The ion dependent change in the mechanism of charge storage of chemically preintercalated bilayered vanadium oxide electrodes

NASA Astrophysics Data System (ADS)

Clites, Mallory; Pomerantseva, Ekaterina

2017-08-01

Chemical pre-intercalation is a soft chemistry synthesis approach that allows for the insertion of inorganic ions into the interlayer space of layered battery electrode materials prior to electrochemical cycling. Previously, we have demonstrated that chemical pre-intercalation of Na+ ions into the structure of bilayered vanadium oxide (δ-V2O5) results in record high initial capacities above 350 mAh g-1 in Na-ion cells. This performance is attributed to the expanded interlayer spacing and predefined diffusion pathways achieved by the insertion of charge-carrying ions. However, the effect of chemical pre-intercalation of δ-V2O5 has not been studied for other ion-based systems beyond sodium. In this work, we report the effect of the chemically preintercalated alkali ion size on the mechanism of charge storage of δ- MxV2O5 (M = Li, Na, K) in Li-ion, Na-ion, and K-ion batteries, respectively. The interlayer spacing of the δ-MxV2O5 varied depending on inserted ion, with 11.1 Å achieved for Li-preintercalated δ-V2O5, 11.4 Å for Na-preintercalated δ- V2O5, and 9.6 Å for K-preintercalated δ-V2O5. Electrochemical performance of each material has been studied in its respective ion-based system (δ-LixV2O5 in Li-ion cells, δ-NaxV2O5 in Na-ion cells, and δ-KxV2O5 in K-ion cells). All materials demonstrated high initial capacities above 200 mAh g-1. However, the mechanism of charge storage differed depending on the charge-carrying ion, with Li-ion cells demonstrating predominantly pseudocapacitive behavior and Naion and K-ion cells demonstrating a significant portion of capacity from diffusion-limited intercalation processes. In this study, the combination of increased ionic radii of the charge-carrying ions and decreased synthesized interlayer spacing of the bilayered vanadium oxide phase correlates to an increase in the portion of capacity attributed diffusion-limited charge-storage processes.

Determination of diffusing species from marker experiments in the system Ni Ti O

NASA Astrophysics Data System (ADS)

Schirmer, S.; Lindner, J. K. N.; Mändl, S.

2007-04-01

Surface modification of NiTi for improved biocompatibility is a pressing issue. Using oxygen plasma immersion ion implantation (PIII), it is possible to form closed TiO2 layers on NiTi3 on NiTi. Using 60Ni marker ions implanted at 180 keV, it is shown conclusively that mobile Ni are the diffusing species, with the onset of diffusion occurring between 300 and 400 °C. Additionally, Ni is selectively removed from the oxide by preferential sputtering from the surface.

Innovative oxide materials for electrochemical energy conversion and oxygen separation

NASA Astrophysics Data System (ADS)

Belousov, V. V.

2017-10-01

Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

Modulation of Crystal Surface and Lattice by Doping: Achieving Ultrafast Metal-Ion Insertion in Anatase TiO2.

PubMed

Wang, Hsin-Yi; Chen, Han-Yi; Hsu, Ying-Ya; Stimming, Ulrich; Chen, Hao Ming; Liu, Bin

2016-10-26

We report that an ultrafast kinetics of reversible metal-ion insertion can be realized in anatase titanium dioxide (TiO 2 ). Niobium ions (Nb 5+ ) were carefully chosen to dope and drive anatase TiO 2 into very thin nanosheets standing perpendicularly onto transparent conductive electrode (TCE) and simultaneously construct TiO 2 with an ion-conducting surface together with expanded ion diffusion channels, which enabled ultrafast metal ions to diffuse across the electrolyte/solid interface and into the bulk of TiO 2 . To demonstrate the superior metal-ion insertion rate, the electrochromic features induced by ion intercalation were examined, which exhibited the best color switching speed of 4.82 s for coloration and 0.91 s for bleaching among all reported nanosized TiO 2 devices. When performed as the anode for the secondary battery, the modified TiO 2 was capable to deliver a highly reversible capacity of 61.2 mAh/g at an ultrahigh specific current rate of 60 C (10.2 A/g). This fast metal-ion insertion behavior was systematically investigated by the well-controlled electrochemical approaches, which quantitatively revealed both the enhanced surface kinetics and bulk ion diffusion rate. Our study could provide a facile methodology to modulate the ion diffusion kinetics for metal oxides.

Control of Silver Diffusion in Low-Temperature Co-Fired Diopside Glass-Ceramic Microwave Dielectrics

PubMed Central

Chou, Chen-Chia; Chang, Chun-Yao; Chen, Guang-Yu; Feng, Kuei-Chih; Tsao, Chung-Ya

2017-01-01

Electrode material for low-temperature co-fired diopside glass-ceramic used for microwave dielectrics was investigated in the present work. Diffusion of silver from the electrode to diopside glass-ceramics degrades the performance of the microwave dielectrics. Two approaches were adopted to resolve the problem of silver diffusion. Firstly, silicon-oxide (SiO2) powder was employed and secondly crystalline phases were chosen to modify the sintering behavior and inhibit silver ions diffusion. Nanoscale amorphous SiO2 powder turns to the quartz phase uniformly in dielectric material during the sintering process, and prevents the silver from diffusion. The chosen crystalline phase mixing into the glass-ceramics enhances crystallinity of the material and inhibits silver diffusion as well. The result provides a method to decrease the diffusivity of silver ions by adding the appropriate amount of SiO2 and appropriate crystalline ceramics in diopside glass-ceramic dielectric materials. Finally, we used IEEE 802.11a 5.8 GHz as target specification to manufacture LTCC antenna and the results show that a good broadband antenna was made using CaMgSi2O6 with 4 wt % silicon oxide. PMID:29286330

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Oxidation kinetics of Haynes 230 alloy in air at temperatures between 650 and 850 °C

NASA Astrophysics Data System (ADS)

Jian, Li; Jian, Pu; Bing, Hua; Xie, Guangyuan

Haynes 230 alloy was oxidized in air at temperatures between 650 and 850 °C. Thermogravimetry was used to measure the kinetics of oxidation. The formed oxides were identified by the thin film (small angle) X-ray diffraction technique. Cr 2O 3 and MnCr 2O 4 were found in the oxide scale. Multi-stage oxidation kinetics was observed, and each stage follows Wagner's parabolic law. The first slow oxidation stage corresponded to the growth of an Cr 2O 3 layer, controlled by Cr ions diffusion through the dense Cr 2O 3 scale. The faster second stage was a result of rapid diffusion of Mn ions passing through the established Cr 2O 3 scale to form MnCr 2O 4 on top of the Cr 2O 3 layer. A duplex oxide scale is expected. The third stage, with a rate close to that of the first stage, only appeared for oxidation in the intermediate temperature range, i.e., 750-800 °C, which can be explained by the interruption of the Mn flux that forms MnCr 2O 4.

Cobalt Modification of Thin Rutile Films Magnetron-Sputtered in Vacuum

NASA Astrophysics Data System (ADS)

Afonin, N. N.; Logacheva, V. A.

2018-04-01

Using X-ray phase analysis, atomic force microscopy, and secondary ion mass-spectrometry, the phase formation and component distribution in a Co-TiO2 film system have been investigated during magnetron sputtering of the metal on the oxide and subsequent vacuum annealing. It has been found that cobalt diffuses deep into titanium oxide to form complex oxides CoTi2O5 and CoTiO3. A mechanism behind their formation at grain boundaries throughout the thickness of the TiO2 film is suggested. It assumes the reactive diffusion of cobalt along grain boundaries in the oxide. A quantitative model of reactive interdiffusion in a bilayer polycrystalline metal-oxide film system with limited solubility of components has been developed. The individual diffusion coefficients of cobalt and titanium have been determined in the temperature interval 923-1073 K.

On the Role of Built-in Electric Fields on the Ignition of Oxide Coated NanoAluminum: Ion Mobility versus Fickian Diffusion

DTIC Science & Technology

2010-01-01

on Al ion diffu- sion can be computed using the Nernst –Planck equation . The Nernst –Plank equation is given in Eq. 4,22 J = − D dC dx − zFDC RT d dx...The use of the bulk diffusion equation is reason- able since during the time scales considered the movement of only the atoms initially on the surface

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

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

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE PAGES

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; ...

2017-12-05

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Oxidation mechanism of T91 steel in liquid lead-bismuth eutectic: with consideration of internal oxidation

PubMed Central

Ye, Zhongfei; Wang, Pei; Dong, Hong; Li, Dianzhong; Zhang, Yutuo; Li, Yiyi

2016-01-01

Clarification of the microscopic events that occur during oxidation is of great importance for understanding and consequently controlling the oxidation process. In this study the oxidation product formed on T91 ferritic/martensitic steel in oxygen saturated liquid lead-bismuth eutectic (LBE) at 823 K was characterized at the nanoscale using focused-ion beam and transmission electron microscope. An internal oxidation zone (IOZ) under the duplex oxide scale has been confirmed and characterized systematically. Through the microscopic characterization of the IOZ and the inner oxide layer, the micron-scale and nano-scale diffusion of Cr during the oxidation in LBE has been determined for the first time. The micron-scale diffusion of Cr ensures the continuous advancement of IOZ and inner oxide layer, and nano-scale diffusion of Cr gives rise to the typical appearance of the IOZ. Finally, a refined oxidation mechanism including the internal oxidation and the transformation of IOZ to inner oxide layer is proposed based on the discussion. The proposed oxidation mechanism succeeds in bridging the gap between the existing models and experimental observations. PMID:27734928

Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

NASA Technical Reports Server (NTRS)

Philipp, W. H.; May, C. E.

1983-01-01

The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

Dislocations Accelerate Oxygen Ion Diffusion in La 0.8Sr 0.2MnO 3 Epitaxial Thin Films

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

Navickas, Edvinas; Chen, Yan; Lu, Qiyang

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO 3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO 3 and SrTiO 3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced bymore » dislocations, especially in the LSM films on LaAlO 3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO 3. In conclusion, the diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk.« less

Dislocations Accelerate Oxygen Ion Diffusion in La0.8Sr0.2MnO3 Epitaxial Thin Films

PubMed Central

2017-01-01

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO3 and SrTiO3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced by dislocations, especially in the LSM films on LaAlO3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO3. The diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk. PMID:28981249

Dislocations Accelerate Oxygen Ion Diffusion in La 0.8Sr 0.2MnO 3 Epitaxial Thin Films

DOE PAGES

Navickas, Edvinas; Chen, Yan; Lu, Qiyang; ...

2017-10-05

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO 3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO 3 and SrTiO 3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced bymore » dislocations, especially in the LSM films on LaAlO 3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO 3. In conclusion, the diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk.« less

Preparation of 3D nanoporous copper-supported cuprous oxide for high-performance lithium ion battery anodes.

PubMed

Liu, Dequan; Yang, Zhibo; Wang, Peng; Li, Fei; Wang, Desheng; He, Deyan

2013-03-07

Three-dimensional (3D) nanoporous architectures can provide efficient and rapid pathways for Li-ion and electron transport as well as short solid-state diffusion lengths in lithium ion batteries (LIBs). In this work, 3D nanoporous copper-supported cuprous oxide was successfully fabricated by low-cost selective etching of an electron-beam melted Cu(50)Al(50) alloy and subsequent in situ thermal oxidation. The architecture was used as an anode in lithium ion batteries. In the first cycle, the sample delivered an extremely high lithium storage capacity of about 2.35 mA h cm(-2). A high reversible capacity of 1.45 mA h cm(-2) was achieved after 120 cycles. This work develops a promising approach to building reliable 3D nanostructured electrodes for high-performance lithium ion batteries.

Single-Nanowire Electrochemical Probe Detection for Internally Optimized Mechanism of Porous Graphene in Electrochemical Devices.

PubMed

Hu, Ping; Yan, Mengyu; Wang, Xuanpeng; Han, Chunhua; He, Liang; Wei, Xiujuan; Niu, Chaojiang; Zhao, Kangning; Tian, Xiaocong; Wei, Qiulong; Li, Zijia; Mai, Liqiang

2016-03-09

Graphene has been widely used to enhance the performance of energy storage devices due to its high conductivity, large surface area, and excellent mechanical flexibility. However, it is still unclear how graphene influences the electrochemical performance and reaction mechanisms of electrode materials. The single-nanowire electrochemical probe is an effective tool to explore the intrinsic mechanisms of the electrochemical reactions in situ. Here, pure MnO2 nanowires, reduced graphene oxide/MnO2 wire-in-scroll nanowires, and porous graphene oxide/MnO2 wire-in-scroll nanowires are employed to investigate the capacitance, ion diffusion coefficient, and charge storage mechanisms in single-nanowire electrochemical devices. The porous graphene oxide/MnO2 wire-in-scroll nanowire delivers an areal capacitance of 104 nF/μm(2), which is 4.0 and 2.8 times as high as those of reduced graphene oxide/MnO2 wire-in-scroll nanowire and MnO2 nanowire, respectively, at a scan rate of 20 mV/s. It is demonstrated that the reduced graphene oxide wrapping around the MnO2 nanowire greatly increases the electronic conductivity of the active materials, but decreases the ion diffusion coefficient because of the shielding effect of graphene. By creating pores in the graphene, the ion diffusion coefficient is recovered without degradation of the electron transport rate, which significantly improves the capacitance. Such single-nanowire electrochemical probes, which can detect electrochemical processes and behavior in situ, can also be fabricated with other active materials for energy storage and other applications in related fields.

Damage to the Silicon Substrate by Reactive Ion Etching Detected by a Slow Positron Beam

NASA Astrophysics Data System (ADS)

Wei, Long; Tabuki, Yasushi; Tanigawa, Shoichiro

1993-01-01

Defects in reactive ion-etched Si have been investigated by means of a slow positron beam. A thin carbon-containing film (<30 Å) was formed on the Si surface after reactive ion etching (RIE). Vacancy-type defects, which were estimated to distribute over 1200 Å in depth by numerical fitting using the positron trapping model, were observed in the damaged subsurface region of Si. Aside from ion bombardment, ultraviolet radiation is also presumed to affect the formation of vacancies, interstitials in oxide and the formation of vacancies in Si substrate. The ionization-enhanced diffusion (IED) mechanism is expected to promote the diffusion of vacancies and interstitials into Si substrate.

Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer

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

Riley, Jarrett; Siriwardane, Ranjani; Tian, Hanjing

Chemical Looping Gasification (CLG) is an emerging technology that shows promise for efficient coal gasification by eliminating the need for energy intensive gas separations to achieve a non-nitrogen diluted syngas stream. Oxygen from oxygen carriers, such as CaFe 2O 4, are used for coal gasification in place of conventionally produced gaseous oxygen from cryogenic separation of air. These oxygen carriers are unique for their ability to selectively oxidize coal to form syngas and show limited reactivity with syngas components (H 2, CO). To gain a deeper understanding of how these unique oxygen carriers perform and to offer a first attemptmore » at the reaction modeling of solid mediated interactions of this nature, this study was carried out to determine the kinetic parameters associated with the selective oxidation of coal derived char (Wyodak and Illinois #6) with a metal ferrite, CaFe 2O 4. Using thermogravimetric analysis (TGA) coupled with mass spectrometry, the selective oxygen release of metal ferrite in the presence of char by proximal contact was examined. The application of combinatory model fitting approaches was used to describe controlling resistances during oxygen release. A combination of the modified shrinking core model (SCM) with planar oxygen ion diffusion control and reaction order based models was used for kinetic parameter determination. CaFe 2O 4 particle size plays a major role in the prevailing mode of oxygen release. Particle sizes on the order of 40–50 μm tend to favor first order kinetically controlled regimes independent of geometric and diffusion controls. The probability for oxygen ion diffusion controlling regimes increased when the particle size range of the oxygen carrier was increased up to 350 μm. Char type also impacted the prevalence of the controlling regime. Higher ranked chars react in a slower manner, limiting the gradient for oxygen ion release from the oxygen carrier. Activation energies determined for this process range from 120–200kJ/mol and oxygen ion diffusion coefficients are on the order of 10-8 cm 2/s. It is suggested that oxygen ion movement is regulated by lattice diffusion out of partially reduced phases (Ca 2Fe 2O 5) and through reduced outer layers composed of CaO and Fe. The controlled movement of oxygen ions influences the rate of carbon oxidation in the char and therefore the selectivity towards partial oxidation products, which are desirable in CLG applications.« less

Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer

DOE PAGES

Riley, Jarrett; Siriwardane, Ranjani; Tian, Hanjing; ...

2017-05-20

Chemical Looping Gasification (CLG) is an emerging technology that shows promise for efficient coal gasification by eliminating the need for energy intensive gas separations to achieve a non-nitrogen diluted syngas stream. Oxygen from oxygen carriers, such as CaFe 2O 4, are used for coal gasification in place of conventionally produced gaseous oxygen from cryogenic separation of air. These oxygen carriers are unique for their ability to selectively oxidize coal to form syngas and show limited reactivity with syngas components (H 2, CO). To gain a deeper understanding of how these unique oxygen carriers perform and to offer a first attemptmore » at the reaction modeling of solid mediated interactions of this nature, this study was carried out to determine the kinetic parameters associated with the selective oxidation of coal derived char (Wyodak and Illinois #6) with a metal ferrite, CaFe 2O 4. Using thermogravimetric analysis (TGA) coupled with mass spectrometry, the selective oxygen release of metal ferrite in the presence of char by proximal contact was examined. The application of combinatory model fitting approaches was used to describe controlling resistances during oxygen release. A combination of the modified shrinking core model (SCM) with planar oxygen ion diffusion control and reaction order based models was used for kinetic parameter determination. CaFe 2O 4 particle size plays a major role in the prevailing mode of oxygen release. Particle sizes on the order of 40–50 μm tend to favor first order kinetically controlled regimes independent of geometric and diffusion controls. The probability for oxygen ion diffusion controlling regimes increased when the particle size range of the oxygen carrier was increased up to 350 μm. Char type also impacted the prevalence of the controlling regime. Higher ranked chars react in a slower manner, limiting the gradient for oxygen ion release from the oxygen carrier. Activation energies determined for this process range from 120–200kJ/mol and oxygen ion diffusion coefficients are on the order of 10-8 cm 2/s. It is suggested that oxygen ion movement is regulated by lattice diffusion out of partially reduced phases (Ca 2Fe 2O 5) and through reduced outer layers composed of CaO and Fe. The controlled movement of oxygen ions influences the rate of carbon oxidation in the char and therefore the selectivity towards partial oxidation products, which are desirable in CLG applications.« less

Effects of positive ion implantation into antireflection coating of silicon solar cells

NASA Technical Reports Server (NTRS)

Middleton, A. E.; Harpster, J. W.; Collis, W. J.; Kim, C. K.

1971-01-01

The state of technological development of Si solar cells for highest obtained efficiency and radiation resistance is summarized. The various theoretical analyses of Si solar cells are reviewed. It is shown that factors controlling blue response are carrier diffusion length, surface recombination, impurity concentration profile in surface region, high level of surface impurity concentration (degeneracy), reflection coefficient of oxide, and absorption coefficient of Si. The theory of ion implantation of charge into the oxide antireflection coating is developed and side effects are discussed. The experimental investigations were directed at determining whether the blue response of Si solar cells could be improved by phosphorus ion charges introduced into the oxide antireflection coating.

Application of diffusion barriers to the refractory fibers of tungsten, columbium, carbon and aluminum oxide

NASA Technical Reports Server (NTRS)

Douglas, F. C.; Paradis, E. L.; Veltri, R. D.

1973-01-01

A radio frequency powered ion-plating system was used to plate protective layers of refractory oxides and carbide onto high strength fiber substrates. Subsequent overplating of these combinations with nickel and titanium was made to determine the effectiveness of such barrier layers in preventing diffusion of the overcoat metal into the fibers with consequent loss of fiber strength. Four substrates, five coatings, and two metal matrix materials were employed for a total of forty material combinations. The substrates were tungsten, niobium, NASA-Hough carbon, and Tyco sapphire. The diffusion-barrier coatings were aluminum oxide, yttrium oxide, titanium carbide, tungsten carbide with 14% cobalt addition, and zirconium carbide. The metal matrix materials were IN 600 nickel and Ti 6/4 titanium. Adhesion of the coatings to all substrates was good except for the NASA-Hough carbon, where flaking off of the oxide coatings in particular was observed.

Lithium-ion diffusion mechanisms in the battery anode material Li(1+x)V(1-x)O₂.

PubMed

Panchmatia, Pooja M; Armstrong, A Robert; Bruce, Peter G; Islam, M Saiful

2014-10-21

Layered Li(1+x)V(1-x)O2 has attracted recent interest as a potential low voltage and high energy density anode material for lithium-ion batteries. A greater understanding of the lithium-ion transport mechanisms is important in optimising such oxide anodes. Here, stoichiometric LiVO2 and Li-rich Li1.07V0.93O2 are investigated using atomistic modelling techniques. Lithium-ion migration is not found in LiVO2, which has also previously shown to be resistant to lithium intercalation. Molecular dynamics simulations of lithiated non-stoichiometric Li(1.07+y)V0.93O2 suggest cooperative interstitial Li(+) diffusion with favourable migration barriers and diffusion coefficients (D(Li)), which are facilitated by the presence of lithium in the transition metal layers; such transport behaviour is important for high rate performance as a battery anode.

Impact of implanted phosphorus on the diffusivity of boron and its applicability to silicon solar cells

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

Schrof, Julian; Müller, Ralph; Reedy, Robert C.

2015-07-28

Boron diffusivity reduction in extrinsically doped silicon was investigated in the context of a process combination consisting of BBr3 furnace diffusion and preceding Phosphorus ion implantation. The implantation of Phosphorus leads to a substantial blocking of Boron during the subsequent Boron diffusion. First, the influences of ion implantation induced point defects as well as the initial P doping on B diffusivity were studied independently. Here, it was found that not the defects created during ion implantation but the P doping itself results in the observed B diffusion retardation. The influence of the initial P concentration was investigated in more detailmore » by varying the P implantation dose. A secondary ion mass spectrometry (SIMS) analysis of the BSG layer after the B diffusion revealed that the B diffusion retardation is not due to potential P content in the BSG layer but rather caused by the n-type doping of the crystalline silicon itself. Based on the observations the B diffusion retardation was classified into three groups: (i) no reduction of B diffusivity, (ii) reduced B diffusivity, and (iii) blocking of the B diffusion. The retardation of B diffusion can well be explained by the phosphorus doping level resulting in a Fermi level shift and pairing of B and P ions, both reducing the B diffusivity. Besides these main influences, there are probably additional transient phenomena responsible for the blocking of boron. Those might be an interstitial transport mechanism caused by P diffusion that reduces interstitial concentration at the surface or the silicon/BSG interface shift due to oxidation during the BBr3 diffusion process. Lifetime measurements revealed that the residual (non-blocked) B leads to an increased dark saturation current density in the P doped region. Nevertheless, electrical quality is on a high level and was further increased by reducing the B dose as well as by removing the first few nanometers of the silicon surface after the BBr3 diffusion« less

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Stannic oxide spherical nanoparticles: an anode material with long-term cyclability for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kalubarme, Ramchandra S.; Kale, Bharat B.; Gosavi, Suresh W.

2017-08-01

Transition metal oxides are widely used in energy storage applications. Stannic oxide nanostructures are prepared using a controlled, NaOH assisted, simple precipitation method. The morphology of the prepared material confirms the formation of fine nanoparticles having a rutile stannic oxide (SnO2) phase, with cassiterite structure, and size distribution ~20 nm. On testing, as an anode material for a Li-ion battery, stannic oxide delivers a reversible charge capacity of 957 mAh g-1 at an applied current rate of C/10. The stannic oxide shows excellent rate performance displaying capacity of 577 mAh g-1 at 10 C and capacity of 919 mAh g-1 retained after 200 cycles at an applied current rate of C/2. The super performance of stannic oxide fine particles stem from both the effective diffusion of Li-ions to reaction sites through porous channels and weaker stress/strain during Li insertion/desertion owing to its fine size.

Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

PubMed Central

Nayak, Nadiya B.; Nayak, Bibhuti B.

2016-01-01

Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

Solute redistribution and phase stability at FeCr/TiO 2–x interfaces under ion irradiation

DOE PAGES

Xu, Y.; Aguiar, J. A.; Yadav, S. K.; ...

2015-02-26

Cr diffusion in trilayer thin films of 100 nm Fe–18Cr/125 nm TiO 2–x/100 nm Fe–18Cr deposited on MgO substrates at 500 °C was studied by either annealing at 500 °C or Ni 3+ ion irradiation at 500 °C. Microchemistry and microstructure evolution at the metal/oxide interfaces were investigated using (high-resolution) transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy. Diffusion of Cr into the O-deficient TiO 2 layer, with negligible segregation to the FeCr/TiO 2–x interface itself, was observed under both annealing and irradiation. Cr diffusion into TiO 2–x was enhanced in ion-irradiated samples as compared to annealed.more » Irradiation-induced voids and amorphization of TiO 2–x was also observed. The experimental results are rationalized using first-principles calculations that suggest an energetic preference for substituting Ti with Cr in sub-stoichiometric TiO 2. Furthermore, the implications of these results on the irradiation stability of oxide-dispersed ferritic alloys are discussed.« less

Non-uniform lithium-ion migration on micrometre scale for garnet- and NASICON-type solid electrolytes studied by 7Li PGSE-NMR diffusion spectroscopy.

PubMed

Hayamizu, Kikuko; Seki, Shiro; Haishi, Tomoyuki

2018-06-21

The migration behaviours of Li+ in three garnet- and one NASICON-type solid oxide electrolytes were studied on the micrometre scale by pulsed-gradient spin-echo (PGSE) 7Li NMR diffusion spectroscopy to clarify common and specific characteristics of each electrolyte. In these solid electrolytes, clear evidences of grain boundary effects in the diffusion of Li+ were not observed. The Li+ diffusion constants were dependent on parameters such as observation time (Δ) and pulsed field gradient (PFG) strength (g) for all the studied inorganic solid electrolytes. For low Δ values, Li+ ions underwent collisions and diffractions with diffraction distance Rdiffraction [μm]. The apparent Li+ diffusion constants (Dapparent [m2 s-1]) exhibited distributions in a wide range. In this paper, we introduced the apparent diffusion radius, rradius [μm], and compared it with Rdiffraction and mean square displacement (MSD) [μm]; the lengths of these distances were of the micrometre order (10-6 m). The relations between the values of rradius, Rdiffraction and MSD suggested that the migration behaviours of Li+ on the micrometre scale were complicated. Using high Δ and high g values, we obtained an equilibrated value of DLi. The temperature dependences of the number of carrier ions were estimated from the DLi values and ionic conductivities in the four solid oxide electrolytes. For simple comparison and reference, the data of DLi and ionic conductivity of LiPF6 in 1 M solution of propylene carbonate were added.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

DOE PAGES

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; ...

2015-11-03

We studied the dynamics of water in polyethylene oxide (PEO)/LiCl solution with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. Furthermore, the measured diffusion coefficient of interfacial water remained 5–10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li +. Detailed analysis of MD trajectories suggests that Li + is favorably found at the surface of the hydration layer, and the probability to find the caged Li + configuration formed by themore » PEO is lower than for the noncaged Li +-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li + hydration complexes. Moreover, performing the MD simulation with different ions (Na + and K +) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.« less

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; Jalarvo, Niina H.; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S.; Do, Changwoo

2015-11-01

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li+ . Detailed analysis of MD trajectories suggests that Li+ is favorably found at the surface of the hydration layer, and the probability to find the caged Li+ configuration formed by the PEO is lower than for the noncaged Li+-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li+ hydration complexes. Performing the MD simulation with different ions (Na+ and K+ ) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide.

PubMed

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O; Jalarvo, Niina H; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S; Do, Changwoo

2015-11-06

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li(+). Detailed analysis of MD trajectories suggests that Li(+) is favorably found at the surface of the hydration layer, and the probability to find the caged Li(+) configuration formed by the PEO is lower than for the noncaged Li(+)-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li(+) hydration complexes. Performing the MD simulation with different ions (Na(+) and K(+)) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage

NASA Astrophysics Data System (ADS)

Perera, Sanjaya D.; Archer, Randall B.; Damin, Craig A.; Mendoza-Cruz, Rubén; Rhodes, Christopher P.

2017-03-01

Rechargeable magnesium batteries provide the potential for lower cost and improved safety compared with lithium-ion batteries, however obtaining cathode materials with highly reversible Mg-ion capacities is hindered by the high polarizability of divalent Mg-ions and slow solid-state Mg-ion diffusion. We report that incorporating poly(ethylene oxide) (PEO) between the layers of hydrated vanadium pentoxide (V2O5) xerogels results in significantly improved reversible Mg-ion capacities. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by PEO incorporation. Vibrational spectroscopy supports that the polymer interacts with the V2O5 lattice. The V2O5-PEO nanocomposite exhibited a 5-fold enhancement in Mg-ion capacity, improved stability, and improved rate capabilities compared with V2O5 xerogels. The Mg-ion diffusion coefficient of the nanocomposite was increased compared with that of V2O5 xerogels which is attributed to enhanced Mg-ion mobility due to the shielding interaction of PEO with the V2O5 lattice. This study shows that beyond only interlayer spacing, the nature of interlayer interactions of Mg-ions with V2O5, PEO, and H2O are key factors that affect Mg-ion charge transport and storage in layered materials. The design of layered materials with controlled interlayer interactions provides a new approach to develop improved cathodes for magnesium batteries.

Oxidation of a Commercial Nickel-Based Superalloy under Static Loading

NASA Astrophysics Data System (ADS)

Foss, B. J.; Hardy, M. C.; Child, D. J.; McPhail, D. S.; Shollock, B. A.

2014-12-01

The current demands of the aviation industry for increased gas-turbine efficiency necessitate higher turbine entry temperatures, requiring that alloys exhibit superior oxidation resistance. The synergistic effects of oxidation and mechanical stresses pose a complex issue. The purpose of the current research was to examine the effects of stress on the oxidation and oxygen transport in a commercial nickel-based superalloy. Fine grain RR1000 in both polished and shot-peened conditions was studied for classic (zero load) and statically loaded conditions using integrated two-stage isotopic tracing combined with focused-ion-beam secondary ion mass spectrometry (FIB-SIMS). Cr2O3 external oxide formed with semicontinuous TiO2 above and below. Preferential grain boundary Al2O3 internal oxide formation, γ'-dissolution, and recrystallization occurred subsurface. Oxidation mechanisms were dominated by anionic/cationic growth in the external oxide with inward oxygen transport, initially through the partially unprotective external oxide, then along internal oxide/alloy interfaces. Loading did not influence the oxidation products formed but did bring about expedited oxidation kinetics and changes to the oxide morphology. The oxygen diffusivity D {O/ * } (×10-13 cm2s-1) ranged from 0.39 for the polished alloy to 3.7 for the shot-peened condition under compressive stress. Arguably, the most significant effects took place in the subsurface regions. Increased oxidation kinetics were attributed to the development of fast cation diffusion paths as the alloy deformed by creep.

Thermal annealing behavior of nano-size metal-oxide particles synthesized by ion implantation in Fe-Cr alloy

NASA Astrophysics Data System (ADS)

Zheng, C.; Gentils, A.; Ribis, J.; Borodin, V. A.; Descoins, M.; Mangelinck, D.; Dalle, F.; Arnal, B.; Delauche, L.

2017-05-01

Oxide dispersion strengthened (ODS) steels are promising structural materials for the next generation nuclear reactors, as well as fusion facilities. The detailed understanding of the mechanisms involved in the precipitation of nano-oxides during ODS steel production would strongly contribute to the improvement of the mechanical properties and the optimization of manufacturing of ODS steels, with a potentially strong economic impact for their industrialization. A useful tool for the experimental study of nano-oxide precipitation is ion implantation, a technique that is widely used to synthesize precipitate nanostructures in well-controlled conditions. Earlier, we have demonstrated the feasibility of synthesizing aluminum-oxide particles in the high purity Fe-10Cr alloy by consecutive implantation with Al and O ions at room temperature. This paper describes the effects of high-temperature annealing after the ion implantation stage on the development of the aluminum based oxide nanoparticle system. Using transmission electron microscopy and atom probe tomography experiments, we demonstrate that post-implantation heat treatment induces the growth of the nano-sized oxides in the implanted region and nucleation of new oxide precipitates behind the implantation zone as a result of the diffusion driven broadening of implant profiles. A tentative scenario for the development of metal-oxide nano-particles at both ion implantation and heat treatment stages is suggested based on the experimental observations.

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide) based polyether-ester-sulfonate ionomers

NASA Astrophysics Data System (ADS)

Roach, David J.

Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though lithium hopping is about ten times slower than the segmental motion. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments. Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T g) have been investigated using solid-state nuclear magnetic resonance (NMR). Experiments detecting 13C with 1H decoupling under magic angle spinning (MAS) conditions identified the different components and relative mobilities of the polymer backbone of a suite of. lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) 1H-13C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content. Each of the main backbone components (PEO spacer and isophthalate groups) exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and 1H spin-lattice relaxation rate measurements. The temperature dependences of 13C linewidths were used to both qualitatively and quantitatively examine the effects of cation content on PEO mobility. Variable contact time 1H-13C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, determined from the rate of magnetization transfer from 1H to 13C nuclei, in all ionic samples becomes similar for T [special characters omitted] 1.1 Tg, indicating that the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results compliment previous findings and present an improved picture of the dependence of backbone dynamics on cation type and density in these amorphous PEO-based ionomer systems. 7Li PFG NMR experiments provided measurements of the self-diffusion coefficients for Li+ cations in the PEO600-y Li ionomer series over a range of temperatures. When the Tg values are taken into account, the self-diffusion coefficients of Li+ in each sample follow a similar trendline, indicating that lithium diffusion is independent of ion concentration at any given reduced inverse temperature, Tg/T. Ion aggregation increases Tg and slows both lithium cation diffusion and displacement, but there is no further slowing beyond the Tg effect in the PEO600-y Li ionomers samples. The differences in activation energies obtained from diffusion measurements and relaxation times suggest that at least one additional barrier must be overcome for cations emerge from local hopping motion to macroscopic cation transpfort. Using the Nernst- Einstein equation lithium diffusion coefficients were also calculated from conductivity measurements. The differences between the diffusion measured by the two separate techniques indicate the presence of ion pairs. The activation energy of lithium diffusion was found to be nearly identical between the PFG NMR and conductivity, suggesting that the conductivity and ionic diffusion are related to the same ionic dynamics. As the ion content within the PEO600-y Li samples increases the relative concentration of nonconducting ion pairs decrease. Also an increase in temperature causes a fraction of ion pairs to thermally dissociate into positive triple ions.

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

First-principles investigation of diffusion and defect properties of Fe and Ni in Cr2O3

NASA Astrophysics Data System (ADS)

Rak, Zs.; Brenner, D. W.

2018-04-01

Diffusion of Fe and Ni and the energetics of Fe- and Ni-related defects in chromium oxide (α-Cr2O3) are investigated using first-principles Density Functional Theory calculations in combination with the climbing-image nudged elastic band method. The orientations of the spin magnetic moments of the migrating ions are taken into account and their effects on migration barriers are examined. Several possible diffusion pathways were explored through interstitial and vacancy mechanisms, and it was found that the principal mode of ion transport in Cr2O3 is via vacancies. Both interstitial- and vacancy-mediated diffusions are anisotropic, with diffusion being faster in the z-direction. The energetics of defect formation indicates that the Ni-related defects are less stable than the Fe-related ones. This is consistent with Ni-diffusion being faster than Fe-diffusion. The results are compared with previous theoretical and experimental data and possible implications in corrosion control are discussed.

Formation of tungsten oxide nanowires by ion irradiation and vacuum annealing

NASA Astrophysics Data System (ADS)

Zheng, Xu-Dong; Ren, Feng; Wu, Heng-Yi; Qin, Wen-Jing; Jiang, Chang-Zhong

2018-04-01

Here we reported the fabrication of tungsten oxide (WO3-x ) nanowires by Ar+ ion irradiation of WO3 thin films followed by annealing in vacuum. The nanowire length increases with increasing irradiation fluence and with decreasing ion energy. We propose that the stress-driven diffusion of the irradiation-induced W interstitial atoms is responsible for the formation of the nanowires. Comparing to the pristine film, the fabricated nanowire film shows a 106-fold enhancement in electrical conductivity, resulting from the high-density irradiation-induced vacancies on the oxygen sublattice. The nanostructure exhibits largely enhanced surface-enhanced Raman scattering effect due to the oxygen vacancy. Thus, ion irradiation provides a powerful approach for fabricating and tailoring the surface nanostructures of semiconductors.

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Impact of implanted phosphorus on the diffusivity of boron and its applicability to silicon solar cells

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

Schrof, Julian, E-mail: julian.schrof@ise.fraunhofer.de; Müller, Ralph; Benick, Jan

2015-07-28

Boron diffusivity reduction in extrinsically doped silicon was investigated in the context of a process combination consisting of BBr{sub 3} furnace diffusion and preceding Phosphorus ion implantation. The implantation of Phosphorus leads to a substantial blocking of Boron during the subsequent Boron diffusion. First, the influences of ion implantation induced point defects as well as the initial P doping on B diffusivity were studied independently. Here, it was found that not the defects created during ion implantation but the P doping itself results in the observed B diffusion retardation. The influence of the initial P concentration was investigated in moremore » detail by varying the P implantation dose. A secondary ion mass spectrometry (SIMS) analysis of the BSG layer after the B diffusion revealed that the B diffusion retardation is not due to potential P content in the BSG layer but rather caused by the n-type doping of the crystalline silicon itself. Based on the observations the B diffusion retardation was classified into three groups: (i) no reduction of B diffusivity, (ii) reduced B diffusivity, and (iii) blocking of the B diffusion. The retardation of B diffusion can well be explained by the phosphorus doping level resulting in a Fermi level shift and pairing of B and P ions, both reducing the B diffusivity. Besides these main influences, there are probably additional transient phenomena responsible for the blocking of boron. Those might be an interstitial transport mechanism caused by P diffusion that reduces interstitial concentration at the surface or the silicon/BSG interface shift due to oxidation during the BBr{sub 3} diffusion process. Lifetime measurements revealed that the residual (non-blocked) B leads to an increased dark saturation current density in the P doped region. Nevertheless, electrical quality is on a high level and was further increased by reducing the B dose as well as by removing the first few nanometers of the silicon surface after the BBr{sub 3} diffusion.« less

Tuning the Shell Number of Multishelled Metal Oxide Hollow Fibers for Optimized Lithium-Ion Storage.

PubMed

Sun, Jin; Lv, Chunxiao; Lv, Fan; Chen, Shuai; Li, Daohao; Guo, Ziqi; Han, Wei; Yang, Dongjiang; Guo, Shaojun

2017-06-27

Searching the long-life transition-metal oxide (TMO)-based materials for future lithium-ion batteries (LIBs) is still a great challenge because of the mechanical strain resulting from volume change of TMO anodes during the lithiation/delithiation process. To well address this challenging issue, we demonstrate a controlled method for making the multishelled TMO hollow microfibers with tunable shell numbers to achieve the optimal void for efficient lithium-ion storage. Such a particularly designed void can lead to a short diffusion distance for fast diffusion of Li + ions and also withstand a large volume variation upon cycling, both of which are the key for high-performance LIBs. Triple-shelled TMO hollow microfibers are a quite stable anode material for LIBs with high reversible capacities (NiO: 698.1 mA h g -1 at 1 A g -1 ; Co 3 O 4 : 940.2 mA h g -1 at 1 A g -1 ; Fe 2 O 3 : 997.8 mA h g -1 at 1 A g -1 ), excellent rate capability, and stability. The present work opens a way for rational design of the void of multiple shells in achieving the stable lithium-ion storage through the biomass conversion strategy.

SnS2 /Sb2 S3 Heterostructures Anchored on Reduced Graphene Oxide Nanosheets with Superior Rate Capability for Sodium-Ion Batteries.

PubMed

Wang, Shijian; Liu, Shuaishuai; Li, Xuemei; Li, Cong; Zang, Rui; Man, Zengming; Wu, Yuhan; Li, Pengxin; Wang, Guoxiu

2018-03-12

Tin disulfide, as a promising high-capacity anode material for sodium-ion batteries, exhibits high theoretical capacity but poor practical electrochemical properties due to its low electrical conductivity. Constructing heterostructures has been considered to be an effective approach to enhance charge transfer and ion-diffusion kinetics. In this work, composites of SnS 2 /Sb 2 S 3 heterostructures with reduced graphene oxide nanosheets were synthesized by a facile one-pot hydrothermal method. When applied as anode material in sodium-ion batteries, the composite showed a high reversible capacity of 642 mA h g -1 at a current density of 0.2 A g -1 and good cyclic stability without capacity loss in 100 cycles. In particular, SnS 2 /Sb 2 S 3 heterostructures exhibited outstanding rate performance with capacities of 593 and 567 mA h g -1 at high current densities of 2 and 4 A g -1 , respectively, which could be ascribed to the dramatically improved Na + diffusion kinetics and electrical conductivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

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

Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo

2015-09-16

Micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous Ni xCo (3-x)(CO 3) y and Ni xCo (3-x)O 4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline Ni xCo (3-x)O 4. The micelle templated mesopores are interconnected and providemore » transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g -1. Amongst the mixed-metal oxides, Ni 2CoO 4 exhibits the highest specific capacity of 239 mA h g -1 after galvanostatic cycling at a current density of 1 A g -1 for 10 cycles. We attribute the superior performance of Ni 2CoO 4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.« less

Thermodynamics and Cation Diffusion in the Oxygen Ion Conductor Lsgm

NASA Astrophysics Data System (ADS)

Martin, M.; Schulz, O.

Perovskite type oxides based on LaGaO3 are of large technical interest because of their high oxygen-ion conductivity. Lanthanum gallate doped with Sr on A- and Mg on B-sites, La1-xSrxGa1-yMgyO3-(x+y)/2 (LSGM), reaches higher oxygen-ion conductivities than yttria-doped zirconia (YSZ). Thus LSGM represents a promising alternative for YSZ as electrolyte in solid oxide fuel cells (SOFC). Cells using thin LSGM-layers as electrolyte are expected to operate at intermediate temperatures around 700°C for more than 30000 hours without severe degradation. A potential long term degradation effect of LSGM is kinetic demixing of the electrolyte, caused by different cation diffusion coefficients. In this paper we report on experimental studies concerning the phase diagram of LSGM and the diffusion of cations. Cation self-diffusion of 139La, 84Sr and 25Mg and cation impurity diffusion of 144Nd, 89Y and 56Fe in polycrystalline LSGM samples was investigated by secondary ion mass spectrometry (SIMS) for temperatures between 900°C and 1400°C. It was found that diffusion occurs by means of bulk and grain boundaries. The bulk diffusion coefficients are similar for all cations with activation energies which are strongly dependent on temperature. At high temperatures, the activation energies are about 5 eV, while at low temperatures values of about 2 eV are found. These results are explained by a frozen in defect structure at low temperatures. This means that the observed activation energy at low temperatures represents only the migration energy of the different cations while the observed activation energy at high temperatures is the sum of the defect formation energy and the migration energy. The migration energies for all cations are nearly identical, although 139La, 84Sr and 144Nd are occupying A-sites while 25Mg and 56Fe are occupying B-sites in the perovskite-structure. To explain these experimental findings we propose a defect cluster containing cation vacancies in both the A- and the B-sublattice and anion vacancies as well.

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

PubMed

Khetan, Vishal; Valle, Nathalie; Duday, David; Michotte, Claude; Delplancke-Ogletree, Marie-Paule; Choquet, Patrick

2014-03-26

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

Porous membrane electrochemical cell for uranium and transuranic recovery from molten salt electrolyte

DOEpatents

Willit, James L [Ratavia, IL

2007-09-11

An improved process and device for the recovery of the minor actinides and the transuranic elements (TRU's) from a molten salt electrolyte. The process involves placing the device, an electrically non-conducting barrier between an anode salt and a cathode salt. The porous barrier allows uranium to diffuse between the anode and cathode, yet slows the diffusion of uranium ions so as to cause depletion of uranium ions in the catholyte. This allows for the eventual preferential deposition of transuranics present in spent nuclear fuel such as Np, Pu, Am, Cm. The device also comprises an uranium oxidation anode. The oxidation anode is solid uranium metal in the form of spent nuclear fuel. The spent fuel is placed in a ferric metal anode basket which serves as the electrical lead or contact between the molten electrolyte and the anodic uranium metal.

Porous membrane electrochemical cell for uranium and transuranic recovery from molten salt electrolyte

DOEpatents

Willit, James L [Batavia, IL

2010-09-21

An improved process and device for the recovery of the minor actinides and the transuranic elements (TRU's) from a molten salt electrolyte. The process involves placing the device, an electrically non-conducting barrier between an anode salt and a cathode salt. The porous barrier allows uranium to diffuse between the anode and cathode, yet slows the diffusion of uranium ions so as to cause depletion of uranium ions in the catholyte. This allows for the eventual preferential deposition of transuranics present in spent nuclear fuel such as Np, Pu, Am, Cm. The device also comprises an uranium oxidation anode. The oxidation anode is solid uranium metal in the form of spent nuclear fuel. The spent fuel is placed in a ferric metal anode basket which serves as the electrical lead or contact between the molten electrolyte and the anodic uranium metal.

