represents two or more positively charged metal ions, selected predominantly and preferably from the first row of transition metals are disclosed herein. The Li.sub.2MO.sub.2 compounds have a layered-type structure, which can be used as positive electrodes for lithium electrochemical cells, or as a precursor for the in-situ electrochemical fabrication of LiMO.sub.2 electrodes. The Li.sub.2MO.sub.2 compounds of the invention may have additional functions in lithium cells, for example, as end-of-discharge indicators, or as negative electrodes for lithium cells.

Safety shutdown separators

DOEpatents

Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

2015-06-30

The present invention pertains to electrochemical cells which comprise (a) an anode; (b) a cathode; (c) a solid porous separator, such as a polyolefin, xerogel, or inorganic oxide separator; and (d) a nonaqueous electrolyte, wherein the separator comprises a porous membrane having a microporous coating comprising polymer particles which have not coalesced to form a continuous film. This microporous coating on the separator acts as a safety shutdown layer that rapidly increases the internal resistivity and shuts the cell down upon heating to an elevated temperature, such as 110.degree. C. Also provided are methods for increasing the safety of an electrochemical cell by utilizing such separators with a safety shutdown layer.

The role of AlF3 coatings in improving electrochemical cycling of Li-enriched nickel-manganese oxide electrodes for Li-ion batteries.

PubMed

Sun, Yang-Kook; Lee, Min-Joon; Yoon, Chong S; Hassoun, Jusef; Amine, Khalil; Scrosati, Bruno

2012-03-02

A Li[Li(0.19)Ni(0.16)Co(0.08)Mn(0.57)]O(2) cathode was coated with AlF(3) on the surface. The AlF(3)-coating enhanced the overall electrochemical characteristics of the electrode while overcoming the typical shortcomings of lithium-enriched cathodes. This improvement was attributed to the transformation of the initial electrode layer to a spinel phase, induced by the Li chemical leaching effect of the AlF(3) coating layer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corrosion resistance and biological activity of TiO2 implant coatings produced in oxygen-rich environments.

PubMed

Zhang, Rui; Wan, Yi; Ai, Xing; Liu, Zhanqiang; Zhang, Dong

2017-01-01

The physical and chemical properties of bio-titanium alloy implant surfaces play an important role in their corrosion resistance and biological activity. New turning and turning-rolling processes are presented, employing an oxygen-rich environment in order to obtain titanium dioxide layers that can both protect implants from corrosion and also promote cell adhesion. The surface topographies, surface roughnesses and chemical compositions of the sample surfaces were obtained using scanning electron microscopy, a white light interferometer, and the Auger electron spectroscopy, respectively. The corrosion resistance of the samples in a simulated body fluid was determined using electrochemical testing. Biological activity on the samples was also analyzed, using a vitro cell culture system. The results show that compared with titanium oxide layers formed using a turning process in air, the thickness of the titanium oxide layers formed using turning and turning-rolling processes in an oxygen-rich environment increased by 4.6 and 7.3 times, respectively. Using an oxygen-rich atmosphere in the rolling process greatly improves the corrosion resistance of the resulting samples in a simulated body fluid. On samples produced using the turning-rolling process, cells spread quickly and exhibited the best adhesion characteristics.

Modeling electrochemical deposition inside nanotubes to obtain metal-semiconductor multiscale nanocables or conical nanopores.

PubMed

Lebedev, Konstantin; Mafé, Salvador; Stroeve, Pieter

2005-08-04

Nanocables with a radial metal-semiconductor heterostructure have recently been prepared by electrochemical deposition inside metal nanotubes. First, a bare nanoporous polycarbonate track-etched membrane is coated uniformly with a metal film by electroless deposition. The film forms a working electrode for further deposition of a semiconductor layer that grows radially inside the nanopore when the deposition rate is slow. We propose a new physical model for the nanocable synthesis and study the effects of the deposited species concentration, potential-dependent reaction rate, and nanopore dimensions on the electrochemical deposition. The problem involves both axial diffusion through the nanopore and radial transport to the nanopore surface, with a surface reaction rate that depends on the axial position and the time. This is so because the radial potential drop across the deposited semiconductor layer changes with the layer thickness through the nanopore. Since axially uniform nanocables are needed for most applications, we consider the relative role of reaction and axial diffusion rates on the deposition process. However, in those cases where partial, empty-core deposition should be desirable (e.g., for producing conical nanopores to be used in single nanoparticle detection), we give conditions where asymmetric geometries can be experimentally realized.