Electrochemical Ionization and Analyte Charging in the Array of Micromachined UltraSonic Electrospray (AMUSE) Ion Source

PubMed Central

Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

2010-01-01

Electrochemistry and ion transport in a planar array of mechanically-driven, droplet-based ion sources are investigated using an approximate time scale analysis and in-depth computational simulations. The ion source is modeled as a controlled-current electrolytic cell, in which the piezoelectric transducer electrode, which mechanically drives the charged droplet generation using ultrasonic atomization, also acts as the oxidizing/corroding anode (positive mode). The interplay between advective and diffusive ion transport of electrochemically generated ions is analyzed as a function of the transducer duty cycle and electrode location. A time scale analysis of the relative importance of advective vs. diffusive ion transport provides valuable insight into optimality, from the ionization prospective, of alternative design and operation modes of the ion source operation. A computational model based on the solution of time-averaged, quasi-steady advection-diffusion equations for electroactive species transport is used to substantiate the conclusions of the time scale analysis. The results show that electrochemical ion generation at the piezoelectric transducer electrodes located at the back-side of the ion source reservoir results in poor ionization efficiency due to insufficient time for the charged analyte to diffuse away from the electrode surface to the ejection location, especially at near 100% duty cycle operation. Reducing the duty cycle of droplet/analyte ejection increases the analyte residence time and, in turn, improves ionization efficiency, but at an expense of the reduced device throughput. For applications where this is undesirable, i.e., multiplexed and disposable device configurations, an alternative electrode location is incorporated. By moving the charging electrode to the nozzle surface, the diffusion length scale is greatly reduced, drastically improving ionization efficiency. The ionization efficiency of all operating conditions considered is expressed as a function of the dimensionless Peclet number, which defines the relative effect of advection as compared to diffusion. This analysis is general enough to elucidate an important role of electrochemistry in ionization efficiency of any arrayed ion sources, be they mechanically-driven or electrosprays, and is vital for determining optimal design and operation conditions. PMID:20607111

Three-dimensional hollow-structured binary oxide particles as an advanced anode material for high-rate and long cycle life lithium-ion batteries

DOE PAGES

Wang, Deli; Wang, Jie; He, Huan; ...

2015-12-30

Transition metal oxides are among the most promising anode candidates for next-generation lithium-ion batteries for their high theoretical capacity. However, the large volume expansion and low lithium ion diffusivity leading to a poor charging/discharging performance. In this study, we developed a surfactant and template-free strategy for the synthesis of a composite of Co xFe 3–xO 4 hollow spheres supported by carbon nanotubes via an impregnation–reduction–oxidation process. The synergy of the composite, as well as the hollow structures in the electrode materials, not only facilitate Li ion and electron transport, but also accommodate large volume expansion. Using state-of-the-art electron tomography, wemore » directly visualize the particles in 3-D, where the voids in the hollow structures serve to buffer the volume expansion of the material. These improvements result in a high reversible capacity as well as an outstanding rate performance for lithium-ion battery applications. As a result, this study sheds light on large-scale production of hollow structured metal oxides for commercial applications in energy storage and conversion.« less

Characterization of silicon-gate CMOS/SOS integrated circuits processed with ion implantation

NASA Technical Reports Server (NTRS)

Woo, D. S.

1977-01-01

Progress in developing the application of ion implantation techniques to silicon gate CMOS/SOS processing is described. All of the conventional doping techniques such as in situ doping of the epi-film and diffusion by means of doped oxides are replaced by ion implantation. Various devices and process parameters are characterized to generate an optimum process by the use of an existing SOS test array. As a result, excellent circuit performance is achieved. A general description of the all ion implantation process is presented.

K2 Mn4 O8 /Reduced Graphene Oxide Nanocomposites for Excellent Lithium Storage and Adsorption of Lead Ions.

PubMed

Hao, Shu-Meng; Qu, Jin; Yang, Jing; Gui, Chen-Xi; Wang, Qian-Qian; Li, Qian-Jie; Li, Xiaofeng; Yu, Zhong-Zhen

2016-03-01

Ion diffusion efficiency at the solid-liquid interface is an important factor for energy storage and adsorption from aqueous solution. Although K 2 Mn 4 O 8 (KMO) exhibits efficient ion diffusion and ion-exchange capacities, due to its high interlayer space of 0.70 nm, how to enhance its mass transfer performance is still an issue. Herein, novel layered KMO/reduced graphene oxide (RGO) nanocomposites are fabricated through the anchoring of KMO nanoplates on RGO with a mild solution process. The face-to-face structure facilitates fast transfer of lithium and lead ions; thus leading to excellent lithium storage and lead ion adsorption. The anchoring of KMO on RGO not only increases electrical conductivity of the layered nanocomposites, but also effectively prevents aggregation of KMO nanoplates. The KMO/RGO nanocomposite with an optimal RGO content exhibits a first cycle charge capacity of 739 mA h g -1 , which is much higher than that of KMO (326 mA h g -1 ). After 100 charge-discharge cycles, it still retains a charge capacity of 664 mA h g -1 . For the adsorption of lead ions, the KMO/RGO nanocomposite exhibits a capacity of 341 mg g -1 , which is higher than those of KMO (305 mg g -1 ) and RGO (63 mg g -1 ) alone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass

PubMed Central

Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

2015-01-01

In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant. PMID:26658671

Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass.

PubMed

Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

2015-12-14

In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant.

Ion-enhanced oxidation of aluminum as a fundamental surface process during target poisoning in reactive magnetron sputtering

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

Kuschel, Thomas; Keudell, Achim von

2010-05-15

Plasma deposition of aluminum oxide by reactive magnetron sputtering (RMS) using an aluminum target and argon and oxygen as working gases is an important technological process. The undesired oxidation of the target itself, however, causes the so-called target poisoning, which leads to strong hysteresis effects during RMS operation. The oxidation occurs by chemisorption of oxygen atoms and molecules with a simultaneous ion bombardment being present. This heterogenous surface reaction is studied in a quantified particle beam experiment employing beams of oxygen molecules and argon ions impinging onto an aluminum-coated quartz microbalance. The oxidation and/or sputtering rates are measured with thismore » microbalance and the resulting oxide layers are analyzed by x-ray photoelectron spectroscopy. The sticking coefficient of oxygen molecules is determined to 0.015 in the zero coverage limit. The sputtering yields of pure aluminum by argon ions are determined to 0.4, 0.62, and 0.8 at 200, 300, and 400 eV. The variation in the effective sticking coefficient and sputtering yield during the combined impact of argon ions and oxygen molecules is modeled with a set of rate equations. A good agreement is achieved if one postulates an ion-induced surface activation process, which facilitates oxygen chemisorption. This process may be identified with knock-on implantation of surface-bonded oxygen, with an electric-field-driven in-diffusion of oxygen or with an ion-enhanced surface activation process. Based on these fundamental processes, a robust set of balance equations is proposed to describe target poisoning effects in RMS.« less

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

Over 95% of large-scale length uniformity in template-assisted electrodeposited nanowires by subzero-temperature electrodeposition.

PubMed

Shin, Sangwoo; Kong, Bo Hyun; Kim, Beom Seok; Kim, Kyung Min; Cho, Hyung Koun; Cho, Hyung Hee

2011-07-23

In this work, we report highly uniform growth of template-assisted electrodeposited copper nanowires on a large area by lowering the deposition temperature down to subzero centigrade. Even with highly disordered commercial porous anodic aluminum oxide template and conventional potentiostatic electrodeposition, length uniformity over 95% can be achieved when the deposition temperature is lowered down to -2.4°C. Decreased diffusion coefficient and ion concentration gradient due to the lowered deposition temperature effectively reduces ion diffusion rate, thereby favors uniform nanowire growth. Moreover, by varying the deposition temperature, we show that also the pore nucleation and the crystallinity can be controlled.

Electrostatic Estimation of Intercalant Jump-Diffusion Barriers Using Finite-Size Ion Models.

PubMed

Zimmermann, Nils E R; Hannah, Daniel C; Rong, Ziqin; Liu, Miao; Ceder, Gerbrand; Haranczyk, Maciej; Persson, Kristin A

2018-02-01

We report on a scheme for estimating intercalant jump-diffusion barriers that are typically obtained from demanding density functional theory-nudged elastic band calculations. The key idea is to relax a chain of states in the field of the electrostatic potential that is averaged over a spherical volume using different finite-size ion models. For magnesium migrating in typical intercalation materials such as transition-metal oxides, we find that the optimal model is a relatively large shell. This data-driven result parallels typical assumptions made in models based on Onsager's reaction field theory to quantitatively estimate electrostatic solvent effects. Because of its efficiency, our potential of electrostatics-finite ion size (PfEFIS) barrier estimation scheme will enable rapid identification of materials with good ionic mobility.

On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

PubMed

Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

2016-09-14

The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L -1 cobalt ions. For concentrations ≤0.025 mol L -1 cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The i m -t m relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

Mechanisms Underlying Ionic Mobilities in Nanocomposite Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Hanson, Benjamin; Pryamitsyn, Victor

2014-03-01

Recently, a number of experiments have demonstrated that addition of ceramics with nanoscale dimensions can lead to substantial improvements in the low temperature conductivity of the polymeric materials. However, the origin of such behaviors, and more generally, the manner by which nanoscale fillers impact the ion mobilities remain unresolved. In this communication, we report the results of atomistic molecular dynamics simulations which used multibody polarizable force-fields to study lithium ion diffusivities in an amorphous poly(ethylene-oxide) (PEO) melt containing well-dispersed TiO2 nanoparticles. We observed that the lithium ion diffusivities decrease with increased particle loading. Our analysis suggests that the ion mobilities are correlated to the nanoparticle-induced changes in the polymer segmental dynamics. Interestingly, the changes in polymer segmental dynamics were seen to be related to the nanoparticle's influence on the polymer conformational features. Overall, our results indicate that addition of nanoparticle fillers modify polymer conformations and the polymer segmental dynamics, and thereby influence the ion mobilities of polymer electrolytes.

The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

DOE PAGES

Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; ...

2016-04-29

Single nanowires of two manganese oxide polymorphs (α-MnO 2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO 2 as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO 2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between thismore » electrochemical performance, the electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li + diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li +.« less

Applying Nanoscale Kirkendall Diffusion for Template-Free, Kilogram-Scale Production of SnO2 Hollow Nanospheres via Spray Drying System

PubMed Central

Cho, Jung Sang; Ju, Hyeon Seok; Kang, Yun Chan

2016-01-01

A commercially applicable and simple process for the preparation of aggregation-free metal oxide hollow nanospheres is developed by applying nanoscale Kirkendall diffusion to a large-scale spray drying process. The precursor powders prepared by spray drying are transformed into homogeneous metal oxide hollow nanospheres through a simple post-treatment process. Aggregation-free SnO2 hollow nanospheres are selected as the first target material for lithium ion storage applications. Amorphous carbon microspheres with uniformly dispersed Sn metal nanopowder are prepared in the first step of the post-treatment process under a reducing atmosphere. The post-treatment of the Sn-C composite powder at 500 °C under an air atmosphere produces carbon- and aggregation-free SnO2 hollow nanospheres through nanoscale Kirkendall diffusion. The hollow and filled SnO2 nanopowders exhibit different cycling performances, with their discharge capacities after 300 cycles being 643 and 280 mA h g−1, respectively, at a current density of 2 A g−1. The SnO2 hollow nanospheres with high structural stability exhibit superior cycling and rate performances for lithium ion storage compared to the filled ones. PMID:27033088

Applying Nanoscale Kirkendall Diffusion for Template-Free, Kilogram-Scale Production of SnO2 Hollow Nanospheres via Spray Drying System

NASA Astrophysics Data System (ADS)

Cho, Jung Sang; Ju, Hyeon Seok; Kang, Yun Chan

2016-04-01

A commercially applicable and simple process for the preparation of aggregation-free metal oxide hollow nanospheres is developed by applying nanoscale Kirkendall diffusion to a large-scale spray drying process. The precursor powders prepared by spray drying are transformed into homogeneous metal oxide hollow nanospheres through a simple post-treatment process. Aggregation-free SnO2 hollow nanospheres are selected as the first target material for lithium ion storage applications. Amorphous carbon microspheres with uniformly dispersed Sn metal nanopowder are prepared in the first step of the post-treatment process under a reducing atmosphere. The post-treatment of the Sn-C composite powder at 500 °C under an air atmosphere produces carbon- and aggregation-free SnO2 hollow nanospheres through nanoscale Kirkendall diffusion. The hollow and filled SnO2 nanopowders exhibit different cycling performances, with their discharge capacities after 300 cycles being 643 and 280 mA h g-1, respectively, at a current density of 2 A g-1. The SnO2 hollow nanospheres with high structural stability exhibit superior cycling and rate performances for lithium ion storage compared to the filled ones.

Two-Dimensional Metal Oxide Nanomaterials for Next-Generation Rechargeable Batteries.

PubMed

Mei, Jun; Liao, Ting; Kou, Liangzhi; Sun, Ziqi

2017-12-01

The exponential increase in research focused on two-dimensional (2D) metal oxides has offered an unprecedented opportunity for their use in energy conversion and storage devices, especially for promising next-generation rechargeable batteries, such as lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs), as well as some post-lithium batteries, including lithium-sulfur batteries, lithium-air batteries, etc. The introduction of well-designed 2D metal oxide nanomaterials into next-generation rechargeable batteries has significantly enhanced the performance of these energy-storage devices by providing higher chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier-/charge-transport kinetics, which have greatly promoted the development of nanotechnology and the practical application of rechargeable batteries. Here, the recent progress in the application of 2D metal oxide nanomaterials in a series of rechargeable LIBs, NIBs, and other post lithium-ion batteries is reviewed relatively comprehensively. Current opportunities and future challenges for the application of 2D nanomaterials in energy-storage devices to achieve high energy density, high power density, stable cyclability, etc. are summarized and outlined. It is believed that the integration of 2D metal oxide nanomaterials in these clean energy devices offers great opportunities to address challenges driven by increasing global energy demands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Over 95% of large-scale length uniformity in template-assisted electrodeposited nanowires by subzero-temperature electrodeposition

PubMed Central

2011-01-01

In this work, we report highly uniform growth of template-assisted electrodeposited copper nanowires on a large area by lowering the deposition temperature down to subzero centigrade. Even with highly disordered commercial porous anodic aluminum oxide template and conventional potentiostatic electrodeposition, length uniformity over 95% can be achieved when the deposition temperature is lowered down to -2.4°C. Decreased diffusion coefficient and ion concentration gradient due to the lowered deposition temperature effectively reduces ion diffusion rate, thereby favors uniform nanowire growth. Moreover, by varying the deposition temperature, we show that also the pore nucleation and the crystallinity can be controlled. PMID:21781335

A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries.

PubMed

Guo, Shaohua; Yu, Haijun; Jian, Zelang; Liu, Pan; Zhu, Yanbei; Guo, Xianwei; Chen, Mingwei; Ishida, Masayoshi; Zhou, Haoshen

2014-08-01

A layered sodium manganese oxide material (NaMn3 O5 ) is introduced as a novel cathode materials for sodium-ion batteries. Structural characterizations reveal a typical Birnessite structure with lamellar stacking of the synthetic nanosheets. Electrochemical tests reveal a particularly large discharge capacity of 219 mAh g(-1) in the voltage rang of 1.5-4.7 V vs. Na/Na(+) . With an average potential of 2.75 V versus sodium metal, layered NaMn3 O5 exhibits a high energy density of 602 Wh kg(-1) , and also presents good rate capability. Furthermore, the diffusion coefficient of sodium ions in the layered NaMn3 O5 electrode is investigated by using the galvanostatic intermittent titration technique. The results greatly contribute to the development of room-temperature sodium-ion batteries based on earth-abundant elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Secondary ion mass spectrometric investigation on ruthenium oxide systems: a comparison between poly- and nanocrystalline deposits

PubMed

Barison; Barreca; Daolio; Fabrizio; Piccirillo

2000-01-01

The influence of different RuO(2) crystallite sizes was investigated by secondary ion mass spectrometry (SIMS) on the oxide deposited on various support materials (Ni, Ti, Al(2)O(3), oxidized Si(100)). In order to examine the effect of an oxidic environment on the film structure, RuO(2) 20%-TiO(2) 80% at. mixed oxide was deposited on Ti. The polycrystalline coatings were prepared by heating the Ru (and Ti)-containing solution dropped on the supports.1 RuO(2) nanocrystalline coatings were grown by chemical vapor deposition (CVD) from Ru(COD)(eta(3)-allyl)(2).2 The identification of mixed oxide clusters showed the higher reactivity of Ni and Al(2)O(3) over the other substrates. Diffusion and migration characteristics were observed to be influenced by the nature of the support. The results are complementary to those of a previous SIMS investigation.3 Copyright 2000 John Wiley & Sons, Ltd.

Mechanisms of lithium transport in amorphous polyethylene oxide.

PubMed

Duan, Yuhua; Halley, J W; Curtiss, Larry; Redfern, Paul

2005-02-01

We report calculations using a previously reported model of lithium perchlorate in polyethylene oxide in order to understand the mechanism of lithium transport in these systems. Using an algorithm suggested by Voter, we find results for the diffusion rate which are quite close to experimental values. By analysis of the individual events in which large lithium motions occur during short times, we find that no single type of rearrangement of the lithium environment characterizes these events. We estimate the free energies of the lithium ion as a function of position during these events by calculation of potentials of mean force and thus derive an approximate map of the free energy as a function of lithium position during these events. The results are consistent with a Marcus-like picture in which the system slowly climbs a free energy barrier dominated by rearrangement of the polymer around the lithium ions, after which the lithium moves very quickly to a new position. Reducing the torsion forces in the model causes the diffusion rates to increase.

First principles studies of structure stability and lithium intercalation of ZnCo2 O4

NASA Astrophysics Data System (ADS)

Zhang, Yanning; Liu, Weiwei; Beijing Computational Science Research Center Team

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary transition metal oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as anode for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, lithium intercalation and diffusion barrier of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our theoretical studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

First principles calculations of stability and lithium intercalation potentials of ZnCo2O4

NASA Astrophysics Data System (ADS)

Yu, L. C.; Wu, J.; Liu, H.; Zhang, Y. N.

2015-03-01

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary tin oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as the anode material for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, diffusion barrier and lithium intercalation potentials of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our DFT studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

Ion beam synthesis of indium-oxide nanocrystals for improvement of oxide resistive random-access memories

NASA Astrophysics Data System (ADS)

Bonafos, C.; Benassayag, G.; Cours, R.; Pécassou, B.; Guenery, P. V.; Baboux, N.; Militaru, L.; Souifi, A.; Cossec, E.; Hamga, K.; Ecoffey, S.; Drouin, D.

2018-01-01

We report on the direct ion beam synthesis of a delta-layer of indium oxide nanocrystals (In2O3-NCs) in silica matrices by using ultra-low energy ion implantation. The formation of the indium oxide phase can be explained by (i) the affinity of indium with oxygen, (ii) the generation of a high excess of oxygen recoils generated by the implantation process in the region where the nanocrystals are formed and (iii) the proximity of the indium-based nanoparticles with the free surface and oxidation from the air. Taking advantage of the selective diffusivity of implanted indium in SiO2 with respect to Si3N4, In2O3-NCs have been inserted in the SiO2 switching oxide of micrometric planar oxide-based resistive random access memory (OxRAM) devices fabricated using the nanodamascene process. Preliminary electrical measurements show switch voltage from high to low resistance state. The devices with In2O3-NCs have been cycled 5 times with identical operating voltages and RESET current meanwhile no switch has been observed for non implanted devices. This first measurement of switching is very promising for the concept of In2O3-NCs based OxRAM memories.

New insight into the promoting role of process on the CeO₂-WO₃/TiO₂ catalyst for NO reduction with NH₃ at low-temperature.

PubMed

Zhang, Shule; Zhong, Qin; Shen, Yuge; Zhu, Li; Ding, Jie

2015-06-15

This study aimed at investigating the reason of high catalytic activity for CeO2-WO3/TiO2 catalyst from the aspects of WO3 interaction with other species and the NO oxidation process. Analysis by X-ray diffractometry, photoluminescence spectra, diffuse reflectance UV-visible, X-ray photoelectron spectroscopy, density functional theory calculations, electron paramagnetic resonance spectroscopy, temperature-programmed-desorption of NO and in situ diffuse reflectance infrared transform spectroscopy showed that WO3 could interact with CeO2 to improve the electron gaining capability of CeO2 species. In addition, WO3 species acted as electron donating groups to transfer the electrons to CeO2 species. The two aspects enhanced the formation of reduced CeO2 species to improve the formation of superoxide ions. Furthermore, the Ce species were the active sites for the NO adsorption and the superoxide ions over the catalyst needed oxidizing the adsorbed NO to improve the NO oxidation. This process was responsible for the high catalytic activity of CeO2-WO3/TiO2 catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

Can disc diffusion susceptibility tests assess the antimicrobial activity of engineered nanoparticles?

NASA Astrophysics Data System (ADS)

Kourmouli, Angeliki; Valenti, Marco; van Rijn, Erwin; Beaumont, Hubertus J. E.; Kalantzi, Olga-Ioanna; Schmidt-Ott, Andreas; Biskos, George

2018-03-01

The use of disc diffusion susceptibility tests to determine the antibacterial activity of engineered nanoparticles (ENPs) is questionable because their low diffusivity practically prevents them from penetrating through the culture media. In this study, we investigate the ability of such a test, namely the Kirby-Bauer disc diffusion test, to determine the antimicrobial activity of Au and Ag ENPs having diameters from 10 to 40 nm on Escherichia coli cultures. As anticipated, the tests did not show any antibacterial effects of Au nanoparticles (NPs) as a result of their negligible diffusivity through the culture media. Ag NPs on the other hand exhibited a strong antimicrobial activity that was independent of their size. Considering that Ag, in contrast to Au, dissolves upon oxidation and dilution in aqueous solutions, the apparent antibacterial behavior of Ag NPs is attributed to the ions they release. The Kirby-Bauer method, and other similar tests, can therefore be employed to probe the antimicrobial activity of ENPs related to their ability to release ions rather than to their unique size-dependent properties. [Figure not available: see fulltext.

Effect of the nano-oxide layer as a Mn diffusion barrier in specular spin valves

NASA Astrophysics Data System (ADS)

Jang, S. H.; Kang, T.; Kim, H. J.; Kim, K. Y.

2002-07-01

In previous work an enhanced giant magnetoresistance (GMR) effect in spin valves (SVs) with a nano-oxide layer (NOL) after annealing at about 250-300 degC has been reported. We have shown that SVs with a NOL also have higher thermal stability of the MR ratio at 300 degC. From secondary-ion-mass spectroscopy and x-ray photoelectron spectroscopy depth profile analysis, the mechanism of the improved thermal stability of the SVs with a NOL is shown to be related to MnO formation within the NOL. Thus, Mn atoms from the FeMn layer are trapped, and Mn diffusion is inhibited by the NOL during annealing.

Ionic-to-Electronic Conductivity Crossover in CdTe-AgI-As2Te3 Glasses: An 110mAg Tracer Diffusion Study.

PubMed

Kassem, M; Alekseev, I; Bokova, M; Le Coq, D; Bychkov, E

2018-04-12

Conductivity isotherms of (CdTe) x (AgI) 0.5- x/2 (As 2 Te 3 ) 0.5- x/2 glasses (0.0 ≤ x ≤ 0.15) reveal a nonmonotonic behavior with increasing CdTe content reminiscent of mixed cation effect in oxide and chalcogenide glasses. Nevertheless, the apparent similarity appears to be partly incorrect. Using 110m Ag tracer diffusion measurements, we show that semiconducting CdTe additions produce a dual effect: (i) decreasing the Ag + ion transport by a factor of ≈200 with a simultaneous increase of the diffusion activation energy and (ii) increasing the electronic conductivity by 1.5 orders of magnitude. Consequently, the conductivity minimum at x = 0.05 reflects an ionic-to-electronic transport crossover; the silver-ion transport number decreases by 3 orders of magnitude with increasing x.

Implications of Occupational Disorder on Ion Mobility in Li4Ti5O12 Battery Materials.

PubMed

Heenen, Hendrik H; Scheurer, Christoph; Reuter, Karsten

2017-06-14

Lithium-titanium-oxide (Li 4 Ti 5 O 12 , LTO) is unique among battery materials due to its exceptional cyclability and high rate capability. This performance is believed to derive at least partly from the occupational disorder introduced via mixed Li/Ti occupancy in the LTO spinel-like structure. We explore the vast configuration space accessible during high-temperature LTO synthesis by Monte Carlo sampling and indeed find lowest-energy structures to be characterized by a high degree of microscopic inhomogeneity. Dynamical simulations in corresponding configurations reveal the dominant fraction of Li ions to be immobile on nanosecond time scales. However, Ti antisite-like defects stabilized by the configurational disorder give rise to a novel correlated ion diffusion mechanism. The resulting fast but localized diffusion could be a key element in the sudden rise in conductivity found in LTO in the early stages of charging and questions the validity of ion mobility measurements for this and other configurationally disordered materials.

Scalable Graphene-Based Membranes for Ionic Sieving with Ultrahigh Charge Selectivity.

PubMed

Hong, Seunghyun; Constans, Charlotte; Surmani Martins, Marcos Vinicius; Seow, Yong Chin; Guevara Carrió, Juan Alfredo; Garaj, Slaven

2017-02-08

Nanostructured graphene-oxide (GO) laminate membranes, exhibiting ultrahigh water flux, are excellent candidates for next generation nanofiltration and desalination membranes, provided the ionic rejection could be further increased without compromising the water flux. Using microscopic drift-diffusion experiments, we demonstrated the ultrahigh charge selectivity for GO membranes, with more than order of magnitude difference in the permeabilities of cationic and anionic species of equivalent hydration radii. Measuring diffusion of a wide range of ions of different size and charge, we were able to clearly disentangle different physical mechanisms contributing to the ionic sieving in GO membranes: electrostatic repulsion between ions and charged chemical groups; and the compression of the ionic hydration shell within the membrane's nanochannels, following the activated behavior. The charge-selectivity allows us to rationally design membranes with increased ionic rejection and opens up the field of ion exchange and electrodialysis to the GO membranes.

Directing the Branching Growth of Cuprous Oxide by OH- Ions

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Si, Yunfei; Xue, Dongfeng

The effect of OH- ions on the branching growth of cuprous oxide microcrystals was systematically studied by a reduction route, where copper-citrate complexes were reduced by glucose under alkaline conditions. Different copper salts including Cu(NO3)2, CuCl2, CuSO4, and Cu(Ac)2 were used in this work. The results indicate that the Cu2O branching growth habit is closely correlated to the concentration of OH- ions, which plays an important role in directing the diffusion-limited branching growth of Cu2O and influencing the reduction power of glucose. A variety of Cu2O branching patterns including 6-pod, 8-pod and 24-pod branches, have been achieved without using template and surfactant. The current method can provide a good platform for studying the growth mechanism of microcrystal branching patterns.

Laboratory Experiments to Study Spherical, Iron Oxide Concretion Growth Without Solid Nuclei: Implications for Understanding Meridiani "Blueberries"

NASA Astrophysics Data System (ADS)

Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.

2006-03-01

Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.

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.

High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

NASA Astrophysics Data System (ADS)

Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

2018-03-01

Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

Inorganic nanostructured materials for high performance electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-01-01

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Inorganic nanostructured materials for high performance electrochemical supercapacitors.

PubMed

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-02-21

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Electrochemical Advanced Oxidation Process for Shipboard Final Purification of Filtered Black Water, Gray Water, and Bilge Water, Vol. 1

DTIC Science & Technology

2001-08-01

doped SnO2 developed by Memming and M`llers (1972) is most directly applicable to our electrodes. This model ignores the effect of ions in the...electron transfer model of Memming and M`llers (1972) with the surface charging/ ion complexation model of Davis et al. (1978). The combined model...model of Memming and M`llers. The model of Davis et al. represents the diffuse double layer by an analytical expression which describes only pure

Excess oxygen limited diffusion and precipitation of iron in amorphous silicon dioxide

NASA Astrophysics Data System (ADS)

Leveneur, J.; Langlois, M.; Kennedy, J.; Metson, James B.

2017-10-01

In micro- and nano- electronic device fabrication, and particularly 3D designs, the diffusion of a metal into sublayers during annealing needs to be minimized as it is usually detrimental to device performance. Diffusion also causes the formation and growth of nanoprecipitates in solid matrices. In this paper, the diffusion behavior of low energy, low fluence, ion implanted iron into a thermally grown silicon oxide layer on silicon is investigated. Different ion beam analysis and imaging techniques were used. Magnetization measurements were also undertaken to provide evidence of nanocrystalline ordering. While standard vacuum furnace annealing and electron beam annealing lead to fast diffusion of the implanted species towards the Si/SiO2 interface, we show that furnace annealing in an oxygen rich atmosphere prevents the diffusion of iron that, in turn, limits the growth of the nanoparticles. The diffusion and particle growth is also greatly reduced when oxygen atoms are implanted in the SiO2 prior to Fe implantation, effectively acting as a diffusion barrier. The excess oxygen is hypothesized to trap Fe atoms and reduce their mean free path during the diffusion. Monte-Carlo simulations of the diffusion process which consider the random walk of Fe, Fick's diffusion of O atoms, Fe precipitation, and desorption of the SiO2 layer under the electron beam annealing were performed. Simulation results for the three preparation conditions are found in good agreement with the experimental data.

Self-aligned periodic Ni nano dots embedded in nano-oxide layer

NASA Astrophysics Data System (ADS)

Doi, M.; Izumi, M.; Kawasaki, S.; Miyake, K.; Sahashi, M.

The Ni nano constriction dots embedded in the Ta-nano-oxide layer (NOL) was prepared by the ion beam sputtering (IBS) method. After the various conditions of the oxidations, the structural analyses of the NOL were performed by RHEED, AES and in situ STM/AFM observations. From the current image of the conductive AFM for NOL, the periodically aligned metallic dots with the size around 5-10 nm were successfully observed. The mechanism of the formation of the self-organized aligned Ni nano constriction dots is discussed from the standpoint of the grain size, the crystal orientation, the preferred oxidation of Ta at the diffused interface.

Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion Batteries

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

Zhou, Hui; Upreti, Shailesh; Chernova, Natasha A.

2015-10-15

The mixed-metal phases, (Li{sub 2}Mn{sub 1-y}Fe{sub y}P{sub 2}O{sub 7}, 0 {le} y {le} 1), were synthesized using a 'wet method', and found to form a solid solution in the P2{sub 1}/a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+ oxidation state for both the Mn and Fe. The electrochemical capacity improves as the Fe concentration increases, as do the intensities of the redox peaks of the cyclic voltammogram, indicating higher lithium-ion diffusivity in the iron phase. The two Li{sup +} ions in the three-dimensional tunnel structure of the pyrophosphate phase allows for the cycling of moremore » than one lithium per redox center. Cyclic voltammograms show a second oxidation peak at 5 V and 5.3 V, indicative of the extraction of the second lithium ion, in agreement with ab initio computation predictions. Thus, electrochemical capacities exceeding 200 Ah/kg may be achieved if a stable electrolyte is found.« less

A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

NASA Astrophysics Data System (ADS)

Majari Kasmaee, L.; Gobal, F.

Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co-Doped Graphitic Nanotubes as High-Performance Lithium-Ion Battery Anodes.

PubMed

Tabassum, Hassina; Zou, Ruqiang; Mahmood, Asif; Liang, Zibin; Wang, Qingfei; Zhang, Hao; Gao, Song; Qu, Chong; Guo, Wenhan; Guo, Shaojun

2018-02-01

Yolk-shell nanostructures have received great attention for boosting the performance of lithium-ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li + ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co-doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni 2 O 3 , Mn 3 O 4 ) through combining pyrolysis with an oxidation method is reported herein. The as-made TMO@BNG exhibits the TMO-dependent lithium-ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium-ion storage capacity of 1554 mA h g -1 at the current density of 96 mA g -1 , good rate ability (410 mA h g -1 at 1.75 A g -1 ), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Rare earth ions doped ZnO: Synthesis, characterization and preliminary photoactivity assessment

NASA Astrophysics Data System (ADS)

Cerrato, Erik; Gionco, Chiara; Berruti, Ilaria; Sordello, Fabrizio; Calza, Paola; Paganini, Maria Cristina

2018-08-01

This work reports the effect of doping zinc oxide with lanthanide ions on structural, EPR and UV visible properties. Bare and doped samples were synthesized using the simple and green hydrothermal process. Different rare earth ions (RE = La, Ce, Pr, Er and Yb) with 1% molar ratio RE/Zn were used. The samples have been studied using X Ray Diffraction, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and UV visible diffuse reflectance spectroscopy. Finally, electron paramagnetic resonance (EPR) spectroscopy, was used to assess the materials photoactivity under UV irradiation, both in solid state, to see the charge carriers' generation and in solution, evaluating the OH• radical formation using the DMPO (5,5-Dimethyl-1-Pyrroline-N-Oxide) spin trapping technique. The results suggest that the synthesized materials could be interesting systems for the photocatalytic abatement of emerging organic persistent pollutants in wastewater treatment plants.

Effects of oxygen-inserted layers on diffusion of boron, phosphorus, and arsenic in silicon for ultra-shallow junction formation

NASA Astrophysics Data System (ADS)

Zhang, X.; Connelly, D.; Takeuchi, H.; Hytha, M.; Mears, R. J.; Rubin, L. M.; Liu, T.-J. K.

2018-03-01

The effects of oxygen-inserted (OI) layers on the diffusion of boron (B), phosphorus (P), and arsenic (As) in silicon (Si) are investigated, for ultra-shallow junction formation by high-dose ion implantation followed by rapid thermal annealing. The projected range (Rp) of the implanted dopants is shallower than the depth of the OI layers. Secondary ion mass spectrometry is used to compare the dopant profiles in silicon samples that have OI layers against the dopant profiles in control samples that do not have OI layers. Diffusion is found to be substantially retarded by the OI layers for B and P, and less for As, providing shallower junction depth. The experimental results suggest that the OI layers serve to block the diffusion of Si self-interstitials and thereby effectively reduce interstitial-aided diffusion beyond the depth of the OI layers. The OI layers also help to retain more dopants within the Si, which technology computer-aided design simulations indicate to be beneficial for achieving shallower junctions with lower sheet resistance to enable further miniaturization of planar metal-oxide-semiconductor field-effect transistors for improved integrated-circuit performance and cost per function.

Integrated Solid/Nanoporous Copper/Oxide Hybrid Bulk Electrodes for High-performance Lithium-Ion Batteries

PubMed Central

Hou, Chao; Lang, Xing-You; Han, Gao-Feng; Li, Ying-Qi; Zhao, Lei; Wen, Zi; Zhu, Yong-Fu; Zhao, Ming; Li, Jian-Chen; Lian, Jian-She; Jiang, Qing

2013-01-01

Nanoarchitectured electroactive materials can boost rates of Li insertion/extraction, showing genuine potential to increase power output of Li-ion batteries. However, electrodes assembled with low-dimensional nanostructured transition metal oxides by conventional approach suffer from dramatic reductions in energy capacities owing to sluggish ion and electron transport kinetics. Here we report that flexible bulk electrodes, made of three-dimensional bicontinuous nanoporous Cu/MnO2 hybrid and seamlessly integrated with Cu solid current collector, substantially optimizes Li storage behavior of the constituent MnO2. As a result of the unique integration of solid/nanoporous hybrid architecture that simultaneously enhances the electron transport of MnO2, facilitates fast ion diffusion and accommodates large volume changes on Li insertion/extraction of MnO2, the supported MnO2 exhibits a stable capacity of as high as ~1100 mA h g−1 for 1000 cycles, and ultrahigh charge/discharge rates. It makes the environmentally friendly and low-cost electrode as a promising anode for high-performance Li-ion battery applications. PMID:24096928

Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

NASA Astrophysics Data System (ADS)

Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

2018-02-01

The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

2018-01-01

Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

Protection of pure iron against high-temperature oxidation using metaborate and metasilicate coatings

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

Husain, Z.

1993-04-01

Sodium metaborate and metasilicate coatings protect pure iron in the temperature range 800 to 1,000 C. Metaborate and metasilicate inhibit oxidation. Protective vonsenite (4 FeO [times] Fe[sub 2]O[sub 3] [times] B[sub 2]O[sub 3]) forms with metaborate, and protective fayalite (2FeO [times] SiO[sub 2]) forms with metasilicate. It is proposed that noncoherent blocking layers of these compounds effectively decrease the interface area for iron ion diffusion.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

Tunneled Mesoporous Carbon Nanofibers with Embedded ZnO Nanoparticles for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Lee, Do-Young; Ahn, Hyo-Jin

2017-04-12

Carbon and metal oxide composites have received considerable attention as anode materials for Li-ion batteries (LIBs) owing to their excellent cycling stability and high specific capacity based on the chemical and physical stability of carbon and the high theoretical specific capacity of metal oxides. However, efforts to obtain ultrafast cycling stability in carbon and metal oxide composites at high current density for practical applications still face important challenges because of the longer Li-ion diffusion pathway, which leads to poor ultrafast performance during cycling. Here, tunneled mesoporous carbon nanofibers with embedded ZnO nanoparticles (TMCNF/ZnO) are synthesized by electrospinning, carbonization, and postcalcination. The optimized TMCNF/ZnO shows improved electrochemical performance, delivering outstanding ultrafast cycling stability, indicating a higher specific capacity than previously reported ZnO-based anode materials in LIBs. Therefore, the unique architecture of TMCNF/ZnO has potential for use as an anode material in ultrafast LIBs.

Doped δ-bismuth oxides to investigate oxygen ion transport as a metric for condensed phase thermite ignition.

PubMed

Wang, Xizheng; Zhou, Wenbo; DeLisio, Jeffery B; Egan, Garth C; Zachariah, Michael R

2017-05-24

Nanothermites offer high energy density and high burn rates, but are mechanistically only now being understood. One question of interest is how initiation occurs and how the ignition temperature is related to microscopic controlling parameters. In this study, we explored the potential role of oxygen ion transport in Bi 2 O 3 as a controlling mechanism for condensed phase ignition reaction. Seven different doped δ-Bi 2 O 3 were synthesized by aerosol spray pyrolysis. The ignition temperatures of Al/doped Bi 2 O 3 , C/doped Bi 2 O 3 and Ta/doped Bi 2 O 3 were measured by temperature-jump/time-of-flight mass spectrometer coupled with a high-speed camera respectively. These results were then correlated to the corresponding oxygen ion conductivity (directly proportional to ion diffusivity) for these doped Bi 2 O 3 measured by impedance spectroscopy. We find that ignition of thermite with doped Bi 2 O 3 as oxidizer occurs at a critical oxygen ion conductivity (∼0.06 S cm -1 ) of doped Bi 2 O 3 in the condensed-phase so long as the aluminum is in a molten state. These results suggest that oxygen ion transport limits the condensed state Bi 2 O 3 oxidized thermite ignition. We also find that the larger oxygen vacancy concentration and the smaller metal-oxide bond energy in doped Bi 2 O 3 , the lower the ignition temperature. The latter suggests that we can consider the possibility of manipulating microscopic properties within a crystal, to tune the resultant energetic properties.

Improvements of anti-corrosion and mechanical properties of NiTi orthopedic materials by acetylene, nitrogen and oxygen plasma immersion ion implantation

NASA Astrophysics Data System (ADS)

Poon, Ray W. Y.; Ho, Joan P. Y.; Liu, Xuanyong; Chung, C. Y.; Chu, Paul K.; Yeung, Kelvin W. K.; Lu, William W.; Cheung, Kenneth M. C.

2005-08-01

Nickel-titanium shape memory alloys (NiTi) are useful materials in orthopedics and orthodontics due to their unique super-elasticity and shape memory effects. However, the problem associated with the release of harmful Ni ions to human tissues and fluids has been raising safety concern. Hence, it is necessary to produce a surface barrier to impede the out-diffusion of Ni ions from the materials. We have conducted acetylene, nitrogen and oxygen plasma immersion ion implantation (PIII) into NiTi alloys in an attempt to improve the surface properties. All the implanted and annealed samples surfaces exhibit outstanding corrosion and Ni out-diffusion resistance. Besides, the implanted layers are mechanically stronger than the substrate underneath. XPS analyses disclose that the layer formed by C2H2 PIII is composed of mainly TiCx with increasing Ti to C concentration ratios towards the bulk. The nitrogen PIII layer is observed to be TiN, whereas the oxygen PIII layer is composed of oxides of Ti4+, Ti3+ and Ti2+.

Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries

DOE PAGES

Smith, Kassiopeia A.; Savva, Andreas I.; Deng, Changjian; ...

2017-03-23

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformationmore » to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less

Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries

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

Smith, Kassiopeia A.; Savva, Andreas I.; Deng, Changjian

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformationmore » to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less

Effects of the polarizability and packing density of transparent oxide films on water vapor permeation.

PubMed

Koo, Won Hoe; Jeong, Soon Moon; Choi, Sang Hun; Kim, Woo Jin; Baik, Hong Koo; Lee, Sung Man; Lee, Se Jong

2005-06-09

The tin oxide and silicon oxide films have been deposited on polycarbonate substrates as gas barrier films, using a thermal evaporation and ion beam assisted deposition process. The oxide films deposited by ion beam assisted deposition show a much lower water vapor transmission rate than those by thermal evaporation. The tin oxide films show a similar water vapor transmission rate to the silicon oxide films in thermal evaporation but a lower water vapor transmission rate in IBAD. These results are related to the fact that the permeation of water vapor with a large dipole moment is affected by the chemistry of oxides and the packing density of the oxide films. The permeation mechanism of water vapor through the oxide films is discussed in terms of the chemical interaction with water vapor and the microstructure of the oxide films. The chemical interaction of water vapor with oxide films has been investigated by the refractive index from ellipsometry and the OH group peak from X-ray photoelectron spectroscopy, and the microstructure of the composite oxide films was characterized using atomic force microscopy and a transmission electron microscope. The activation energy for water vapor permeation through the oxide films has also been measured in relation to the permeation mechanism of water vapor. The diffusivity of water vapor for the tin oxide films has been calculated from the time lag plot, and its implications are discussed.

Surface modifications of AISI 420 stainless steel by low energy Yttrium ions

NASA Astrophysics Data System (ADS)

Nassisi, Vincenzo; Delle Side, Domenico; Turco, Vito; Martina, Luigi

2018-01-01

In this work, we study surface modifications of AISI 420 stainless steel specimens in order to improve their surface properties. Oxidation resistance and surface micro-hardness were analyzed. Using an ion beam delivered by a Laser Ion Source (LIS) coupled to an electrostatic accelerator, we performed implantation of low energy yttrium ions on the samples. The ions experienced an acceleration passing through a gap whose ends had a potential difference of 60 kV. The gap was placed immediately before the samples surface. The LIS produced high ions fluxes per laser pulse, up to 3x1011 ions/cm2, resulting in a total implanted flux of 7x1015 ions/cm2. The samples were characterized before and after ion implantation using two analytical techniques. They were also thermally treated to investigate the oxide scale. The crystal phases were identified by an X-ray diffractometer, while the micro-hardness was assayed using the scratch test and a profilometer. The first analysis was applied to blank, implanted and thermally treated sample surface, while the latter was applied only to blank and implanted sample surfaces. We found a slight increase in the hardness values and an increase to oxygen resistance. The implantation technique we used has the advantages, with respect to conventional methods, to modify the samples at low temperature avoiding stray diffusion of ions inside the substrate bulk.

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

DOE PAGES

Liu, Qi; Li, Zhe-Fei; Liu, Yadong; ...

2015-01-20

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g -1 and 1,550 Wh kg -1) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol–gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g -1, approaching the theoretical value (443 mAh g -1), a long cyclability andmore » significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. Finally, this method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.« less

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.

Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

PubMed

Jin, Zhen; Yang, Meng; Chen, Shao-Hua; Liu, Jin-Huai; Li, Qun-Xiang; Huang, Xing-Jiu

2017-02-21

Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO 2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO 2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in a SiO2-CaO-MgO-Al2O3 molten slag at 1723 K.

PubMed

Gao, Yunming; Yang, Chuanghuang; Zhang, Canlei; Qin, Qingwei; Chen, George Z

2017-06-21

Production of metallic iron through molten oxide electrolysis using inert electrodes is an alternative route for fast ironmaking without CO 2 emissions. The fact that many inorganic oxides melt at ultrahigh temperatures (>1500 K) challenges conventional electro-analytical techniques used in aqueous, organic and molten salt electrolytes. However, in order to design a feasible and effective electrolytic process, it is necessary to best understand the electrochemical properties of iron ions in molten oxide electrolytes. In this work, a magnesia-stabilised zirconia (MSZ) tube with a closed end was used to construct an integrated three-electrode cell with a "MSZ|Pt|O 2 (air)" assembly functioning as the solid electrolyte, the reference electrode and also the counter electrode. Electrochemical reduction of iron ions was systematically investigated on an iridium (Ir) wire working electrode in a SiO 2 -CaO-MgO-Al 2 O 3 molten slag at 1723 K by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis (PE). The results show that the electroreduction of the Fe 2+ ion to Fe on the Ir electrode in the molten slag follows a single two-electron transfer step, and the rate of the process is diffusion controlled. The peak current on the obtained CVs is proportional to the concentration of the Fe 2+ ion in the molten slag and the square root of scan rate. The diffusion coefficient of Fe 2+ ions in the molten slag containing 5 wt% FeO at 1723 K was derived to be (3.43 ± 0.06) × 10 -6 cm 2 s -1 from CP analysis. However, a couple of subsequent processes, i.e. alloy formation on the Ir electrode surface and interdiffusion, were found to affect the kinetics of iron deposition. An ECC mechanism is proposed to account for the CV observations. The findings from this work confirm that zirconia-based solid electrolytes can play an important role in electrochemical fundamental research in high temperature molten slag electrolytes.

Method of fabricating optical waveguides by ion implantation doping

DOEpatents

Appleton, B.R.; Ashley, P.R.; Buchal, C.J.

1987-03-24

A method for fabricating high-quality optical waveguides in optical quality oxide crystals by ion implantation doping and controlled epitaxial recrystallization is provided. Masked LiNbO/sub 3/ crystals are implanted with high concentrations of Ti dopant at ion energies of about 360 keV while maintaining the crystal near liquid nitrogen temperature. Ion implantation doping produces an amorphous, Ti-rich nonequilibrium phase in the implanted region. Subsequent thermal annealing in a water-saturated oxygen atmosphere at up to 1000/degree/C produces solid-phase epitaxial regrowth onto the crystalline substrate. A high-quality crystalline layer results which incorporates the Ti into the crystal structure at much higher concentrations than is possible by standard diffusion techniques, and this implanted region has excellent optical waveguiding properties.

Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes.

PubMed

Savoie, Brett M; Webb, Michael A; Miller, Thomas F

2017-02-02

Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li + conductivity remains a barrier to technological viability. SPEs are designed to maximize Li + diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li + diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li + diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li + diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.

Structure, hydrolysis, and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2016-09-01

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries. Here, we employ Car-Parrinello molecular dynamics simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction, and diffusion of aqueous V2+, V3+, VO2+, and VO 2+ ions at 300 K. The results indicate that the first hydration shell of both V2+ and V3+ contains six water molecules, while VO2+ is coordinated to five and VO 2+ to three water ligands. The first acidity constants (pKa) estimated using metadynamics simulations are 2.47, 3.06, and 5.38 for aqueous V3+, VO 2+ , and VO2+, respectively, while V2+ is predicted to be a fairly weak acid in aqueous solution with a pKa value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO 2+ ion has a significant impact on water hydrolysis leading to a much higher pKa value of 4.8. This should result in a lower propensity of aqueous VO 2+ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V 3 + < VO 2 + < V O 2 + < V 2 + and thus correlate with the simulated hydrolysis constants, namely, the higher the pKa value, the greater the diffusion coefficient.

Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, December 31, 1993

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

Doyle, F.M.

1993-12-31

The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in term of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the thirteenth quarter, wet oxidation tests were done on coal samples from the Pennsylvania State Coal Bank. As-received and oxidized coal samples were studied bymore » Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy to detect functional groups that might be responsible for changing the hydrophobicity of coal samples. Coal samples from the Pennsylvania State Coal Bank were oxidized for 5 hours at room temperature using 10% H{sub 2}O{sub 2} at pH 1.0, 1.0 M HNO{sub 3} or 0.05 M Fe{sub 2}(SO{sub 4}){sub 3} at pH 1.0. Details of the experimental procedure used in the wet oxidation tests were provided in our September 30, 1993 report, along with results of ion-exchange analysis and film flotation tests on as-received and oxidized coal samples. Table II shows the weight percentage of carboxylic and phenolic group oxygen generated by oxidation with different treatments, as determined by ion-exchange. DRIFT spectroscopic analysis was done on as-received and oxidized samples to identify different functionalities directly, to supplement the information on carboxylic and phenolic groups obtained indirectly by ion-exchange methods. The procedure for DRIFT analysis was reported in our June 30, 1993 report.« less

In situ study of Li-ions diffusion and deformation in Li-rich cathode materials by using scanning probe microscopy techniques

NASA Astrophysics Data System (ADS)

Zeng, Kaiyang; Li, Tao; Tian, Tian

2017-08-01

In this paper, the scanning probe microscopy (SPM) based techniques, namely, conductive-AFM, electrochemical strain microscopy (ESM) and AM-FM (amplitude modulation-frequency modulation) techniques, are used to in situ characterize the changes in topography, conductivity and elastic properties of Li-rich layered oxide cathode (Li1.2Mn0.54Ni0.13Co0.13O2) materials, in the form of nanoparticles, when subject to the external electric field. Nanoparticles are the basic building blocks for composite cathode in a Li-ion rechargeable battery. Characterization of the structure and electrochemical properties of the nanoparticles is very important to understand the performance and reliability of the battery materials and devices. In this study, the conductivity, deformation and mechanical properties of the Li-rich oxide nanoparticles under different polarities of biases are studied using the above-mentioned SPM techniques. This information can be correlated with the Li+-ion diffusion and migration in the particles under external electrical field. The results also confirm that the SPM techniques are ideal tools to study the changes in various properties of electrode materials at nano- to micro-scales during or after the ‘simulated’ battery operation conditions. These techniques can also be used to in situ characterize the electrochemical performances of other energy storage materials, especially in the form of the nanoparticles.

Energetic Nitrogen Ions within the Inner Magnetosphere of Saturn

NASA Astrophysics Data System (ADS)

Sittler, E. C.; Johnson, R. E.; Richardson, J. D.; Jurac, S.; Moore, M.; Cooper, J. F.; Mauk, B. H.; Smith, H. T.; Michael, M.; Paranicus, C.; Armstrong, T. P.; Tsurutani, B.; Connerney, J. E. P.

2003-05-01

Titan's interaction with Saturn's magnetosphere will result in the energetic ejection of atomic nitrogen atoms into Saturn's magnetosphere due to dissociation of N2 by electrons, ions, and UV photons. The ejection of N atoms into Saturn's magnetosphere will form a nitrogen torus around Saturn with mean density of about 4 atoms/cm3 with source strength of 4.5x1025 atoms/sec. These nitrogen atoms are ionized by photoionization, electron impact ionization and charge exchange reactions producing an N+ torus of 1-4 keV suprathermal ions centered on Titan's orbital position. We will show Voyager plasma observations that demonstrate presence of a suprathermal ion component within Saturn's outer magnetosphere. The Voyager LECP data also reported the presence of inward diffusing energetic ions from the outer magnetosphere of Saturn, which could have an N+ contribution. If so, when one conserves the first and second adiabatic invariant the N+ ions will have energies in excess of 100 keV at Dione's L shell and greater than 400 keV at Enceladus' L shell. Energetic charged particle radial diffusion coefficients are also used to constrain the model results. But, one must also consider the solar wind as another important source of keV ions, in the form of protons and alpha particles, for Saturn's outer magnetosphere. Initial estimates indicate that a solar wind source could dominate in the outer magnetosphere, but various required parameters for this estimate are highly uncertain and will have to await Cassini results for confirmation. We show that satellite sweeping and charged particle precipitation within the middle and outer magnetosphere will tend to enrich N+ ions relative to protons within Saturn's inner magnetosphere as they diffuse radially inward for radial diffusion coefficients that do not violate observations. Charge exchange reactions within the inner magnetosphere can be an important loss mechanism for O+ ions, but to a lesser degree for N+ ions. Initial LECP results using composition data at energies greater than 200 keV/nucl., showed that heavy ions within Saturn's inner magnetosphere dominated over protons, but that contrary to original suggestions that these ions were O+ , we now argue that they are instead N+ ions. With energetic N+ ions bombarding the icy satellite surfaces chemical reactions can occur at the end of the ion tracks and produce nitrogen oxides or other nitrogen containing molecules such that the radiology within the icy surfaces is driven by the impacting energetic nitrogen ions. These can accumulate over the lifetime of the Saturn system.

Chemically reduced graphene oxide-P25-Au nanocomposite materials and their photoelectrocatalytic and photocatalytic applications.

PubMed

Praveen, Raju; Ramaraj, Ramasamy

2016-10-05

Visible light active photocatalysts consisting of gold nanoparticle (Au NP) decorated chemically reduced graphene oxide-P25 nanocomposite materials (CRGO-P25-Au NCMs) were prepared through a one-pot chemical reduction method. The nanocomposite materials were characterized using diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and electrochemical impedance spectroscopy (EIS) analyses. The performances of CRGO-P25-Au NCM modified ITO electrodes were evaluated towards the photoelectrochemical oxidation of methanol. The photoelectrode fabricated using CRGO-P25-Au NCM exhibited a higher photocurrent of 293 μA cm -2 compared to other control electrodes. The CRGO-P25-Au NCMs were also used for the photocatalytic reduction of highly toxic chromium(vi) ions to chromium(iii) ions in the presence of oxalic acid as a sacrificial electron donor. The results showed that around 75% of the Cr(vi) ions were photocatalytically reduced to Cr(iii) ions by the CRGO-P25-Au NCM within the light irradiation time of 1 h. In both applications, the enhanced catalytic activity of the CRGO-P25-Au NCM was attributed to the improved visible light absorption and the reduced charge recombination exerted by the interaction of CRGO and Au NPs with P25 and their synergistic effects.

The influence of aliovalent impurities on the oxidation kinetics of nickel at high temperatures

NASA Astrophysics Data System (ADS)

Mrowec, S.; Grzesik, Z.; Rajchel, B.; Gil, A.; Dabek, J.

2005-01-01

The influence of chromium and sodium on the nickel oxidation kinetics has been studied as a function of temperature (1373-1673 K) and oxygen activity (10-105 Pa O2), using microthermogravimetric techniques. It has been shown that the oxidation of Ni-Cr and Ni-Na alloys, like that of pure nickel, follows strictly the parabolic rate law being thus diffusion controlled. In agreement with the defect model of Ni1-yO, it has been found that the oxidation rate of the Ni-Cr alloy is higher than that of pure nickel, the reaction rate is pressure independent and the activation energy of this process is lower. This implies that the concentration of double ionized cation vacancies in a Ni1-yO-Cr2O3 solid solution is fixed on a constant level by trivalent chromium ions, substitutionally incorporated into the cation sublattice of this oxide. In the case of the Ni-Na alloy, on the other hand, the oxidation rate is lower than that of pure nickel, the activation energy is higher and the oxidation rate increases more rapidly with oxygen pressure. These results can again be explained in terms of the doping effect, by assuming that univalent sodium ions dissolve substitutionally in the cation sublattice of nickel oxide.

Effect of sharp maximum in ion diffusivity for liquid xenon

NASA Astrophysics Data System (ADS)

Lankin, A. V.; Orekhov, M. A.

2016-11-01

Ion diffusion in a liquid usually could be treated as a movement of an ion cluster in a viscous media. For small ions this leads to a special feature: diffusion coefficient is either independent of the ion size or increases with it. We find a different behavior for small ions in liquid xenon. Calculation of the dependence of an ion diffusion coefficient in liquid xenon on the ion size is carried out. Classical molecular dynamics method is applied. Calculated dependence of the ion diffusion coefficient on its radius has sharp maximums at the ion radiuses 1.75 and 2 Å. Every maximum is placed between two regions with different stable ion cluster configurations. This leads to the instability of these configurations in a small region between them. Consequently ion with radius near 1.75 or 2 Å could jump from one configuration to another. This increases the speed of the diffusion. A simple qualitative model for this effect is suggested. The decomposition of the ion movement into continuous and jump diffusion shows that continuous part of the diffusion is the same as for the ion cluster in the stable region.

Oxidation of metals and alloys in controlled atmospheres using in situ transmission electron microscopy and Auger spectrography

NASA Technical Reports Server (NTRS)

Rao, D. B.; Heinemann, K.; Douglass, D. L.

1976-01-01

Single-crystalline thin films of copper were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of .005 Torr in situ in a high-resolution electron microscope. The specimens were prepared by epitaxial vapor deposition onto polished 100 and 110 faces of rocksalt and mounted in a hot stage inside an ultra-high-vacuum specimen chamber of the microscope. Large amounts of sulfur, carbon, and oxygen were detected by Auger electron spectroscopy on the surface of the as-received films and were removed in situ by ion-sputter etching immediately prior to the oxidation. The nucleation and growth characteristics of Cu2O on Cu were studied. Results show that neither stacking faults nor dislocations are associated with the Cu2O nucleation sites. The growth of Cu2O nuclei is linear with time. The experimental findings, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving (a) the formation of a surface-charge layer, (b) oxygen saturation in the metal and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

The First National Student Conference: NASA University Research Centers at Minority Institutions

NASA Technical Reports Server (NTRS)

Daso, Endwell O. (Editor); Mebane, Stacie (Editor)

1997-01-01

The conference includes contributions from 13 minority universities with NASA University Research Centers. Topics discussed include: leadership, survival strategies, life support systems, food systems, simulated hypergravity, chromium diffusion doping, radiation effects on dc-dc converters, metal oxide glasses, crystal growth of Bil3, science and communication on wheels, semiconductor thin films, numerical solution of random algebraic equations, fuzzy logic control, spatial resolution of satellite images, programming language development, nitric oxide in the thermosphere and mesosphere, high performance polyimides, crossover control in genetic algorithms, hyperthermal ion scattering, etc.

Exploring Lithium Deficiency in Layered Oxide Cathode for Li-Ion Battery

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

Cho, Sung-Jin; Uddin, Md-Jamal; Alaboina, Pankaj K.

Abstract or short description: The ever-growing demand for high capacity cathode materials is on the rise since the futuristic applications are knocking on the door. Conventional approach to developing such cathode relies on the lithium-excess materials to operate the cathode at high voltage and extract more lithium-ion. Yet, they fail to satiate the needs because of their unresolved issues upon cycling such as, for lithium manganese-rich layered oxides – their voltage fading, and for as nickel-based layered oxides – the structural transition. Here, in contrast, lithium-deficient ratio is demonstrated as a new approach to attain high capacity at high voltagemore » for layered oxide cathodes. Rapid and cost effective lithiation of a porous hydroxide precursor with lithium deficient ratio acted as a driving force to partially convert the layered material to spinel phase yielding in a multiphase structure (MPS) cathode material. Upon cycling, MPS revealed structural stability at high voltage and high temperature and resulted in fast lithium-ion diffusion by providing a distinctive SEI chemistry – MPS displayed minimum lithium loss in SEI and formed a thinner SEI. MPS thus offer high energy and high power applications and provides a new perspective compared to the conventional layered cathode materials denying the focus for lithium excess material.« less

Magneto-Ionic Control of Interfacial Magnetic Anisotorpy

NASA Astrophysics Data System (ADS)

Bauer, Uwe; Emori, Satoru; Beach, Geoffrey

2014-03-01

Voltage control of magnetism could bring about revolutionary new spintronic memory and logic devices. Here, we examine domain wall (DW) dynamics in ultrathin Co films and nanowires under the influence of a voltage applied across a gadolinium oxide gate dielectric that simultaneously acts as an oxygen ion conductor. We investigate two electrode configurations, one with a continuous gate dielectric and the other with a patterned gate dielectric which exhibits an open oxide edge right underneath the electrode perimeter. We demonstrate that the open oxide edge acts as a fast diffusion path for oxygen ions and allows voltage-induced switching of magnetic anisotropy at the nanoscale by modulating interfacial chemistry rather than charge density. At room temperature this effect is limited to the vicinity of the open oxide edge, but at a temperature of 100°C it allows complete control over magnetic anisotropy across the whole electrode area, due to higher oxygen ion mobility at elevated temperature. We then harness this novel ``magneto-ionic'' effect to create unprecedentedly strong voltage-induced anisotropy modifications of 3000 fJ/Vm and create electrically programmable DW traps with pinning strengths of 650 Oe, enough to bring to a standstill DWs travelling at speeds of at least 20 m/s. This work is supported by the National Science Foundation through grant ECCS-1128439.

Microwave exfoliated graphene oxide/TiO{sub 2} nanowire hybrid for high performance lithium ion battery

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

Ishtiaque Shuvo, Mohammad Arif; Rodriguez, Gerardo; Karim, Hasanul

Lithium ion battery (LIB) is a key solution to the demand of ever-improving, high energy density, clean-alternative energy systems. In LIB, graphite is the most commonly used anode material; however, lithium-ion intercalation in graphite is limited, hindering the battery charge rate and capacity. To date, one of the approaches in LIB performance improvement is by using porous carbon (PC) to replace graphite as anode material. PC's pore structure facilitates ion transport and has been proven to be an excellent anode material candidate in high power density LIBs. In addition, to overcome the limited lithium-ion intercalation obstacle, nanostructured anode assembly hasmore » been extensively studied to increase the lithium-ion diffusion rate. Among these approaches, high specific surface area metal oxide nanowires connecting nanostructured carbon materials accumulation have shown promising results for enhanced lithium-ion intercalation. Herein, we demonstrate a hydrothermal approach of growing TiO{sub 2} nanowires (TON) on microwave exfoliated graphene oxide (MEGO) to further improve LIB performance over PC. This MEGO-TON hybrid not only uses the high surface area of MEGO but also increases the specific surface area for electrode–electrolyte interaction. Therefore, this new nanowire/MEGO hybrid anode material enhances both the specific capacity and charge–discharge rate. Scanning electron microscopy and X-ray diffraction were used for materials characterization. Battery analyzer was used for measuring the electrical performance of the battery. The testing results have shown that MEGO-TON hybrid provides up to 80% increment of specific capacity compared to PC anode.« less

Ultra-low-energy ion-beam synthesis of nanometer-separated Si nanoparticles and Ag nanocrystals 2D layers

NASA Astrophysics Data System (ADS)

Carrada, M.; Haj Salem, A.; Pecassou, B.; Paillard, V.; Ben Assayag, G.

2018-03-01

2D networks of Si and Ag nanocrystals have been fabricated in the same SiO2 matrix by Ultra-Low-Energy Ion-Beam-Synthesis. Our synthesis scheme differs from a simple sequential ion implantation and its key point is the control of the matrix integrity through an appropriate intermediate thermal annealing. Si nanocrystal layer is synthesised first due to high thermal budget required for nucleation, while the second Ag nanocrystal plane is formed during a subsequent implantation due to the high diffusivity of Ag in silica. The aim of this work is to show how it is possible to overcome the limitation related to ion mixing and implantation damage to obtain double layers of Si-NCs and Ag-NCs with controlled characteristics. For this, we take advantage of annealing under slight oxidizing ambient to control the oxidation of Si-NCs and the Si excess in the matrix. The nanocrystal characteristics and in particular their position and size can be adjusted thanks to a compromise between the implantation energy, the implanted dose for both Si and Ag ions and the intermediate annealing conditions (atmosphere, temperature and duration).

Studies on human fetal lens crystallins under oxidative stress and protective effects of tea polyphenols.

PubMed

Xiang, H; Pan, S; Li, S

1998-09-01

To investigate the oxidative modification of water-soluble crystallins of human fetal lens with H2O2 and fourteen metal ions with or without EDTA. Tea-polyphenols (TP) was added to above solutions in order to testing their antioxidative abilities. The experiments were performed at 37 degrees C with final concentration of 2.5 mg/ml protein, 0.1 mM metal ions, 0.3 mM EDTA and 1.0 mM H2O2. Then the TP was added to the solution with CuSO4 and H2O2, after 5 or 24 hours, the crystallins were analysed with SDS-PAGE and IEF. There were marked oxidative modifications of lens protein in H2O2 and copper without EDTA. In SDS-PAGE patterns, we found an increase in those species above of bands higher than 30 kD and some diffuse bands from 30 to 17 kD after 5 hours. In IEF patterns, there were a general increase on acidity with loss of the more basic species. When the TP was added, there was not any difference with control group. The results indicate that exposure of water-soluble protein to H2O2 and copper leads to covalent crosslinking and cleavage of polypeptides. After 24 hours, the development of the oxidative modifications of crystallins continues, comparison with the catalytic strength, copper ions stronger than the iron ions. On other hand, this work reported that the anti-oxidative action of TP is strong.

Defect-Tolerant Diffusion Channels for Mg 2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO 4 and Mg x Fe 2–xB 2O 5

DOE PAGES

Bo, Shou-Hang; Grey, Clare P.; Khalifah, Peter G.

2015-06-10

The reversible room temperature intercalation of Mg 2+ ions is difficult to achieve, but may offer substantial advantages in the design of next-generation batteries if this electrochemical process can be successfully realized. Two types of quadruple ribbon-type transition metal borates (Mg xFe 2-xB 2O 5 and MgVBO 4) with high theoretical capacities (186 mAh/g and 360 mAh/g) have been synthesized and structurally characterized through the combined Rietveld refinement of synchrotron and time-of-flight neutron diffraction data. Neither MgVBO 4 nor Mg xFe 2-xB 2O 5 can be chemically oxidized at room temperature, though Mg can be dynamically removed from themore » latter phase at elevated temperatures (approximately 200 - 500 °C). Findings show that Mg diffusion in the Mg xFe 2-xB 2O 5 structure is more facile for the inner two octahedral sites than for the two outer octahedral sites in the ribbons, a result supported by both the refined site occupancies after Mg removal and by bond valence sum difference map calculations of diffusion paths in the pristine material. Mg diffusion in this pyroborate Mg xFe 2-xB 2O 5 framework is also found to be tolerant to the presence of Mg/Fe disorder since Mg ions can diffuse through interstitial channels which bypass Fe-containing sites.« less

The oxidation of Inconel-690 alloy at 600 K in air

NASA Astrophysics Data System (ADS)

Allen, G. C.; Dyke, J. M.; Harris, S. J.; Morris, A.

1988-03-01

The alloy Inconel-690 has been oxidised at 600 K in air for periods varying between 30 s and 120 h and the composition of the oxide layer formed examined by scanning Auger microscopy (SAM), scanning electron microscopy with energy dispersive analysis of X-rays (SEM/EDAX), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). Analysis of the spectra revealed the formation of a layer of essentially α-Cr 2O 3 at room temperature. Oxidation at 600 K resulted in the formation of a duplex oxide film with a thin outer layer of iron(III) oxide. Beneath this was a mixed chromium, iron, nickel oxide. Following 8 h of oxidation at 600 K the oxide was approximately 10 nm thick but this was found to vary with the physical surface of the underlying alloy which also appeared to affect the relative rates of diffusion of the ionic species during film growth.

Electro-diffusion in a plasma with two ion species

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

Kagan, Grigory; Tang Xianzhu

2012-08-15

Electric field is a thermodynamic force that can drive collisional inter-ion-species transport in a multicomponent plasma. In an inertial confinement fusion capsule, such transport causes fuel ion separation even with a target initially prepared to have equal number densities for the two fuel ion species. Unlike the baro-diffusion driven by ion pressure gradient and the thermo-diffusion driven by ion and electron temperature gradients, electro-diffusion has a critical dependence on the charge-to-mass ratio of the ion species. Specifically, it is shown here that electro-diffusion vanishes if the ion species have the same charge-to-mass ratio. An explicit expression for the electro-diffusion ratiomore » is obtained and used to investigate the relative importance of electro- and baro-diffusion mechanisms. In particular, it is found that electro-diffusion reinforces baro-diffusion in the deuterium and tritium mix, but tends to cancel it in the deuterium and helium-3 mix.« less

Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

PubMed Central

Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

2018-01-01

Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

Building one-dimensional oxide nanostructure arrays on conductive metal substrates for lithium-ion battery anodes.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized alumina membrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Hierarchically Nanostructured Transition Metal Oxides for Lithium-Ion Batteries.

PubMed

Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo; Pang, Huan

2018-03-01

Lithium-ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li-ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed.

Relationship between ion migration and interfacial degradation of CH3NH3PbI3 perovskite solar cells under thermal conditions.

PubMed

Kim, Seongtak; Bae, Soohyun; Lee, Sang-Won; Cho, Kyungjin; Lee, Kyung Dong; Kim, Hyunho; Park, Sungeun; Kwon, Guhan; Ahn, Seh-Won; Lee, Heon-Min; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

2017-04-26

Organic-inorganic hybrid perovskite solar cells (PSCs) have been extensively studied because of their outstanding performance: a power conversion efficiency exceeding 22% has been achieved. The most commonly used PSCs consist of CH 3 NH 3 PbI 3 (MAPbI 3 ) with a hole-selective contact, such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spiro-bifluorene (spiro-OMeTAD), for collecting holes. From the perspective of long-term operation of solar cells, the cell performance and constituent layers (MAPbI 3 , spiro-OMeTAD, etc.) may be influenced by external conditions like temperature, light, etc. Herein, we report the effects of temperature on spiro-OMeTAD and the interface between MAPbI 3 and spiro-OMeTAD in a solar cell. It was confirmed that, at high temperatures (85 °C), I - and CH 3 NH 3 + (MA + ) diffused into the spiro-OMeTAD layer in the form of CH 3 NH 3 I (MAI). The diffused I - ions prevented oxidation of spiro-OMeTAD, thereby degrading the electrical properties of spiro-OMeTAD. Since ion diffusion can occur during outdoor operation, the structural design of PSCs must be considered to achieve long-term stability.

Development of w/o microemulsion for transdermal delivery of iodide ions.

PubMed

Lou, Hao; Qiu, Ni; Crill, Catherine; Helms, Richard; Almoazen, Hassan

2013-03-01

The objective of this study was to develop a water-in-oil (w/o) microemulsion which can be utilized as a transdermal delivery for iodide ions. Several w/o microemulsion formulations were prepared utilizing Span 20, ethanol, Capryol 90®, and water. The selected formulations had 5%, 10%, 15%, 20%, and a maximum of 23% w/w water content. Potassium iodide (KI) was incorporated in all formulations at 5% w/v. Physicochemical characterizations were conducted to evaluate the structure and stability. These studies included: mean droplet size, pH, viscosity, conductivity, and chemical stability tests. In vitro human skin permeation studies were conducted to evaluate the diffusion of the iodide ion through human skin. The w/o microemulsion formulations were stable and compatible with iodide ions with water content ranging from 5% to 23% w/w. The addition of KI influenced the physicochemical properties of microemulsion as compared to blank microemulsion formulations. In vitro human skin permeation studies indicated that selected formulations improved iodide ion diffusion significantly as compared to control (KI solution; P value<0.05). Iodide ions were entrapped within the aqueous core of w/o microemulsion. Span 20, ethanol and Capryol 90 protected the iodide ions against oxidation and formed a stable microemulsion. It is worth to note that according to Hofmeister series, iodide ions tend to lower the interfacial tension between water and oil and consequently enhance overall stability. This work illustrates that microemulsion system can be utilized as a vehicle for the transdermal administration of iodide.

Oxidative particle mixtures for groundwater treatment

DOEpatents

Siegrist, Robert L.; Murdoch, Lawrence C.

2000-01-01

The invention is a method and a composition of a mixture for degradation and immobilization of contaminants in soil and groundwater. The oxidative particle mixture and method includes providing a material having a minimal volume of free water, mixing at least one inorganic oxidative chemical in a granular form with a carrier fluid containing a fine grained inorganic hydrophilic compound and injecting the resulting mixture into the subsurface. The granular form of the inorganic oxidative chemical dissolves within the areas of injection, and the oxidative ions move by diffusion and/or advection, therefore extending the treatment zone over a wider area than the injection area. The organic contaminants in the soil and groundwater are degraded by the oxidative ions, which form solid byproducts that can sorb significant amounts of inorganic contaminants, metals, and radionuclides for in situ treatment and immobilization of contaminants. The method and composition of the oxidative particle mixture for long-term treatment and immobilization of contaminants in soil and groundwater provides for a reduction in toxicity of contaminants in a subsurface area of contamination without the need for continued injection of treatment material, or for movement of the contaminants, or without the need for continuous pumping of groundwater through the treatment zone, or removal of groundwater from the subsurface area of contamination.

Method of fabricating optical waveguides by ion implantation doping

DOEpatents

Appleton, Bill R.; Ashley, Paul R.; Buchal, Christopher J.

1989-01-01

A method for fabricating high-quality optical waveguides in optical quality oxide crystals by ion implantation doping and controlled epitaxial recrystallization is provided. Masked LiNbO.sub.3 crystals are implanted with high concentrations of Ti dopant at ion energies of about 350 keV while maintaining the crystal near liquid nitrogen temperature. Ion implantation doping produces an amorphous, Ti-rich nonequilibrium phase in the implanted region. Subsequent thermal annealing in a water-saturated oxygen atmosphere at up to 1000.degree. C. produces solid-phase epitaxial regrowth onto the crystalline substrate. A high-quality single crystalline layer results which incorporates the Ti into the crystal structure at much higher concentrations than is possible by standard diffusion techniques, and this implanted region has excellent optical waveguides properties.

Anisotropic vacancy-mediated phonon mode softening in Sm and Gd doped ceria.

PubMed

Jung, Dong-Hyuk; Lee, Ji-Hwan; Kilic, Mehmet Emin; Soon, Aloysius

2018-04-18

Ceria doped with Sm and Gd (SDC and GDC) has been suggested as a promising candidate for the electrolyte used in solid oxide fuel cells (SOFCs), since it has relatively high oxygen ion conductivity at intermediate temperature. There have been many previous experimental and computational studies to investigate the properties, structure, and effect of vacancies, etc. for SDC and GDC. However, in these previous studies, it is commonly assumed that the interaction between oxygen vacancies is negligible and many focus only on the mono-vacancy system. In addition, the possibility of anisotropic vibrational motion of the oxygen ions around vacancies is often neglected. In this paper, using both first-principle density-functional theory and classical molecular dynamics calculations, we investigate the structural and vibrational properties of the optimized SDC and GDC structures, such as bonding analysis, phonon density-of-state and mean-square-displacement of the oxygen ions. Also, we report the direction-dependent vibrations at the specific frequency of the oxygen ions near the vacancies, activation energies, and diffusion coefficients of SDC and GDC which can extend our understanding of diffusion dynamics in doped ceria-based electrolytes for SOFC applications.

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review

NASA Astrophysics Data System (ADS)

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2012-12-01

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

PubMed

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2013-01-07

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Structure and mechanisms underlying ion transport in ternary polymer electrolytes containing ionic liquids

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

We use all atom molecular dynamics simulations to investigate the influence of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) ionic liquid on the structure and transport properties of poly(ethylene oxide) (PEO) polymer electrolytes doped with LiPF6 salt. We observe enhanced diffusivities of the Li+, PF6-, and BMIM+ ions with increasing loading of the ionic liquid. Interplay between the different ion-ion and ion-polymer interactions is seen to lead to a destabilization of the Li-PF6 coordination and increase in the strength of association between the Li+ cations and the polymer backbone. As a consequence, the polymer segmental relaxation times are shown to be only moderately affected by the addition of ionic liquids. The ionic-liquid induced changes in the mobilities of Li+ ions are seen to be correlated to polymer segmental relaxation times. However, the mobilities of BMIM+ ions are seen to be more strongly correlated to the BMIM-PF6 ion-pair relaxation times.

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

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

Zhang, Qinghua; He, Xu; Shi, Jinan

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE PAGES

Zhang, Qinghua; He, Xu; Shi, Jinan; ...

2017-07-24

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

New route for hollow materials

NASA Astrophysics Data System (ADS)

Rivaldo-Gómez, C. M.; Ferreira, F. F.; Landi, G. T.; Souza, J. A.

2016-08-01

Hollow micro/nano structures form an important family of functional materials. We have used the thermal oxidation process combined with the passage of electric current during a structural phase transition to disclose a colossal mass diffusion transfer of Ti ions. This combination points to a new route for fabrication of hollow materials. A structural phase transition at high temperature prepares the stage by giving mobility to Ti ions and releasing vacancies to the system. The electric current then drives an inward delocalization of vacancies, condensing into voids, and finally turning into a big hollow. This strong physical phenomenon leading to a colossal mass transfer through ionic diffusion is suggested to be driven by a combination of phase transition and electrical current followed by chemical reaction. We show this phenomenon for Ti leading to TiO2 microtube formation, but we believe that it can be used to other metals undergoing structural phase transition at high temperatures.

Cobalt oxide-carbon nanosheet nanoarchitecture as an anode for high-performance lithium-ion battery.

PubMed

Wang, Huanlei; Mao, Nan; Shi, Jing; Wang, Qigang; Yu, Wenhua; Wang, Xin

2015-02-04

To improve the electrochemical performance of cobalt oxide owing to its inherent poor electrical conductivity and large volume expansion/contraction, Co3O4-carbon nanosheet hybrid nanoarchitectures were synthesized by a facile and scalable chemical process. However, it is still a challenge to control the size of Co3O4 particles down to ∼5 nm. Herein, we created nanosized cobalt oxide anchored 3D arrays of carbon nanosheets by the control of calcination condition. The uniformly dispersed Co3O4 nanocrystals on carbon nanosheets held a diameter down to ∼5 nm. When tested as anode materials for lithium-ion batteries, high lithium storage over 1200 mAh g(-1) is achieved, whereas high rate capability with capacity of about 390 mAh g(-1) at 10 A g(-1) is maintained through nanoscale diffusion distances and interconnected porous structure. After 500 cycles, the cobalt oxide-carbon nansheets hybrid display a reversible capacity of about 970 mAh g(-1) at 1 A g(-1). The synergistic effect between nanosized cobalt oxide and sheetlike interconnected carbon nanosheets lead to the greatly improved specific capacity and the initial Coulombic efficiency of the hybrids.

Fast self-diffusion of ions in CH 3 NH 3 PbI 3 : the interstiticaly mechanism versus vacancy-assisted mechanism

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

Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang

2016-01-01

The stability of organic-inorganic halide perovskites is a major challenge for their applications and has been extensively studied. Among the possible underlying reasons, ion self-diffusion has been inferred to play important roles. While theoretical studies congruously support that iodine is more mobile, experimental studies only observe the direct diffusion of the MA ion and possible diffusion of iodine. The discrepancy may result from the incomplete understanding of ion diffusion mechanisms. With the help of first-principles calculations, we studied ion diffusion in CH3NH3PbI3 (MAPbI3) through not only the vacancy-assisted mechanisms presumed in previous theoretical studies, but also the neglected interstiticaly mechanisms.more » We found that compared to the diffusion through the vacancy-assisted mechanism, MA ion diffusion through the interstiticaly mechanism has a much smaller barrier which could explain experimental observations. For iodine diffusion, both mechanisms can yield relatively small barriers. Depending on the growth conditions, defect densities of vacancies and interstitials can vary and so do the diffusion species as well as diffusion mechanisms. Our work thus supports that both MA and iodine ion diffusion could contribute to the performance instability of MAPbI3. While being congruous with experimental results, our work fills the research gap by providing a full understanding of ion diffusion in halide perovskites.« less

Determination of the diffusion coefficient of hydrogen ion in hydrogels.

PubMed

Schuszter, Gábor; Gehér-Herczegh, Tünde; Szűcs, Árpád; Tóth, Ágota; Horváth, Dezső

2017-05-17

The role of diffusion in chemical pattern formation has been widely studied due to the great diversity of patterns emerging in reaction-diffusion systems, particularly in H + -autocatalytic reactions where hydrogels are applied to avoid convection. A custom-made conductometric cell is designed to measure the effective diffusion coefficient of a pair of strong electrolytes containing sodium ions or hydrogen ions with a common anion. This together with the individual diffusion coefficient for sodium ions, obtained from PFGSE-NMR spectroscopy, allows the determination of the diffusion coefficient of hydrogen ions in hydrogels. Numerical calculations are also performed to study the behavior of a diffusion-migration model describing ionic diffusion in our system. The method we present for one particular case may be extended for various hydrogels and diffusing ions (such as hydroxide) which are relevant e.g. for the development of pH-regulated self-healing mechanisms and hydrogels used for drug delivery.

Electrochemical separation of uranium in the molten system LiF-NaF-KF-UF4

NASA Astrophysics Data System (ADS)

Korenko, M.; Straka, M.; Szatmáry, L.; Ambrová, M.; Uhlíř, J.

2013-09-01

This article is focused on the electrochemical investigation (cyclic voltammetry and related studies) of possible reduction of U4+ ions to metal uranium in the molten system LiF-NaF-KF(eut.)-UF4 that can provide basis for the electrochemical extraction of uranium from molten salts. Two-step reduction mechanism for U4+ ions involving one electron exchange in soluble/soluble U4+/U3+ system and three electrons exchange in the second step were found on the nickel working electrode. Both steps were found to be reversible and diffusion controlled. Based on cyclic voltammetry, the diffusion coefficients of uranium ions at 530 °C were found to be D(U4+) = 1.64 × 10-5 cm2 s-1 and D(U3+) 1.76 × 10-5 cm2 s-1. Usage of the nickel spiral electrode for electrorefining of uranium showed fairly good feasibility of its extraction. However some oxidant present during the process of electrorefining caused that the solid deposits contained different uranium species such as UF3, UO2 and K3UO2F5.

Electrochemical evidences and consequences of significant differences in ions diffusion rate in polyacrylate-based ion-selective membranes.

PubMed

Woźnica, Emilia; Mieczkowski, Józef; Michalska, Agata

2011-11-21

The origin and effect of surface accumulation of primary ions within the ion-selective poly(n-butyl acrylate)-based membrane, obtained by thermal polymerization, is discussed. Using a new method, based on the relation between the shape of a potentiometric plot and preconditioning time, the diffusion of copper ions in the membrane was found to be slow (the diffusion coefficient estimated to be close to 10(-11) cm(2) s(-1)), especially when compared to ion-exchanger counter ions--sodium cations diffusion (a diffusion coefficient above 10(-9) cm(2) s(-1)). The higher mobility of sodium ions than those of the copper-ionophore complex results in exposed ion-exchanger role leading to undesirably exposed sensitivity to sodium or potassium ions.

Flexible holey graphene paper electrodes with enhanced rate capability for energy storage applications.

PubMed

Zhao, Xin; Hayner, Cary M; Kung, Mayfair C; Kung, Harold H

2011-11-22

The unique combination of high surface area, high electrical conductivity and robust mechanical integrity has attracted great interest in the use of graphene sheets for future electronics applications. Their potential applications for high-power energy storage devices, however, are restricted by the accessible volume, which may be only a fraction of the physical volume, a consequence of the compact geometry of the stack and the ion mobility. Here we demonstrated that remarkably enhanced power delivery can be realized in graphene papers for the use in Li-ion batteries by controlled generation of in-plane porosity via a mechanical cavitation-chemical oxidation approach. These flexible, holey graphene papers, created via facile microscopic engineering, possess abundant ion binding sites, enhanced ion diffusion kinetics, and excellent high-rate lithium-ion storage capabilities, and are suitable for high-performance energy storage devices. © 2011 American Chemical Society

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

In-Situ TEM Visualization Of Vacancy Injection And Chemical Partition During Oxidation Of Ni-Cr Nanoparticles

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

Wang, Chong M.; Genc, Arda; Cheng, Huikai

2014-01-14

Oxidation of alloy often involves chemical partition and injection of vacancies. Chemical partition is the consequence of selective oxidation, while injection of vacancies is associated with the differences of diffusivity of cations and anions. It is far from clear as how the injected vacancies behave during oxidation of metal. Using in-situ transmission electron microscopy, we captured unprecedented details on the collective behavior of injected vacancies during oxidation of metal, featuring an initial multi-site oxide nucleation, vacancy supersaturation, nucleation of a single cavity, sinking of vacancies into the cavity and accelerated oxidation of the particle. High sensitive energy dispersive x-ray spectroscopymore » mapping reveals that Cr is preferentially oxidized even at the initial oxidation, leading to a structure that Cr oxide is sandwiched near the inner wall of the hollow particle. The work provides a general guidance on tailoring of nanostructured materials involving multi-ion exchange such as core-shell structured composite nanoparticles.« less

In-Situ TEM visualization of vacancy injection and chemical partition during oxidation of Ni-Cr nanoparticles

PubMed Central

Wang, Chong-Min; Genc, Arda; Cheng, Huikai; Pullan, Lee; Baer, Donald R.; Bruemmer, Stephen M.

2014-01-01

Oxidation of alloy often involves chemical partition and injection of vacancies. Chemical partition is the consequence of selective oxidation, while injection of vacancies is associated with the differences of diffusivity of cations and anions. It is far from clear as how the injected vacancies behave during oxidation of metal. Using in-situ transmission electron microscopy, we captured unprecedented details on the collective behavior of injected vacancies during oxidation of metal, featuring an initial multi-site oxide nucleation, vacancy supersaturation, nucleation of a single cavity, sinking of vacancies into the cavity and accelerated oxidation of the particle. High sensitive energy dispersive x-ray spectroscopy mapping reveals that Cr is preferentially oxidized even at the initial oxidation, leading to a structure that Cr oxide is sandwiched near the inner wall of the hollow particle. The work provides a general guidance on tailoring of nanostructured materials involving multi-ion exchange such as core-shell structured composite nanoparticles. PMID:24418778

Post-annealing-free, room temperature processed nanocrystalline indium tin oxide thin films for plastic electronics

NASA Astrophysics Data System (ADS)

Nyoung Jang, Jin; Jong Lee, You; Jang, YunSung; Yun, JangWon; Yi, Seungjun; Hong, MunPyo

2016-06-01

In this study, we confirm that bombardment by high energy negative oxygen ions (NOIs) is the key origin of electro-optical property degradations in indium tin oxide (ITO) thin films formed by conventional plasma sputtering processes. To minimize the bombardment effect of NOIs, which are generated on the surface of the ITO targets and accelerated by the cathode sheath potential on the magnetron sputter gun (MSG), we introduce a magnetic field shielded sputtering (MFSS) system composed of a permanent magnetic array between the MSG and the substrate holder to block the arrival of energetic NOIs. The MFSS processed ITO thin films reveal a novel nanocrystal imbedded polymorphous structure, and present not only superior electro-optical characteristics but also higher gas diffusion barrier properties. To the best of our knowledge, no gas diffusion barrier composed of a single inorganic thin film formed by conventional plasma sputtering processes achieves such a low moisture permeability.

Sputtering and ion plating for aerospace applications

NASA Technical Reports Server (NTRS)

Spalvins, T.

1981-01-01

Sputtering and ion plating technologies are reviewed in terms of their potential and present uses in the aerospace industry. Sputtering offers great universality and flexibility in depositing any material or in the synthesis of new ones. The sputter deposition process has two areas of interest: thin film and fabrication technology. Thin film sputtering technology is primarily used for aerospace mechanical components to reduce friction, wear, erosion, corrosion, high temperature oxidation, diffusion and fatigue, and also to sputter-construct temperature and strain sensors for aircraft engines. Sputter fabrication is used in intricate aircraft component manufacturing. Ion plating applications are discussed in terms of the high energy evaporant flux and the high throwing power. Excellent adherence and 3 dimensional coverage are the primary attributes of this technology.

Sputtering and ion plating for aerospace applications

NASA Technical Reports Server (NTRS)

Spalvins, T.

1981-01-01

Sputtering and ion plating technologies are reviewed in terms of their potential and present uses in the aerospace industry. Sputtering offers great universality and flexibility in depositing any material or in the synthesis of new ones. The sputter deposition process has two areas of interest: thin film and fabrication technology. Thin film sputtering technology is primarily used for aerospace mechanical components to reduce friction, wear, erosion, corrosion, high temperature oxidation, diffusion and fatigue, and also to sputter-construct temperature and strain sensors for aircraft engines. Sputter fabrication is used in intricate aircraft component manufacturing. Ion plating applications are discussed in terms of the high energy evaporant flux and the high throwing power. Excellent adherence and 3-dimensional coverage are the primary attributes of this technology.

Characterization of double oxide system Cu-Cr-O supported on γ-Al2O3

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Kolev, H.; Krstić, J.; Dimitrov, D.; Ivanov, K.; Loncarević, D.; Jovanović, D.; Mitov, I.

2009-09-01

Series of alumina supported chromium-copper catalysts were prepared by co-impregnation method. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. Dispersion and porosity was also obtained. The experimental and catalytic test results have drawn a conclusion that an interaction between copper and chromium ions takes place. This interaction is responsible for the enhanced catalytic activity of studied catalysts in reaction of total oxidation of industrial formaldehyde production exhaust gas, which contains CO, dimethyl ether and methanol as main components.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

The influence of polarizability and charge transfer on specific ion effects in the dynamics of aqueous salt solutions

NASA Astrophysics Data System (ADS)

Nguyen, Mary; Rick, Steven W.

2018-06-01

The diffusion rates for water molecules in salt solutions depend on the identity of the ions, as well as their concentration. Among the alkali metal ions, cesium and potassium increase and sodium strongly decreases the diffusion constant of water. The origin of the difference can be understood by examining the simulation results using different potential models. In this work, aqueous solutions of salts are simulated with a variety of models. Commonly used non-polarizable models, which otherwise reproduce many experimental properties, do not capture the trend in the diffusion constant, while models which include polarization and/or charge transfer interactions do. For the non-polarizable models, the diffusion constant decreases too strongly with salt concentration. The changes in the water diffusion constant with increasing salt concentration match the diffusion constant of the ion. The ion diffusion constant is dependent on the residence time for water in the ion solvation shell. The non-polarizable models over-estimate the residence time, relative to the translational diffusion constant and so tend to under-estimate the ion and water diffusion constants.

The mobility and diffusion of ions in gases

NASA Technical Reports Server (NTRS)

Mcdaniel, E. W.; Mason, E. A.

1973-01-01

Experimental and theoretical aspects of the mobility and diffusion of ions in gases are studied in detail. Some of the subjects discussed include ion-ion interaction, boundary condition and ion and electron behavior. Also discussed in separate chapters are the problems of the diffusion coefficients and the afterglow techniques. Finally, a special chapter studies the kinetic theory of diffusion and mobility, stressing the low-, medium- and high-field theory.

Metal-Organic Framework Derived Porous Hollow Co3O4/N-C Polyhedron Composite with Excellent Energy Storage Capability.

PubMed

Kang, Wenpei; Zhang, Yu; Fan, Lili; Zhang, Liangliang; Dai, Fangna; Wang, Rongming; Sun, Daofeng

2017-03-29

Metal-organic frameworks (MOFs) derived transition metal oxides exhibit enhanced performance in energy conversion and storage. In this work, porous hollow Co 3 O 4 with N-doped carbon coating (Co 3 O 4 /N-C) polyhedrons have been prepared using cobalt-based MOFs as a sacrificial template. Assembled from tiny nanoparticles and N-doped carbon coating, Co 3 O 4 /N-C composite shortens the diffusion length of Li + /Na + ions and possesses an enhanced conductivity. And the porous and hollow structure is also beneficial for tolerating volume changes in the galvanostatic discharge/charge cycles as lithium/sodium battery anode materials. As a result, it can exhibit impressive cycling and rating performance. At 1000 mA g -1 , the specific capacities maintaine stable values of ∼620 mAh g -1 within 2000 cycles as anodes in lithium ion battery, while the specific capacity keeps at 229 mAh g -1 within 150 cycles as sodium ion battery anode. Our work shows comparable cycling performance in lithium ion battery but even better high-rate cycling stability as sodium ion battery anode. Herein, we provide a facile method to construct high electrochemical performance oxide/N-C composite electrode using new MOFs as sacrificial template.

Importance of Diffuse Metal Ion Binding to RNA

PubMed Central

Tan, Zhi-Jie; Chen, Shi-Jie

2016-01-01

RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding. PMID:22010269

Importance of diffuse metal ion binding to RNA.

PubMed

Tan, Zhi-Jie; Chen, Shi-Jie

2011-01-01

RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding.

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

Dees, D. W.; Kawauchi, S.; Abraham, D. P.