Si-FeSi2/C nanocomposite anode materials produced by two-stage high-energy mechanical milling

NASA Astrophysics Data System (ADS)

Yang, Yun Mo; Loka, Chadrasekhar; Kim, Dong Phil; Joo, Sin Yong; Moon, Sung Whan; Choi, Yi Sik; Park, Jung Han; Lee, Kee-Sun

2017-05-01

High capacity retention Silicon-based nanocomposite anode materials have been extensively explored for use in lithium-ion rechargeable batteries. Here we report the preparation of Si-FeSi2/C nanocomposite through scalable a two-stage high-energy mechanical milling process, in which nano-scale Si-FeSi2 powders are besieged by the carbon (graphite/amorphous phase) layer; and investigation of their structure, morphology and electrochemical performance. Raman analysis revealed that the carbon layer structure comprised of graphitic and amorphous phase rather than a single amorphous phase. Anodes fabricated with the Si-FeSi2/C showed excellent electrochemical behavior such as a first discharge capacity of 1082 mAh g-1 and a high capacity retention until the 30th cycle. A remarkable coulombic efficiency of 99.5% was achieved within a few cycles. Differential capacity plots of the Si-FeSi2/C anodes revealed a stable lithium reaction with Si for lithiation/delithiation. The enhanced electrochemical properties of the Si-FeSi2/C nanocomposite are mainly attributed to the nano-size Si and stable solid electrolyte interface formation and highly conductive path driven by the carbon layer.

Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

An Electrochemical Quartz Crystal Microbalance Multisensor System Based on Phthalocyanine Nanostructured Films: Discrimination of Musts

PubMed Central

Garcia-Hernandez, Celia; Medina-Plaza, Cristina; Garcia-Cabezon, Cristina; Martin-Pedrosa, Fernando; del Valle, Isabel; de Saja, Jose Antonio; Rodríguez-Méndez, Maria Luz

2015-01-01

An array of electrochemical quartz crystal electrodes (EQCM) modified with nanostructured films based on phthalocyanines was developed and used to discriminate musts prepared from different varieties of grapes. Nanostructured films of iron, nickel and copper phthalocyanines were deposited on Pt/quartz crystals through the Layer by Layer technique by alternating layers of the corresponding phthalocyanine and poly-allylamine hydrochloride. Simultaneous electrochemical and mass measurements were used to study the mass changes accompanying the oxidation of electroactive species present in must samples obtained from six Spanish varieties of grapes (Juan García, Prieto Picudo, Mencía Regadío, Cabernet Sauvignon, Garnacha and Tempranillo). The mass and voltammetric outputs were processed using three-way models. Parallel Factor Analysis (PARAFAC) was successfully used to discriminate the must samples according to their variety. Multi-way partial least squares (N-PLS) evidenced the correlations existing between the voltammetric data and the polyphenolic content measured by chemical methods. Similarly, N-PLS showed a correlation between mass outputs and parameters related to the sugar content. These results demonstrated that electronic tongues based on arrays of EQCM sensors can offer advantages over arrays of mass or voltammetric sensors used separately. PMID:26610494

Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

DOE PAGES

Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; ...

2014-11-15

Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2MnO 3·(1-x)LiMO 2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopymore » is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.« less

An electrochemically-driven dual-mode display device with both reflective and emissive modes using poly(p-phenylenevinylene) derivatives

NASA Astrophysics Data System (ADS)

Tsuneyasu, Shota; Jin, Lu; Nakamura, Kazuki; Kobayashi, Norihisa

2016-04-01

We demonstrate a novel electrochemical dual-mode displaying (DMD) device, which enables control of both coloration and light emission using an electrochemical reaction. The coloration control of the DMD device was based on an electrochromic (EC) reaction, whereas the light emission of the device was caused by an electrochemiluminescence (ECL) mechanism. This novel DMD device consisted of a pair of facing conductive polymer-modified electrodes: comb-shaped interdigitated Au electrodes modified with poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) layers and poly(2,3-dihydrothieno-1,4-dioxin)-poly(styrene sulfonate) (PEDOT/PSS) film-modified indium tin oxide (ITO) electrodes. When a bias voltage was applied between the PEDOT/PSS film-modified ITO electrode and the comb-shaped electrodes, a color change of the device was observed by the EC reaction of the MEH-PPV and PEDOT/PSS. On the other hand, an emission was obtained when the bias voltage was applied between two comb-shaped interdigitated electrodes. The orange emission was ascribed to the ECL reaction of the MEH-PPV layer, which resulted from the formation of a p-i-n junction in this layer.

Alternating-polarity operation for complete regeneration of electrochemical deionization system

DOEpatents

Tran, Tri D.; Lenz, David J.

2002-01-01

An electrically regeneratable battery of electrochemical cells for capacitive deionization (including electrochemical purification) and regeneration of electrodes is operated at alternate polarities during consecutive cycles. By polarizing the cells, ions are removed from the electrolyte and are held in the electric double layers formed at the carbon aerogel surfaces of the electrodes. As the electrodes of each cell of the battery are saturated with the removed ions, the battery is regenerated electrically at a reversed polarity from that during the deionization step of the cycle, thus significantly minimizing secondary wastes.

Electrochemical method of controlling thiolate coverage on a conductive substrate such as gold

DOEpatents

Porter, M.D.; Weisshaar, D.E.

1998-10-27

An electrochemical method is described for forming a partial monomolecular layer of a predetermined extent of coverage of a thiolate of the formula, XRS-, therein R can be a linear or branched chain hydrocarbon or an aromatic or the like and X can be any compatible end group, e.g., OH, COOH, CH{sub 3} or the like, upon a substrate such as gold, which involves applying in an electrochemical system a constant voltage preselected to yield the desired predetermined extent of coverage. 13 figs.