Galvanostatic Intermittent Titration Technique (GITT) experiments were conducted to determine the lithium diffusion coefficient of LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}, used as the active material in a lithium-ion battery porous composite positive electrode. An electrochemical model, based on concentrated solution porous electrode theory, was developed to analyze the GITT experimental results and compare to the original GITT analytical theory. The GITT experimental studies on the oxide active material were conducted between 3.5 and 4.5 V vs. lithium, with the maximum lithium diffusion coefficient value being 10{sup -10} cm{sup 2} s{sup -1} at 3.85 V. The lithium diffusion coefficient values obtainedmore » from this study agree favorably with the values obtained from an earlier electrochemical impedance spectroscopy study.« less

Synthesis of NiO nanotubes for use as negative electrodes in lithium ion batteries

NASA Astrophysics Data System (ADS)

Needham, S. A.; Wang, G. X.; Liu, H. K.

Nickel oxide (NiO) nanotubes have been produced for the first time via a template processing method. The synthesis involved a two step chemical reaction in which nickel hydroxide (Ni(OH) 2) nanotubes were firstly formed within the walls of an anodic aluminium oxide (AAO) template. The template was then dissolved away using concentrated NaOH, and the freed nanotubes were converted to NiO by heat treatment in air at 350 °C. Individual nanotubes measured 60 μm in length with a 200 nm outer diameter and a wall thickness of 20-30 nm. The NiO nanotube powder was used in Li-ion cells for assessment of the lithium storage ability. Preliminary testing indicates that the cells demonstrate controlled and sustainable lithium diffusion after the formation of an SEI. Reversible capacities in the 300 mAh g -1 range were typical.

Dynamic Structural Changes of SiO₂ Supported Pt-Ni Bimetallic Catalysts over Redox Treatments Revealed by NMR and EPR

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

Xu, Suochang; Walter, Eric D.; Zhao, Zhenchao

2015-08-18

SiO 2 supported Pt-Ni bimetallic catalysts with different nickel loadings were prepared and their structural changes after redox treatments were studied by XRD, NMR, and EPR. It is found that the paramagnetic Ni species are mainly located on the surface of silica lattice. The relaxation of detected 29Si nuclei in our samples is mainly governed by a spin-diffusion mechanism. The paramagnetic effects are reflected in the spin-lattice relaxation of Q 4 species, with the oxidized samples presenting faster relaxation rates than the corresponding reduced ones. Meanwhile the Q 3 species, which are in close contact with the paramagnetic nickel ions,more » are “spectrally invisible”. In reducing atmosphere Ni gradually diffuses into Pt NPs to form PtNi alloys. While under oxidization treatment, the alloyed Ni atoms migrate outward from the core of Pt NPs and are oxidized. The main EPR spectrum results from reduced nickel species, and the reduced samples show stronger EPR signal than the corresponding oxidized ones. However, in the reduced samples, the superparamagnetic or ferromagnetic metallic Ni particles were inside the PtNi NPs, making their influence on the 29Si relaxation in the SiO 2 support weaker than the oxidized samples.« less

Red Phosphorus Nanodots on Reduced Graphene Oxide as a Flexible and Ultra-Fast Anode for Sodium-Ion Batteries.

PubMed

Liu, Yihang; Zhang, Anyi; Shen, Chenfei; Liu, Qingzhou; Cao, Xuan; Ma, Yuqiang; Chen, Liang; Lau, Christian; Chen, Tian-Chi; Wei, Fei; Zhou, Chongwu

2017-06-27

Sodium-ion batteries offer an attractive option for potential low cost and large scale energy storage due to the earth abundance of sodium. Red phosphorus is considered as a high capacity anode for sodium-ion batteries with a theoretical capacity of 2596 mAh/g. However, similar to silicon in lithium-ion batteries, several limitations, such as large volume expansion upon sodiation/desodiation and low electronic conductance, have severely limited the performance of red phosphorus anodes. In order to address the above challenges, we have developed a method to deposit red phosphorus nanodots densely and uniformly onto reduced graphene oxide sheets (P@RGO) to minimize the sodium ion diffusion length and the sodiation/desodiation stresses, and the RGO network also serves as electron pathway and creates free space to accommodate the volume variation of phosphorus particles. The resulted P@RGO flexible anode achieved 1165.4, 510.6, and 135.3 mAh/g specific charge capacity at 159.4, 31878.9, and 47818.3 mA/g charge/discharge current density in rate capability test, and a 914 mAh/g capacity after 300 deep cycles in cycling stability test at 1593.9 mA/g current density, which marks a significant performance improvement for red phosphorus anodes for sodium-ion chemistry and flexible power sources for wearable electronics.

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

NASA Technical Reports Server (NTRS)

Hooker, M. W.; Rast, H. E.; Rogers, D. K.

1989-01-01

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Multifunctional Organic-Semiconductor Interfacial Layers for Solution-Processed Oxide-Semiconductor Thin-Film Transistor.

PubMed

Kwon, Guhyun; Kim, Keetae; Choi, Byung Doo; Roh, Jeongkyun; Lee, Changhee; Noh, Yong-Young; Seo, SungYong; Kim, Myung-Gil; Kim, Choongik

2017-06-01

The stabilization and control of the electrical properties in solution-processed amorphous-oxide semiconductors (AOSs) is crucial for the realization of cost-effective, high-performance, large-area electronics. In particular, impurity diffusion, electrical instability, and the lack of a general substitutional doping strategy for the active layer hinder the industrial implementation of copper electrodes and the fine tuning of the electrical parameters of AOS-based thin-film transistors (TFTs). In this study, the authors employ a multifunctional organic-semiconductor (OSC) interlayer as a solution-processed thin-film passivation layer and a charge-transfer dopant. As an electrically active impurity blocking layer, the OSC interlayer enhances the electrical stability of AOS TFTs by suppressing the adsorption of environmental gas species and copper-ion diffusion. Moreover, charge transfer between the organic interlayer and the AOS allows the fine tuning of the electrical properties and the passivation of the electrical defects in the AOS TFTs. The development of a multifunctional solution-processed organic interlayer enables the production of low-cost, high-performance oxide semiconductor-based circuits. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

NASA Astrophysics Data System (ADS)

Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

2017-06-01

Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

Redox properties of samarium, europium and ytterbium in molten eutectic mixture of sodium, potassium and cesium chlorides

NASA Astrophysics Data System (ADS)

Golovanova, O. A.; Tropin, O. A.; Volkovich, V. A.

2017-09-01

The redox behavior of samarium, europium and ytterbium ions was investigated in the ternary 6NaCl-9KCl- 5CsCl eutectic based melts between 823 and 1073 K employing cyclic voltammetry on a tungsten working electrode. Ln(II)/Ln(III) (Ln=Sm, Eu, Yb) reduction-oxidation is reversible and controlled by diffusion of the electroactive species at the potential scan rates up to 0.1 V/s. Formal standard redox potentials E*Ln(II)/Ln(III) were determined, and the thermodynamic and transport properties of the corresponding Ln(III) and Ln(II) ions were estimated.

Nucleation and growth kinetics of electrodeposited sulfate-doped polypyrrole: determination of the diffusion coefficient of SO(4)(2-) in the polymeric membrane.

PubMed

Licona-Sánchez, T de J; Alvarez-Romero, G A; Mendoza-Huizar, L H; Galán-Vidal, C A; Palomar-Pardavé, M; Romero-Romo, M; Herrera-Hernández, H; Uruchurtu, J; Juárez-García, J M

2010-08-05

A kinetic study for the electrosynthesis of polypyrrole (Ppy) doped with SO(4)(2-) ions is presented. Ppy films were electrochemically polymerized onto a graphite-epoxy resin electrode. Experimental current density transients (j-t) were obtained for three different potentiometric behaviors: anionic, cationic, and a combination. Theoretical models were used to fit the experimental j-t data to determine the nucleation and growth processes controlling the polymer synthesis. It was encountered that, in all cases, pyrrole electropolimerization involves two concomitant processes, namely, a Ppy diffusion limited multiple 3D nucleation and growth and pyrrole electro-oxidation on the growing surface of the Ppy nuclei. SEM analysis of the electrodes surfaces reveals that Ppy deposition occurred over most of the electrode surface by multiple nucleation of hemispheres, as the theoretical model used for the analysis of the current transients required. Hemispherical particles formed the polymeric film displaying different sizes. The order for the particle size was as follows: anionic > anionic-cationic > cationic. These results are congruent with those obtained by theoretical analysis of the corresponding current transients. Analysis of the impedance measurements recorded on the anionic Ppy film, immersed in an aqueous solution with different sulfate ion concentrations evidenced that SO(4)(2-) ions diffuse through the Ppy film provoking a decrease of its electrical resistance and an increase of its dielectric constant. From the Warburg impedance coefficient, the sulfate coefficient of diffusion in the Ppy film was 1.38 x 10(-9) cm(2) s(-1).

Ternary CNTs@TiO2/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries

PubMed Central

Madian, Mahmoud; Ummethala, Raghunandan; Abo El Naga, Ahmed Osama; Ismail, Nahla; Rümmeli, Mark Hermann; Eychmüller, Alexander; Giebeler, Lars

2017-01-01

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li+ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li+ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability. PMID:28773032

Ternary CNTs@TiO₂/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries.

PubMed

Madian, Mahmoud; Ummethala, Raghunandan; Naga, Ahmed Osama Abo El; Ismail, Nahla; Rümmeli, Mark Hermann; Eychmüller, Alexander; Giebeler, Lars

2017-06-20

TiO₂ nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO₂/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO₂/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO₂ and TiO₂/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li⁺ ion diffusivity, promoting a strongly favored lithium insertion into the TiO₂/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

Molecular Dynamics Simulation of Salt Diffusion in Polyelectrolyte Assemblies.

PubMed

Zhang, Ran; Duan, Xiaozheng; Ding, Mingming; Shi, Tongfei

2018-06-05

The diffusion of salt ions and charged probe molecules in polyelectrolyte assemblies is often assumed to follow a theoretical hopping model, in which the diffusing ion is hopping between charged sites of chains based on electroneutrality. However, experimental verification of diffusing pathway at such microscales is difficult, and the corresponding molecular mechanisms remain elusive. In this study, we perform all-atom molecular dynamics (MD) simulations of salt diffusion in polyelectrolyte (PE) assembly of poly (sodium 4-styrenesulfonate) (PSS) and poly (diallyldimethylammonium chloride) (PDAC). Besides the ion hopping mode, the diffusing trajectories are found presenting common features of a jump process, i.e., subjecting to PE relaxation, water pockets in the structure open and close, thus the ion can move from one pocket to another. Anomalous subdiffusion of ions and water is observed due to the trapping scenarios in these water pockets. The jump events are much rarer compared with ion hopping but significantly increases salt diffusion with increasing temperature. Our result strongly indicates that salt diffusion in hydrated PDAC/PSS is a combined process of ion hopping and jump motion. This provides new molecular explanation for the coupling of salt motion with chain motion and the nonlinear increase of salt diffusion at glass transition temperature.

Polymer-electrolyte-gated nanowire synaptic transistors for neuromorphic applications

NASA Astrophysics Data System (ADS)

Zou, Can; Sun, Jia; Gou, Guangyang; Kong, Ling-An; Qian, Chuan; Dai, Guozhang; Yang, Junliang; Guo, Guang-hua

2017-09-01

Polymer-electrolytes are formed by dissolving a salt in polymer instead of water, the conducting mechanism involves the segmental motion-assisted diffusion of ion in the polymer matrix. Here, we report on the fabrication of tin oxide (SnO2) nanowire synaptic transistors using polymer-electrolyte gating. A thin layer of poly(ethylene oxide) and lithium perchlorate (PEO/LiClO4) was deposited on top of the devices, which was used to boost device performances. A voltage spike applied on the in-plane gate attracts ions toward the polymer-electrolyte/SnO2 nanowire interface and the ions are gradually returned after the pulse is removed, which can induce a dynamic excitatory postsynaptic current in the nanowire channel. The SnO2 synaptic transistors exhibit the behavior of short-term plasticity like the paired-pulse facilitation and self-adaptation, which is related to the electric double-effect regulation. In addition, the synaptic logic functions and the logical function transformation are also discussed. Such single SnO2 nanowire-based synaptic transistors are of great importance for future neuromorphic devices.

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

NASA Astrophysics Data System (ADS)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

Influence of crystal orientation and ion bombardment on the nitrogen diffusivity in single-crystalline austenitic stainless steel

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

Martinavicius, A.; Abrasonis, G.; Moeller, W.

2011-10-01

The nitrogen diffusivity in single-crystalline AISI 316L austenitic stainless steel (ASS) during ion nitriding has been investigated at different crystal orientations ((001), (110), (111)) under variations of ion flux (0.3-0.7 mA cm{sup -2}), ion energy (0.5-1.2 keV), and temperature (370-430 deg. C). The nitrogen depth profiles obtained from nuclear reaction analysis are in excellent agreement with fits using the model of diffusion under the influence of traps, from which diffusion coefficients were extracted. At fixed ion energy and flux, the diffusivity varies by a factor up to 2.5 at different crystal orientations. At (100) orientation, it increases linearly with increasingmore » ion flux or energy. The findings are discussed on the basis of atomistic mechanisms of interstitial diffusion, potential lattice distortions, local decomposition, and ion-induced lattice vibrational excitations.« less

Copper drift in high-dielectric-constant tantalum oxide thin films under bias temperature stress

NASA Astrophysics Data System (ADS)

Jain, Pushkar; Juneja, Jasbir S.; Mallikarjunan, A.; Rymaszewski, E. J.; Lu, T.-M.

2006-04-01

The use of high-dielectric-constant (high-κ) materials for embedded capacitors is becoming increasingly important. Tantalum oxide (Ta2O5) is a prominent candidate as a high-κ material for embedded capacitor use. Metal drift in Ta2O5 (κ˜25) was investigated by bias temperature stress and triangular voltage sweep testing techniques on metal/Ta2O5/SiO2/Si structures. At a temperature of 300°C and 0.75MV/cm bias conditions, Al, Ta, and Ti do not diffuse in Ta2O5, but Cu clearly showed a drift. The Cu drift is attributed to the lack of a stable Cu oxide which can limit Cu ion generation and penetration.

Enhanced Antimicrobial Activity Of Antibiotics Mixed With Metal Nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Kumar, Neeraj; Bhanjana, Gaurav; Thakur, Rajesh; Dilbaghi, Neeraj

2011-12-01

Current producers of antimicrobial technology have a long lasting, environmentally safe, non-leaching, water soluble solution that will eventually replace all poisons and heavy metals. The transition metal ions inevitably exist as metal complexes in biological systems by interaction with the numerous molecules possessing groupings capable of complexation or chelation. Nanoparticles of metal oxides offer a wide variety of potential applications in medicine due to the unprecedented advances in nanobiotechnology research. the bacterial action of antibiotics like penicillin, erythryomycin, ampicillin, streptomycin, kanamycin etc. and that of a mixture of antibiotics and metal and metal oxide nanoparticles like zinc oxide, zirconium, silver and gold on microbes was examined by the agar-well-diffusion method, enumeration of colony-forming units (CFU) and turbidimetry.

3D free-standing nitrogen-doped reduced graphene oxide aerogel as anode material for sodium ion batteries with enhanced sodium storage.

PubMed

Zhang, Jiao; Li, Chuanqi; Peng, Zhikun; Liu, Yushan; Zhang, Jianmin; Liu, Zhongyi; Li, Dan

2017-07-07

Sodium ion batteries have drawn extensive attentions for large-scale energy storage to replace lithium ion batteries primarily due to the natural abundance of sodium resource and low cost, but their energy density and electrochemical performance are hindered by the sluggish diffusion kinetics of sodium ion. Herein, free-standing nitrogen-doped graphene aerogel has been fabricated via hydrothermal reaction as the potential anode material for sodium ion batteries. The three dimensional porous network structure of the graphene aerogel provides sufficient interstitial space for sodium ion accommodation, allowing fast and reversible ion intercalation/de-intercalation. The nitrogen doping could introduce defects on the graphene sheets, making the feasible transport of large-sized sodium ion. Benefiting from the effective structure and nitrogen doping, the obtained material demonstrates high reversible capacities, good cycling performance (287.9 mA h g -1 after 200 cycles at a current density of 100 mA g -1 ), especially superior rate capability (151.9 mA h g -1 at a high current density of 5 A g -1 ).

The heavy ion diffusion region in magnetic reconnection in the Earth's magnetotail

NASA Astrophysics Data System (ADS)

Liu, Y. H.; Mouikis, C. G.; Kistler, L. M.; Wang, S.; Roytershteyn, V.; Karimabadi, H.

2015-05-01

While the plasma in the Earth's magnetotail predominantly consists of protons and electrons, there are times when a significant amount of oxygen is present. When magnetic reconnection occurs, the behavior of these heavy ions can be significantly different from that of the protons, due to their larger gyroradius. In this study, we investigate the heavy ion distribution functions in the reconnection ion diffusion region from a 2.5D three-species particle-in-cell numerical simulation and compare those with Cluster observations from the near-Earth magnetotail. From the simulation results, we find that the heavy ions are demagnetized and accelerated in a larger diffusion region, the heavy ion diffusion region. The ion velocity distribution functions show that, inside the heavy ion diffusion region, heavy ions appear as counterstreaming beams along z in the GSM x-z plane, while drifting in y, carrying cross-tail current. We compare this result with Cluster observations in the vicinity of reconnection regions in the near-Earth magnetotail and find that the simulation predictions are consistent with the observed ion distribution functions in the ion diffusion region, as well as the inflow, exhaust, and separatrix regions. Based on the simulation and observation results, the presence of a multiscale diffusion region model, for O+ abundant reconnection events in the Earth's magnetotail, is demonstrated. A test particle simulation shows that in the diffusion region, the H+ gains energy mainly through Ex, while the O+ energy gain comes equally from Ex and Ey.

Development of an optical thermal history coating sensor based on the oxidation of a divalent rare earth ion phosphor

NASA Astrophysics Data System (ADS)

Yáñez-González, Álvaro; Ruiz-Trejo, Enrique; van Wachem, Berend; Skinner, Stephen; Beyrau, Frank; Heyes, Andrew

2016-11-01

The measurement of temperatures in gas turbines, boilers, heat exchangers and other components exposed to hot gases is essential to design energy efficient systems and improve maintenance procedures. When on-line measurements, such as those performed with thermocouples and pyrometers, are not possible or inconvenient, the maximum temperatures of operation can be recorded and measured off-line after operation. Although thermal paints have been used for many years for this purpose, a novel technique based on irreversible changes in the optical properties of thermographic phosphors, can overcome some of the disadvantages of previous methods. In particular, oxidation of the divalent rare earth ion phosphor BaMgAl10O17:Eu (BAM:Eu) has shown great potential for temperature sensing between 700 °C and 1200 °C. The emission spectra of this phosphor change with temperature, which permits to define an intensity ratio between different lines in the spectra that can be used as a measurand of the temperature. In this paper, the study of the sensing capabilities of a sensor coating based on BAM:Eu phosphor material is addressed for the first time. The sensitivity of the intensity ratio is investigated in the temperature range from 800 °C to 1100 °C, and is proved to be affected by ionic diffusion of transition metals from the substrate. The use of an interlayer made of zirconia proves efficient in reducing ionic diffusion and coatings with this diffusion barrier present sensitivity comparable to that of the powder material.

Understanding the conductive channel evolution in Na:WO3-x-based planar devices

NASA Astrophysics Data System (ADS)

Shang, Dashan; Li, Peining; Wang, Tao; Carria, Egidio; Sun, Jirong; Shen, Baogen; Taubner, Thomas; Valov, Ilia; Waser, Rainer; Wuttig, Matthias

2015-03-01

An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices.An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07545e

Composite oxygen ion transport element

DOEpatents

Chen, Jack C [Getzville, NY; Besecker, Charles J [Batavia, IL; Chen, Hancun [Williamsville, NY; Robinson, Earil T [Mentor, OH

2007-06-12

A composite oxygen ion transport element that has a layered structure formed by a dense layer to transport oxygen ions and electrons and a porous support layer to provide mechanical support. The dense layer can be formed of a mixture of a mixed conductor, an ionic conductor, and a metal. The porous support layer can be fabricated from an oxide dispersion strengthened metal, a metal-reinforced intermetallic alloy, a boron-doped Mo.sub.5Si.sub.3-based intermetallic alloy or combinations thereof. The support layer can be provided with a network of non-interconnected pores and each of said pores communicates between opposite surfaces of said support layer. Such a support layer can be advantageously employed to reduce diffusion resistance in any type of element, including those using a different material makeup than that outlined above.

Ethanol Reduced Molybdenum Trioxide for Li-ion Capacitors

DOE PAGES

Li, Tianqi; Beidaghi, Majid; Xiao, Xu; ...

2016-05-06

Orthorhombic molybdenum trioxide (α-MoO 3) is a layered oxide with promising performance as electrode material for Li-ion capacitors. In this study, we show that expansion of the interlayer spacing (by ~0.32 Å) of the structure along the b-axis, introduced by partial reduction of α-MoO 3 and formation of MoO 3-x (x=0.06–0.43), results in enhanced diffusion of Li ions. Binder-free hybrid electrodes made of MoO 3-x nanobelts and carbon nanotubes show excellent electrical conductivity. The combination of increased interlayer spacing and enhanced electron transport leads to high gravimetric and volumetric capacitances of about 420 F/g or F/cm 3 and excellent cyclemore » life of binder-free MoO 3-x electrodes.« less

Study of iodine migration in zirconia using stable and radioactive ion implantation

NASA Astrophysics Data System (ADS)

Chevarier, N.; Brossard, F.; Chevarier, A.; Crusset, D.; Moncoffre, N.

1998-03-01

The large uranium fission cross section leading to iodine and the behaviour of this element in the cladding tube during energy production and afterwards during waste storage is a crucial problem, especially for 129I which is a very long half-life isotope ( T = 1.59 × 10 7yr). Since a combined external and internal oxidation of the zircaloy cladding tube occurs during the reactor processing, iodine diffusion parameters in zirconia are needed. In order to obtain these data, stable iodine atoms were first introduced by ion implantation into zirconia with an energy of 200 keV and a dose equal to 8 × 10 15at cm -2. Diffusion profiles were measured using 3 MeV alpha-particle Rutherford Backscattering Spectrometry at each step of the annealing procedure between 700°C and 900°C. In such experiments a reduced iodine concentration was observed, which correlated to a diffusion-like process. Similar analysis has been performed using radioactive 131I implanted at a very low dose of 10 9 at cm -2. In this case the iodine release is deduced from gamma-ray spectroscopy measurements. The results are discussed in this paper.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging.

PubMed

He, Yadong; Qiao, Rui; Vatamanu, Jenel; Borodin, Oleg; Bedrov, Dmitry; Huang, Jingsong; Sumpter, Bobby G

2016-01-07

Molecular simulations of the diffusion of EMIM(+) and TFSI(-) ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching ∼5 × 10(-9) m(2)/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

DOE PAGES

He, Yadong; Qiao, Rui; Vatamanu, Jenel; ...

2015-12-07

In molecular simulations of the diffusion of EMIM+ and TESI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching similar to 5 x 10 -9 m 2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Moreover, analysis of these results revealed that the fast (ormore » slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. Finally, the molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.« less

Application of electrochemical advanced oxidation processes to the mineralization of the herbicide diuron.

PubMed

Pipi, Angelo R F; Sirés, Ignasi; De Andrade, Adalgisa R; Brillas, Enric

2014-08-01

Here, solutions with 0.185mM of the herbicide diuron of pH 3.0 have been treated by electrochemical advanced oxidation processes (EAOPs) like electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) or solar PEF (SPEF). Trials were performed in stirred tank reactors of 100mL and in a recirculation flow plant of 2.5L using a filter-press reactor with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 electrogeneration. Oxidant hydroxyl radicals were formed from water oxidation at the anode and/or in the bulk from Fenton's reaction between added Fe(2+) and generated H2O2. In both systems, the relative oxidation ability of the EAOPs increased in the sequence EO-H2O2

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

DOE PAGES

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

2015-10-28

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

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

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–y Mn y O 4 (0.4 ≤ y ≤ 1)

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

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1-yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2-yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. Amore » bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Nuclear microscopy of diffuse plaques in the brains of transgenic mice

NASA Astrophysics Data System (ADS)

Rajendran, Reshmi; Ren, Minqin; Casadesus, Gemma; Smith, Mark A.; Perry, George; Huang, En; Ong, Wei Yi; Halliwell, Barry; Watt, Frank

2005-04-01

Using nuclear microscopy, extracellular diffuse amyloid deposits in fresh unstained brain tissue from Alzheimer's disease transgenic mice Tg2576 have been identified and analyzed for trace element content. Off-axis scanning transmission ion microscopy (STIM) images can be obtained which are similar to the images produced using direct STIM. Since the proton beam current required for off-axis STIM is compatible with PIXE and RBS, we can identify the plaque location and analyze for trace elements simultaneously. Analysis of the diffuse plaques showed an increase in the transition metals iron and zinc compared with the surrounding area of comparable areal density. This supports the theory that redox interactions between Aβ and metals could be at the heart of a pathological feedback system wherein Aβ amyloidosis and oxidative stress promote each other, possibly via Fenton chemistry.

Nanocrystalline SnO2 formation using energetic ion beam.

PubMed

Mohanty, T; Batra, Y; Tripathi, A; Kanjilal, D

2007-06-01

Nanocrystalline tin oxide (SnO2) thin films grown by RF magnetron sputtering technique were characterized by UV-Visible absorption spectroscopy and Photoluminescence spectroscopy. From atomic force microscopic (AFM) and Glancing angle X-ray diffraction (GAXRD) measurements, the radius of grains was found to be approximately 6+/-2 nm. The thin films were bombarded with 250 keV Xe2+ ion beam to observe the stability of nanophases against radiation. For ion bombarded films, optical absorption band edge is shifted towards red region. Atomic force microscopy studies show that the radius of the grains was increased to approximately 8 +/- 1 nm and the grains were nearly uniform in size. The size of the grains has been reduced after ion bombardment in the case of films grown on Si. During this process, defects such as vacancies, voids were generated in the films as well as in the substrates. Ion bombardment induces local temperature increase of thin films causing melting of films. Ion beam induced defects enhances the diffusion of atoms leading to uniformity in size of grains. The role of matrix on ion beam induced grain growth is discussed.

Synthesis of Three-Dimensional Nanoporous Li-Rich Layered Cathode Oxides for High Volumetric and Power Energy Density Lithium-Ion Batteries.

PubMed

Qiu, Bao; Yin, Chong; Xia, Yonggao; Liu, Zhaoping

2017-02-01

As rechargeable Li-ion batteries have expanded their applications into on-board energy storage for electric vehicles, the energy and power must be increased to meet the new demands. Li-rich layered oxides are one of the most promising candidate materials; however, it is very difficult to make them compatible with high volumetric energy density and power density. Here, we develop an innovative approach to synthesize three-dimensional (3D) nanoporous Li-rich layered oxides Li[Li 0.144 Ni 0.136 Co 0.136 Mn 0.544 ]O 2 , directly occurring at deep chemical delithiation with carbon dioxide. It is found that the as-prepared material presents a micrometer-sized spherical structure that is typically composed of interconnected nanosized subunits with narrow distributed pores at 3.6 nm. As a result, this unique 3D micro-/nanostructure not only has a high tap density over 2.20 g cm -3 but also exhibits excellent rate capability (197.6 mA h g -1 at 1250 mA g -1 ) as an electrode. The excellent electrochemical performance is ascribed to the unique nanoporous micro-nanostructures, which facilitates the Li + diffusion and enhances the structural stability of the Li-rich layered cathode materials. Our work offers a comprehensive designing strategy to construct 3D nanoporous Li-rich layered oxides for both high volumetric energy density and power density in Li-ion batteries.

Designing High Capacity, Stable Lithium-Manganese Oxide Insertion Electrodes with First Principles Computations

NASA Astrophysics Data System (ADS)

Reed, John; van der Ven, Anton; Ceder, Gerbrand

2001-03-01

The viability of rechargeable lithium batteries in many applications hinges on finding electrode materials with high capacity, excellent chemical and phase stability, and low cost. LiCoO_2, the intercalation oxide currently used is too expensive and unsafe for large-scale batteries. Manganese oxides are a possible low cost alternative, but spinel LiMn_2O _4, the common form of the material, has too low a capacity and some stability problems. Recently, layered LiMnO _2, isostructural to LiCoO _2, has been synthesized. After a few battery cycles this material irreversibly transforms to a spinel structure, with loss of battery capacity. In this work we use Density Functional Theory to investigate why LiMnO2 transforms so rapidly to spinel but LiCoO 2 does not, even though both are known to be thermodynamically unstable towards this transformation. We find that the difference between the two compound is due to remarkably rapid diffusion of Mn ^3+. Diffusion of Mn^3+ occurs by disproportionation into Mn ^2+ an Mn ^4+ which gives the system a remarkable flexibility in its hybridization with the oxygen ions, even at the saddle point for diffusion. This knowledge has now been used to suggest compositional modifications of LiMnO 2 which slow down or even prevent the transformation to a spinel.

Ionomers for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph

For ionic actuators and battery separators, it is vital to utilize single-ion conducting ionomers that avoid the detrimental polarization of other ions. Single-ion conducting ionomers are synthesized based on DFT calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for battery separators that conduct Li+ or Na+. Characterization by X-ray scattering, dielectric spectroscopy, FTIR, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. 7Li NMR diffusion measurements find that diffusion is faster than expected by conductivity using the Nernst-Einstein equation, which means that the majority of Li diffusion occurs by ion pairs moving with the polymer segmental motion. Segmental motion only contributes to ionic conduction in the rare event that one of these ion pairs has an extra Li (a positive triple ion). This leads us to a new metric for ion-conducting soft materials, the product of the cation number density p0 and their diffusion coefficient D; p0D is the diffusive flux of lithium ions. This new metric has a maximum at intermediate ion content that corresponds to the overlap of ion pair polarizability volumes. At higher ion contents, the ion pairs interact strongly and form larger aggregation states that retard segmental motion of both mobile ion pairs and triple ions.

Observations of Ag diffusion in ion implanted SiC

DOE PAGES

Gerczak, Tyler J.; Leng, Bin; Sridharan, Kumar; ...

2015-03-17

The nature and magnitude of Ag diffusion in SiC has been a topic of interest in connection with the performance of tristructural isotropic (TRISO) coated particle fuel for high temperature gas-cooled nuclear reactors. Ion implantation diffusion couples have been revisited to continue developing a more complete understanding of Ag fission product diffusion in SiC. Ion implantation diffusion couples fabricated from single crystal 4H-SiC and polycrystalline 3C-SiC substrates and exposed to 1500–1625°C, were investigated in this study by transmission electron microscopy and secondary ion mass spectrometry (SIMS). The high dynamic range of SIMS allowed for multiple diffusion régimes to be investigated,more » including enhanced diffusion by implantation-induced defects and grain boundary (GB) diffusion in undamaged SiC. Lastly, estimated diffusion coefficients suggest GB diffusion in bulk SiC does not properly describe the release observed from TRISO fuel.« less

Molecular Facts on the Structure and Dynamics of Electrolyte Species in Cu-Cl Cycle for Hydrogen Generation: An Insight from Molecular Dynamic Simulations.

PubMed

Sahu, Pooja; Ali, Sk Musharaf; Shenoy, K T; Mohan, S

2018-04-12

The Cu complex, which is the key chemical species in well-known Cu-Cl hybrid thermochemical cycles and also in numerous metal hydrometallurgical and sedimentary deposit processes, displays a wide variety of structural and dynamical characteristics that are further complicated by the presence of multiple oxidation states of Cu ions with different coordination chemistries, therefore they are difficult to explore from experiments alone. In this article, an attempt has been made to understand the coordination behavior of the Cu complex using MD simulations. The study provides compelling evidence of the experimentally observed multiple stoichiometries of Cu ions, i.e., 1:6:0, 1:5:1, and 1:4:2 for Cu + :H 2 O:Cl - and 1:6:0 for Cu 2+ :H 2 O:Cl - . The presence of the anionic Cu complex, [Cu + Cl 2 ] - ·2H 2 O, [Cu + Cl 2 ] - ·3H 2 O, [Cu 2+ Cl 3 ] - ·H 2 O, and [Cu 2+ Cl 3 ] - ·2H 2 O, was captured in the presence of excess chloride ions. Furthermore, the probability distribution profiles have been estimated to determine the most possible complex in the considered systems. The results establish structural and dynamical reformation of the Cu complex with change in the salt concentration or variation in the solvent medium in which they are dissolved. Moreover, the structure and kinetics of the Cu ions in the Cu-Cl electrolyzer have been explored over a large range of the electric field by extending the simulated systems for varied strengths of the electric fields. It has been observed that with an increase in the strength of the electric field, the water molecules lose their coordination strength with central Cu ions, which, on the other hand, results in a significant change in the structure of the captured complex. The diffusion dynamics of the ions is altered while applying the electric field, which is furthermore modified while increasing the strength of electric field beyond a critical limit. In fact, the diffusion mechanism of the ions was seen to be transformed from Brownian-like to linear motion and then to hopping diffusion with the increasing strength of the electric field. To the best of our knowledge, this is the first time when the multiple oxidation states of the Cu ion are explored using MD simulations, and the coexisting pictures of the multiple coordinations and the solvent effects have been clearly revealed. Also to date, the present article is the first one to report the insights of the structure and the dynamics of the ions in the Cu-Cl electrolyzer over a wide range of the electric field. The present studies will be very helpful in understanding the mechanism involved in numerous metal hydrometallurgical and sedimentary deposit processes and to comprehend the analogies involved in the electrode reactions of the Cu-Cl cycle for hydrogen generation.

Spatiotemporal dynamics of charged species in the afterglow of plasmas containing negative ions.

PubMed

Kaganovich, I D; Ramamurthi, B N; Economou, D J

2001-09-01

The spatiotemporal evolution of charged species densities and wall fluxes during the afterglow of an electronegative discharge has been investigated. The decay of a plasma with negative ions consists of two stages. During the first stage of the afterglow, electrons dominate plasma diffusion and negative ions are trapped inside the vessel by the static electric field; the flux of negative ions to the walls is nearly zero. During this stage, the electron escape frequency increases considerably in the presence of negative ions, and can eventually approach free electron diffusion. During the second stage of the afterglow, electrons have disappeared, and positive and negative ions diffuse to the walls with the ion-ion ambipolar diffusion coefficient. Theories for plasma decay have been developed for equal and strongly different ion (T(i)) and electron (T(e)) temperatures. In the case T(i)=T(e), the species spatial profiles are similar and an analytic solution exists. When detachment is important in the afterglow (weakly electronegative gases, e.g., oxygen) the plasma decay crucially depends on the product of negative ion detachment frequency (gamma(d)) and diffusion time (tau(d)). If gamma(d)tau(d)>2, negative ions convert to electrons during their diffusion towards the walls. The presence of detached electrons results in "self-trapping" of the negative ions, due to emerging electric fields, and the negative ion flux to the walls is extremely small. In the case T(i)

The diffusion of ions in unconsolidated sediments

USGS Publications Warehouse

Manheim, F.T.

1970-01-01

Diffusion in unconsolidated sediments generally proceeds at rates ranging from half to one twentieth of those applying to diffusion of ions and molecules in free solution. Diffusion rates are predictable with respect to porosity and path tortuosity in host sediments, and can be conveniently measured by determinations of electrical resistivity on bulk sediment samples. Net ion flux is further influenced by reactions of diffusing species with enclosing sediments, but such influences should not be confused with or lumped with diffusion processes. ?? 1970.

Proton transfer and the diffusion of H+ and OH- ions along water wires.

PubMed

Lee, Song Hi; Rasaiah, Jayendran C

2013-09-28

Hydrogen and hydroxide ion transport in narrow carbon nanotubes (CNTs) of diameter 8.1 Å and lengths up to 582 Å are investigated by molecular dynamics simulations using a dissociating water model. The diffusion coefficients of the free ions in an open chain are significantly larger than in periodically replicated wires that necessarily contain D or L end defects, and both are higher than they are in bulk water. The free hydroxide ion diffuses faster than the free hydronium ion in short CNTs, unlike diffusion in liquid water, and both coefficients increase and converge to nearly the same value with increasing tube length. The diffusion coefficients of the two ions increase further when the tubes are immersed in a water reservoir and they move easily out of the tube, suggesting an additional pathway for proton transport via OH(-) ions in biological channels.

Robust binder-free anodes assembled with ultralong mischcrystal TiO2 nanowires and reduced graphene oxide for high-rate and long cycle life lithium-ion storage

NASA Astrophysics Data System (ADS)

Shi, Yongzheng; Yang, Dongzhi; Yu, Ruomeng; Liu, Yaxin; Hao, Shu-Meng; Zhang, Shiyi; Qu, Jin; Yu, Zhong-Zhen

2018-04-01

To satisfy increasing power demands of mobile devices and electric vehicles, rationally designed electrodes with short diffusion length are highly imperative to provide highly efficient ion and electron transport paths for high-rate and long-life lithium-ion batteries. Herein, binder-free electrodes with the robust three-dimensional conductive network are prepared by assembling ultralong TiO2 nanowires with reduced graphene oxide (RGO) sheets for high-performance lithium-ion storage. Ultralong TiO2 nanowires are synthesized and used to construct an interconnecting network that avoids the use of inert auxiliary additives of polymer binders and conductive agents. By thermal annealing, a small amount of anatase is generated in situ in the TiO2(B) nanowires to form abundant TiO2(B)/anatase interfaces for accommodating additional lithium ions. Simultaneously, RGO sheets efficiently enhance the electronic conductivity and enlarge the specific surface area of the TiO2/RGO nanocomposite. The robust 3D network in the binder-free electrode not only effectively avoids the agglomeration of TiO2/RGO components during the long-term charging/discharging process, but also provides direct and fast ion/electron transport paths. The binder-free electrode exhibits a high reversible capacity of 259.9 mA h g-1 at 0.1 C and an excellent cycling performance with a high reversible capacity of 111.9 mA h g-1 at 25 C after 5000 cycles.

Characteristic length scale dependence on conductivity for La2-xErxMo2O9 (0.05 ≤ x ≤ 0.3) oxide ion conductors

NASA Astrophysics Data System (ADS)

Paul, T.; Ghosh, A.

2016-05-01

Structural property of polycrystalline La2-xErxMo2O9 has been investigated. Rietveld refinements at room temperature of the materials suggest a single phase nature with cubic symmetry (space group P213). The electron density contour plot confirms the nature of different cation-oxygen bonds. Time dependent mean square displacement (√) and the spatial extent of the sub-diffusive motion (√) are evaluated using the linear response theory. The localized hop at O2 and O3 sites is found to be favorable for oxygen ion migration for these systems.

Preparation of Hollow Fe2O3 Nanorods and Nanospheres by Nanoscale Kirkendall Diffusion, and Their Electrochemical Properties for Use in Lithium-Ion Batteries.

PubMed

Cho, Jung Sang; Park, Jin-Sung; Kang, Yun Chan

2016-12-13

A novel process for the preparation of aggregate-free metal oxide nanopowders with spherical (0D) and non-spherical (1D) hollow nanostructures was introduced. Carbon nanofibers embedded with iron selenide (FeSe) nanopowders with various nanostructures are prepared via the selenization of electrospun nanofibers. Ostwald ripening occurs during the selenization process, resulting in the formation of a FeSe-C composite nanofiber exhibiting a hierarchical structure. These nanofibers transform into aggregate-free hollow Fe 2 O 3 powders via the complete oxidation of FeSe and combustion of carbon. Indeed, the zero- (0D) and one-dimensional (1D) FeSe nanocrystals transform into the hollow-structured Fe 2 O 3 nanopowders via a nanoscale Kirkendall diffusion process, thus conserving their overall morphology. The discharge capacities for the 1000 th cycle of the hollow-structured Fe 2 O 3 nanopowders obtained from the FeSe-C composite nanofibers prepared at selenization temperatures of 500, 800, and 1000 °C at a current density of 1 A g -1 are 932, 767, and 544 mA h g -1 , respectively; and their capacity retentions from the second cycle are 88, 92, and 78%, respectively. The high structural stabilities of these hollow Fe 2 O 3 nanopowders during repeated lithium insertion/desertion processes result in superior lithium-ion storage performances.

Electro-fenton and photoelectro-fenton degradation of sulfanilic acid using a boron-doped diamond anode and an air diffusion cathode.

PubMed

El-Ghenymy, Abdellatif; Garrido, José Antonio; Centellas, Francesc; Arias, Conchita; Cabot, Pere Lluís; Rodríguez, Rosa María; Brillas, Enric

2012-04-05

The mineralization of sulfanilic acid has been studied by electro-Fenton (EF) and photoelectro-Fenton (PEF) reaction with UVA light using an undivided electrochemical cell with a boron-doped diamond (BDD) anode and an air diffusion cathode able to generate H(2)O(2). Organics were then oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between generated H(2)O(2) and added Fe(2+). The UVA irradiation in PEF enhanced the production of hydroxyl radicals in the bulk, accelerating the removal of organics and photodecomposed intermediates like Fe(III)-carboxylate complexes. Partial decontamination of 1.39 mM sulfanilic acid solutions was achieved by EF until 100 mA cm(-2) at optimum conditions of 0.4 mM Fe(2+) and pH 3.0. The increase in current density and substrate content led to an almost total mineralization. In contrast, the PEF process was more powerful, yielding almost complete mineralization in less electrolysis time under comparable conditions. The kinetics for sulfanilic acid decay always followed a pseudo-first-order reaction. Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic, and oxamic acids were identified as generated carboxylic acids. NH(4)(+) ion was preferentially released in both treatments, along with NO(3)(-) ion in smaller proportion.

Field ion microscopic studies of the CO oxidation on platinum: Bistability and oscillations

NASA Astrophysics Data System (ADS)

Gorodetskii, V.; Drachsel, W.; Ehsasi, M.; Block, J. H.

1994-05-01

The oscillating CO oxidation is investigated on a Pt-field emitter tip by using the field ion mode of surface imaging of Oad sites with O2 as imaging gas. Based on data of the titration reactions [V. Gorodetskii, W. Drachsel, and J. H. Block, J. Chem. Phys. 100, C. E. UPDATE (1994)], external control parameters for the regions of bistability and of self-sustained isothermal oscillations could be found. On a field emitter tip, oscillations can be generated in a rather large parameter space. The anticlockwise hysteresis of O+2 ion currents in temperature cycles occurs in agreement with results on single crystal planes. Unexpected regular oscillation sequences could occasionally be obtained on the small surface areas of a field emitter tip and measured as function of the CO partial pressure and of the temperature. Different stages within oscillating cycles were documented by field ion images. Oscillations of total ion currents are correlated with variations in the spatial brightness of field ion images. In the manifold of single crystal planes of a field emitter {331} planes around the {011} regions are starting points for oscillations which mainly proceed along [100] vicinals. This excludes the {111} regions from autonomous oscillations. With slightly increased CO partial pressures fast local oscillations at a few hundred surface sites of the Pt(001) plane display short-living CO islands of 40 to 50 Å diameter. Temporal oscillations of the total O+2 ion current are mainly caused by surface plane specific spatial oscillations. The synchronization is achieved by diffusion reaction fronts rather than by gas phase synchronization.

Forging Fast Ion Conducting Nanochannels with Swift Heavy Ions: The Correlated Role of Local Electronic and Atomic Structure

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

Sachan, Ritesh; Cooper, Valentino R.; Liu, Bin

2016-12-19

Atomically disordered oxides have attracted significant attention in recent years due to the possibility of enhanced ionic conductivity. However, the correlation between atomic disorder, corresponding electronic structure, and the resulting oxygen diffusivity is not well understood. The disordered variants of the ordered pyrochlore structure in gadolinium titanate (Gd 2Ti 2O 7) are seen as a particularly interesting prospect due to intrinsic presence of a vacant oxygen site in the unit atomic structure, which could provide a channel for fast oxygen conduction. In this paper, we provide insights into the subangstrom scale on the disordering-induced variations in the local atomic environmentmore » and its effect on the electronic structure in high-energy ion irradiation-induced disordered nanochannels, which can be utilized as pathways for fast oxygen ion transport. With the help of an atomic plane-by-plane-resolved analyses, the work shows how the presence of various types of TiO x polyhedral that exist in the amorphous and disordered crystalline phase modify the electronic structures relative to the ordered pyrochlore phase in Gd 2Ti 2O 7. Finally, the correlated molecular dynamics simulations on the disordered structures show a remarkable enhancement in oxygen diffusivity as compared with ordered pyrochlore lattice and make that a suitable candidate for applications requiring fast oxygen conduction.« less

Lattice-cell orientation disorder in complex spinel oxides

DOE PAGES

Chen, Yan; Cheng, Yongqiang; Li, Juchuan; ...

2016-11-07

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

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

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Novel mesoporous MnCo2O4 nanorods as oxygen reduction catalyst at neutral pH in microbial fuel cells.

PubMed

Kumar, Ravinder; Singh, Lakhveer; Wahid, Zularisam Ab; Mahapatra, Durga Madhab; Liu, Hong

2018-04-01

The aim of this work was to evaluate the comparative performance of hybrid metal oxide nanorods i.e. MnCo 2 O 4 nanorods (MCON) and single metal oxide nanorods i.e. Co 3 O 4 nanorods (CON) as oxygen reduction catalyst in microbial fuel cells (MFC). Compared to the single metal oxide, the hybrid MCON exhibited a higher BET surface area and provided additional positively charged ions, i.e., Co 2+ /Co 3+ and Mn 3+ /Mn 4+ on its surfaces, which increased the electro-conductivity of the cathode and improved the oxygen reduction kinetics significantly, achieved an i o of 6.01 A/m 2 that was 12.4% higher than CON. Moreover, the porous architecture of MCON facilitated the diffusion of electrolyte, reactants and electrons during the oxygen reduction, suggested by lower diffusion (R d ), activation (R act ) and ohmic resistance (R ohm ) values. This enhanced oxygen reduction by MCON boosted the power generation in MFC, achieving a maximum power density of 587 mW/m 2 that was ∼29% higher than CON. Published by Elsevier Ltd.

TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Tsuda, H.; Halbig, M. C.; Singh, M.; Hasegawa, Y; Mori, S.; Asthana, R.

2017-01-01

Silicon Carbide (SiC) is a promising material for thermostructural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, Mo-B and TiCu. In this presentation, we report the microstructure of diffusion bonded SA-THX mainly with TiCu interlayers obtained by TEM observations, and the influence of metallic interlayers on the joint microstructure and microhardness will be discussed.

Dynamics and Thermochemistry of Oxygen Uptake by a Mixed Ce-Pr Oxide

NASA Astrophysics Data System (ADS)

Sinev, M. Yu.; Fattakhova, Z. T.; Bychkov, V. Yu.; Lomonosov, V. I.; Gordienko, Yu. A.

2018-03-01

The dynamics of oxygen uptake by mixed Ce0.55Pr0.45O2-x oxide is studied in a pulsed oxygen supply mode using in situ high-temperature heat flow differential scanning calorimetry. It is stated that the oxidation proceeds in two regimes: a fast one at the beginning of the oxidation process, and a slow one, which is controlled by the diffusion of oxygen through the bulk of the solid at the later stages of the process. Analysis of the shape of calorimetric profiles reveals some processes, accompanied by heat release, that occur in the sample in the absence of oxygen in the gas phase. These could be due to both the redistribution of consumed oxygen in the oxide lattice and the lattice relaxation associated with the transformation of phases with different arrangements of oxygen vacancies in them. The heat effect (which diminishes from 60 to 40 kJ/mol in the course of oxygen uptake) associated with the oxidation of the reduced form of mixed Ce-Pr oxide, corresponds to the oxidation of praseodymium ions from (3+) to (4+).

Cathodic electrodeposition of mixed molybdenum tungsten oxides from peroxo-polymolybdotungstate solutions.

PubMed

Kondrachova, Lilia; Hahn, Benjamin P; Vijayaraghavan, Ganesh; Williams, Ryan D; Stevenson, Keith J

2006-12-05

Mixed molybdenum tungsten trioxide films of varying stoichiometry (MoxW1 - xO3, 0 < x < 1) were prepared by cathodic electrodeposition on indium tin oxide (ITO)-coated glass substrates from aqueous peroxo-polymolybdotungstate solutions. Electrochemical quartz crystal microbalance (EQCM), cyclic voltammetry, and chronocoulometry were used to gain insight into the electrodeposition mechanism. The compositional and structural properties were characterized for MoxW1 - xO3 films deposited at intermediate potentials (-0.35 V vs Ag/AgCl) and sintered at 250 degrees C using energy-dispersive spectroscopy, X-ray diffraction, and Raman spectroscopy. These studies reveal that films consist of homogeneously mixed MoxW1 - xO3, with an enriched Mo content ranging in composition from 0.4 < x < 0.7 depending upon the mol % Mo present in the deposition solution. Chronoamperometry and spectroelectrochemical measurements were conducted to estimate lithium ion diffusion coefficients and coloration efficiencies for the mixed metal oxide films in 1 M LiClO4/propylene carbonate. The subtle interplay between structural and compositional properties due to the uniform mixing of Mo and W oxide components shows that electrochromic and lithium ion transport properties are moderately enhanced relative to those of single-component WO3 and MoO3 and demonstrate improved structural stability over pure MoO3 polymorphs during electrochemical cycling.

Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

PubMed

Pramana, Stevin S; Klooster, Wim T; White, T J

2007-08-01

Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

Integrating 3D Flower-Like Hierarchical Cu2NiSnS4 with Reduced Graphene Oxide as Advanced Anode Materials for Na-Ion Batteries.

PubMed

Yuan, Shuang; Wang, Sai; Li, Lin; Zhu, Yun-hai; Zhang, Xin-bo; Yan, Jun-min

2016-04-13

Development of an anode material with high performance and low cost is crucial for implementation of next-generation Na-ion batteries (NIBs) electrode, which is proposed to meet the challenges of large scale renewable energy storage. Metal chalcogenides are considered as promising anode materials for NIBs due to their high theoretical capacity, low cost, and abundant sources. Unfortunately, their practical application in NIBs is still hindered because of low conductivity and morphological collapse caused by their volume expansion and shrinkage during Na(+) intercalation/deintercalation. To solve the daunting challenges, herein, we fabricated novel three-dimensional (3D) Cu2NiSnS4 nanoflowers (CNTSNs) as a proof-of-concept experiment using a facile and low-cost method. Furthermore, homogeneous integration with reduced graphene oxide nanosheets (RGNs) endows intrinsically insulated CNTSNs with superior electrochemical performances, including high specific capacity (up to 837 mAh g(-1)), good rate capability, and long cycling stability, which could be attributed to the unique 3D hierarchical structure providing fast ion diffusion pathway and high contact area at the electrode/electrolyte interface.

Fluorine-doped SnO2 nanoparticles anchored on reduced graphene oxide as a high-performance lithium ion battery anode

NASA Astrophysics Data System (ADS)

Cui, Dongming; Zheng, Zhong; Peng, Xue; Li, Teng; Sun, Tingting; Yuan, Liangjie

2017-09-01

The composite of fluorine-doped SnO2 anchored on reduced graphene oxide (F-SnO2/rGO) has been synthesized through a hydrothermal method. F-SnO2 particles with average size of 8 nm were uniformly anchored on the surfaces of rGO sheets and the resulting composite had a high loading of F-SnO2 (ca. 90%). Benefiting from the remarkably improved electrical conductivity and Li-ion diffusion in the electrode by F doping and rGO incorporation, the composite material exhibited high reversible capacity, excellent long-term cycling stability and superior rate capability. The electrode delivered a large reversible capacity of 1037 mAh g-1 after 150 cycles at 100 mA g-1 and high rate capacities of 860 and 770 mAh g-1 at 1 and 2 A g-1, respectively. Moreover, the electrode could maintain a high reversible capacities of 733 mAh g-1 even after 250 cycles at 500 mA g-1. The outstanding electrochemical performance of the as-synthesized composite make it a promising anode material for high-energy lithium ion batteries.

Far-field analysis of coupled bulk and boundary layer diffusion toward an ion channel entrance.

PubMed Central

Schumaker, M F; Kentler, C J

1998-01-01

We present a far-field analysis of ion diffusion toward a channel embedded in a membrane with a fixed charge density. The Smoluchowski equation, which represents the 3D problem, is approximated by a system of coupled three- and two-dimensional diffusions. The 2D diffusion models the quasi-two-dimensional diffusion of ions in a boundary layer in which the electrical potential interaction with the membrane surface charge is important. The 3D diffusion models ion transport in the bulk region outside the boundary layer. Analytical expressions for concentration and flux are developed that are accurate far from the channel entrance. These provide boundary conditions for a numerical solution of the problem. Our results are used to calculate far-field ion flows corresponding to experiments of Bell and Miller (Biophys. J. 45:279, 1984). PMID:9591651

Nanoporous graphene obtained by hydrothermal process in H2O2 and its application for supercapacitors

NASA Astrophysics Data System (ADS)

Lv, Jinlong; Liang, Tongxiang

2016-08-01

Nanohole graphene oxide (NHGO) was obtained in a homogeneous aqueous mixture of graphene oxide (GO) and H2O2 at 120 °C. Supercapacitors were fabricated as the electrode material by using NHGO. A specific capacitance of 240.1 F g-1 was obtained at a current density of 1 A g-1 in 6 m KOH electrolyte and specific capacitance remained 193.6 F g-1 at the current density of 20 A g-1. This was attributed to reducing the inner space between the double-layers, enhanced ion diffusion and large specific surface area. Supercapacitor prepared with NHGO electrodes also exhibited an excellent cycle stability.

Selective Metal Exsolution in BaFe 2-yMy(PO 4) 2 (M = Co 2+, Ni 2+) Solid Solutions

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

Alcover, Ignacio Blazquez; Daviero-Minaud, Sylvie; David, Rénald

2015-08-19

The 2D-Ising ferromagnetic phase BaFe 2+ 2(PO 4) 2 shows exsolution of up to one-third of its iron content (giving BaFe 3+ 1.33(PO 4) 2) under mild oxidation conditions, leading to nanosized Fe 2O 3 exsolved clusters. Here we have prepared BaFe 2–yMy(PO 4) 2 (M = Co 2+, Ni 2+; y = 0, 0.5, 1, 1.5) solid solutions to investigate the feasibility and selectivity of metal exsolution in these mixed metallic systems. For all the compounds, after 600 °C thermal treatment in air, a complete oxidation of Fe 2+ to Fe 3+ leaves stable M 2+ ions, as verifiedmore » by 57Fe Mössbauer spectroscopy, TGA, TEM, microprobe, and XANES. Furthermore, the size of the nanometric α-Fe 2O 3clusters coating the main phase strongly depends on the y M metal concentration. For M-rich phases the iron diffusion is hampered so that a significant fraction of superparamagnetic α-Fe2O3 particles (100% for BaFe 0.5–xCo 1.5(PO 4) 2) was detected even at 78 K. Although Ni 2+and Co 2+ ions tend to block Fe diffusion, the crystal structure of BaFe 0.67Co 1(PO 4) 2demonstrates a fully ordered rearrangement of Fe 3+ and Co 2+ ions after Fe exsolution. We found that the magnetic behaviors of the Fe-depleted materials are mostly dominated by antiferromagnetic exchange, while Co 2+-rich compounds show metamagnetic transitions reminiscent of the BaCo 2(PO 4) 2 soft helicoidal magnet.« less

Lithium Polymer Electrolytes Based On PMMA / PEG And Penetrant Diffusion In Kraton Penta-Block Ionomer

NASA Astrophysics Data System (ADS)

Meng, Yan

The study of diffusion in polymeric material is critical to many research fields and applications, such as polymer morphology, protective coatings (paints and varnishes), separation membranes, transport phenomena, polymer electrolytes, polymer melt, and controlled release of drugs from polymer carriers [1-9]. However, it is still a challenge to understand, predict and control the diffusion of molecules and ions of different sizes in polymers [2]. This work studied the medium to long range diffusion of species (i.e., ions and molecules) in solid polymer electrolytes based on poly(ethylene glycol)/poly(methyl methacrylate) (PEG/PMMA) for Li-based batteries, and polymeric permselective membranes via pulsed-field gradient NMR and a.c. impedance. Over the past decades polymer electrolytes have attracted much attention because of their promising technological application as an ion-conducting medium in solid-state batteries, fuel cells, electrochromic displays, and chemical sensors [10, 11]. However, despite numerous studies related to ionic transport in these electrolytes the understanding of the migration mechanism is still far from being complete, and progress in the field remains largely empirical [10, 12-15]. Among various candidates for solid polymer electrolyte (SPE) material, the miscible polymer pair, poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA), is an attractive one, because there is a huge difference in mobility between PEO and PMMA in their blends, and PEO chains remain exceptionally mobile in the blend even at temperature below the glass transition temperature of the blend [ 16]. Thus the mechanical strength and dimensional stability is maintained by PMMA component, while the chain motions or rearrangements of the PEO component virtually contribute to the ion transport [17]. The current work prepared two types of SPE based on poly(ethylene glycol) (PEG) /PMMA (40/60 by weight) for Li-based batteries: lithium bis(trifluoromethylsulfonylimide) (LiN(SO2CF3)2, LiTFSI) doped SPE and single-ion SPE. PEG, which is the very low molecular weight version of PEO, was used instead of PLO due to PEG's advantages of being noncrystalline, higher mobility, and having relatively high ionic conductivity when doped with alkali metal salts [18]. The medium to long range diffusion of species (i.e., ions and molecules) were studied via pulsed-field gradient NMR and a.c. impedance, along with other properties. For the LiTFSI doped system, the samples are named with their F0 to Li ratios. The order of diffusivity of ions is 16:1> 24:1> 8:1, while the order of a.c. conductivity is 24:1 > 16:1> 8:1. The largest diffusion 7Li coefficient is 1.4 x 108 cm 2/s in 16:1 at 77°C , and the largest a.c. conductivity is 1.43x 10-5S/cm for 24:1 at 68°C. The discrepancy between the diffusivity order and conductivity order is attributed to the formation of neutral contact ion pairs by a substantial fraction of ions in 16:1 . As the salt concentration is increased as 24:1→16:1→8:1, there is the transition of mostly free ions (i.e., 24:1)→free ions+contact ion pairs (i.e.. 16:1)→free ions+contact ion pairs+higher aggregates (i.e., 8:1). For the single-ion system, ion pairing of lithium PMMA ionomer is a serious problem due to the relatively low acidity of its corresponding acid and the low dielectric constant of the solvent (i.e. PEG). The Li+ diffusivity is fair (on the order of 10-8 cm2/s at 65°C, 77°C, and 89°C), but the fraction of free Li+ is only 1-2%. This severely limits the resulting a.c. conductivity, which is 2.72x 10-7 S/cm for 40P600 at 81°C. The second project involves studying the transport properties of a sulfonated pentablock copolymer, poly(para-methylstyrene)--b-hydrogenated polybutadiene-b-polystyrene-bhydrogenated polybutadiene - b-poly(para-methylstyrene) with polystyrene sulfonated in the midblock(PMS-HPB-sS-HPB-PMS), as pemrselective membranes for protective clothing, with high permeability to water and low permeability to hazardous organic chemicals. In addition, this work also contributes to study of polymer electrolyte membrane for fuel cell systems, because water transport in polymer electrolyte membranes (PEMs) has a profound effect on the performance of a fuel cell, yet is surprisingly the least studied property of PEMs[19]. The self-diffusion coefficients of different penetrant molecules, i.e., water, dimethyl methylphosphonate (DMMP), and ethanol in the said ionomer were accurately measured with PFG NMR as functions of temperature and concentration of solvents. Water exhibited self-diffusion coefficients two orders of magnitude higher than DMMP, while ethanol lies in between. Their effective volume to surface ratios of domains where diffusion took place were determined. The volume to surface ratios of water and DMMP are quite different, suggesting they may have different local geometry of the pores they reside in, while the V p/Seff ratios for water and ethanol are similar, thereby suggesting similar local environments of these solvents in the ionomer.

Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

DOE PAGES

Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.; ...

2014-09-30

Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li 1.2Mn 0.55Ni 0.15Co 0.1O 2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxidemore » occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(Li Lioct →Li Litet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [Li TM oct → Li Litet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [Mn TMoct Mn Litet Mn Lioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.« less

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

PubMed

Ong, Mitchell T; Verners, Osvalds; Draeger, Erik W; van Duin, Adri C T; Lordi, Vincenzo; Pask, John E

2015-01-29

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE PAGES

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary; ...

2017-09-21

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

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

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Spectroscopic And Electrochemical Studies Of Electrochromic Hydrated Nickel Oxide Films

NASA Astrophysics Data System (ADS)

Yu, P. C.; Nazri, G.; Lampert, C. M.

1986-09-01

The electrochrcrnic properties of hydrated nickel oxide thin films electrochemically deposited by anodization onto doped tin oxide-coated glass have been studied by transmittance measurements, cyclic voltammetry, Fourier-transform infrared spectroscopy, and ion-backscattering spectrometry. The spectral transmittance is reported for films switched in both the bleached and colored states. The photopic transmittance (Tp) can be switched from T (bleached) = 0.77 to T (colored) = 0.21, and the solar transmittance (Ts) can be switched from Ts(bleached) = 0.73 to TS (colored) = 0.35. Also reported is the near-infrared transmittance (TNIR)which was found to switch fran T N,IR (bleached) = 0.72 to TNIR (colored) = 0.55. The bleached condition is noted to have very low solar absorption in both the visible and solar regions. Ion-backscattering spectrometry was performed on the hydrated nickel oxide film, yielding a camposition of Ni01.0 (dehydrated) and a film thickness of 125 A. Cyclic voltammetry showed that, for films in the bleached or colored state, the reversible reaction is Ni(0H), = NiOOH + H+ + e . Voltammnetry also showed that the switching of the film is controlled by the diffusion or protons, where OH plays a role in the reaction mechanism. Analysis of the hydrated nickel-oxide thin films by Fourier-transform infrared spectroscopy revealed that both the bleached and colored states contain lattice water and hydroxyl groups. The surface hydroxyl groups play an important role in the coloration and bleaching of the anodically deposited nickel oxide thin films.

Chemistry of the metal-polymer interfacial region.

PubMed

Leidheiser, H; Deck, P D

1988-09-02

In many polymer-metal systems, chemical bonds are formed that involve metal-oxygen-carbon complexes. Infrared and Mössbauer spectroscopic studies indicate that carboxylate groups play an important role in some systems. The oxygen sources may be the polymer, the oxygen present in the oxide on the metal surface, or atmospheric oxygen. Diffusion of metal ions from the substrate into the polymer interphase may occur in some systems that are cured at elevated temperatures. It is unclear whether a similar, less extensive diffusion occurs over long time periods in systems maintained at room temperature. The interfacial region is dynamic, and chemical changes occur with aging at room temperature. Positron annihilation spectroscopy may have application to characterizing the voids at the metal-polymer interface.

Theory and simulation of ion conduction in the pentameric GLIC channel.

PubMed

Zhu, Fangqiang; Hummer, Gerhard

2012-10-09

GLIC is a bacterial member of the large family of pentameric ligand-gated ion channels. To study ion conduction through GLIC and other membrane channels, we combine the one-dimensional potential of mean force for ion passage with a Smoluchowski diffusion model, making it possible to calculate single-channel conductance in the regime of low ion concentrations from all-atom molecular dynamics (MD) simulations. We then perform MD simulations to examine sodium ion conduction through the GLIC transmembrane pore in two systems with different bulk ion concentrations. The ion potentials of mean force, calculated from umbrella sampling simulations with Hamiltonian replica exchange, reveal a major barrier at the hydrophobic constriction of the pore. The relevance of this barrier for ion transport is confirmed by a committor function that rises sharply in the barrier region. From the free evolution of Na(+) ions starting at the barrier top, we estimate the effective diffusion coefficient in the barrier region, and subsequently calculate the conductance of the pore. The resulting diffusivity compares well with the position-dependent ion diffusion coefficient obtained from restrained simulations. The ion conductance obtained from the diffusion model agrees with the value determined via a reactive-flux rate calculation. Our results show that the conformation in the GLIC crystal structure, with an estimated conductance of ~1 picosiemens at 140 mM ion concentration, is consistent with a physiologically open state of the channel.

Metal-Organic Framework-Derived Metal Oxide Embedded in Nitrogen-Doped Graphene Network for High-Performance Lithium-Ion Batteries.

PubMed

Sui, Zhu-Yin; Zhang, Pei-Ying; Xu, Meng-Ying; Liu, Yu-Wen; Wei, Zhi-Xiang; Han, Bao-Hang

2017-12-13

Metal-organic frameworks (MOFs) are hybrid inorganic-organic materials that can be used as effective precursors to prepare various functional nanomaterials for energy-related applications. Nevertheless, most MOF-derived metal oxides exhibit low electrical conductivity and mechanical strain. These characteristics limit their electrochemical performance and hamper their practical application. Herein, we report a rational strategy for enhancing the lithium storage performance of MOF-derived metal oxide. The hierarchically porous Co 3 O 4 @NGN is successfully prepared by embedding ZIF-67-derived Co 3 O 4 particles in a nitrogen-doped graphene network (NGN). The high electrical conductivity and porous structure of the NGN accelerates the diffusion of electrolyte ions and buffers stress resulting from the volume changes of Co 3 O 4 . As an anode material, the Co 3 O 4 @NGN shows high capacity (1030 mA h g -1 at 100 mA g -1 ), outstanding rate performance (681 mA h g -1 at 1000 mA g -1 ), and good cycling stability (676 mA h g -1 at 1000 mA g -1 after 400 cycles).

The reactive element effect of ceria particle dispersion on alumina growth: A model based on microstructural observations

PubMed Central

Wang, X.; Peng, X.; Tan, X.; Wang, F.

2016-01-01

The oxidation kinetics of alumina-forming metals can be affected by adding a small amount of a reactive (normally rare earth) element oxide (RExOy) and the segregation of the reactive element (RE) ions to the growing alumina grain boundaries (GBs) has been considered as a responsible reason. However, this interpretation remains a controversial issue as to how RE ions are produced by RExOy which is thermodynamically and chemically stable in metals. The question is answered by a model that is based on transmission electron microscopy (TEM) investigation of a CeO2-dispersed nickel aluminide oxidized in air at 1100 °C. The CeO2 dispersion is incorporated into the alumina scale by the inward growth of inner α-Al2O3, where it partially dissolves producing tetravalent Ce cations which then transform to trivalent cations by trapping electrons. The trivalent cations segregate to the α-Al2O3 GBs and diffuse outward along first the GBs and later the twin boundaries (TBs) in the outer γ-Al2O3 layer, being precipitated as Ce2O3 particles near surface. PMID:27406938

Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang; Yuan, Changzhou; Lou, Xiong Wen David

2012-10-02

Metal oxide nanostructures are promising electrode materials for lithium-ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2-3 times higher than that of the carbon/graphite-based materials. However, their cycling stability and rate performance still can not meet the requirements of practical applications. It is therefore urgent to improve their overall device performance, which depends on not only the development of advanced electrode materials but also in a large part "how to design superior electrode architectures". In the article, we will review recent advances in strategies for advanced metal oxide-based hybrid nanostructure design, with the focus on the binder-free film/array electrodes. These binder-free electrodes, with the integration of unique merits of each component, can provide larger electrochemically active surface area, faster electron transport and superior ion diffusion, thus leading to substantially improved cycling and rate performance. Several recently emerged concepts of using ordered nanostructure arrays, synergetic core-shell structures, nanostructured current collectors, and flexible paper/textile electrodes will be highlighted, pointing out advantages and challenges where appropriate. Some future electrode design trends and directions are also discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-Dependent Lithium-Ion Diffusion and Activation Energy of Li1.2Co0.13Ni0.13Mn0.54O2 Thin-Film Cathode at Nanoscale by Using Electrochemical Strain Microscopy.

PubMed

Yang, Shan; Yan, Binggong; Wu, Jiaxiong; Lu, Li; Zeng, Kaiyang

2017-04-26

This paper presents the in situ mapping of temperature-dependent lithium-ion diffusion at the nanometer level in thin film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode using electrochemical strain microscopy. The thin-film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode exhibits higher lithium-ion diffusivities with increasing temperature, which explains the higher capacity observed in the lithium-ion batteries with a Li-rich cathode at elevated temperature. In addition, the activation energy for lithium-ion diffusion can be extracted in an Arrhenius-type plot at the level of grain structure with the assumption that the ionic movement is diffusion controlled. Compared with the grain interiors, the grain boundaries show relatively lower activation energy; hence, it is the preferred diffusion path for lithium ions. This study has bridged the gap between atomistic calculations and traditional macroscopic experiments, showing direct evidence as well as mechanisms for ionic diffusion for Li-rich cathode material.

Tuning the metal-insulator crossover and magnetism in SrRuO 3 by ionic gating

DOE PAGES

Yi, Hee Taek; Gao, Bin; Xie, Wei; ...

2014-10-13

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. We report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO 3. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90–250 K and 70–100 K,more » respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications.« less

Tuning the metal-insulator crossover and magnetism in SrRuO₃ by ionic gating.

PubMed

Yi, Hee Taek; Gao, Bin; Xie, Wei; Cheong, Sang-Wook; Podzorov, Vitaly

2014-10-13

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. Here we report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO₃. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90-250 K and 70-100 K, respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications.

Effect of Ion Streaming on Diffusion of Dust Grains in Dissipative System

NASA Astrophysics Data System (ADS)

Begum, M.; Das, N.

2018-01-01

The presence of strong electric fields in the sheath region of laboratory complex plasma induces an ion drift and perturbs the field around dust grains. The downstream focusing of ions leads to the formation of oscillatory kind of attractive wake potential which superimpose with the normal Debye-Hückel (DH) potential. The structural properties of complex plasma and diffusion coefficient of dust grains in the presence of such a wake potential have been investigated using Langevin dynamics simulation in the subsonic regime of ion flow. The study reveals that the diffusion of dust grains is strongly affected by the ion flow, so that the diffusion changes its character in the wake potential to the DH potential dominant regimes. The dependence of the diffusion coefficient on the parameters, such as the neutral pressure, dust grain size, ion flow velocity, and Coulomb coupling parameter, have been calculated for the subsonic regime by using the Green-Kubo expression, which is based on the integrated velocity autocorrelation function. It is found that the diffusion and the structural property of the system is intimately connected with the interaction potential and significantly get affected in the presence of ion flow in the subsonic regime.

Topotactic Metal-Insulator Transition in Epitaxial SrFeO x Thin Films

DOE PAGES

Khare, Amit; Shin, Dongwon; Yoo, Tae Sup; ...

2017-07-31

Multivalent transition metal oxides provide fascinating and rich physics related to oxygen stoichiometry. In particular, the adoptability of various valence states of transition metals enables perovskite oxides to display mixed (oxygen) ionic and electronic conduction and catalytic activity useful in many practical applications, including solid-oxide fuel cells (SOFCs), rechargeable batteries, gas sensors, and memristive devices. For proper realization of the ionic conduction and catalytic activity, it is essential to understand the reversible oxidation and reduction process, which is governed by oxygen storage/release steps in oxides. Topotactic phase transformation facilitates the redox process in perovskites with specific oxygen vacancy ordering bymore » largely varying the oxygen concentration of a material without losing the lattice framework. The concentration and diffusion of oxide ions (O 2–), the valence state of the transition metal cations, and the thermodynamic structural integrity together provide fundamental understanding and ways to explicitly control the redox reaction.[6] In addition, it offers an attractive route for tuning the emergent physical properties of transition metal oxides, via strong coupling between the crystal lattice and electronic structure.« less

Studies of implanted iron in silicon by channeling and Rutherford backscattering

NASA Technical Reports Server (NTRS)

Wang, P. W.; Cheng, H. S.; Gibson, W. M.; Corbett, J. W.

1986-01-01

Different amounts of 100-keV iron ions have been implanted into high-resistivity p-type FZ-silicon samples. The implantation damage, recovery of damage during various annealing periods and temperatures, movement of iron atoms under annealing and oxidation, and the kinds of defects created after implantation, annealing, or oxidation are all investigated by channeling and backscattering measurements. It is found that the critical fluence of 100-keV iron implanted into silicon at room temperature is about 2.5 x 10 to the 14th Fe/sq cm, and that iron atoms are gettered by silicon oxidation. In this supersaturated region, iron atoms diffuse slightly towards bulk silicon during high-temperature annealing (greater than or equal to 1100 C) but not at all during low-temperature annealing (less than or equal to 1000 C) in dry nitrogen ambient.

Confined Transformation Derived Ultrathin Titanate Nanosheets/ Graphene Films for Excellent Na/K Ion Storage.

PubMed

Zeng, Cheng; Xie, Fangxi; Yang, Xianfeng; Jaroniec, Mietek; Zhang, Lei; Qiao, Shizhang

2018-05-02

Confined transformation of assembled two-dimensional MXene (titanium carbide) and reduced graphene oxide (rGO) nanosheets was employed to prepare the free-standing films of the integrated ultrathin sodium titanate (NTO)/potassium titanate (KTO) nanosheets sandwiched between graphene layers. The ultrathin Ti-based nanosheets reduce the diffusion distance while rGO layers enhance conductivity. Incorporation of graphene into the titanate films produced efficient binder-free anodes for ion storage. The resulting NTO/rGO electrode for sodium ion batteries exhibited an excellent rate performance and long cycling stability characterized by reversible capacity of 72 mA h g-1 at 5 A g-1 after 10000 cycles. Moreover, flexible KTO/rGO electrode for potassium ion batteries maintained a reversible capacity of 75 mA h g-1 after 700 cycles at 2 A g-1. These results demonstrate the superiority of the unique sandwich-type electrodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dielectric functions, chemical and atomic compositions of the near surface layers of implanted GaAs by In+ ions

NASA Astrophysics Data System (ADS)

Kulik, M.; Kołodyńska, D.; Bayramov, A.; Drozdziel, A.; Olejniczak, A.; Żuk, J.

2018-06-01

The surfaces of (100) GaAs were irradiated with In+ ions. The implanted samples were isobaric annealed at 800 °C and then of dielectric function, the surface atomic concentrations of atoms and also the chemical composition of the near surface layers in these implanted semiconductor samples were obtained. The following investigation methods were used: spectroscopic ellipsometry (SE), Rutherford backscattering spectrometry analyses (RBSA) and X-ray photoelectron spectroscopy (XPS) in the study of the above mentioned quantities, respectively. The change of the shape spectra of the dielectric functions at about 3.0 eV phonon energy, diffusion of In+ ions as well as chemical composition changes were observed after ion implantation and the thermal treatment. Due to displacement of Ga ions from GaAs by the In+ ions the new chemical compound InAs was formed. The relative amounts Ga2O3 and As2O3 ratio increase in the native oxide layers with the fluences increase after the thermal treatment of the samples. Additionally, it was noticed that the quantities of InO2 increase with the increasing values of the irradiated ions before thermal treatment.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Hou, Yong; Kang, Dongdong; Gao, Cheng; Jin, Fengtao; Yuan, Jianmin

2018-01-01

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion-ion pair potentials are computed using the modified Gordon-Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green-Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Probing the oxidation kinetics of small permalloy particles

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

Dong, Xiaolei; Song, Xiao; Yin, Shiliu

2017-02-15

The oxidation of permalloys is important to apply in a wide range. The oxidation and diffusion mechanisms of small permalloy particles with different Fe content are studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. Fe{sub 2}O{sub 3}/(Ni, Fe){sub 3}O{sub 4} plays a key role in the morphology evolution and diffusion mechanisms of small NiFe particles upon oxidation. The activation energies of grain boundary diffusion for the NiFe alloys increase from 141 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to ~50 wt%. We have developed a diffusion process resolved temperature programed oxidation (PR-TPO) analysis method.more » Three diffusion mechanisms have been recognized by using this method: In addition to the grain boundary diffusion and lattice diffusion, our TGA analysis suggests that the phase conversion from Fe{sub 2}O{sub 3} to (Ni, Fe){sub 3}O{sub 4} induces diffusion change and affects the diffusion process at the intermediate temperature. Relevant oxidation kinetics and diffusion mechanisms are discussed. - Graphical abstract: The oxidation mechanisms of small Permalloy particles with different Fe content is studied by using thermal gravimetric analysis (TGA) and microstructure characterizations. The activation energies of grain boundary diffusion for the NiFe alloys increases from 140 kJ/mol to 208 kJ/mol as the Fe content increases from 0 to 50 wt% as determined by TGA. We have developed a diffusion process resolved temperature programed oxidation (DPR-TPO) analysis method, and three diffusion mechanisms have been recognized by using this method: In addition to the well-known grain boundary diffusion and lattice diffusion, we found that the phase conversion from Fe{sub 2}O{sub 3} to (Ni, Fe){sub 3}O{sub 4} will induce diffusion changes and affect the diffusion process at the intermediate temperature. The diffusion processes can be characterized by the corresponding characteristic peak temperatures in temperature programmed oxidation (TPO) analysis. This work not only give insight knowledge about the oxidation and diffusion processes of small permalloy particles, but also, provides a useful tool for analyzing solid-gas reactions of other materials. - Highlights: • The oxidation kinetics of small NiFe particles were studied by using thermoanalysis. • Grain boundary, lattice, and phase conversion induced diffusions were recognized. • The activation energy of oxidation increases with the Fe content in the alloy. • Each diffusion process corresponds to a characteristic temperature in TPO analysis. • NiFe alloys with ~5–10 wt% Fe content have the lowest oxidation rates.« less

Electron Currents and Heating in the Ion Diffusion Region of Asymmetric Reconnection

NASA Technical Reports Server (NTRS)

Graham, D. B.; Khotyaintsev, Yu. V.; Norgren, C.; Vaivads, A.; Andre, M.; Lindqvist, P. A.; Marklund, G. T.; Ergun, R. E.; Paterson, W. R.; Gershman, D. J.;

Ti diffusion in ion prebombarded MgO(100). I. A model for quantitative analysis

NASA Astrophysics Data System (ADS)

Lu, M.; Lupu, C.; Styve, V. J.; Lee, S. M.; Rabalais, J. W.

2002-01-01

Enhancement of Ti diffusion in MgO(100) prebombarded with 7 keV Ar+ has been observed. Diffusion was induced by annealing to 1000 °C following the prebombardment and Ti evaporation. Such a sample geometry and experimental procedure alleviates the continuous provision of freely mobile defects introduced by ion irradiation during annealing for diffusion, making diffusion proceed in a non-steady-state condition. Diffusion penetration profiles were obtained by using secondary ion mass spectrometry depth profiling techniques. A model that includes a depth-dependent diffusion coefficient was proposed, which successfully explains the observed non-steady-state radiation enhanced diffusion. The diffusion coefficients are of the order of 10-20 m2/s and are enhanced due to the defect structure inflected by the Ar+ prebombardment.

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

Li, Tianqi; Beidaghi, Majid; Xiao, Xu

Orthorhombic molybdenum trioxide (α-MoO 3) is a layered oxide with promising performance as electrode material for Li-ion capacitors. In this study, we show that expansion of the interlayer spacing (by ~0.32 Å) of the structure along the b-axis, introduced by partial reduction of α-MoO 3 and formation of MoO 3-x (x=0.06–0.43), results in enhanced diffusion of Li ions. Binder-free hybrid electrodes made of MoO 3-x nanobelts and carbon nanotubes show excellent electrical conductivity. The combination of increased interlayer spacing and enhanced electron transport leads to high gravimetric and volumetric capacitances of about 420 F/g or F/cm 3 and excellent cyclemore » life of binder-free MoO 3-x electrodes.« less

High-performance tin oxide-nitrogen doped graphene aerogel hybrids as anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tan, Chunhui; Cao, Jing; Khattak, Abdul Muqsit; Cai, Feipeng; Jiang, Bo; Yang, Gai; Hu, Suqin

2014-12-01

Tin dioxide nanoparticles on nitrogen doped graphene aerogel (SnO2-NGA) hybrid are synthesized by one-step hydrothermal method and successfully applied in lithium-ion batteries as a free-standing anode. The electrochemical performance of SnO2-NGA hybrid is investigated by galvanostatic charge-discharge cycling, rate capability test, cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the SnO2-NGA hybrid with freestanding spongy-like structure exhibit remarkable lithium storage capacity (1100 mAh g-1 after 100 cycles), good cycling stability and high rate capability. The outstanding performance is attributed to the uniform SnO2 nanoparticles, unique spongy-like structure and N doping defect for Li+ diffusion.

Synthesis of advanced aluminide intermetallic coatings by low-energy Al-ion radiation

NASA Astrophysics Data System (ADS)

Shen, Mingli; Gu, Yan; Zhao, Panpan; Zhu, Shenglong; Wang, Fuhui

2016-05-01

Metals that work at high temperatures (for instance, superalloys in gas-turbines) depend on thermally grown oxide (TGO, commonly alumina) to withstand corrosion attack. Nickel Aluminide (NiAl) as one superior alumina TGO former plays an important role in protective coatings for turbine blades in gas-turbine engines used for aircraft propulsion and power generation. Lowering TGO growth rate is essentially favored for offering sustainable protection, especially in thermal barrier coatings (TBC). However, it can only be achieved currently by a strategy of adding the third element (Pt or reactive elements) into NiAl during traditional diffusion- or deposition-based synthesis of the coating. Here we present a highly flexible Al-ion radiation-based synthesis of advanced NiAl coatings, achieving low TGO growth rate without relying on the third element addition. Our results expand the strategy for lowering TGO growth rate and demonstrate potentials for ion radiation in advancing materials synthesis.

Synthesis of advanced aluminide intermetallic coatings by low-energy Al-ion radiation

PubMed Central

Shen, Mingli; Gu, Yan; Zhao, Panpan; Zhu, Shenglong; Wang, Fuhui

2016-01-01

Metals that work at high temperatures (for instance, superalloys in gas-turbines) depend on thermally grown oxide (TGO, commonly alumina) to withstand corrosion attack. Nickel Aluminide (NiAl) as one superior alumina TGO former plays an important role in protective coatings for turbine blades in gas-turbine engines used for aircraft propulsion and power generation. Lowering TGO growth rate is essentially favored for offering sustainable protection, especially in thermal barrier coatings (TBC). However, it can only be achieved currently by a strategy of adding the third element (Pt or reactive elements) into NiAl during traditional diffusion- or deposition-based synthesis of the coating. Here we present a highly flexible Al-ion radiation-based synthesis of advanced NiAl coatings, achieving low TGO growth rate without relying on the third element addition. Our results expand the strategy for lowering TGO growth rate and demonstrate potentials for ion radiation in advancing materials synthesis. PMID:27194417

Synthesis of advanced aluminide intermetallic coatings by low-energy Al-ion radiation.

PubMed

Shen, Mingli; Gu, Yan; Zhao, Panpan; Zhu, Shenglong; Wang, Fuhui

2016-05-19

Metals that work at high temperatures (for instance, superalloys in gas-turbines) depend on thermally grown oxide (TGO, commonly alumina) to withstand corrosion attack. Nickel Aluminide (NiAl) as one superior alumina TGO former plays an important role in protective coatings for turbine blades in gas-turbine engines used for aircraft propulsion and power generation. Lowering TGO growth rate is essentially favored for offering sustainable protection, especially in thermal barrier coatings (TBC). However, it can only be achieved currently by a strategy of adding the third element (Pt or reactive elements) into NiAl during traditional diffusion- or deposition-based synthesis of the coating. Here we present a highly flexible Al-ion radiation-based synthesis of advanced NiAl coatings, achieving low TGO growth rate without relying on the third element addition. Our results expand the strategy for lowering TGO growth rate and demonstrate potentials for ion radiation in advancing materials synthesis.

Overview of SIMS-Based Experimental Studies of Tracer Diffusion in Solids and Application to Mg Self-Diffusion

DOE PAGES

Kulkarni, Nagraj S.; Bruce Warmack, Robert J.; Radhakrishnan, Bala; ...

2014-09-23

Tracer diffusivities provide the most fundamental information on diffusion in materials and are the foundation of robust diffusion databases. Compared to traditional radiotracer techniques that utilize radioactive isotopes, the secondary ion mass spectrometry (SIMS) based thin-film technique for tracer diffusion is based on the use of enriched stable isotopes that can be accurately profiled using SIMS. Experimental procedures & techniques that are utilized for the measurement of tracer diffusion coefficients are presented for pure magnesium, which presents some unique challenges due to the ease of oxidation. The development of a modified Shewmon-Rhines diffusion capsule for annealing Mg and an ultra-highmore » vacuum (UHV) system for sputter deposition of Mg isotopes are discussed. Optimized conditions for accurate SIMS depth profiling in polycrystalline Mg are provided. An automated procedure for the correction of heat-up and cool-down times during tracer diffusion annealing is discussed. The non-linear fitting of a SIMS depth profile data using the thin film Gaussian solution to obtain the tracer diffusivity along with the background tracer concentration and tracer film thickness is discussed. An Arrhenius fit of the Mg self-diffusion data obtained using the low-temperature SIMS measurements from this study and the high-temperature radiotracer measurements of Shewmon and Rhines (1954) was found to be a good representation of both types of diffusion data that cover a broad range of temperatures between 250 - 627° C (523 900 K).« less

Diffusion mechanism in the sodium-ion battery material sodium cobaltate.

PubMed

Willis, T J; Porter, D G; Voneshen, D J; Uthayakumar, S; Demmel, F; Gutmann, M J; Roger, M; Refson, K; Goff, J P

2018-02-16

High performance batteries based on the movement of Li ions in Li x CoO 2 have made possible a revolution in mobile electronic technology, from laptops to mobile phones. However, the scarcity of Li and the demand for energy storage for renewables has led to intense interest in Na-ion batteries, including structurally-related Na x CoO 2 . Here we have determined the diffusion mechanism for Na 0.8 CoO 2 using diffuse x-ray scattering, quasi-elastic neutron scattering and ab-initio molecular dynamics simulations, and we find that the sodium ordering provides diffusion pathways and governs the diffusion rate. Above T ~ 290 K the so-called partially disordered stripe superstructure provides channels for quasi-1D diffusion, and melting of the sodium ordering leads to 2D superionic diffusion above T ~ 370 K. We obtain quantitative agreement between our microscopic study of the hopping mechanism and bulk self-diffusion measurements. Our approach can be applied widely to other Na- or Li-ion battery materials.

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

DOE PAGES

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; ...

2014-12-19

We report that lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF more » $$\\bar{6}$$ anion. Li + prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li + solvation. Corresponding analysis for the PF $$\\bar{6}$$ anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. In conclusion, these results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.« less

Diffusion Barriers to Increase the Oxidative Life of Overlay Coatings

NASA Technical Reports Server (NTRS)

Nesbitt, James A.; Lei, Jih-Fen

1999-01-01

Currently, most blades and vanes in the hottest section of aero gas turbine engines require some type of coating for oxidation protection. Newly developed single crystal superalloys have the mechanical potential to operate at increasingly higher component temperatures. However, at these elevated temperatures, coating/substrate interdiffusion can shorten the protective life of the coating. Diffusion barriers between overlay coatings and substrates are being examined to extend the protective life of the coating. A previously- developed finite-difference diffusion model has been modified to predict the oxidative life enhancement due to use of a diffusion barrier. The original diffusion model, designated COSIM, simulates Al diffusion in the coating to the growing oxide scale as well as Al diffusion into the substrate. The COSIM model incorporates an oxide growth and spalling model to provide the rate of Al consumption during cyclic oxidation. Coating failure is predicted when the Al concentration at the coating surface drops to a defined critical level. The modified COSIM model predicts the oxidative life of an overlay coating when a diffusion barrier is present eliminating diffusion of Al from the coating into the substrate. Both the original and the modified diffusion models have been used to predict the effectiveness of a diffusion barrier in extending the protective life of a NiCrAl overlay coating undergoing cyclic oxidation at 1100 C.

An Ab Initio and Kinetic Monte Carlo Simulation Study of Lithium Ion Diffusion on Graphene

PubMed Central

Zhong, Kehua; Yang, Yanmin; Xu, Guigui; Zhang, Jian-Min; Huang, Zhigao

2017-01-01

The Li+ diffusion coefficients in Li+-adsorbed graphene systems were determined by combining first-principle calculations based on density functional theory with Kinetic Monte Carlo simulations. The calculated results indicate that the interactions between Li ions have a very important influence on lithium diffusion. Based on energy barriers directly obtained from first-principle calculations for single-Li+ and two-Li+ adsorbed systems, a new equation predicting energy barriers with more than two Li ions was deduced. Furthermore, it is found that the temperature dependence of Li+ diffusion coefficients fits well to the Arrhenius equation, rather than meeting the equation from electrochemical impedance spectroscopy applied to estimate experimental diffusion coefficients. Moreover, the calculated results also reveal that Li+ concentration dependence of diffusion coefficients roughly fits to the equation from electrochemical impedance spectroscopy in a low concentration region; however, it seriously deviates from the equation in a high concentration region. So, the equation from electrochemical impedance spectroscopy technique could not be simply used to estimate the Li+ diffusion coefficient for all Li+-adsorbed graphene systems with various Li+ concentrations. Our work suggests that interactions between Li ions, and among Li ion and host atoms will influence the Li+ diffusion, which determines that the Li+ intercalation dependence of Li+ diffusion coefficient should be changed and complex. PMID:28773122

Tunneling Characteristics Depending on Schottky Barriers and Diffusion Current in SiOC.

PubMed

Oh, Teresa; Kim, Chy Hyung

2016-02-01

To obtain a diffusion current in SiOC, the aluminum doped zinc oxide films were deposited on SiOC/Si wafer by a RF magnetron sputtering. All the X-ray patterns of the SiOC films showed amorphous phases. The level of binding energy of Si atoms will lead to an additional potential modulation by long range Coulombic and covalent interactions with oxygen ions. The growth of the AZO film was affected by the characteristics of SiOC, resulting in similar trends in XPS spectra and a shift to higher AZO lattice d values than the original AZO d values in XRD analyses. The charges trapped by the defects at the interlayer between AZO and SiOC films induced the decreased mobility of carriers. In the absence of trap charges, AZO grown on SiOC film such as the sample prepared at O2 = 25 or 30 sccm, which has low charge carrier concentration and high mobility, showed high mobility in an ambipolar characteristic of oxide semiconductor due to the tunneling effect and diffusion current. The structural matching of an interface between AZO and amorphous SiOC enhanced the height of Schottky Barrier (SB), and then the mobility was increased by the tunneling effect from band to band through the high SB.

Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-11-01

The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential.

PubMed

Xu, Weiwei; Li, Qian; Shang, Jing; Liu, Jia; Feng, Xiang; Zhu, Tong

2015-10-01

Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites. Copyright © 2015. Published by Elsevier B.V.

Na Diffusion in Quasi One-Dimensional Ion Conductor NaMn2O4 Observed by μ+SR

NASA Astrophysics Data System (ADS)

Umegaki, Izumi; Nozaki, Hiroshi; Harada, Masashi; Månsson, Martin; Sakurai, Hiroya; Kawasaki, Ikuto; Watanabe, Isao; Sugiyama, Jun

A quasi one-dimensional (1D) compound, NaMn2O4, in which Mn2O4 zigzag chains form a 1D channel along the b-axis and Na ions locate at the center of the channel, is thought to be a good Na ionic conductor. In order to study Na-ion diffusion, we have measured μ+SR spectra using a powder sample in the temperature range between 100 and 500 K. A diffusive behavior was clearly observed above 325 K. Assuming a thermal activate process for jump diffusion of Na-ion between two nearest neighboring sites, a self diffusion coefficient of Na ion (DNa) and its activation energy (Ea) were estimated as DNa = (3.1 ± 0.2) × 10 - 11 cm2/s at 350 K and Ea = 180(9) meV.

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Plasma processes in inert gas thrusters

NASA Technical Reports Server (NTRS)

Kaufman, H. R.; Robinson, R. S.

1979-01-01

Inert gas thrusters, particularly with large diameters, have continued to be of interest for space propulsion applications. Two plasma processes are treated in this study: electron diffusion across magnetic fields and double ion production in inert-gas thrusters. A model is developed to describe electron diffusion across a magnetic field that is driven by both density and potential gradients, with Bohm diffusion used to predict the diffusion rate. This model has applications to conduction across magnetic fields inside a discharge chamber, as well as through a magnetic baffle region used to isolate a hollow cathode from the main chamber. A theory for double ion production is presented, which is not as complete as the electron diffusion theory described, but it should be a useful tool for predicting double ion sputter erosion. Correlations are developed that may be used, without experimental data, to predict double ion densities for the design of new and especially larger ion thrusters.

Enhanced Scattering of Diffuse Ions on Front of the Earth's Quasi-Parallel Bow Shock: a Case Study

NASA Astrophysics Data System (ADS)

Kis, A.; Matsukiyo, S.; Otsuka, F.; Hada, T.; Lemperger, I.; Dandouras, I. S.; Barta, V.; Facsko, G. I.

2017-12-01

In the analysis we present a case study of three energetic upstream ion events at the Earth's quasi-parallel bow shock based on multi-spacecraft data recorded by Cluster. The CIS-HIA instrument onboard Cluster provides partial energetic ion densities in 4 energy channels between 10 and 32 keV.The difference of the partial ion densities recorded by the individual spacecraft at various distances from the bow shock surface makes possible the determination of the spatial gradient of energetic ions.Using the gradient values we determined the spatial profile of the energetic ion partial densities as a function of distance from the bow shock and we calculated the e-folding distance and the diffusion coefficient for each event and each ion energy range. Results show that in two cases the scattering of diffuse ions takes place in a normal way, as "by the book", and the e-folding distance and diffusion coefficient values are comparable with previous results. On the other hand, in the third case the e-folding distance and the diffusion coefficient values are significantly lower, which suggests that in this case the scattering process -and therefore the diffusive shock acceleration (DSA) mechanism also- is much more efficient. Our analysis provides an explanation for this "enhanced" scattering process recorded in the third case.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes

PubMed Central

2015-01-01

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption. PMID:26369420

Diffusion of water and sodium counter-ions in nanopores of a β-lactoglobulin crystal: a molecular dynamics study

NASA Astrophysics Data System (ADS)

Malek, Kourosh; Odijk, Theo; Coppens, Marc-Olivier

2005-07-01

The dynamics of water and sodium counter-ions (Na+) in a C2221 orthorhombic β-lactoglobulin crystal is investigated by means of 5 ns molecular dynamics simulations. The effect of the fluctuation of the protein atoms on the motion of water and sodium ions is studied by comparing simulations in a rigid and in a flexible lattice. The electrostatic interactions of sodium ions with the positively charged LYS residues inside the crystal channels significantly influence the ionic motion. According to our results, water molecules close to the protein surface undergo an anomalous diffusive motion. On the other hand, the motion of water molecules further away from the protein surface is normal diffusive. Protein fluctuations affect the diffusion constant of water, which increases from 0.646 ± 0.108 to 0.887 ± 0.41 nm2 ns-1, when protein fluctuations are taken into account. The pore size (0.63-1.05 nm) and the water diffusivities are in good agreement with previous experimental results. The dynamics of sodium ions is disordered. LYS residues inside the pore are the main obstacles to the motion of sodium ions. However, the simulation time is still too short for providing a precise description of anomalous diffusion of sodium ions. The results are not only of interest for studying ion and water transport through biological nanopores, but may also elucidate water-protein and ion-protein interactions in protein crystals.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

PubMed

Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

2018-03-21

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

Distribution of Gd(III) ions at the graphene oxide/water interface.

PubMed

Amirov, Rustem R; Shayimova, Julia; Dimiev, Ayrat M

2018-10-01

Graphene oxide (GO) have emerged recently as a novel material for sorbing metal cations from aqueous media. However, the literature data on sorption capacity differ by more than one order in magnitude, and the nature of the chemical bonding between GO and metal cations remains unclear. In this work we show that Gd 3+ ions are bound to GO by both coordinate-covalent bonding and electrostatic attraction with prevailing the former. We provide the complete account for the GO sorption toward Gd 3+ as the function of the Gd 3+ /GO ratio and pH of solution. The upper limits of the strong bonding are determined as 0.70 and 0.16 mmol(Gd 3+ )/g(GO) in the neutral and in the intrinsically acidic solutions, respectively. At large excess of Gd 3+ in the neutral solutions, the sorption capacity reaches 1.45 mmol(Gd 3+ )/g(GO). The effectiveness of water, hydrochloric acid and EDTA as desorbing eluents is compared. We experimentally demonstrate the existence of the Gd 3+ concentration gradient within the diffuse layer at the GO/water interface, and its exponential character on the distance from the GO surface. The thickness of the diffuse layer and the position of the slipping plane are estimated. Such characteristics, typical for colloid systems, show that in solutions, GO flakes form distinct phase, even though they are just one atom thick. Copyright © 2018 Elsevier Inc. All rights reserved.

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

PubMed

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Mechanistic study of plasma damage to porous low-k: Process development and dielectric recovery

NASA Astrophysics Data System (ADS)

Shi, Hualiang

Low-k dielectrics with porosity are being introduced to reduce the RC delay of Cu/low-k interconnect. However, during the O2 plasma ashing process, the porous low-k dielectrics tend to degrade due to methyl depletion, moisture uptake, and densification, increasing the dielectric constant and leakage current. This dissertation presents a study of the mechanisms of plasma damage and dielectric recovery. The kinetics of plasma interaction with low-k dielectrics was investigated both experimentally and theoretically. By using a gap structure, the roles of ion, photon, and radical in producing damage on low-k dielectrics were differentiated. Oxidative plasma induced damage was proportional to the oxygen radical density, enhanced by VUV photon, and increased with substrate temperature. Ion bombardment induced surface densification, blocking radical diffusion. Two analytical models were derived to quantify the plasma damage. Based on the radical diffusion, reaction, and recombination inside porous low-k dielectrics, a plasma altered layer model was derived to interpret the chemical effect in the low ion energy region. It predicted that oxidative plasma induced damage can be reduced by decreasing pore radius, substrate temperature, and oxygen radical density and increasing carbon concentration and surface recombination rate inside low-k dielectrics. The model validity was verified by experiments and Monte-Carlo simulations. This model was also extended to the patterned low-k structure. Based on the ion collision cascade process, a sputtering yield model was introduced to interpret the physical effect in the high ion energy region. The model validity was verified by checking the ion angular and energy dependences of sputtering yield using O2/He/Ar plasma, low-k dielectrics with different k values, and a Faraday cage. Low-k dielectrics and plasma process were optimized to reduce plasma damage, including increasing carbon concentration in low-k dielectrics, switching plasma generator from ICP to RIE, increasing hard mask thickness, replacing O2 by CO2 plasma, increasing CO addition in CO/O 2 plasma, and increasing N2 addition in CO2/N 2 plasma. By combining analytical techniques with the Kramers-Kronig dispersion relation and quantum chemistry calculation, the origin of dielectric loss was ascribed to the physisorbed water molecules. Post-ash CH4 plasma treatment, vapor silylation process, and UV radiation were developed to repair plasma damage.

Layered Lithium-Rich Oxide Nanoparticles Doped with Spinel Phase: Acidic Sucrose-Assistant Synthesis and Excellent Performance as Cathode of Lithium Ion Battery.

PubMed

Chen, Min; Chen, Dongrui; Liao, Youhao; Zhong, Xiaoxin; Li, Weishan; Zhang, Yuegang

2016-02-01

Nanolayered lithium-rich oxide doped with spinel phase is synthesized by acidic sucrose-assistant sol-gel combustion and evaluated as the cathode of a high-energy-density lithium ion battery. Physical characterizations indicate that the as-synthesized oxide (LR-SN) is composed of uniform and separated nanoparticles of about 200 nm, which are doped with about 7% spinel phase, compared to the large aggregated ones of the product (LR) synthesized under the same condition but without any assistance. Charge/discharge demonstrates that LR-SN exhibits excellent rate capability and cyclic stability: delivering an average discharge capacity of 246 mAh g(-1) at 0.2 C (1C = 250 mA g(-1)) and earning a capacity retention of 92% after 100 cycles at 4 C in the lithium anode-based half cell, compared to the 227 mA g(-1) and the 63% of LR, respectively. Even in the graphite anode-based full cell, LR-SN still delivers a capacity of as high as 253 mAh g(-1) at 0.1 C, corresponding to a specific energy density of 801 Wh kg(-1), which are the best among those that have been reported in the literature. The separated nanoparticles of the LR-SN provide large sites for charge transfer, while the spinel phase doped in the nanoparticles facilitates lithium ion diffusion and maintains the stability of the layered structure during cycling.

Disorder induced semiconductor to metal transition and modifications of grain boundaries in nanocrystalline zinc oxide thin film

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

Singh, Fouran; Kumar, Vinod; Chaudhary, Babloo

2012-10-01

This paper report on the disorder induced semiconductor to metal transition (SMT) and modifications of grain boundaries in nanocrystalline zinc oxide thin film. Disorder is induced using energetic ion irradiation. It eliminates the possibility of impurities induced transition. However, it is revealed that some critical concentration of defects is needed for inducing such kind of SMT at certain critical temperature. Above room temperature, the current-voltage characteristics in reverse bias attributes some interesting phenomenon, such as electric field induced charge transfer, charge trapping, and diffusion of defects. The transition is explained by the defects induced disorder and strain in ZnO crystallitesmore » created by high density of electronic excitations.« less

Rotation driven translational diffusion of polyatomic ions in water: A novel mechanism for breakdown of Stokes-Einstein relation

NASA Astrophysics Data System (ADS)

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2017-04-01

While most of the existing theoretical and simulation studies have focused on simple, spherical, halide and alkali ions, many chemically, biologically, and industrially relevant electrolytes involve complex non-spherical polyatomic ions like nitrate, chlorate, and sulfate to name only a few. Interestingly, some polyatomic ions in spite of being larger in size show anomalously high diffusivity and therefore cause a breakdown of the venerable Stokes-Einstein (S-E) relation between the size and diffusivity. Here we report a detailed analysis of the dynamics of anions in aqueous potassium nitrate (KNO3) and aqueous potassium acetate (CH3COOK) solutions. The two ions, nitrate (-NO3) and acetate (CH3-CO2 ), with their similar size show a large difference in diffusivity values. We present evidence that the translational motion of these polyatomic ions is coupled to the rotational motion of the ion. We show that unlike the acetate ion, nitrate ion with a symmetric charge distribution among all periphery oxygen atoms shows a faster rotational motion with large amplitude rotational jumps which enhances its translational motion due to translational-rotational coupling. By creating a family of modified-charge model systems, we have analysed the rotational motion of asymmetric polyatomic ions and the contribution of it to the translational motion. These model systems help clarifying and establishing the relative contribution of rotational motion in enhancing the diffusivity of the nitrate ion over the value predicted by the S-E relation and also over the other polyatomic ions having asymmetric charge distribution like the acetate ion. In the latter case, reduced rotational motion results in lower diffusivity values than those with symmetric charge distribution. We propose translational-rotational coupling as a general mechanism of the breakdown of the S-E relation in the case of polyatomic ions.

Rotation driven translational diffusion of polyatomic ions in water: A novel mechanism for breakdown of Stokes-Einstein relation.

PubMed

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2017-04-28

While most of the existing theoretical and simulation studies have focused on simple, spherical, halide and alkali ions, many chemically, biologically, and industrially relevant electrolytes involve complex non-spherical polyatomic ions like nitrate, chlorate, and sulfate to name only a few. Interestingly, some polyatomic ions in spite of being larger in size show anomalously high diffusivity and therefore cause a breakdown of the venerable Stokes-Einstein (S-E) relation between the size and diffusivity. Here we report a detailed analysis of the dynamics of anions in aqueous potassium nitrate (KNO 3 ) and aqueous potassium acetate (CH 3 COOK) solutions. The two ions, nitrate (NO3-) and acetate (CH 3 CO2-), with their similar size show a large difference in diffusivity values. We present evidence that the translational motion of these polyatomic ions is coupled to the rotational motion of the ion. We show that unlike the acetate ion, nitrate ion with a symmetric charge distribution among all periphery oxygen atoms shows a faster rotational motion with large amplitude rotational jumps which enhances its translational motion due to translational-rotational coupling. By creating a family of modified-charge model systems, we have analysed the rotational motion of asymmetric polyatomic ions and the contribution of it to the translational motion. These model systems help clarifying and establishing the relative contribution of rotational motion in enhancing the diffusivity of the nitrate ion over the value predicted by the S-E relation and also over the other polyatomic ions having asymmetric charge distribution like the acetate ion. In the latter case, reduced rotational motion results in lower diffusivity values than those with symmetric charge distribution. We propose translational-rotational coupling as a general mechanism of the breakdown of the S-E relation in the case of polyatomic ions.

Transport coefficients of gaseous ions in an electric field

NASA Technical Reports Server (NTRS)

Whealton, J. H.; Mason, E. A.

1974-01-01

A general theory of ion mobility formulated by Kihara (1953) is extended to ion diffusion and to mixtures of neutral gases. The theory assumes that only binary collisions between ions and neutral particles need to be taken into account and that the velocity distribution function of the neutral particles is Maxwellian. These assumptions make it possible to use a linearized Boltzmann equation. Questions of mobility are considered along with aspects of diffusion and deviations from Fick's law of diffusion.

Strong Pitch-Angle Diffusion of Ring Current Ions in Geomagnetic Storm-Associated Conditions

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Gamayunov, K. V.; Gallagher, D. L.; Spann, J. F.

2005-01-01

Do electromagnetic ion cyclotron (EMIC) waves cause strong pitch-angle diffusion of RC ions? This question is the primary motivation of this paper and has been affirmatively answered from the theoretical point of view. The materials that are presented in the Results section show clear evidence that strong pitch-angle diffusion takes place in the inner magnetosphere indicating an important role for the wave-particle interaction mechanism in the formation of RC ions and EMIC waves.

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.

Current-Induced Transistor Sensorics with Electrogenic Cells

PubMed Central

Fromherz, Peter

2016-01-01

The concepts of transistor recording of electroactive cells are considered, when the response is determined by a current-induced voltage in the electrolyte due to cellular activity. The relationship to traditional transistor recording, with an interface-induced response due to interactions with the open gate oxide, is addressed. For the geometry of a cell-substrate junction, the theory of a planar core-coat conductor is described with a one-compartment approximation. The fast electrical relaxation of the junction and the slow change of ion concentrations are pointed out. On that basis, various recording situations are considered and documented by experiments. For voltage-gated ion channels under voltage clamp, the effects of a changing extracellular ion concentration and the enhancement/depletion of ion conductances in the adherent membrane are addressed. Inhomogeneous ion conductances are crucial for transistor recording of neuronal action potentials. For a propagating action potential, the effects of an axon-substrate junction and the surrounding volume conductor are distinguished. Finally, a receptor-transistor-sensor is described, where the inhomogeneity of a ligand–activated ion conductance is achieved by diffusion of the agonist and inactivation of the conductance. Problems with regard to a development of reliable biosensors are mentioned. PMID:27120627

Understanding the conductive channel evolution in Na:WO(3-x)-based planar devices.

PubMed

Shang, Dashan; Li, Peining; Wang, Tao; Carria, Egidio; Sun, Jirong; Shen, Baogen; Taubner, Thomas; Valov, Ilia; Waser, Rainer; Wuttig, Matthias

2015-04-14

An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO(3-x)) films on a soda-lime glass substrate, from which Na(+) diffuses into the WO(3-x) films during the deposition. The entire process of Na(+) migration driven by an alternating electric field is visualized in the Na-doped WO(3-x) films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na(+) mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices.

Thermally grown oxide and diffusions for automatic processing of integrated circuits

NASA Technical Reports Server (NTRS)

Kennedy, B. W.

1979-01-01

A totally automated facility for semiconductor oxidation and diffusion was developed using a state-of-the-art diffusion furnace and high temperature grown oxides. Major innovations include: (1) a process controller specifically for semiconductor processing; (2) an automatic loading system to accept wafers from an air track, insert them into a quartz carrier and then place the carrier on a paddle for insertion into the furnace; (3) automatic unloading of the wafers back onto the air track, and (4) boron diffusion using diborane with plus or minus 5 percent uniformity. Processes demonstrated include Wet and dry oxidation for general use and for gate oxide, boron diffusion, phosphorous diffusion, and sintering.

Behaviour of human endothelial cells on surface modified NiTi alloy.

PubMed

Plant, Stuart D; Grant, David M; Leach, Lopa

2005-09-01

Intravascular stents are being designed which utilise the shape memory properties of NiTi alloy. Despite the clinical advantages afforded by these stents their application has been limited by concerns about the large nickel ion content of the alloy. In this study, the surface chemistry of NiTi alloy was modified by mechanical polishing and oxidising heat treatments and subsequently characterised using X-ray photon spectroscopy (XPS). The effect of these surfaces on monolayer formation and barrier integrity of human umbilical vein endothelial cells (HUVEC) was then assessed by confocal imaging of the adherens junctional molecule VE-cadherin, perijunctional actin and permeability to 42kDa dextrans. Dichlorofluoroscein assays were used to measure oxidative stress in the cells. XPS analysis of NiTi revealed its surface to be dominated by TiO(2). However, where oxidation had occurred after mechanical polishing or post polishing heat treatments at 300 and 400 degrees C in air, a significant amount of metallic nickel or nickel oxide species (10.5 and 18.5 at%) remained on the surface. Exposure of HUVECs to these surfaces resulted in increased oxidative stress within the cells, loss of VE-cadherin and F-actin and significantly increased paracellular permeability. These pathological phenomena were not found in cells grown on NiTi which had undergone heat treatment at 600 degrees C. At this temperature thickening of the TiO(2) layer had occurred due to diffusion of titanium ions from the bulk of the alloy, displacing nickel ions to sub-surface areas. This resulted in a significant reduction in nickel ions detectable on the sample surface (4.8 at%). This study proposes that the integrity of human endothelial monolayers on NiTi is dependent upon the surface chemistry of the alloy and that this can be manipulated, using simple oxidising heat treatments.

Specific aquaporins facilitate the diffusion of hydrogen peroxide across membranes.

PubMed

Bienert, Gerd P; Møller, Anders L B; Kristiansen, Kim A; Schulz, Alexander; Møller, Ian M; Schjoerring, Jan K; Jahn, Thomas P

2007-01-12

The metabolism of aerobic organisms continuously produces reactive oxygen species. Although potentially toxic, these compounds also function in signaling. One important feature of signaling compounds is their ability to move between different compartments, e.g. to cross membranes. Here we present evidence that aquaporins can channel hydrogen peroxide (H2O2). Twenty-four aquaporins from plants and mammals were screened in five yeast strains differing in sensitivity toward oxidative stress. Expression of human AQP8 and plant Arabidopsis TIP1;1 and TIP1;2 in yeast decreased growth and survival in the presence of H2O2. Further evidence for aquaporin-mediated H2O2 diffusion was obtained by a fluorescence assay with intact yeast cells using an intracellular reactive oxygen species-sensitive fluorescent dye. Application of silver ions (Ag+), which block aquaporin-mediated water diffusion in a fast kinetics swelling assay, also reversed both the aquaporin-dependent growth repression and the H2O2-induced fluorescence. Our results present the first molecular genetic evidence for the diffusion of H2O2 through specific members of the aquaporin family.

TEM Analysis of Interfaces in Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Tsuda, H.; Halbig, M. C.; Singh, M.; Hasegawa, Y.; Mori, S.; Asthana R.

2016-01-01

Silicon Carbide (SiC) is a promising material for thermo-structural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, and Mo-B. In this presentation, the result of microstructural analysis obtained by TEM observations and the influence of metallic interlayers and fiber orientation of SA-THX on the joint microstructure will be discussed.

Slow positron studies of hydrogen activation/passivation on SiO2/Si(100) interfaces

NASA Astrophysics Data System (ADS)

Lynn, K. G.; Asoka-Kumar, P.

The hydrogen atoms are one of the most common impurity species found in semiconductor systems owing to its large diffusivity, and are easily incorporated either in a controlled process like in ion implantation or in an uncontrolled process like the one at the fabrication stage. Hydrogen can passivate dangling bonds and dislocations in these systems and hence can be used to enhance the electrical properties. In a SiO2/Si system, hydrogen can passivate electronic states at the interface and can alter the fixed or mobile charges in the oxide layer. Since hydrogen is present in almost all of the environments of SiO2/Si wafer fabrication, the activation energy of hydrogen atoms is of paramount importance to a proper understanding of SiO2/Si based devices and has not been measured on the technologically most important Si(100) face. There are no direct, nondestructive methods available to observe hydrogen injection into the oxide layer and subsequent diffusion. The positrons are used as a 'sensitive', nondestructive probe to observe hydrogen interaction in the oxide layer and the interface region. A new way is described of characterizing the changes in the density of the interface states under a low temperature annealing using positrons.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

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

Chen, Yan; Cheng, Yongqiang; Li, Juchuan

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Ionic-Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?

PubMed

Kerner, Ross A; Rand, Barry P

2018-01-04

Ambipolar transport describes the nonequilibrium, coupled motion of positively and negatively charged particles to ensure that internal electric fields remain small. It is commonly invoked in the semiconductor community where the motion of excess electrons and holes drift and diffuse together. However, the concept of ambipolar transport is not limited to semiconductor physics. Materials scientists working on ion conducting ceramics understand ambipolar transport dictates the coupled diffusion of ions and the rate is limited by the ion with the lowest diffusion coefficient. In this Perspective, we review a third application of ambipolar transport relevant to mixed ionic-electronic conducting materials for which the motion of ions is expected to be coupled to electronic carriers. In this unique situation, the ambipolar diffusion model has been successful at explaining the photoenhanced diffusion of metal ions in chalcogenide glasses and other properties of materials. Recent examples of photoenhanced phenomena in metal halide perovskites are discussed and indicate that mixed ionic-electronic ambipolar transport is similarly important for a deep understanding of these emerging materials.

Role of sulfate, chloride, and nitrate anions on the degradation of fluoroquinolone antibiotics by photoelectro-Fenton.

PubMed

Villegas-Guzman, Paola; Hofer, Florian; Silva-Agredo, Javier; Torres-Palma, Ricardo A

2017-12-01

Taking ciprofloxacin (CIP) as a fluoroquinolone antibiotic model, this work explores the role of common anions (sulfate, nitrate, and chloride) during the application of photoelectro-Fenton (PEF) at natural pH to degrade this type of compound in water. The system was composed of an IrO 2 anode, Ti, or gas diffusion electrode (GDE) as cathode, Fe 2+ , and UV (254 nm). To determine the implications of these anions, the degradation pathway and efficiency of the PEF sub-processes (UV photolysis, anodic oxidation, and electro-Fenton at natural pH) were studied in the individual presence of the anions. The results highlight that degradation routes and kinetics are strongly dependent on electrolytes. When chloride and nitrate ions were present, indirect electro-chemical oxidation was identified by electro-generated HOCl and nitrogenated oxidative species, respectively. Additionally, direct photolysis and direct oxidation at the anode surface were identified as degradation routes. As a consequence of the different pathways, six primary CIP by-products were identified. Therefore, a scheme was proposed representing the pathways involved in the degradation of CIP when submitted to PEF in water with chloride, nitrate, and sulfate ions, showing the complexity of this process. Promoted by individual and synergistic actions of this process, the PEF system leads to a complete elimination of CIP with total removal of antibiotic activity against Staphylococcus aureus and Escherichia coli, and significant mineralization. Finally, the role of the anions was tested in seawater containing CIP, in which the positive contributions of the anions were partially suppressed by its OH radical scavenger action. The findings are of interest for the understanding of the degradation of antibiotics via the PEF process in different matrices containing sulfate, nitrate, and chloride ions.

Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

2016-06-01

In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

Chromium Grain-boundary Segregation and Effect of Ion Beam Cleaning on Fe-Ni-Cr Alloys

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

Saraf, Laxmikant V.

2011-04-01

The grain boundaries play important role to control the mechanical strength of ternary alloys. From spacecrafts to naval vessels to nuclear reactors, stress corrosion cracking, brittleness, oxidation mostly originates at the grain boundaries and cause long term structural stability problems in most of the metallic structures [1]. Fe-Ni-Cr based ternary metal alloys have been widely studied for more than fifty years [2, 3]. Despite of vast amount of research, chromium diffusion in stainless steel or other Ni-Fe-Cr based ternary alloys is still an open scientific problem with challenges in structural stability and corrosion resistance [4]. Particularly, austenite Fe-Ni-Cr is lookedmore » upon favorably in space and jet engine industry for their improved resistance to stress corrosion cracking [5]. In solid oxide fuel cells (SOFC), Ni-alloys are frequently used as interconnects and seals [6]. In this communication, simultaneous energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) mapping is utilized to study chemical and structural aspects of chromium segregation in Fe-Ni-Cr alloy. A focused Ga-ion beam is also utilized to study the effect of ion beam cleaning on EBSD image quality (IQ) and inverse pole figure (IPF) maps of Fe-Ni-Cr alloy.« less

Compositional and Ionic-Size Controls on the Diffusion of Divalent Cations in Garnet: Insights from Atomistic Simulations

NASA Astrophysics Data System (ADS)

Carlson, W. D.

2012-12-01

Divalent cations in garnet (Mg, Fe, Mn, Ca) diffuse at rates that depend strongly on the host-crystal composition and on the ionic radius of the diffusant. Understanding of the nanoscale basis for these behaviors comes from atomistic simulations that calculate energies in the static limit for the defects and transition-state configurations associated with each diffusive step. Diffusion of divalent cations requires (a) creation of a cation-vacancy defect in a dodecahedral site and of a charge-compensating oxygen-vacancy defect that may or may not be in close spatial association; (b) except in the case of self-diffusion, creation of an impurity defect in which a foreign atom replaces the normal atom in a dodecahedral site adjacent to the vacancy; and (c) during the diffusive process, motion of the diffusing atom to a 'saddlepoint' position that represents the transition-state configuration. Comparisons of the system's energy in these various states, in structures of different composition and for ions of different ionic size, allows assessment of the nanoscale controls on diffusion kinetics. Molecular-statics calculations quantify defect energies and identify the transition-state configuration: the maximum energy along the diffusion path between two adjacent dodecahedral sites results when the diffusing ion is surrounded symmetrically by the six oxygen atoms that lie between the two sites. Across the range of end-member compositions, self-diffusion coefficients measured at identical conditions, and the tracer diffusivity of a single ion measured at identical conditions, can each vary by five orders of magnitude or more. Measured activation energies for these motions, however, are all equivalent to within ±6%. Calculated activation energies are in agreement with observations, in that they vary by only ±10%. Calculated vacancy-formation energies, on the other hand, are significantly larger in expanded structures; for example, that energy is greater for Prp than for Grs by ~ 470 kJ/mol. Thus in expanded structures, much higher vacancy concentrations can be produced at the same energetic cost, greatly enhancing rates of diffusion. The primary explanation for the more rapid diffusion of divalent cations in structures with larger cell dimensions therefore comes not from reduced saddlepoint strain energies in more compliant structures, but instead from the smaller energy required to create vacancy defects. Diffusivities of divalent cations exhibit a curious parabolic dependence on ionic size: for each structure, an optimally-sized ion exists, close in size to the dominant ion, that exhibits the fastest diffusion. Larger ions — and enigmatically, smaller ions — both diffuse more slowly. Calculated impurity-defect energies show that undersized impurity ions are bound more tightly in their sites, but the effects are too small in comparison to corresponding reductions in strain energy for the transition-state configuration to account for observed rate differences. Calculated vacancy-association energies reveal a slight tendency for vacancies to associate preferentially with larger impurity ions, but again the effect appears to be too small to provide a full explanation for observed behaviors.

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

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

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE PAGES

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon; ...

2016-11-04

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Kinetics of Ta ions penetration into porous low-k dielectrics under bias-temperature stress

NASA Astrophysics Data System (ADS)

He, Ming; Ou, Ya; Wang, Pei-I.; Lu, Toh-Ming

2010-05-01

It is known that Ta, a popular diffusion barrier material, can itself penetrate into low-k dielectrics under bias-temperature stress. In this work, we derived a model which directly correlates the diffusivity of Ta ions to the rate of flatband voltage shift (FBS) of the Ta/methyl silsesquixane (MSQ)/Si capacitors. From our experimentally measured constant FBS rate, the Ta diffusivity and activation energy were determined. It appears that an increase in the porosity of MSQ film enhances the Ta diffusivity but does not affect the associated activation energy. This suggests the Ta ion diffusion is mainly through interconnected pore surfaces.

Thermomechanical Stresses Analysis of a Single Event Burnout Process

NASA Astrophysics Data System (ADS)

Tais, Carlos E.; Romero, Eduardo; Demarco, Gustavo L.

2009-06-01

This work analyzes the thermal and mechanical effects arising in a power Diffusion Metal Oxide Semiconductor (DMOS) during a Single Event Burnout (SEB) process. For studying these effects we propose a more detailed simulation structure than the previously used by other authors, solving the mathematical models by means of the Finite Element Method. We use a cylindrical heat generation region, with 5 W, 10 W, 50 W and 100 W for emulating the thermal phenomena occurring during SEB processes, avoiding the complexity of the mathematical treatment of the ion-semiconductor interaction.

Jahn–Teller Assisted Na Diffusion for High Performance Na Ion Batteries

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

Li, Xin; Wang, Yan; Wu, Di

2016-08-30

Na energy storage technology is strategically attractive for large scale applications such as grid energy storage. Here, we show in this paper that there is a clear relation between the Jahn$-$Teller activity of a transition metal ion at the end of charge and the mobility of Na in a cathode material. This is particularly important as mobility at the end of charge limits the capacity of current materials. Consequently, by using this classical piece of physics in the battery world, it is possible to create higher capacity Na-cathode materials. Even more exciting is that the ideal element to impart thismore » effect on cathodes is Fe, which is the least expensive of the transition metal oxides and can therefore enable low cost cathode materials.« less

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

NASA Astrophysics Data System (ADS)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

Supramolecular assembled three-dimensional graphene hybrids: Synthesis and applications in supercapacitors

NASA Astrophysics Data System (ADS)

Ni, Lubin; Zhang, Wang; Wu, Zhen; Sun, Chunyu; Cai, Yin; Yang, Guang; Chen, Ming; Piao, Yuanzhe; Diao, Guowang

2017-02-01

Graphene-based materials have received worldwide attention in the focus of forefront energy storage investigations. Currently, the design of novel three-dimensional (3D) graphene structures with high energy capability, superior electron and ion conductivity, and robust mechanical flexibility is still a great challenge. Herein, we have successfully demonstrated a novel approach to fabricate 3D assembled graphene through the supramolecular interactions of β-cyclodextrin polymers (β-CDP) with an adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD). The incorporation of PEG-AD linker into rGO sheets increased the interlayer spacing of rGO sheets to form 3D graphene materials, which can provide efficient 3D electron transfer pathways and ion diffusion channels, and facilitate the infiltration of gel electrolyte. The as-prepared 3D self-assembled graphene materials exhibit significantly improved electrochemical performances of supercapacitor in terms of high specific capacitance, remarkable rate capability, and excellent cycling stability compared to pristine reduced graphene oxide. This study shed new lights to the construction of three dimensional self-assembled graphene materials and their urgent applications in energy storage.

H+ diffusion and electrochemical stability of Li1+x+yAlxTi2-xSiyP3-yO12 glass in aqueous Li/air battery electrolytes

NASA Astrophysics Data System (ADS)

Ding, Fei; Xu, Wu; Shao, Yuyan; Chen, Xilin; Wang, Zhiguo; Gao, Fei; Liu, Xingjiang; Zhang, Ji-Guang

2012-09-01

It is well known that LATP (Li1+x+yAlxTi2-xSiyP3-yO12) glass is a good lithium (Li)-ion conductor. However, the interaction between LATP glass and H+ ions in aqueous electrolytes (including the diffusion and surface adsorption of H+ ions) needs to be well understood before the long-term application of LATP glass in an aqueous electrolyte can be realized. In this work, we investigate H+-ion diffusion in LATP glass and their interactions with the glass surface using both experimental and modeling approaches. Our results indicate that the apparent H+-related current observed in the initial cyclic voltammetry scan should be attributed to the adsorption of H+ ions on the LATP glass rather than the bulk diffusion of H+ ions. Furthermore, density functional theory calculations indicate that the H+-ion diffusion energy barrier (3.21 eV) is much higher than that for Li+ ions (0.79 eV) and Na+ ions (0.79 eV) in a NASICON-type LiTi2(PO4)3 material. As a result, H+-ion conductivity in LATP glass is negligible at room temperature. However, significant surface corrosion was found after the LATP glass in a strong alkaline electrolyte. Therefore, to prevent LATP glass from corrosion, appropriate electrolytes must be developed for long-term operation of LATP in aqueous Li-air batteries.

Well-aligned polycrystalline lanthanum silicate oxyapatite grown by reactive diffusion between solid La{sub 2}SiO{sub 5} and gases [SiO+1/2O{sub 2}

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

Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp; Hasegawa, Ryo; Kitagawa, Takuya

2016-03-15

The c-axis-oriented polycrystalline lanthanum silicate oxyapatite, La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} (□ denotes a vacancy in the Si site), was successfully prepared by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO+1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The polycrystal was characterized using optical microscopy, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy, micro-Raman spectroscopy, X-ray diffractometry, and impedance spectroscopy. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site at ca. 1.9%. The bulk oxide-ion conductivity along the grain-alignment direction steadily increased from 9.2 × 10{sup −3} to 1.17 ×more » 10{sup −2} S/cm with increasing temperature from 923 to 1073 K. The activation energy of conduction was 0.23(2) eV. - Graphical abstract: We have successfully prepared the highly c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO + 1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site of ca. 1.9%. - Highlights: • The c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is successfully prepared. • Crystal structure of La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is determined by single-crystal XRD. • The polycrystal shows relatively high oxide ion conductivity along the common c-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.« less

Venus ionosphere: photochemical and thermal diffusion control of ion composition.

PubMed

Bauer, S J; Donahue, T M; Hartle, R E; Taylor, H A

1979-07-06

The major photochemical sources and sinks for ten of the ions measured by the ion mass spectrometer on the Pioneer Venus bus and orbiter spacecraft that are consistent with the neutral gas composition measured on the same spacecraft have been identified. The neutral gas temperature (Tn) as a function of solar zenith angle (chi) derived from measured ion distributions in photochemical equilibrium is given by Tn (K) = 323 cos(1/5)chi. Above 200 kilometers, the altitude behavior of ions is generally controlled by plasma diffusion, with important modifications for minor ions due to thermal diffusion resulting from the observed gradients of plasma temperatures. The dayside equilibrium distributions of ions are sometimes perturbed by plasma convection, while lateral transport of ions from the dayside seems to be a major source of the nightside ionosphere.

Iron-antimony-based hybrid oxides as high-performance anodes for lithium-ion storage

NASA Astrophysics Data System (ADS)

Nguyen, Tuan Loi; Kim, Doo Soo; Hur, Jaehyun; Park, Min Sang; Yoon, Sukeun; Kim, Il Tae

2018-06-01

We report a facile approach to synthesize Fe-Sb-based hybrid oxides nanocomposites consisting of Sb, Sb2O3, and Fe3O4 for use as new anode materials for lithium-ion batteries. The composites are synthesized via galvanic replacement between Fe3+ and Sb at high temperature in triethylene glycol medium. The phase, morphology, and composition changes of the composites involved in the various stages of the replacement reaction are characterized using X-ray diffractometry, high-resolution transmission electron microscopy, and energy dispersive X-ray spectroscopy. The as-prepared composites have different compositions with very small particle sizes (<< 10 nm). The FexSbyOz-18 h composite, for instance, exhibits high capacity, better cyclic stability, and rate performance than other composites, with a highly stable specific capacity of 434 mAh g-1 at 500 cycles. The excellent electrochemical performance can be ascribed to the high interfacial contact area between the nanocomposite and electrolyte, stable structure of the composites owing to a mixture of inactive phases generated by the conversion reaction between Li+ and oxide metal-whose structure serves as an electron conductor, inhibits agglomeration of Sb particles, and acts as an effective buffer against volume change of Sb during cycling-and high Li+ diffusion ability.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

Interlayer-expanded molybdenum disulfide nanocomposites for electrochemical magnesium storage.

PubMed

Liang, Yanliang; Yoo, Hyun Deog; Li, Yifei; Shuai, Jing; Calderon, Hector A; Robles Hernandez, Francisco Carlos; Grabow, Lars C; Yao, Yan

2015-03-11

Mg rechargeable batteries (MgRBs) represent a safe and high-energy battery technology but suffer from the lack of suitable cathode materials due to the slow solid-state diffusion of the highly polarizing divalent Mg ion. Previous methods improve performance at the cost of incompatibility with anode/electrolyte and drastic decrease in volumetric energy density. Herein we report interlayer expansion as a general and effective atomic-level lattice engineering approach to transform inactive intercalation hosts into efficient Mg storage materials without introducing adverse side effects. As a proof-of-concept we have combined theory, synthesis, electrochemical measurement, and kinetic analysis to improve Mg diffusion behavior in MoS2, which is a poor Mg transporting material in its pristine form. First-principles simulations suggest that expanded interlayer spacing allows for fast Mg diffusion because of weakened Mg-host interactions. Experimentally, the expansion was realized by inserting a controlled amount of poly(ethylene oxide) into the lattice of MoS2 to increase the interlayer distance from 0.62 nm to up to 1.45 nm. The expansion boosts Mg diffusivity by 2 orders of magnitude, effectively enabling the otherwise barely active MoS2 to approach its theoretical storage capacity as well as to achieve one of the highest rate capabilities among Mg-intercalation materials. The interlayer expansion approach can be leveraged to a wide range of host materials for the storage of various ions, leading to novel intercalation chemistry and opening up new opportunities for the development of advanced materials for next-generation energy storage.

Study of the interaction of inorganic and organic compounds of cell culture medium with a Ti surface.

PubMed

Burgos-Asperilla, L; García-Alonso, M C; Escudero, M L; Alonso, C

2010-02-01

The interaction between Ti and each component of Dulbecco's modified Eagle's medium was studied in depth using different techniques, such as the measurement of the corrosion potential, electrochemical impedance spectroscopy and polarization curves. The characterization of metal surfaces was carried out by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). The adsorption process of each component was studied using the quartz crystal balance (QCM). The QCM and XPS results reveal that the adsorption kinetics for phosphate and calcium ions is slow. However, the bovine serum albumin (BSA) totally covers the Ti surface rapidly. Because the passive film (titanium oxide) has acidic hydroxyl groups, the calcium ions would have a bridging effect on the electrostatic adsorption of phosphate ions as well as that of BSA. The polarization curves reveal that the adsorbed glucose permits the ionic diffusion of the oxygen to the electrode, while the BSA and fetal bovine serum (FBS) adsorbed after 7 days of immersion act as a diffusive barrier. The impedance measurement and data fitting to the electrical equivalent circuit model show that the resistance of the proteins/TiO(2) interface, for Ti immersed in FBS, is higher than those obtained for BSA, due to the proteins present in the solution as well as the fact that the adsorbed proteins on the surface are greater.

Method of applying a cerium diffusion coating to a metallic alloy

DOEpatents

Jablonski, Paul D [Salem, OR; Alman, David E [Benton, OR

2009-06-30

A method of applying a cerium diffusion coating to a preferred nickel base alloy substrate has been discovered. A cerium oxide paste containing a halide activator is applied to the polished substrate and then dried. The workpiece is heated in a non-oxidizing atmosphere to diffuse cerium into the substrate. After cooling, any remaining cerium oxide is removed. The resulting cerium diffusion coating on the nickel base substrate demonstrates improved resistance to oxidation. Cerium coated alloys are particularly useful as components in a solid oxide fuel cell (SOFC).

Molecular dynamics simulations of lithium silicate/vanadium pentoxide interfacial lithium ion diffusion in thin film lithium ion-conducting devices

NASA Astrophysics Data System (ADS)

Li, Weiqun

The lithium ion diffusion behavior and mechanism in the glassy electrolyte and the electrolyte/cathode interface during the initial stage of lithium ion diffusing from electrolyte into cathode were investigated using Molecular Dynamics simulation technique. Lithium aluminosilicate glass electrolytes with different R (ratio of the concentration of Al to Li) were simulated. The structural features of the simulated glasses are analyzed using Radial Distribution Function (RDF) and Pair Distribution Function (PDF). The diffusion coefficient and activation energy of lithium ion diffusion in simulated lithium aluminosilicate glasses were calculated and the values are consistent with those in experimental glasses. The behavior of lithium ion diffusion from the glassy electrolyte into a polycrystalline layered intercalation cathode has been studied. The solid electrolyte was a model lithium silicate glass while the cathode was a nanocrystalline vanadia with amorphous V2O5 intergranular films (IGF) between the V2O5 crystals. Two different orientations between the V2O5 crystal planes are presented for lithium ion intercalation via the amorphous vanadia IGF. A series of polycrystalline vanadia cathodes with 1.3, 1.9, 2.9 and 4.4 nm thickness IGFs were simulated to examine the effects of the IGF thickness on lithium ion transport in the polycrystalline vanadia cathodes. The simulated results showed that the lithium ions diffused from the glassy electrolyte into the IGF of the polycrystalline vanadia cathode and then part of those lithium ions diffused into the crystalline V2O5 from the IGF. The simulated results also showed an ordering of the vanadium ion structure in the IGF near the IGF/V2 O5 interface. The ordering structure still existed with glass former silica additive in IGF. Additionally, 2.9 run is suggested to be the optimal thickness of the IGF, which is neither too thick to decrease the capacity of the cathode nor too thin to impede the transport of lithium from glassy electrolyte into the cathode. Parallel molecular dynamic simulation technique was also used for a larger electrolyte/cathode interface system, which include more atoms and more complicated microstructures. Simulation results from larger electrolyte/cathode interface system prove that there is no size effect on simulation of smaller electrolyte/cathode interface system from statistical point of view.

Magnetic Reconnection Dynamics in the Presence of Low-energy Ion Component: PIC Simulations of Hidden Particle Population

NASA Astrophysics Data System (ADS)

Khotyaintsev, Y. V.; Divin, A. V.; Toledo Redondo, S.; Andre, M.; Vaivads, A.; Markidis, S.; Lapenta, G.

2015-12-01

Magnetospheric and astrophysical plasmas are rarely in the state of thermal equilibrium. Plasma distribution functions may contain beams, supra-thermal tails, multiple ion and electron populations which are not thermalized over long time scales due to the lack of collisions between particles. In particular, the equatorial region of the dayside Earth's magnetosphere is often populated by plasma containing hot and cold ion components of comparable densities [Andre and Cully, 2012], and such ion distribution alters properties of the magnetic reconnection regions at the magnetopause [Toledo-Redondo et. al., 2015]. Motivated by these recent findings and also by fact that this region is one of the targets of the recently launched MMS mission, we performed 2D PIC simulations of magnetic reconnection in collisionless plasma with hot and cold ion components. We used a standard Harris current sheet, to which a uniform cold ion background is added. We found that introduction of the cold component modifies the structure of reconnection diffusion region. Diffusion region displays three-scale structure, with the cold Ion Diffusion Region (cIDR) scale appearing in-between the Electron Diffusion Region (EDR) and Ion Diffusion Region (IDR) scales. Structure and strength of the Hall magnetic field depends weakly on cold ion temperature or density, and is rather controlled by the conditions (B, n) upstream the reconnection region. The cold ions are accelerated predominantly transverse to the magnetic field by the Hall electric fields inside the IDR, leading to a large ion pressure anisotropy, which is unstable to ion Weibel-type or mirror-type mode. On the opposite, acceleration of cold ions is mostly field-aligned at the reconnection jet fronts downstream the X-line, producing intense ion phase-space holes there. Despite comparable reconnection rates produced , we find that the overall evolution of reconnection in presence of cold ion population is more dynamic compared to the case with a single hot ion component.

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

NASA Technical Reports Server (NTRS)

Moulot, Jacques; Faur, Mircea; Faur, Maria; Goradia, Chandra; Goradia, Manju; Bailey, Sheila

1995-01-01

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

NASA Technical Reports Server (NTRS)

Moulot, Jacques; Faur, M.; Faur, M.; Goradia, C.; Goradia, M.; Bailey, S.

1995-01-01

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3 and MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductors materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating should work well for all III-V compound-based solar cells.

Chromium oxide as a metal diffusion barrier layer: An x-ray absorption fine structure spectroscopy study

NASA Astrophysics Data System (ADS)

Ahamad Mohiddon, Md.; Lakshun Naidu, K.; Ghanashyam Krishna, M.; Dalba, G.; Ahmed, S. I.; Rocca, F.

2014-01-01

The interaction at the interface between chromium and amorphous Silicon (a-Si) films in the presence of a sandwich layer of chromium oxide is investigated using X-ray absorption fine structure (XAFS) spectroscopy. The oxidized interface was created, in situ, prior to the deposition of a 400 nm tick a-Si layer over a 50 nm tick Cr layer. The entire stack of substrate/metallic Cr/Cr2O3/a-Si was then annealed at temperatures from 300 up to 700 °C. Analysis of the near edge and extended regions of each XAFS spectrum shows that only a small fraction of Cr is able to diffuse through the oxide layer up to 500 °C, while the remaining fraction is buried under the oxide layer in the form of metallic Cr. At higher temperatures, diffusion through the oxide layer is enhanced and the diffused metallic Cr reacts with a-Si to form CrSi2. At 700 °C, the film contains Cr2O3 and CrSi2 without evidence of unreacted metallic Cr. The activation energy and diffusion coefficient of Cr are quantitatively determined in the two temperature regions, one where the oxide acts as diffusion barrier and another where it is transparent to Cr diffusion. It is thus demonstrated that chromium oxide can be used as a diffusion barrier to prevent metal diffusion into a-Si.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Mixed ionic and electronic conducting membranes for hydrogen generation and separation

NASA Astrophysics Data System (ADS)

Cui, Hengdong

Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process conditions of interest. Over 10 mumol·cm-2·s-1 (micromoles per square cm per second) of area specific hydrogen flux has been achieved employing a membrane of this material with thickness of 0.2 mm. This flux is several orders of magnitude higher than the hydrogen generation rates reported using other MIEC materials under similar operating conditions.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

PubMed

Kamcev, Jovan; Paul, Donald R; Manning, Gerald S; Freeman, Benny D

2017-02-01

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl 2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

Mechanisms of Stochastic Diffusion of Energetic Ions in Spherical Tori

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

Ya.I. Kolesnichenko; R.B. White; Yu.V. Yakovenko

Stochastic diffusion of the energetic ions in spherical tori is considered. The following issues are addressed: (I) Goldston-White-Boozer diffusion in a rippled field; (ii) cyclotron-resonance-induced diffusion caused by the ripple; (iii) effects of non-conservation of the magnetic moment in an axisymmetric field. It is found that the stochastic diffusion in spherical tori with a weak magnetic field has a number of peculiarities in comparison with conventional tokamaks; in particular, it is characterized by an increased role of mechanisms associated with non-conservation of the particle magnetic moment. It is concluded that in current experiments on National Spherical Torus eXperiment (NSTX) themore » stochastic diffusion does not have a considerable influence on the confinement of energetic ions.« less

Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

DOE PAGES

Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

2015-04-21

Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2/O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings revealmore » an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.« less

Carbon mediated reduction of silicon dioxide and growth of copper silicide particles in uniform width channels

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

Pizzocchero, Filippo; Bøggild, Peter; Booth, Timothy J.

We show that surface arc-discharge deposited carbon plays a critical intermediary role in the breakdown of thermally grown oxide diffusion barriers of 90 nm on a silicon wafer at 1035 °C in an Ar/H{sub 2} atmosphere, resulting in the formation of epitaxial copper silicide particles in ≈ 10 μm wide channels, which are aligned with the intersections of the (100) surface of the wafer and the (110) planes on an oxidized silicon wafer, as well as endotaxial copper silicide nanoparticles within the wafer bulk. We apply energy dispersive x-ray spectroscopy, in combination with scanning and transmission electron microscopy of focusedmore » ion beam fabricated lammelas and trenches in the structure to elucidate the process of their formation.« less

Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

PubMed

Sun, Yige; Tang, Jie; Zhang, Kun; Yuan, Jinshi; Li, Jing; Zhu, Da-Ming; Ozawa, Kiyoshi; Qin, Lu-Chang

2017-02-16

Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g -1 , which is about three times of 372 mA h g -1 , the value expected for the LiC 6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

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

Moulot, J.; Faur, M.; Faur, M.

1995-10-01

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause amore » significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, the authors demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface.« less

Development of high-efficiency solar cells on silicon web

NASA Technical Reports Server (NTRS)

Meier, D. L.; Greggi, J.; Rai-Choudhury, P.

1986-01-01

Work is reported aimed at identifying and reducing sources of carrier recombination both in the starting web silicon material and in the processed cells. Cross-sectional transmission electron microscopy measurements of several web cells were made and analyzed. The effect of the heavily twinned region on cell efficiency was modeled, and the modeling results compared to measured values for processed cells. The effects of low energy, high dose hydrogen ion implantation on cell efficiency and diffusion length were examined. Cells were fabricated from web silicon known to have a high diffusion length, with a new double layer antireflection coating being applied to these cells. A new contact system, to be used with oxide passivated cells and which greatly reduces the area of contact between metal and silicon, was designed. The application of DLTS measurements to beveled samples was further investigated.

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

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

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

DIFFUSIVE-Magnetoresistance(DMR) Proton(PMR)/Hydrogen-ion WATER: PRE-``Fert''/``Grunberg'' GMR[and CMR]: Quo-Vadis ``Honesty''???: PLAGIARISM!!!

NASA Astrophysics Data System (ADS)

Fart, Albart; Gruntbug, Peter; Siegel, Edward

2011-03-01

Proton/Hydrogen-ion Diffusive-Magnetoresistance(DMR) of Siegel[APS March-Mtgs.(70s)] based upon Siegel[Int'l. Conf. Mag.-Alloys and Oxides("ICMAO"), The Technion(77); J. Mag. Mag. Mtls. 7, 312(78)] FIRST experimental-discovery of GMR and FIRST theoretical prediction of CMR[ibid. 7, 338 (78)], facilitates NEW water production in global-warming exacerbated dry arid/semi-arid regions: Only HYDROGEN is/can be "FLYING-WATER"!!! (aka "chemical-rain-in-pipelines"). EMET/TRUTH-in-the-``SEANCES'', would-be "Sciences": C. Perelman-Corredoira [Against the Tide(07)] featuring Martin-Bradshaw ["Healing the SHAME That BINDS You"(80s)] systemic sociological-dysfunctionality(S-D), and Grigory Perelman's HEROIC ETHICS (refusal of both pure-maths Poincare-conjecture proof 2007 Fields-medal and 2010 Clay-Institute so-called/media-hyped/P.Red/spin-doctored millennium-prize million-dollar would-be award, militates as well in the current "SEANCE" of physics/maths politics/media-hype/P.R /spin-doctoring VS. Siegel FIRST experimental GMR a never-acknowledged full decade PRE-"Fert"(88) /"Grunberg(89)" ``Phales-GroPE''/Thompson-CSF/ KFZ-JEWlich 2007 physics Wolf/Japan/Nobel-prizes!!!

Processing of La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films by dual-ion-beam sputtering

NASA Astrophysics Data System (ADS)

Madakson, P.; Cuomo, J. J.; Yee, D. S.; Roy, R. A.; Scilla, G.

1988-03-01

High-quality La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films, with zero resistance at 88 K, have been made by dual-ion-beam sputtering of metal and oxide targets at elevated temperatures. The films are about 1.0 micron thick and are single phase after annealing. The substrates investigated are Nd-YAP, MgO, SrF2, Si, CaF2, ZrO2-(9 pct)Y2O3, BaF2, Al2O3, and SrTiO3. Characterization of the films was carried out using Rutherford backscattering spectroscopy, resistivity measurements, TEM, X-ray diffraction, and SIMS. Substrate/film interaction was observed in every case. This generally involves diffusion of the substrate into the film, which is accompanied by, for example, the replacement of Ba by Sr in the YBa2Cu2O7 structure, in the case of SrTiO3 substrate. The best substrates were those that did not significantly diffuse into the film and which did not react chemically with the film.

Single ion dynamics in molten sodium bromide

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

Alcaraz, O.; Trullas, J.; Demmel, F.

We present a study on the single ion dynamics in the molten alkali halide NaBr. Quasielastic neutron scattering was employed to extract the self-diffusion coefficient of the sodium ions at three temperatures. Molecular dynamics simulations using rigid and polarizable ion models have been performed in parallel to extract the sodium and bromide single dynamics and ionic conductivities. Two methods have been employed to derive the ion diffusion, calculating the mean squared displacements and the velocity autocorrelation functions, as well as analysing the increase of the line widths of the self-dynamic structure factors. The sodium diffusion coefficients show a remarkable goodmore » agreement between experiment and simulation utilising the polarisable potential.« less

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

DOE PAGES

Shan, Xiaoqiang; Charles, Daniel S.; Xu, Wenqian; ...

2017-11-22

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO 2.H 2O birnessite phase and a (Co 0.83Mn 0.13Va 0.04)tetra(Co 0.38Mn 1.62) octaO 3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacitymore » towards Na-ions in an aqueous electrolyte (121 mA h g -1 at a scan rate of 1 mV s -1 in the half-cell and 81 mA h g -1 at a current density of 2 A g -1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g -1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.« less

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

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

Shan, Xiaoqiang; Charles, Daniel S.; Xu, Wenqian

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO 2.H 2O birnessite phase and a (Co 0.83Mn 0.13Va 0.04)tetra(Co 0.38Mn 1.62) octaO 3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacitymore » towards Na-ions in an aqueous electrolyte (121 mA h g -1 at a scan rate of 1 mV s -1 in the half-cell and 81 mA h g -1 at a current density of 2 A g -1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g -1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.« less

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

PubMed

Ravella, Uday K; Liu, Jingjing; Corbel, Gwenaël; Skinner, Stephen J; Lacorre, Philippe

2016-08-23

Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 μm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inter-cusp Ion and Electron Transport in a Nstar-derivative Ion Thruster

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Ion and Electron Transport in an Nstar-derivative Ion Thruster. Revised

NASA Technical Reports Server (NTRS)

Foster, John E.

2001-01-01

Diffusion of electrons and ions to anode surfaces between the magnetic cusps of a NASA Solar Electric Propulsion Technology Application Readiness ion thruster has been characterized. Ion flux measurements were made at the anode and at the screen grid electrode. The measurements indicated that the average ion current density at the anode and at the screen grid were approximately equal. Additionally, it was found that the electron flux to the anode between cusps is best described by the classical cross-field diffusion coefficient.

Secondary Ion Mass Spectrometry for Mg Tracer Diffusion: Issues and Solutions

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

Tuggle, Jay; Giordani, Andrew; Kulkarni, Nagraj S

2014-01-01

A Secondary Ion Mass Spectrometry (SIMS) method has been developed to measure stable Mg isotope tracer diffusion. This SIMS method was then used to calculate Mg self- diffusivities and the data was verified against historical data measured using radio tracers. The SIMS method has been validated as a reliable alternative to the radio-tracer technique for the measurement of Mg self-diffusion coefficients and can be used as a routine method for determining diffusion coefficients.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

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

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Building one-dimensional oxidenanostructure arrays on conductive metal substrates for lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized aluminamembrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Nano-textured high sensitivity ion sensitive field effect transistors

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

Hajmirzaheydarali, M.; Sadeghipari, M.; Akbari, M.

2016-02-07

Nano-textured gate engineered ion sensitive field effect transistors (ISFETs), suitable for high sensitivity pH sensors, have been realized. Utilizing a mask-less deep reactive ion etching results in ultra-fine poly-Si features on the gate of ISFET devices where spacing of the order of 10 nm and less is achieved. Incorporation of these nano-sized features on the gate is responsible for high sensitivities up to 400 mV/pH in contrast to conventional planar structures. The fabrication process for this transistor is inexpensive, and it is fully compatible with standard complementary metal oxide semiconductor fabrication procedure. A theoretical modeling has also been presented to predict themore » extension of the diffuse layer into the electrolyte solution for highly featured structures and to correlate this extension with the high sensitivity of the device. The observed ultra-fine features by means of scanning electron microscopy and transmission electron microscopy tools corroborate the theoretical prediction.« less

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Ascorbic Acid-Assisted Eco-friendly Synthesis of NiCo2O4 Nanoparticles as an Anode Material for High-Performance Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Karunakaran, Gopalu; Maduraiveeran, Govindhan; Kolesnikov, Evgeny; Balasingam, Suresh Kannan; Viktorovich, Lysov Dmitry; Ilinyh, Igor; Gorshenkov, Mikhail V.; Sasidharan, Manickam; Kuznetsov, Denis; Kundu, Manab

2018-05-01

We have synthesized NiCo2O4 nanoparticles (NCO NPs) using an ascorbic acid-assisted co-precipitation method for the first time. When NCO NPs are used as an anode material for lithium-ion batteries, the cell exhibits superior lithium storage properties, such as high capacity (700 mA h g-1 after 300 cycles at 200 mA g-1), excellent rate capabilities (applied current density range 100-1200 mA g-1), and impressive cycling stability (at 1200 mA g-1 up to 650 cycles). The enhanced electrochemical properties of NCO NPs are due to the nanometer dimensions which not only offers a smooth charge-transport pathway and short diffusion paths of the lithium ions but also adequate spaces for volume expansion during Li storage. Hence, this eco-friendly synthesis approach will provide a new strategy for the synthesis of various nanostructured metal oxide compounds, for energy conversion and storage systems applications.

Analysis and evalaution in the production process and equipment area of the low-cost solar array project. [including modifying gaseous diffusion and using ion implantation

NASA Technical Reports Server (NTRS)

Goldman, H.; Wolf, M.

1979-01-01

The manufacturing methods for photovoltaic solar energy utilization are assessed. Economic and technical data on the current front junction formation processes of gaseous diffusion and ion implantation are presented. Future proposals, including modifying gaseous diffusion and using ion implantation, to decrease the cost of junction formation are studied. Technology developments in current processes and an economic evaluation of the processes are included.

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

Diffusion Behavior of Mn and Si Between Liquid Oxide Inclusions and Solid Iron-Based Alloy at 1473 K

NASA Astrophysics Data System (ADS)

Kim, Sun-Joong; Tago, Hanae; Kim, Kyung-Ho; Kitamura, Shin-ya; Shibata, Hiroyuki

2018-06-01

In order to clarify the changes in the composition of oxide inclusions in steel, the effect of the metal and oxide composition on the reaction between solid Fe-based alloys and liquid multi-component oxides was investigated using the diffusion couple method at 1473 K. The measured concentration gradients of Mn and Si in the metal indicated that Mn diffused into the metal from the oxide, while the diffusion of Si occurred in the opposite direction. In addition, the MnO content in the oxide decreased with heat treatment time, while the SiO2 content increased. The compositional changes in both phases indicated that the Mn content in the metal near the interface increased with heat treatment with decreasing MnO content in the oxide. Assuming local equilibrium at the interface, the calculated [Mn]2/[Si] ratio at the interface in equilibrium with the oxide increased with increases in the MnO/SiO2 ratio in the oxide. The difference in the [Mn]2/[Si] ratios between the interface and the metal matrix increased, which caused the diffusion of Mn and Si between the multi-component oxide and metal. By measuring the diffusion lengths of Mn and Si in the metal, the chemical diffusion coefficients of Mn and Si were obtained to calculate the composition changes in Mn and Si in the metal. The calculated changes in Mn and Si in the metal agreed with the experimental results.

Facile synthesis of hierarchical porous VOx@carbon composites for supercapacitors.

PubMed

Zhao, Chunxia; Cao, Jinqiao; Yang, Yunxia; Chen, Wen; Li, Junshen

2014-08-01

Hierarchical or micro-nano structured porous VOx@carbon composites were synthesized by a one-step method using phenolic resin as the carbon precursor and ammonium metavanadate as the source of vanadium oxides. The effects of the vanadium source loading on the microstructure and electrochemical properties of the composites were investigated. X-ray diffraction results showed that as the vanadium oxides source loading increased, vanadium oxides in the composites changed oxidation states from V2O3 to mixed states of V2O3 and VO2. Electrochemical test results indicated that the micro-nano porous structure of the composites could facilitate the ion diffusion in the rich porous structure and then promote the electrochemical reaction. More importantly, we found that vanadium oxides greatly enhanced the electrochemical performance of the materials, due to the faradic capacitance generated from vanadium oxide nanoparticles. A maximum specific capacitance of 171 F/g was obtained from VOx@carbon composite with vanadium loading of ∼44 wt%. Further increasing the VOx loading over this fraction was not beneficial. Our results suggested that hierarchical porous VOx@carbon composites were promising candidates for supercapacitor applications. Copyright © 2013 Elsevier Inc. All rights reserved.

Transport, charge exchange and loss of energetic heavy ions in the earth's radiation belts - Applicability and limitations of theory

NASA Technical Reports Server (NTRS)

Spjeldvik, W. N.

1981-01-01

Computer simulations of processes which control the relative abundances of ions in the trapping regions of geospace are compared with observations from discriminating ion detectors. Energy losses due to Coulomb collisions between ions and exospheric neutrals are considered, along with charge exchange losses and internal charge exchanges. The time evolution of energetic ion fluxes of equatorially mirroring ions under radial diffusion is modelled to include geomagnetic and geoelectric fluctutations. Limits to the validity of diffusion transport theory are discussed, and the simulation is noted to contain provisions for six ionic charge states and the source effect on the radiation belt oxygen ion distributions. Comparisons are made with ion flux data gathered on Explorer 45 and ISEE-1 spacecraft and results indicate that internal charge exchanges cause the radiation belt ion charge state to be independent of source charge rate characteristics, and relative charge state distribution is independent of the radially diffusive transport rate below the charge state redistribution zone.

Palladium nanoparticles decorated on reduced graphene oxide rotating disk electrodes toward ultrasensitive hydrazine detection: effects of particle size and hydrodynamic diffusion.

PubMed

Krittayavathananon, Atiweena; Srimuk, Pattarachai; Luanwuthi, Santamon; Sawangphruk, Montree

2014-12-16

Although metal nanoparticle/graphene composites have been widely used as the electrode in electrochemical sensors, two effects, consisting of the particle size of the nanoparticles and the hydrodynamic diffusion of analytes to the electrodes, are not yet fully understood. In this work, palladium nanoparticles/reduced graphene oxide (PdNPs/rGO) composites were synthesized using an in situ polyol method. Palladium(II) ions and graphene oxide were reduced together with a reducing agent, ethylene glycol. By varying the concentration of palladium(II) nitrate, PdNPs with different sizes were decorated on the surface of rGO sheets. The as-fabricated PdNPs/rGO rotating disk electrodes (RDEs) were investigated toward hydrazine detection. Overall, a 3.7 ± 1.4 nm diameter PdNPs/rGO RDE exhibits high performance with a rather low limit of detection of about 7 nM at a rotation speed of 6000 rpm and provides a wide linear range of 0.1-1000 μM with R(2) = 0.995 at 2000 rpm. This electrode is highly selective to hydrazine without interference from uric acid, glucose, ammonia, caffeine, methylamine, ethylenediamine, hydroxylamine, n-butylamine, adenosine, cytosine, guanine, thymine, and l-arginine. The PdNPs/rGO RDEs with larger sizes show lower detection performance. Interestingly, the detection performance of the electrodes is sensitive to the hydrodynamic diffusion of hydrazine. The as-fabricated electrode can detect trace hydrazine in wastewater with high stability, demonstrating its practical use as an electrochemical sensor. These findings may lead to an awareness of the effect of the hydrodynamic diffusion of analyte that has been previously ignored, and the 3.7 ± 1.4 nm PdNPs/rGO RDE may be useful toward trace hydrazine detection, especially in wastewater from related chemical industries.

Separation of copper ions from iron ions using PVA-g-(acrylic acid/N-vinyl imidazole) membranes prepared by radiation-induced grafting.

PubMed

Ajji, Zaki; Ali, Ali M

2010-01-15

Acrylic acid (AAc), N-vinyl imidazole (Azol) and their binary mixtures were graft copolymerized onto poly(vinyl alcohol) membranes using gamma irradiation. The ability of the grafted membranes to separate Cu ions from Fe ions was investigated with respect to the grafting yield and the pH of the feed solution. The data showed that the diffusion of copper ions from the feed compartment to the receiver compartment depends on the grafting yield of the membranes and the pH of the feed solution. To the contrary, iron ions did not diffuse through the membranes of all grafting yields. However, a limited amount of iron ions diffused in strong acidic medium. This study shows that the prepared membranes could be considered for the separation of copper ions from iron ions. The temperature of thermal decomposition of pure PVA-g-AAc/Azol membrane, PVA-g-AAc/Azol membrane containing copper ions, and PVA-g-AAc/Azol membrane containing iron ions were determined using TGA analyzer. It was shown that the presence of Cu and Fe ions increases the decomposition temperature, and the membranes bonded with iron ions are more stable than those containing copper ions.

Stabilization of the Thermal Decomposition of Poly(Propylene Carbonate) Through Copper Ion Incorporation and Use in Self-Patterning

NASA Astrophysics Data System (ADS)

Spencer, Todd J.; Chen, Yu-Chun; Saha, Rajarshi; Kohl, Paul A.

2011-06-01

Incorporation of copper ions into poly(propylene carbonate) (PPC) films cast from γ-butyrolactone (GBL), trichloroethylene (TCE) or methylene chloride (MeCl) solutions containing a photo-acid generator is shown to stabilize the PPC from thermal decomposition. Copper ions were introduced into the PPC mixtures by bringing the polymer mixture into contact with copper metal. The metal was oxidized and dissolved into the PPC mixture. The dissolved copper interferes with the decomposition mechanism of PPC, raising its decomposition temperature. Thermogravimetric analysis shows that copper ions make PPC more stable by up to 50°C. Spectroscopic analysis indicates that copper ions may stabilize terminal carboxylic acid groups, inhibiting PPC decomposition. The change in thermal stability based on PPC exposure to patterned copper substrates was used to provide a self-aligned patterning method for PPC on copper traces without the need for an additional photopatterning registration step. Thermal decomposition of PPC is then used to create air isolation regions around the copper traces. The spatial resolution of the self-patterning PPC process is limited by the lateral diffusion of the copper ions within the PPC. The concentration profiles of copper within the PPC, patterning resolution, and temperature effects on the PPC decomposition have been studied.

Nonstoichiometric La(2 - x)GeO(5 - delta) monoclinic oxide as a new fast oxide ion conductor.

PubMed

Ishihara, T; Arikawa, H; Akbay, T; Nishiguchi, H; Takita, Y

2001-01-17

Oxide ion conductivity in La(2)GeO(5)-based oxide was investigated and it was found that La-deficient La(2)GeO(5) exhibits oxide ion conductivity over a wide range of oxygen partial pressure. The crystal structure of La(2)GeO(5) was estimated to be monoclinic with P2(1)/c space group. Conductivity increased with increasing the amount of La deficiency and the maximum value was attained at x = 0.39 in La(2 - x)GeO(5 - delta). The oxide ion transport number in La(2)GeO(5)-based oxide was estimated to be unity by the electromotive force measurement in H(2)-O(2) and N(2)-O(2) gas concentration cells. At a temperature higher than 1000 K, the oxide ion conductivity of La(1.61)GeO(5 - delta) was almost the same as that of La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3 - delta) or Ce(0.85)Gd(0.15)O(2 - delta), which are well-known fast oxide ion conductors. On the other hand, a change in the activation energy for oxide ion conductivity was observed at 973 K, and at intermediate temperature, the oxide ion conductivity of La(1.61)GeO(5 - delta) became much smaller than that of these well-known fast oxide ion conductors. The change in the activation energy of the oxide ion conductivity seems to be caused by a change in the local oxygen vacancy structure. However, doping a small amount of Sr for La in La(2)GeO(5) was effective to stabilize the high-temperature crystal structure to low temperature. Consequently, doping a small amount of Sr increases the oxide ion conductivity of La(2)GeO(5)-based oxide at low temperature.

Method and reaction pathway for selectively oxidizing organic compounds

DOEpatents

Camaioni, Donald M.; Lilga, Michael A.

1998-01-01

A method of selectively oxidizing an organic compound in a single vessel comprises: a) combining an organic compound, an acid solution in which the organic compound is soluble, a compound containing two oxygen atoms bonded to one another, and a metal ion reducing agent capable of reducing one of such oxygen atoms, and thereby forming a mixture; b) reducing the compound containing the two oxygen atoms by reducing one of such oxygen atoms with the metal ion reducing agent to, 1) oxidize the metal ion reducing agent to a higher valence state, and 2) produce an oxygen containing intermediate capable of oxidizing the organic compound; c) reacting the oxygen containing intermediate with the organic compound to oxidize the organic compound into an oxidized organic intermediate, the oxidized organic intermediate having an oxidized carbon atom; d) reacting the oxidized organic intermediate with the acid counter ion and higher valence state metal ion to bond the acid counter ion to the oxidized carbon atom and thereby produce a quantity of an ester incorporating the organic intermediate and acid counter ion; and e) reacting the oxidized organic intermediate with the higher valence state metal ion and water to produce a quantity of alcohol which is less than the quantity of ester, the acid counter ion incorporated in the ester rendering the carbon atom bonded to the counter ion less reactive with the oxygen containing intermediate in the mixture than is the alcohol with the oxygen containing intermediate.

Formation of Deep Sea Umber Deposits Linked to Microbial Metal Oxidation at the South Atlantic Ridge

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-04-01

Umber deposits are important metalliferous deposits, which occur in off-axis half-graben structures at ancient and modern ocean floor. The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biochemical mechanisms involved to the precipitation of Mn oxides and co-precipitation of Fe oxyhydroxides and Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data suggest that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic Fe(II)-oxidizing bacteria, which constitute a trophic base that may support the activities of heterotrophic Mn(II)-oxidizing bacteria. The biological origin of umber deposits underscore the importance of geomicrobiologcial interaction in triggering the formation of deep-sea deposits, with important implications for the generation of submarine Mn deposits and crusts.

Synthesis and Electrochemical Property of LiMn2O4 Porous Hollow Nanofiber as Cathode for Lithium-Ion Batteries.

PubMed

Duan, Lianfeng; Zhang, Xueyu; Yue, Kaiqiang; Wu, Yue; Zhuang, Jian; Lü, Wei

2017-12-01

The LiMn 2 O 4 hollow nanofibers with a porous structure have been synthesized by modified electrospinning techniques and subsequent thermal treatment. The precursors were electrospun directly onto the fluorine-doped tin oxide (FTO) glass. The heating rate and FTO as substrate play key roles on preparing porous hollow nanofiber. As cathode materials for lithium-ion batteries (LIBs), LiMn 2 O 4 hollow nanofibers showed the high specific capacity of 125.9 mAh/g at 0.1 C and a stable cycling performance, 105.2 mAh/g after 400 cycles. This unique structure could relieve the structure expansion effectively and provide more reaction sites as well as shorten the diffusion path for Li + for improving electrochemical performance for LIBs.

Contribution of ion beam analysis methods to the development of second generation high temperature superconducting wires

NASA Astrophysics Data System (ADS)

Usov, I. O.; Arendt, P. N.; Foltyn, S. R.; Stan, L.; DePaula, R. F.; Holesinger, T. G.

2010-06-01

One of the crucial steps in the second generation high temperature superconducting wire program was development of the buffer-layer architecture. The architecture designed at the Superconductivity Technology Center at Los Alamos National Laboratory consists of several oxide layers wherein each layer plays a specific role, namely: nucleation layer, diffusion barrier, biaxially textured template, and intermediate layer providing a suitable lattice match to the superconducting Y 1Ba 2Cu 3O 7 (YBCO) compound. This report demonstrates how a wide range of ion beam analysis techniques (SIMS, RBS, channeling, PIXE, PIGE, NRA and ERD) was employed for analysis of each buffer layer and the YBCO film. These results assisted in understanding of a variety of physical processes occurring during the buffer layer fabrication and helped to optimize the buffer-layer architecture as a whole.

An ion displacement membrame model.

PubMed

Hladky, S B; Harris, J D

1967-09-01

The usual assumption in treating the diffusion of ions in an electric field has been that the movement of each ion is independent of the movement of the others. The resulting equation for diffusion by a succession of spontaneous jumps has been well stated by Parlin and Eyring. This paper will consider one simple case in which a different assumption is reasonable. Diffusion of monovalent positive ions is considered as a series of jumps from one fixed negative site to another. The sites are assumed to be full (electrical neutrality). Interaction occurs by the displacement of one ion by another. An ion leaves a site if and only if another ion, not necessarily of the same species, attempts to occupy the same site. Flux ratios and net fluxes are given as functions of the electrical potential, concentration ratios, and number of sites encountered in crossing the membrane. Quantitative comparisons with observations of Hodgkin and Keynes are presented.

Chaotic ion motion in magnetosonic plasma waves

NASA Technical Reports Server (NTRS)

Varvoglis, H.

1984-01-01

The motion of test ions in a magnetosonic plasma wave is considered, and the 'stochasticity threshold' of the wave's amplitude for the onset of chaotic motion is estimated. It is shown that for wave amplitudes above the stochasticity threshold, the evolution of an ion distribution can be described by a diffusion equation with a diffusion coefficient D approximately equal to 1/v. Possible applications of this process to ion acceleration in flares and ion beam thermalization are discussed.

Atomic layer deposited lithium aluminum oxide: (In)dependency of film properties from pulsing sequence

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

Miikkulainen, Ville, E-mail: ville.miikkulainen@helsinki.fi; Nilsen, Ola; Fjellvåg, Helmer

Atomic layer deposition (ALD) holds markedly high potential of becoming the enabling method for achieving the three-dimensional all-solid-state thin-film lithium ion battery (LiB). One of the most crucial components in such a battery is the electrolyte that needs to hold both low electronic conductivity and at least fair lithium ion conductivity being at the same time pinhole free. To obtain these desired properties in an electrolyte film, one necessarily has to have a good control over the elemental composition of the deposited material. The present study reports on the properties of ALD lithium aluminum oxide (Li{sub x}Al{sub y}O{sub z}) thinmore » films. In addition to LiB electrolyte applications, Li{sub x}Al{sub y}O{sub z} is also a candidate low dielectric constant (low-k) etch stop and diffusion barrier material in nanoelectronics applications. The Li{sub x}Al{sub y}O{sub z} films were deposited employing trimethylaluminum-O{sub 3} and lithium tert-butoxide-H{sub 2}O for Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, respectively. The composition was aimed to be controlled by varying the pulsing ratio of those two binary oxide ALD cycles. The films were characterized by several methods for composition, crystallinity and phase, electrical properties, hardness, porosity, and chemical environment. Regardless of the applied pulsing ratio of Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, all the studied ALD Li{sub x}Al{sub y}O{sub z} films of 200 and 400 nm in thickness were polycrystalline in the orthorhombic β-LiAlO{sub 2} phase and also very similar to each other with respect to composition and other studied properties. The results are discussed in the context of both fundamental ALD chemistry and applicability of the films as thin-film LiB electrolytes and low-k etch stop and diffusion barriers.« less

Effective defect diffusion lengths in Ar-ion bombarded 3C-SiC

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

Bayu Aji, L. B.; Wallace, J. B.; Shao, L.

Above room temperature, SiC exhibits pronounced processes of diffusion and interaction of radiation-generated point defects. Here, we use the recently developed pulsed ion beam method to measure effective defect diffusion lengths in 3C-SiC bombarded in the temperature range of 25–200 °C with 500 keV Ar ions. Results reveal a diffusion length of ~10 nm, which exhibits a weak temperature dependence, changing from 9 to 13 nm with increasing temperature. Lastly, these results have important implications for understanding and predicting radiation damage in SiC and for the development of radiation-resistant materials via interface-mediated defect reactions.

Effective defect diffusion lengths in Ar-ion bombarded 3C-SiC

DOE PAGES

Bayu Aji, L. B.; Wallace, J. B.; Shao, L.; ...

2016-04-14

Above room temperature, SiC exhibits pronounced processes of diffusion and interaction of radiation-generated point defects. Here, we use the recently developed pulsed ion beam method to measure effective defect diffusion lengths in 3C-SiC bombarded in the temperature range of 25–200 °C with 500 keV Ar ions. Results reveal a diffusion length of ~10 nm, which exhibits a weak temperature dependence, changing from 9 to 13 nm with increasing temperature. Lastly, these results have important implications for understanding and predicting radiation damage in SiC and for the development of radiation-resistant materials via interface-mediated defect reactions.

Kinetic phase evolution of spinel cobalt oxide during lithiation

DOE PAGES

Li, Jing; He, Kai; Meng, Qingping; ...

2016-09-15

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Kinetic phase evolution of spinel cobalt oxide during lithiation

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

Li, Jing; He, Kai; Meng, Qingping

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Microbial interspecies electron transfer via electric currents through conductive minerals

PubMed Central

Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

2012-01-01

In anaerobic biota, reducing equivalents (electrons) are transferred between different species of microbes [interspecies electron transfer (IET)], establishing the basis of cooperative behaviors and community functions. IET mechanisms described so far are based on diffusion of redox chemical species and/or direct contact in cell aggregates. Here, we show another possibility that IET also occurs via electric currents through natural conductive minerals. Our investigation revealed that electrically conductive magnetite nanoparticles facilitated IET from Geobacter sulfurreducens to Thiobacillus denitrificans, accomplishing acetate oxidation coupled to nitrate reduction. This two-species cooperative catabolism also occurred, albeit one order of magnitude slower, in the presence of Fe ions that worked as diffusive redox species. Semiconductive and insulating iron-oxide nanoparticles did not accelerate the cooperative catabolism. Our results suggest that microbes use conductive mineral particles as conduits of electrons, resulting in efficient IET and cooperative catabolism. Furthermore, such natural mineral conduits are considered to provide ecological advantages for users, because their investments in IET can be reduced. Given that conductive minerals are ubiquitously and abundantly present in nature, electric interactions between microbes and conductive minerals may contribute greatly to the coupling of biogeochemical reactions. PMID:22665802

Effect of carbon ion irradiation on Ag diffusion in SiC

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

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Effect of carbon ion irradiation on Ag diffusion in SiC

DOE PAGES

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.; ...

2015-11-14

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Two-Dimensional Holey Nanoarchitectures Created by Confined Self-Assembly of Nanoparticles via Block Copolymers: From Synthesis to Energy Storage Property

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

Peng, Lele; Fang, Zhiwei; Li, Jing

Advances in liquid-phase exfoliation and surfactant-directed anisotropic growth of two-dimensional (2D) nanosheets have enabled their rapid development. However, it remains challenging to develop assembly strategies that lead to the construction of 2D nanomaterials with well-defined geometry and functional nanoarchitectures that are tailored to specific applications. Here we report a facile self-assembly method leading to the controlled synthesis of 2D transition metal oxide (TMO) nanosheets containing a high density of holes. We utilize graphene oxide sheets as a sacrificial template and Pluronic copolymers as surfactant. By using ZnFe 2O 4 (ZFO) nanoparticles as a model material, we demonstrate that by tuningmore » the molecular weight of the Pluronic copolymers that we can incorporate the ZFO particles and tune the size of the holes in the sheets. The resulting 2D ZFO nanosheets offer synergistic characteristics including increased electrochemically active surface areas, shortened ion diffusion paths, and strong inherent mechanical properties, leading to enhanced lithium-ion storage properties. Post-cycling characterization confirms that the samples maintain structural integrity after electrochemical cycling. In conclusion, our findings demonstrate that this template-assisted self-assembly method is a useful bottom-up route for controlled synthesis of 2D nanoarchitectures, and these holey 2D nanoarchitectures are promising for improving the electrochemical performance of nextgeneration lithium-ion batteries.« less

Two-Dimensional Holey Nanoarchitectures Created by Confined Self-Assembly of Nanoparticles via Block Copolymers: From Synthesis to Energy Storage Property

DOE PAGES

Peng, Lele; Fang, Zhiwei; Li, Jing; ...

2017-12-20

Advances in liquid-phase exfoliation and surfactant-directed anisotropic growth of two-dimensional (2D) nanosheets have enabled their rapid development. However, it remains challenging to develop assembly strategies that lead to the construction of 2D nanomaterials with well-defined geometry and functional nanoarchitectures that are tailored to specific applications. Here we report a facile self-assembly method leading to the controlled synthesis of 2D transition metal oxide (TMO) nanosheets containing a high density of holes. We utilize graphene oxide sheets as a sacrificial template and Pluronic copolymers as surfactant. By using ZnFe 2O 4 (ZFO) nanoparticles as a model material, we demonstrate that by tuningmore » the molecular weight of the Pluronic copolymers that we can incorporate the ZFO particles and tune the size of the holes in the sheets. The resulting 2D ZFO nanosheets offer synergistic characteristics including increased electrochemically active surface areas, shortened ion diffusion paths, and strong inherent mechanical properties, leading to enhanced lithium-ion storage properties. Post-cycling characterization confirms that the samples maintain structural integrity after electrochemical cycling. In conclusion, our findings demonstrate that this template-assisted self-assembly method is a useful bottom-up route for controlled synthesis of 2D nanoarchitectures, and these holey 2D nanoarchitectures are promising for improving the electrochemical performance of nextgeneration lithium-ion batteries.« less

Evolution of Reduced Graphene Oxide-SnS2 Hybrid Nanoparticle Electrodes in Li-Ion Batteries.

PubMed

Modarres, Mohammad H; Lim, Jonathan Hua-Wei; George, Chandramohan; De Volder, Michael

2017-06-22

Hybrid nanomaterials where active battery nanoparticles are synthesized directly onto conductive additives such as graphene hold the promise of improving the cyclability and energy density of conversion and alloying type Li-ion battery electrodes. Here we investigate the evolution of hybrid reduced graphene oxide-tin sulfide (rGO-SnS 2 ) electrodes during battery cycling. These hybrid nanoparticles are synthesized by a one-step solvothermal microwave reaction which allows for simultaneous synthesis of the SnS 2 nanocrystals and reduction of GO. Despite the hybrid architecture of these electrodes, electrochemical impedance spectroscopy shows that the impedance doubles in about 25 cycles and subsequently gradually increases, which may be caused by an irreversible surface passivation of rGO by sulfur enriched conversion products. This surface passivation is further confirmed by post-mortem Raman spectroscopy of the electrodes, which no longer detects rGO peaks after 100 cycles. Moreover, galvanostatic intermittent titration analysis during the 1st and 100th cycles shows a drop in Li-ion diffusion coefficient of over an order of magnitude. Despite reports of excellent cycling performance of hybrid nanomaterials, our work indicates that in certain electrode systems, it is still critical to further address passivation and charge transport issues between the active phase and the conductive additive in order to retain high energy density and cycling performance.

Magnetic, thermodynamic and optical properties of Sb-substituted Ba2PrBiO6 double perovskite oxides

NASA Astrophysics Data System (ADS)

Onodera, K.; Kogawa, T.; Matsukawa, M.; Taniguchi, H.; Nishidate, K.; Matsushita, A.; Shimoda, M.

2018-03-01

We demonstrated crystal structures, magnetic, thermodynamic and optical properties of the B-site substituted perovskite oxides Ba2Pr(Bi1 ‑ x,Sbx ) O6 (x=0, 0.1 and 0.2). Polycrystalline samples of Sb-substituted Ba2PrBiO6 were prepared with the conventional solid-state reaction technique. The X-ray diffraction data revealed that the polycrystalline samples are an almost single phase with a monoclinic structure (C2 /m). Substitution of smaller Sb ion at Bi site causes a monotonic decrease in both the lattice parameters and volume. Magnetization measurements at high temperatures above 200 K show that the effective magnetic moment is estimated to be around 3.15 µB , which is close to that for Pr3+ion. The X-ray photoemission spectroscopy analysis revealed that a prominent peak of Pr3+ is dominant with a smaller shoulder structure of Pr4+. A Schottky-like anomaly observed in the low-temperature specific heat measurement is explained by low-lying splitting of Pr ions under the crystal field effect. Optical spectra were measured using a diffuse-reflectance method. The band gaps were estimated from the optical data to be 0.977 eV and 1.073 eV, at x = 0 and 0.2, respectively. The effect of band gap opening due to Sb substitution is examined by using the density functional theory.

Multifrequency electron paramagnetic resonance and electron-nuclear double-resonance studies of photo-hole processes in AgBr and AgCl emulsion grains

NASA Astrophysics Data System (ADS)

Eachus, R. S.; Pawlik, Th D.; Baetzold, R. C.

2000-10-01

By using a combination of multifrequency EPR spectroscopy, ENDOR spectroscopy and calculations of structure and energy, the reactivities of photo-generated holes in microcrystalline AgBr and AgCl dispersions (photographic emulsions) have been followed in detail. Progress has been facilitated by the use of both gelatin and polyvinyl alcohol (PVA) as peptizers. The initial trapped hole centres produced by band-gap excitation have been identified. In AgBr, this species is [(Br4)3-.V], a neutral complex formed from hole trapping by the four nearest neighbours of a surface Ag+ vacancy (=V). [(Br4)3-.V] reacts with gelatin to produce a transient organic radical at the grain's surface. It does not, however, react with PVA. The formation of the oxidized gelatin radical might involve atomic bromine as an intermediate. In AgCl, the well-known self-trapped hole centre (AgCl6)4- is the initial hole species. The hole diffuses by an electron exchange process until it is trapped by a silver ion on the grain's surface or within its penultimate layer of lattice ions. It is subsequently released from this Ag2+ site to be retrapped at a centre containing four equivalent Cl- ions. The precise identity of this defect has yet to be determined, but its decay also results in the oxidation of gelatin.

The genetic basis of energy conservation in the sulfate-reducing bacterium Desulfovibrio alaskensis G20

PubMed Central

Price, Morgan N.; Ray, Jayashree; Wetmore, Kelly M.; Kuehl, Jennifer V.; Bauer, Stefan; Deutschbauer, Adam M.; Arkin, Adam P.

2014-01-01

Sulfate-reducing bacteria play major roles in the global carbon and sulfur cycles, but it remains unclear how reducing sulfate yields energy. To determine the genetic basis of energy conservation, we measured the fitness of thousands of pooled mutants of Desulfovibrio alaskensis G20 during growth in 12 different combinations of electron donors and acceptors. We show that ion pumping by the ferredoxin:NADH oxidoreductase Rnf is required whenever substrate-level phosphorylation is not possible. The uncharacterized complex Hdr/flox-1 (Dde_1207:13) is sometimes important alongside Rnf and may perform an electron bifurcation to generate more reduced ferredoxin from NADH to allow further ion pumping. Similarly, during the oxidation of malate or fumarate, the electron-bifurcating transhydrogenase NfnAB-2 (Dde_1250:1) is important and may generate reduced ferredoxin to allow additional ion pumping by Rnf. During formate oxidation, the periplasmic [NiFeSe] hydrogenase HysAB is required, which suggests that hydrogen forms in the periplasm, diffuses to the cytoplasm, and is used to reduce ferredoxin, thus providing a substrate for Rnf. During hydrogen utilization, the transmembrane electron transport complex Tmc is important and may move electrons from the periplasm into the cytoplasmic sulfite reduction pathway. Finally, mutants of many other putative electron carriers have no clear phenotype, which suggests that they are not important under our growth conditions, although we cannot rule out genetic redundancy. PMID:25400629

Variables that influence energy partition in asymmetric reconnection

NASA Astrophysics Data System (ADS)

Wang, S.; Chen, L. J.; Bessho, N.; Hesse, M.; Yamada, M.; Yoo, J.

2017-12-01

The energy conversion in the diffusion region during asymmetric reconnection is studied using particle-in-cell (PIC) simulations and measurements from the Magnetospheric Multiscale (MMS) spacecraft. The simulation analysis shows that the energy partition is highly region-dependent and varies with the guide field strength. Without a guide field, within the central electron diffusion region, the input magnetic energy is mostly converted to the electron thermal energies; half of the magnetic energy input to the region extending from the X-line to a few ion inertial lengths downstream where the ion outflow peaks is converted to the plasma energy gain, with approximately equal partition between ions and electrons, similar to the laboratory results from the Magnetic Reconnection Experiment (MRX); over the entire ion diffusion region, about half of the energy goes to ions, and 20% goes to electrons. Electrons obtain energies mainly from the reconnection electric field (Er). For the ion total energy gain in the diffusion region, about 2/3 comes from the in-plane electrostatic field Ein and 1/3 comes from Er. Adding a guide field tends to reduce the plasma energy gain through reducing the contribution from Ein, even though the reconnection rates are similar. The energy partition in the diffusion region observed by MMS is estimated and compared with the results from PIC simulations and MRX experiments.

Electrochemical ion transfer across liquid/liquid interfaces confined within solid-state micropore arrays--simulations and experiments.

PubMed

Strutwolf, Jörg; Scanlon, Micheál D; Arrigan, Damien W M

2009-01-01

Miniaturised liquid/liquid interfaces provide benefits for bioanalytical detection with electrochemical methods. In this work, microporous silicon membranes which can be used for interface miniaturisation were characterized by simulations and experiments. The microporous membranes possessed hexagonal arrays of pores with radii between 10 and 25 microm, a pore depth of 100 microm and pore centre-to-centre separations between 99 and 986 microm. Cyclic voltammetry was used to monitor ion transfer across arrays of micro-interfaces between two immiscible electrolyte solutions (microITIES) formed at these membranes, with the organic phase present as an organogel. The results were compared to computational simulations taking into account mass transport by diffusion and encompassing diffusion to recessed interfaces and overlapped diffusion zones. The simulation and experimental data were both consistent with the situation where the location of the liquid/liquid (l/l) interface was on the aqueous side of the silicon membrane and the pores were filled with the organic phase. While the current for the forward potential scan (transfer of the ion from the aqueous phase to the organic phase) was strongly dependent on the location of the l/l interface, the current peak during the reverse scan (transfer of the ion from the organic phase to the aqueous phase) was influenced by the ratio of the transferring ion's diffusion coefficients in both phases. The diffusion coefficient of the transferring ion in the gelified organic phase was ca. nine times smaller than in the aqueous phase. Asymmetric cyclic voltammogram shapes were caused by the combined effect of non-symmetrical diffusion (spherical and linear) and by the inequality of the diffusion coefficient in both phases. Overlapping diffusion zones were responsible for the observation of current peaks instead of steady-state currents during the forward scan. The characterisation of the diffusion behaviour is an important requirement for application of these silicon membranes in electroanalytical chemistry.

Effect of upstream ULF waves on the energetic ion diffusion at the earth's foreshock: Theory, Simulation, and Observations

NASA Astrophysics Data System (ADS)

Otsuka, F.; Matsukiyo, S.; Kis, A.; Hada, T.

2017-12-01

Spatial diffusion of energetic particles is an important problem not only from a fundamental physics point of view but also for its application to particle acceleration processes at astrophysical shocks. Quasi-linear theory can provide the spatial diffusion coefficient as a function of the wave turbulence spectrum. By assuming a simple power-law spectrum for the turbulence, the theory has been successfully applied to diffusion and acceleration of cosmic rays in the interplanetary and interstellar medium. Near the earth's foreshock, however, the wave spectrum often has an intense peak, presumably corresponding to the upstream ULF waves generated by the field-aligned beam (FAB). In this presentation, we numerically and theoretically discuss how the intense ULF peak in the wave spectrum modifies the spatial parallel diffusion of energetic ions. The turbulence is given as a superposition of non-propagating transverse MHD waves in the solar wind rest frame, and its spectrum is composed of a piecewise power-law spectrum with different power-law indices. The diffusion coefficients are then estimated by using the quasi-linear theory and test particle simulations. We find that the presence of the ULF peak produces a concave shape of the diffusion coefficient when it is plotted versus the ion energy. The results above are used to discuss the Cluster observations of the diffuse ions at the Earth's foreshock. Using the density gradients of the energetic ions detected by the Cluster spacecraft, we determine the e-folding distances, equivalently, the spatial diffusion coefficients, of ions with their energies from 10 to 32 keV. The observed e-folding distances are significantly smaller than those estimated in the past statistical studies. This suggests that the particle acceleration at the foreshock can be more efficient than considered before. Our test particle simulation explains well the small estimate of the e-folding distances, by using the observed wave turbulence spectrum near the shock.

PROCESSES FOR SEPARATING AND RECOVERING CONSTITUENTS OF NEUTRON IRRADIATED URANIUM

DOEpatents

Connick, R.E.; Gofman, J.W.; Pimentel, G.C.

1959-11-10

Processes are described for preparing plutonium, particularly processes of separating plutonium from uranium and fission products in neutron-irradiated uraniumcontaining matter. Specifically, plutonium solutions containing uranium, fission products and other impurities are contacted with reducing agents such as sulfur dioxide, uranous ion, hydroxyl ammonium chloride, hydrogen peroxide, and ferrous ion whereby the plutoninm is reduced to its fluoride-insoluble state. The reduced plutonium is then carried out of solution by precipitating niobic oxide therein. Uranium and certain fission products remain behind in the solution. Certain other fission products precipitate along with the plutonium. Subsequently, the plutonium and fission product precipitates are redissolved, and the solution is oxidized with oxidizing agents such as chlorine, peroxydisulfate ion in the presence of silver ion, permanganate ion, dichromate ion, ceric ion, and a bromate ion, whereby plutonium is oxidized to the fluoride-soluble state. The oxidized solution is once again treated with niobic oxide, thus precipitating the contamirant fission products along with the niobic oxide while the oxidized plutonium remains in solution. Plutonium is then recovered from the decontaminated solution.

Computer-aided engineering of semiconductor integrated circuits

NASA Astrophysics Data System (ADS)

Meindl, J. D.; Dutton, R. W.; Gibbons, J. F.; Helms, C. R.; Plummer, J. D.; Tiller, W. A.; Ho, C. P.; Saraswat, K. C.; Deal, B. E.; Kamins, T. I.

1980-07-01

Economical procurement of small quantities of high performance custom integrated circuits for military systems is impeded by inadequate process, device and circuit models that handicap low cost computer aided design. The principal objective of this program is to formulate physical models of fabrication processes, devices and circuits to allow total computer-aided design of custom large-scale integrated circuits. The basic areas under investigation are (1) thermal oxidation, (2) ion implantation and diffusion, (3) chemical vapor deposition of silicon and refractory metal silicides, (4) device simulation and analytic measurements. This report discusses the fourth year of the program.

Effect of nitrogen segregation on TED and loss of phosphorus in CZ-Si

NASA Astrophysics Data System (ADS)

Fujiwara, N.; Saito, K.; Nakabayashi, Y.; Osuman, H. I.; Toyonaga, K.; Matsumoto, S.; Sato, Y.

2002-01-01

Transient enhanced diffusion (TED) and dose loss (pile-up) are investigated for phosphorus-implanted samples covered with both oxide and nitride films. P ions were implanted into p-type (1 0 0) CZ-Si (dose 5×10 13 cm-3, 100 keV) through a chemical vapor deposition (CVD) Si 3N 4 film. For a half of samples, Si 3N 4 was etched off and SiO 2 films were grown by CVD. Both samples were annealed for 20-360 min at 700 °C. Diffusivity of P and the dose loss were estimated based on the secondary-ion mass spectrometry (SIMS) P profiles. Both Si/Si 3N 4 and Si/SiO 2 interfaces were investigated with transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). There is no significant difference in P diffusivity between the SiO 2 and Si 3N 4 films for the present annealing condition of 700 °C for 20-360 min. Regarding dose loss, a distinct different behavior was observed. In case of the SiO 2 cover film, amount of dose decreases with the annealing time. On the other hand, amount of dose decrease with annealing time up to 180 min, but is recovered for more than 180 min in case of the Si 3N 4 cover film. From TEM and EELS analyses, it is found that nitrogen segregates at the Si/Si 3N 4 interface, resulting in recovery of dose loss.

A molecular theory for nonohmicity of the ion leak across the lipid-bilayer membrane.

PubMed

Fujitani, Y; Bedeaux, D

1997-10-01

The current-voltage relationship of ion leak (i.e., ion transport involving neither special channels nor carriers) across the lipid-bilayer membrane has been observed to be log-linear above the ohmic regime. The coefficient of the linear term has been found to be universal for membranes and penetrants examined. This universality has been explained in terms of diffusion in an external field, where the ion position is described as a Markovian process. Such a diffusion picture can be questioned, however. It is also probable that a leaking ion gets over the potential barrier before experiencing sufficient random collision in the membrane, considering that each ion is surrounded with long lipid molecules aligned almost unidirectionally. As an alternative, we discuss this ion leak in terms of velocity distribution of the ions entering the membrane and density fluctuation of the lipids. We conclude that we can explain the universality without resorting to the diffusion picture.

Conductivity noise in transmembrane ion channels due to ion concentration fluctuations via diffusion.

PubMed

Mak, D O; Webb, W W

1997-03-01

A Green's function approach is developed from first principles to evaluate the power spectral density of conductance fluctuations caused by ion concentration fluctuations via diffusion in an electrolyte system. This is applied to simple geometric models of transmembrane ion channels to obtain an estimate of the magnitude of ion concentration fluctuation noise in the channel current. Pure polypeptide alamethicin forms stable ion channels with multiple conductance states in artificial phospholipid bilayers isolated onto tips of micropipettes with gigaohm seals. In the single-channel current recorded by voltage-clamp techniques, excess noise was found after the background instrumental noise and the intrinsic Johnson and shot noises were removed. The noise que to ion concentration fluctuations via diffusion was isolated by the dependence of the excess current noise on buffer ion concentration. The magnitude of the concentration fluctuation noise derived from experimental data lies within limits estimated using our simple geometric channel models. Variation of the noise magnitude for alamethicin channels in various conductance states agrees with theoretical prediction.

Observation of Li Diffusion in Cathode Sheets of Li-ion Battery by μ+SR

NASA Astrophysics Data System (ADS)

Umegaki, Izumi; Kawauchi, Shigehiro; Nozaki, Hiroshi; Sawada, Hiroshi; Nakano, Hiroyuki; Harada, Masashi; Cottrell, Stephen P.; Coomer, Fiona C.; Telling, Mark; Sugiyama, Jun

In order to know the change in Li diffusion during the operation of Li-ion batteries, we have initiated to measure Li diffusion not only in a powder sample but also in a cathode sheet with μ+SR. As the first step, we have measured μ+SR spectra on a cathode sheet, in which a mixture of a cathode material Li(Ni, Co)O2, a binder, and conducting additives is coated on an Al foil. The zero-field μ+SR spectrum exhibited a typical Kubo-Toyabe (KT) type relaxation at 100 K. By subtracting the contribution of the muons stopped in the Al foil, we found that Li+ ion starts to diffuse above 100 K in the Li(Ni, Co)O2. A self diffusion coefficient (DLi) at 300 K was estimated as 10-11 (cm2/s), which comparable with DLi (300 K) in the cathode materials previously reported. This leads to the future "in operando" measurements of DLi in Li-ion batteries.

Interstitial and Interlayer Ion Diffusion Geometry Extraction in Graphitic Nanosphere Battery Materials.

PubMed

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun; Wang, Bei; Bremer, Peer-Timo; Papka, Michael E; Curtiss, Larry A; Pascucci, Valerio

2016-01-01

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermally annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.

Interstitial and Interlayer Ion Diffusion Geometry Extraction in Graphitic Nanosphere Battery Materials

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

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun

2016-01-01

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermallymore » annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.« less

Interstitial and interlayer ion diffusion geometry extraction in graphitic nanosphere battery materials

DOE PAGES

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun; ...

2016-01-31

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermallymore » annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Lastly, our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.« less

Kinetic isotopic fractionation during diffusion of ionic species in water

NASA Astrophysics Data System (ADS)

Richter, Frank M.; Mendybaev, Ruslan A.; Christensen, John N.; Hutcheon, Ian D.; Williams, Ross W.; Sturchio, Neil C.; Beloso, Abelardo D.

2006-01-01

Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine DLi/DK,D/D,D/D,D/D,andD/D. The measured ratio of the diffusion coefficients for Li and K in water (D Li/D K = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D/D=0.99772±0.00026). This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D/D=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D/D=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.

Anomaly diffuse and dielectric relaxation in strontium doped lanthanum molybdate

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

Liu, Xiao; Fan, Huiqing, E-mail: hqfan3@163.com; Shi, Jing

2011-12-15

Highlights: Black-Right-Pointing-Pointer The anomaly diffuse and dielectric relaxation behaviors are fitted by the Cole-Cole approach. Black-Right-Pointing-Pointer The peak in the LSMO is corresponding to different oxygen ion diffusion process. Black-Right-Pointing-Pointer We first give better explanation about the strange conductivity change caused by doping. Black-Right-Pointing-Pointer The oxygen ion diffusion is due to a combination of the dipolar relaxation and the motion of ions. -- Abstract: The dielectric properties of the La{sub 2-x}Sr{sub x}Mo{sub 2}O{sub 9-{delta}} (x = 0-0.2) ceramics were investigated in the temperature range of 300-800 K. Dielectric measurement reveals that two dielectric anomalies, associated with the oxygen ion diffusion,more » exist in frequency spectrum with x = 0.5. The broad dielectric peaks in tan {delta}({omega}) can be well fitted by a modified Cole-Cole approach. When x = 0.1, only one dielectric relaxation peak is observed, corresponding to different oxygen ion diffusion processes, as distinct from the only relaxation peak in the pure La{sub 2}Mo{sub 2}O{sub 9}. The relaxation parameters {tau}{sub 0}, the dielectric relaxation strength {Delta}, and the activation energy E{sub a} were obtained. The result of this work shows that, the conductivity change caused by doping between the two phases is due to the combination of the dipolar effects and motion of ions.« less

Diffusion kinetics of the glucose/glucose oxidase system in swift heavy ion track-based biosensors

NASA Astrophysics Data System (ADS)

Fink, Dietmar; Vacik, Jiri; Hnatowicz, V.; Muñoz Hernandez, G.; Garcia Arrelano, H.; Alfonta, Lital; Kiv, Arik

2017-05-01

For understanding of the diffusion kinetics and their optimization in swift heavy ion track-based biosensors, recently a diffusion simulation was performed. This simulation aimed at yielding the degree of enrichment of the enzymatic reaction products in the highly confined space of the etched ion tracks. A bunch of curves was obtained for the description of such sensors that depend only on the ratio of the diffusion coefficient of the products to that of the analyte within the tracks. As hitherto none of these two diffusion coefficients is accurately known, the present work was undertaken. The results of this paper allow one to quantify the previous simulation and hence yield realistic predictions of glucose-based biosensors. At this occasion, also the influence of the etched track radius on the diffusion coefficients was measured and compared with earlier prediction.

Molecular Design of High Performance Molecular Devices Based on Direct Ab-initio Molecular Dynamics Method: Diffusion of Lithium Ion on Fluorinated Amorphous Carbon

NASA Astrophysics Data System (ADS)

Kawabata, Hiroshi; Iyama, Tetsuji; Tachikawa, Hiroto

2008-01-01

Hybrid density functional theory (DFT) calculations have been carried out for the lithium adsorbed on a fluorinated graphene surface (F-graphene, C96F24) to elucidate the effect of fluorination of amorphous carbon on the diffusion mechanism of lithium ion. Also, direct molecular orbital-molecular dynamics (MO-MD) calculation [H. Tachikawa and A. Shimizu: J. Phys. Chem. B 109 (2005) 13255] was applied to diffusion processes of the Li+ ion on F-graphene. The B3LYP/LANL2MB calculation showed that the Li+ ion is most stabilized around central position of F-graphene, and the energy was gradually instabilized for the edge region. The direct MO-MD calculations showed that the Li+ ion diffuses on the bulk surface region of F-graphite at 300 K. The nature of the interaction between Li+ and F-graphene was discussed on the basis of theoretical results.

Analysis of fluctuations in semiconductor devices

NASA Astrophysics Data System (ADS)

Andrei, Petru

The random nature of ion implantation and diffusion processes as well as inevitable tolerances in fabrication result in random fluctuations of doping concentrations and oxide thickness in semiconductor devices. These fluctuations are especially pronounced in ultrasmall (nanoscale) semiconductor devices when the spatial scale of doping and oxide thickness variations become comparable with the geometric dimensions of devices. In the dissertation, the effects of these fluctuations on device characteristics are analyzed by using a new technique for the analysis of random doping and oxide thickness induced fluctuations. This technique is universal in nature in the sense that it is applicable to any transport model (drift-diffusion, semiclassical transport, quantum transport etc.) and it can be naturally extended to take into account random fluctuations of the oxide (trapped) charges and channel length. The technique is based on linearization of the transport equations with respect to the fluctuating quantities. It is computationally much (a few orders of magnitude) more efficient than the traditional Monte-Carlo approach and it yields information on the sensitivity of fluctuations of parameters of interest (e.g. threshold voltage, small-signal parameters, cut-off frequencies, etc.) to the locations of doping and oxide thickness fluctuations. For this reason, it can be very instrumental in the design of fluctuation-resistant structures of semiconductor devices. Quantum mechanical effects are taken into account by using the density-gradient model as well as through self-consistent Poisson-Schrodinger computations. Special attention is paid to the presenting of the technique in a form that is suitable for implementation on commercial device simulators. The numerical implementation of the technique is discussed in detail and numerous computational results are presented and compared with those previously published in literature.

Characterization of Novel Thin-Films and Structures for Integrated Circuit and Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Zhao, Zhao

Thin films have been widely used in various applications. This research focuses on the characterization of novel thin films in the integrated circuits and photovoltaic techniques. The ion implanted layer in silicon can be treated as ion implanted thin film, which plays an essential role in the integrated circuits fabrication. Novel rapid annealing methods, i.e. microwave annealing and laser annealing, are conducted to activate ion dopants and repair the damages, and then are compared with the conventional rapid thermal annealing (RTA). In terms of As+ and P+ implanted Si, the electrical and structural characterization confirms that the microwave and laser annealing can achieve more efficient dopant activation and recrystallization than conventional RTA. The efficient dopant activation in microwave annealing is attributed to ion hopping under microwave field, while the liquid phase growth in laser annealing provides its efficient dopant activation. The characterization of dopants diffusion shows no visible diffusion after microwave annealing, some extent of end range of diffusion after RTA, and significant dopant diffusion after laser annealing. For photovoltaic applications, an indium-free novel three-layer thin-film structure (transparent composited electrode (TCE)) is demonstrated as a promising transparent conductive electrode for solar cells. The characterization of TCE mainly focuses on its optical and electrical properties. Transfer matrix method for optical transmittance calculation is validated and proved to be a desirable method for predicting transmittance of TCE containing continuous metal layer, and can estimate the trend of transmittance as the layer thickness changes. TiO2/Ag/TiO2 (TAgT) electrode for organic solar cells (OSCs) is then designed using numerical simulation and shows much higher Haacke figure of merit than indium tin oxide (ITO). In addition, TAgT based OSC shows better performance than ITO based OSC when compatible hole transfer layer is employed. The electrical and structural characterization of hole transfer layers (HTLs) in OSCs reveals MoO3 is the compatible HTL for TAgT anode. In the end, the reactive ink printed Ag film for solar cell contact application is studied by characterizing its electromigration lifetime. A percolative model is proposed and validated for predicting the resistivity and lifetime of printed Ag thin films containing porous structure.

Enhanced electrochemical performance of nickel-cobalt-oxide@reduced graphene oxide//activated carbon asymmetric supercapacitors by the addition of a redox-active electrolyte.

PubMed

Lamiel, Charmaine; Lee, Yong Rok; Cho, Moo Hwan; Tuma, Dirk; Shim, Jae-Jin

2017-12-01

Supercapacitors are an emerging energy-storage system with a wide range of potential applications. In this study, highly porous nickel-cobalt-oxide@reduced graphene oxide (Ni-Co-O@RGO-s) nanosheets were synthesized as an active material for supercapacitors using a surfactant-assisted microwave irradiation technique. The RGO-modified nanocomposite showed a larger specific area, better conductivity, and lower resistivity than the unmodified nanocomposite because the RGO facilitated faster ion diffusion/transport for improved redox activity. The synergistic effect of Ni-Co-O@RGO-s resulted in a high capacitance of 1903Fg -1 (at 0.8Ag -1 ) in a mixed KOH/redox active K 3 Fe(CN) 6 electrolyte. The asymmetric Ni-Co-O@RGO-s//AC supercapacitor device yielded a high energy density and power density of 39Whkg -1 and 7500Wkg -1 , respectively. The porous structure and combination of redox couples from both the electrode and electrolyte provided a highly synergistic effect, which improved the performance of the supercapacitor device. Copyright © 2017 Elsevier Inc. All rights reserved.

Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO3 Prepared by Atomic Layer Deposition.

PubMed

Onn, Tzia Ming; Monai, Matteo; Dai, Sheng; Fonda, Emiliano; Montini, Tiziano; Pan, Xiaoqing; Graham, George W; Fornasiero, Paolo; Gorte, Raymond J

2018-04-11

The concept of self-regenerating or "smart" catalysts, developed to mitigate the problem of supported metal particle coarsening in high-temperature applications, involves redispersing large metal particles by incorporating them into a perovskite-structured support under oxidizing conditions and then exsolving them as small metal particles under reducing conditions. Unfortunately, the redispersion process does not appear to work in practice because the surface areas of the perovskite supports are too low and the diffusion lengths for the metal ions within the bulk perovskite too short. Here, we demonstrate reversible activation upon redox cycling for CH 4 oxidation and CO oxidation on Pd supported on high-surface-area LaFeO 3 , prepared as a thin conformal coating on a porous MgAl 2 O 4 support using atomic layer deposition. The LaFeO 3 film, less than 1.5 nm thick, was shown to be initially stable to at least 900 °C. The activated catalysts exhibit stable catalytic performance for methane oxidation after high-temperature treatment.

Diffusion reaction of oxygen in HfO2/SiO2/Si stacks.

PubMed

Ferrari, S; Fanciulli, M

2006-08-03

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.

Method of doping interconnections for electrochemical cells

DOEpatents

Pal, Uday B.; Singhal, Subhash C.; Moon, David M.; Folser, George R.

1990-01-01

A dense, electronically conductive interconnection layer 26 is bonded on a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) forming a layer of oxide particles of at least one of the metals Ca, Sr, Co, Ba or Mg on a part 24 of a first surface of the air electrode 16, (B) heating the electrode structure, (C) applying a halide vapor containing at least lanthanum halide and chromium halide to the first surface and applying a source of oxygen to a second opposite surface of the air electrode so that they contact at said first surface, to cause a reaction of the oxygen and halide and cause a dense lanthanum-chromium oxide structure to grow, from the first electrode surface, between and around the oxide particles, where the metal oxide particles get incoporated into the lanthanum-chromium oxide structure as it grows thicker with time, and the metal ions in the oxide particles diffuse into the bulk of the lanthamum-chromium oxide structure, to provide a dense, top, interconnection layer 26 on top of the air electrode 16. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

High-Performanced Cathode with a Two-Layered R-P Structure for Intermediate Temperature Solid Oxide Fuel Cells.

PubMed

Huan, Daoming; Wang, Zhiquan; Wang, Zhenbin; Peng, Ranran; Xia, Changrong; Lu, Yalin

2016-02-01

Driven by the mounting concerns on global warming and energy crisis, intermediate temperature solid-oxide fuel cells (IT-SOFCs) have attracted special attention for their high fuel efficiency, low toxic gas emission, and great fuel flexibility. A key obstacle to the practical operation of IT-SOFCs is their sluggish oxygen reduction reaction (ORR) kinetics. In this work, we applied a new two-layered Ruddlesden-Popper (R-P) oxide, Sr3Fe2O7-δ (SFO), as the material for oxygen ion conducting IT-SOFCs. Density functional theory calculation suggested that SFO has extremely low oxygen ion formation energy and considerable energy barrier for O(2-) diffusion. Unfortunately, the stable SrO surface of SFO was demonstrated to be inert to O2 adsorption and dissociation reaction, and thus restricts its catalytic activity toward ORR. Based on this observation, Co partially substituted SFO (SFCO) was then synthesized and applied to improve its surface vacancy concentration to accelerate the oxygen adsorptive reduction reaction rate. Electrochemical performance results suggested that the cell using the SFCO single phase cathode has a peak power density of 685 mW cm(-2) at 650 °C, about 15% higher than those when using LSCF cathode. Operating at 200 mA cm(-2), the new cell using SFCO is quite stable within the 100-h' test.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode.

PubMed

Shinde, Pravin S; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-31

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr(4+) ions from ZrO2 UL and Sn(4+) ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

NASA Astrophysics Data System (ADS)

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

Comment on ``Oxidation of alloys containing aluminum and diffusion in Al2O3'' [J. Appl. Phys. 95, 3217 (2004)

NASA Astrophysics Data System (ADS)

Åkermark, Torbjörn

2005-06-01

The introduction of AlO as the diffusing species can be seen as an attempt to bridge the gap between the two scientific communities: those working on the oxidation of metals and those working on the oxidation of silicon. The attempt is, however, not successful and would have been more successful if the Wagner theory [O. Wagner, Z. Phys. Chem. Abt. B 21, 25 (1993)] would have been used to evaluate the mechanisms. There is also a lack of agreement with the two-stage oxidation experiment, oxidation first in O16 and then in O18. The experimental O18 profile in the oxides formed cannot be explained by the diffusion of AlO, so it is unlikely that AlO is the diffusing species during oxidation.

Building 1D resonance broadened quasilinear (RBQ) code for fast ions Alfvénic relaxations

NASA Astrophysics Data System (ADS)

Gorelenkov, Nikolai; Duarte, Vinicius; Berk, Herbert

2016-10-01

The performance of the burning plasma is limited by the confinement of superalfvenic fusion products, e.g. alpha particles, which are capable of resonating with the Alfvénic eigenmodes (AEs). The effect of AEs on fast ions is evaluated using a resonance line broadened diffusion coefficient. The interaction of fast ions and AEs is captured for cases where there are either isolated or overlapping modes. A new code RBQ1D is being built which constructs diffusion coefficients based on realistic eigenfunctions that are determined by the ideal MHD code NOVA. The wave particle interaction can be reduced to one-dimensional dynamics where for the Alfvénic modes typically the particle kinetic energy is nearly constant. Hence to a good approximation the Quasi-Linear (QL) diffusion equation only contains derivatives in the angular momentum. The diffusion equation is then one dimensional that is efficiently solved simultaneously for all particles with the equation for the evolution of the wave angular momentum. The evolution of fast ion constants of motion is governed by the QL diffusion equations which are adapted to find the ion distribution function.

Three dimensional electrochemical simulation of solid oxide fuel cell cathode based on microstructure reconstructed by marching cubes method

NASA Astrophysics Data System (ADS)

He, An; Gong, Jiaming; Shikazono, Naoki

2018-05-01

In the present study, a model is introduced to correlate the electrochemical performance of solid oxide fuel cell (SOFC) with the 3D microstructure reconstructed by focused ion beam scanning electron microscopy (FIB-SEM) in which the solid surface is modeled by the marching cubes (MC) method. Lattice Boltzmann method (LBM) is used to solve the governing equations. In order to maintain the geometries reconstructed by the MC method, local effective diffusivities and conductivities computed based on the MC geometries are applied in each grid, and partial bounce-back scheme is applied according to the boundary predicted by the MC method. From the tortuosity factor and overpotential calculation results, it is concluded that the MC geometry drastically improves the computational accuracy by giving more precise topology information.

Ultra-Shallow Depth Profiling of Arsenic Implants in Silicon by Hydride Generation-Inductively Coupled Plasma Atomic Emission Spectrometry

NASA Astrophysics Data System (ADS)

Matsubara, Atsuko; Kojima, Hisao; Itoga, Toshihiko; Kanehori, Keiichi

1995-08-01

High resolution depth profiling of arsenic (As) implanted into silicon wafers by a chemical technique is described. Silicon wafers are precisely etched through repeated oxidation by hydrogen peroxide solution and dissolution of the oxide by hydrofluoric acid solution. The etched silicon thickness is determined by inductively-coupled plasma atomic emission spectrometry (ICP-AES). Arsenic concentration is determined by hydride generation ICP-AES (HG-ICP-AES) with prereduction using potassium iodide. The detection limit of As in a 4-inch silicon wafer is 2.4×1018 atoms/cm3. The etched silicon thickness is controlled to less than 4±2 atomic layers. Depth profiling of an ultra-shallow As diffusion layer with the proposed method shows good agreement with profiling using the four-probe method or secondary ion mass spectrometry.

The structure feature of layered M1/3TiNbO5 (M=Fe, Ce) and their photocatalytic oxidization performance for ethyl mercaptan

NASA Astrophysics Data System (ADS)

Dong, Rui; Wang, Yuan; Wang, Ningning; Xu, Lei; He, Jie; Wu, Shanshan; Lan, Yunxiang; Hu, Jinsong

2016-09-01

Layered photocatalytic materials M1/3TiNbO5 (M = Fe, Ce) were prepared by ion-exchange of KTiNbO5 with M(NO3)3. The parent KTiNbO5 was synthesized with titanium (IV) isopropoxide and niobium oxalate by a novel polymerized complex (PC) method. The micro-structures and spectral response features of the as-prepared samples were characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), laser Raman spectroscopy (LRS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The results revealed that there was a significant interaction between the interlayer cation and the terminal Nbdbnd O (Tidbnd O) bond in the NbO6 (TiO6) unit of the laminates. Photocatalytic performance was evaluated in oxidation of ethyl mercaptan under natural and UV light irradiation. It can be deduced that the photocatalytic oxidization performance can be directly affected by the characteristics of the interlayer cations.

Effects of fluoride residue on thermal stability in Cu/porous low-k interconnects

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

Kobayashi, Y.; Ozaki, S.; Nakamura, T.

2014-06-19

We have investigated the effects of fluoride residue on the thermal stability of a Cu/barrier metal (BM)/porous low-k film (k < 2.3) structure. We confirmed that the Cu agglomerated more on a BM/inter layer dielectric (ILD) with a fluoride residue. To consider the effect of fluoride residue on Cu agglomeration, the structural state at the Cu/BM interface was evaluated with a cross-section transmission electron microscope (TEM) and atomic force microscope (AFM). In addition, the chemical bonding state at the Cu/BM interface was evaluated with the interface peeling-off method and X-ray photoelectron spectroscopy (XPS). Moreover, we confirmed the ionization of fluoridemore » residue and oxidation of Cu with fluoride and moisture to clarify the effect of fluoride residue on Cu. Our experimental results indicated that the thermal stability in Cu/porous low-k interconnects was degraded by enhancement of Cu oxidation with fluoride ions diffusion as an oxidizing catalyst.« less

Crystal Structure and Transport Properties of Oxygen-Deficient Perovskite Sr 0.9Y 0.1CoO 3-δ

DOE PAGES

Yang, Tianrang; Mattick, Victoria F.; Chen, Yan; ...

2018-01-29

The present work reports a systematic study on temperature-dependent local crystal structure, oxygen stoichiometry, and electrical/electrochemical properties of an oxygen-deficient Sr 0.9Y 0.1CoO 3-δ (SYC10) perovskite using variable-temperature neutron diffraction (VTND), thermal gravimetric analysis, and electrical/electrochemical methods, respectively. The VTND reveals that the crystal symmetry of SYC10 remains P4/mmm tetragonal up to 900 °C. The tetragonal symmetry reflects the net effects of temperature and oxygen stoichiometry on crystal symmetry. The observed p-type electronic conductivity behavior originates from the charge-ordering between the two distinctive Co-sites. The partial oxide-ion conductivity and diffusivity obtained from oxygen permeation measurements are 2.3 × 10 –2more » S cm –1 and 7.98 × 10–8 cm 2/s at 800 °C in air, respectively. The electrochemical oxygen reduction reaction kinetics of the SYC10 cathode is primarily limited by the charge-transfer process at low temperatures (600–650 °C) and oxide-ion migration from the cathode into the electrolyte at high temperatures (700–800 °C).« less

Highly enhanced low temperature discharge capacity of LiNi1/3Co1/3Mn1/3O2 with lithium boron oxide glass modification

NASA Astrophysics Data System (ADS)

Tan, ShuangYuan; Wang, Lei; Bian, Liang; Xu, JinBao; Ren, Wei; Hu, PengFei; Chang, AiMin

2015-03-01

Although lithium ion battery is known to be an excellent renewable energy provider in electronic markets further application of it has been limited by its notoriously poor performance at low temperature, especially below -20 °C. In this paper, the electrochemical performance of the LiNi1/3Co1/3Mn1/3O2 cathode materials coated by lithium boron oxide (LBO) glass was investigated at a temperature range from 20 to -40 °C. The results show that the LBO coating not only helps to improve the discharge capacity of LiNi1/3Co1/3Mn1/3O2 at room temperature but also increase the discharge capacity retention of the LiNi1/3Co1/3Mn1/3O2 from 22.5% to 57.8% at -40 °C. Electrochemical impedance spectra results reveal that the LBO coating plays an important role in reducing the charge-transfer resistance on the electrolyte-electrode interfaces and improving lithium ion diffusion coefficients. The mechanism associated with the change of the structure and electrical properties are discussed in detail.

Facile synthesis of multi-shell structured binary metal oxide powders with a Ni/Co mole ratio of 1:2 for Li-Ion batteries

NASA Astrophysics Data System (ADS)

Choi, Seung Ho; Park, Sun Kyu; Lee, Jung-Kul; Kang, Yun Chan

2015-06-01

Multi-shell structured binary transition metal oxide powders with a Ni/Co mole ratio of 1:2 are prepared by a simple spray drying process. Precursor powder particles prepared by spray drying from a spray solution of citric acid and ethylene glycol have completely spherical shape, fine size, and a narrow size distribution. The precursor powders turn into multi-shell powders after a post heat-treatment at temperatures between 250 and 800 °C. The multi-shell structured powders are formed by repeated combustion and contraction processes. The multi-shell powders have mixed crystal structures of Ni1-xCo2O4-x and NiO phases regardless of the post-treatment temperature. The reversible capacities of the powders post-treated at 250, 400, 600, and 800 °C after 100 cycles are 584, 913, 808, and 481 mA h g-1, respectively. The low charge transfer resistance and high lithium ion diffusion rate of the multi-shell powders post-treated at 400 °C with optimum grain size result in superior electrochemical properties even at high current densities.

Crystal Structure and Transport Properties of Oxygen-Deficient Perovskite Sr 0.9Y 0.1CoO 3-δ

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

Yang, Tianrang; Mattick, Victoria F.; Chen, Yan

The present work reports a systematic study on temperature-dependent local crystal structure, oxygen stoichiometry, and electrical/electrochemical properties of an oxygen-deficient Sr 0.9Y 0.1CoO 3-δ (SYC10) perovskite using variable-temperature neutron diffraction (VTND), thermal gravimetric analysis, and electrical/electrochemical methods, respectively. The VTND reveals that the crystal symmetry of SYC10 remains P4/mmm tetragonal up to 900 °C. The tetragonal symmetry reflects the net effects of temperature and oxygen stoichiometry on crystal symmetry. The observed p-type electronic conductivity behavior originates from the charge-ordering between the two distinctive Co-sites. The partial oxide-ion conductivity and diffusivity obtained from oxygen permeation measurements are 2.3 × 10 –2more » S cm –1 and 7.98 × 10–8 cm 2/s at 800 °C in air, respectively. The electrochemical oxygen reduction reaction kinetics of the SYC10 cathode is primarily limited by the charge-transfer process at low temperatures (600–650 °C) and oxide-ion migration from the cathode into the electrolyte at high temperatures (700–800 °C).« less

Modeling of Pickup Ion Distributions in the Halley Cometo-Sheath: Empirical Rates of Ionization, Diffusion, Loss and Creation of Fast Neutral Atoms

NASA Technical Reports Server (NTRS)

Huddleston, D.; Neugebauer, M.; Goldstein, B.

1994-01-01

The shape of the velocity distribution of water-group ions observed by the Giotto ion mass spectrometer on its approach to comet Halley is modeled to derive empirical values for the rates on ionization, energy diffusion, and loss in the mid-cometosheath.

Threshold for ion movements in wood cell walls below fiber saturation observed by X-ray fluorescence microscopy (XFM)

Treesearch

Samuel L. Zelinka; Sophie-Charlotte Gleber; Stefan Vogt; Gabriela M. Rodriguez Lopez; Joseph E. Jakes

2015-01-01

Diffusion of chemicals and ions through the wood cell wall plays an important role in wood damage mechanisms. In the present work, free diffusion of ions through wood secondary walls and middle lamellae has been investigated as a function of moisture content (MC) and anatomical direction. Various ions (K, Cl, Zn, Cu) were injected into selected regions of 2 ìm thick...

The dependence of nano-contact magnetoresistance on the bulk scattering spin asymmetry in CoFe alloys with oxidation impurities

NASA Astrophysics Data System (ADS)

Shiokawa, Yohei; Jung, JinWon; Otsuka, Takahiko; Sahashi, Masashi

2015-08-01

Nano-contact magnetoresistance (NCMR) spin-valves (SVs) using an AlOx nano-oxide-layer (NOL) have numerous nanocontacts in the thin AlOx oxide layer. The NCMR theoretically depends on the bulk scattering spin asymmetry ( β) of the ferromagnetic material in the nanocontacts. To determine the relationship between NCMR and β, we investigated the dependence of NCMR on the composition of the ferromagnetic material Co1-xFex. The samples were annealed at 270 °C and 380 °C to enhance the MR ratio. For both annealing temperatures, the magnetorsistance ratio in the low-resistance area product region at less than 1 Ω μm2 was maximized for Co0.5Fe0.5. To evaluate β exactly, we fabricated current-perpendicular-to-plane giant magnetoresistance SVs with Co1-xFex/Cu/Co1-xFex layers and used Valet and Fert's theory to solve the diffusion equation of the spin accumulation for a ferromagnetic layer/non-ferromagnetic layer of five layers with a finite diffusion length. The evaluated β for Co1-xFex was also maximized for Co0.5Fe0.5. Additionally, to determine the difference between the experimental MR ratio of NCMR SVs and the theoretical MR ratio, we fabricated Co0.5Fe0.5 with oxygen impurities and estimated the decrease in β with increasing oxygen impurity concentration. Our Co0.5Fe0.5 nano-contacts fabricated using ion-assisted oxidation may contain oxygen impurities, and the oxygen impurities might cause a decrease in β and the MR ratio.

Pickup protons and water ions at Comet Halley - Comparisons with Giotto observations

NASA Astrophysics Data System (ADS)

Ye, G.; Cravens, T. E.; Gombosi, T. I.

1993-02-01

The cometary ion pickup process along the sun-comet line at Comet Halley is investigated using a quasi-linear diffusion model including both pitch angle and energy diffusion, adiabatic compression, and convective motion with the solar wind flow. The model results are compared with energetic ion distributions observed by instruments on board the Giotto spacecraft. The observed power spectrum index of magnetic turbulence (gamma) is 2-2.5. The present simulation shows that when gamma was 2, the calculated proton distributions were much more isotropic than the observed ones. The numerical solutions of the quasi-linear diffusion equations show that the isotropization of the pickup ion distribution, particularly at the pickup velocity, is not complete even close to the bow shock. Given the observed turbulence level, quasi-linear theory yields pickup ion energy distributions that agree with the observed ones quite well and easily produces energetic ions with energies up to hundreds of keV.

Ion beam analysis of diffusion in heterogeneous materials

NASA Astrophysics Data System (ADS)

Clough, A. S.; Jenneson, P. M.

1998-04-01

Ion-beam analysis has been applied to a variety of problems involving diffusion in heterogeneous materials. An energy loss technique has been used to study both the diffusion of water and the surface segregation of fluoropolymers in polymeric matrices. A scanning micro-beam technique has been developed to allow water concentrations in hydrophilic polymers and cements to be measured together with associated solute elements. It has also been applied to the diffusion of shampoo into hair.

Effect of dual-dielectric hydrogen-diffusion barrier layers on the performance of low-temperature processed transparent InGaZnO thin-film transistors

NASA Astrophysics Data System (ADS)

Tari, Alireza; Wong, William S.

2018-02-01

Dual-dielectric SiOx/SiNx thin-film layers were used as back-channel and gate-dielectric barrier layers for bottom-gate InGaZnO (IGZO) thin-film transistors (TFTs). The concentration profiles of hydrogen, indium, gallium, and zinc oxide were analyzed using secondary-ion mass spectroscopy characterization. By implementing an effective H-diffusion barrier, the hydrogen concentration and the creation of H-induced oxygen deficiency (H-Vo complex) defects during the processing of passivated flexible IGZO TFTs were minimized. A bilayer back-channel passivation layer, consisting of electron-beam deposited SiOx on plasma-enhanced chemical vapor-deposition (PECVD) SiNx films, effectively protected the TFT active region from plasma damage and minimized changes in the chemical composition of the semiconductor layer. A dual-dielectric PECVD SiOx/PECVD SiNx gate-dielectric, using SiOx as a barrier layer, also effectively prevented out-diffusion of hydrogen atoms from the PECVD SiNx-gate dielectric to the IGZO channel layer during the device fabrication.

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.

Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications

NASA Astrophysics Data System (ADS)

Pilo, Alice L.; Zhao, Feifei; McLuckey, Scott A.

2017-06-01

Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides. [Figure not available: see fulltext.

SiGe-on-insulator fabricated via germanium condensation following high-fluence Ge+ ion implantation

NASA Astrophysics Data System (ADS)

Anthony, R.; Haddara, Y. M.; Crowe, I. F.; Knights, A. P.

2017-08-01

Germanium condensation is demonstrated using a two-step wet oxidation of germanium implanted Silicon-On-Insulator (SOI). Samples of 220 nm thick SOI are implanted with a nominal fluence of 5 × 1016 cm-2 Ge+ at an energy of 33 keV. Primary post-implantation wet oxidation is performed initially at 870 °C for 70 min, with the aim of capping the sample without causing significant dose loss via Ge evaporation through the sample surface. This is followed by a secondary higher temperature wet oxidation at either 900 °C, 1000 °C, or 1080 °C. The germanium retained dose and concentration profile, and the oxide thickness is examined after primary oxidation, and various secondary oxidation times, using Rutherford backscattering analysis. A mixed SiGe oxide is observed to form during the primary oxidation followed by a pure silicon oxide after higher temperature secondary oxidation. The peak germanium concentration, which varies with secondary oxidation condition, is found to range from 43 at. % to 95 at. %, while the FWHM of the Ge profile varies from 13 to 5 nm, respectively. It is also observed that both the diffusion of germanium and the rate of oxidation are enhanced at 870 and 900 °C compared to equilibrium expectations. Transmission electron microscopy of a representative sample with secondary oxidation at 1080 °C for 20 min shows that the SiGe layer is crystalline in nature and seeded from the underlying silicon. Raman spectroscopy is used to determine residual strain in the SiGe region following secondary oxidation. The strain is compressive in nature and increases with Ge concentration to a maximum of approximately 1% in the samples probed. In order to elucidate the physical mechanisms, which govern the implantation-condensation process, we fit the experimental profiles of the samples with a model that uses a modified segregation boundary condition; a modified linear rate constant for the oxidation; and an enhanced diffusion coefficient of germanium where the enhancement is inversely proportional to the temperature and decays with increasing time. Comparison of the modeled and experimental results shows reasonable agreement and allows conclusions to be made regarding the dominant physical mechanisms, despite the semi-empirical nature of the model used.

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

DOE PAGES

Tomkiewicz, Alex C.; Tamimi, Mazin A.; Huq, Ashfia; ...

2015-03-02

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of threemore » Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

On the Ageing of High Energy Lithium-Ion Batteries—Comprehensive Electrochemical Diffusivity Studies of Harvested Nickel Manganese Cobalt Electrodes

PubMed Central

Jaguemont, Joris; Van Den Bossche, Peter; Omar, Noshin; Van Mierlo, Joeri

2018-01-01

This paper examines the impact of the characterisation technique considered for the determination of the Li+ solid state diffusion coefficient in uncycled as in cycled Nickel Manganese Cobalt oxide (NMC) electrodes. As major characterisation techniques, Cyclic Voltammetry (CV), Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) were systematically investigated. Li+ diffusion coefficients during the lithiation process of the uncycled and cycled electrodes determined by CV at 3.71 V are shown to be equal to 3.48×10−10 cm2·s−1 and 1.56×10−10 cm2·s−1 , respectively. The dependency of the Li+ diffusion with the lithium content in the electrodes is further studied in this paper with GITT and EIS. Diffusion coefficients calculated by GITT and EIS characterisations are shown to be in the range between 1.76×10−15 cm2·s−1 and 4.06×10−12 cm2·s−1, while demonstrating the same decreasing trend with the lithiation process of the electrodes. For both electrode types, diffusion coefficients calculated by CV show greater values compared to those determined by GITT and EIS. With ageing, CV and EIS techniques lead to diffusion coefficients in the electrodes at 3.71 V that are decreasing, in contrast to GITT for which results indicate increasing diffusion coefficient. After long-term cycling, ratios of the diffusion coefficients determined by GITT compared to CV become more significant with an increase about 1 order of magnitude, while no significant variation is seen between the diffusion coefficients calculated from EIS in comparison to CV. PMID:29360787

On the Ageing of High Energy Lithium-Ion Batteries-Comprehensive Electrochemical Diffusivity Studies of Harvested Nickel Manganese Cobalt Electrodes.

PubMed

Capron, Odile; Gopalakrishnan, Rahul; Jaguemont, Joris; Van Den Bossche, Peter; Omar, Noshin; Van Mierlo, Joeri

2018-01-23

This paper examines the impact of the characterisation technique considered for the determination of the L i + solid state diffusion coefficient in uncycled as in cycled Nickel Manganese Cobalt oxide (NMC) electrodes. As major characterisation techniques, Cyclic Voltammetry (CV), Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) were systematically investigated. L i + diffusion coefficients during the lithiation process of the uncycled and cycled electrodes determined by CV at 3.71 V are shown to be equal to 3 . 48 × 10 - 10 cm 2 ·s - 1 and 1 . 56 × 10 - 10 cm 2 ·s - 1 , respectively. The dependency of the L i + diffusion with the lithium content in the electrodes is further studied in this paper with GITT and EIS. Diffusion coefficients calculated by GITT and EIS characterisations are shown to be in the range between 1 . 76 × 10 - 15 cm 2 ·s - 1 and 4 . 06 × 10 - 12 cm 2 ·s - 1 , while demonstrating the same decreasing trend with the lithiation process of the electrodes. For both electrode types, diffusion coefficients calculated by CV show greater values compared to those determined by GITT and EIS. With ageing, CV and EIS techniques lead to diffusion coefficients in the electrodes at 3.71 V that are decreasing, in contrast to GITT for which results indicate increasing diffusion coefficient. After long-term cycling, ratios of the diffusion coefficients determined by GITT compared to CV become more significant with an increase about 1 order of magnitude, while no significant variation is seen between the diffusion coefficients calculated from EIS in comparison to CV.

Multicomponent diffusion in basaltic melts at 1350 °C

NASA Astrophysics Data System (ADS)

Guo, Chenghuan; Zhang, Youxue

2018-05-01

Nine successful diffusion couple experiments were conducted in an 8-component SiO2-TiO2-Al2O3-FeO-MgO-CaO-Na2O-K2O system at ∼1350 °C and at 1 GPa, to study multicomponent diffusion in basaltic melts. At least 3 traverses were measured to obtain diffusion profiles for each experiment. Multicomponent diffusion matrix at 1350 °C was obtained by simultaneously fitting diffusion profiles of diffusion couple experiments. Furthermore, in order to better constrain the diffusion matrix and reconcile mineral dissolution data, mineral dissolution experiments in the literature and diffusion couple experiments from this study, were fit together. All features of diffusion profiles in both diffusion couple and mineral dissolution experiments were well reproduced by the diffusion matrix. Diffusion mechanism is inferred from eigenvectors of the diffusion matrix, and it shows that the diffusive exchange between network-formers SiO2 and Al2O3 is the slowest, the exchange of SiO2 with other oxide components is the second slowest with an eigenvalue that is only ∼10% larger, then the exchange between divalent oxide components and all the other oxide components is the third slowest with an eigenvalue that is twice the smallest eigenvalue, then the exchange of FeO + K2O with all the other oxide components is the fourth slowest with an eigenvalue that is 5 times the smallest eigenvalue, then the exchange of MgO with FeO + CaO is the third fastest with an eigenvalue that is 6.3 times the smallest eigenvalue, then the exchange of CaO + K2O with all the other oxide components is the second fastest with an eigenvalue that is 7.5 times the smallest eigenvalue, and the exchange of Na2O with all other oxide components is the fastest with an eigenvalue that is 31 times the smallest eigenvalue. The slowest and fastest eigenvectors are consistent with those for simpler systems in most literature. The obtained diffusion matrix was successfully applied to predict diffusion profiles during mineral dissolution in basaltic melts.

Observation of High-Frequency Electrostatic Waves in the Vicinity of the Reconnection Ion Diffusion Region by the Spacecraft of the Magnetospheric Multiscale (MMS) Mission

NASA Technical Reports Server (NTRS)

Zhou, M.; Ashour-Abdalla, M.; Berchem, J.; Walker, R. J.; Liang, H.; El-Alaoui, M.; Goldstein, M. L.; Lindqvist, P.-A.; Marklund, G.; Khotyaintsev, Y. V.;

Diffusivity of dicarboxylic acids molecules to secondary organic material governed by particle phase state

NASA Astrophysics Data System (ADS)

Han, Y.; Gong, Z.; Liu, P.; de Sá, S. S.; McKinney, K. A.; Martin, S. T.

2017-12-01

Atmospheric secondary organic material (SOM) from oxidation of volatile organic compounds can exist in amorphous solid, semisolid, and liquid states depending on a range of factors such as relative humidity (RH), temperature, and reaction history. The phase state of SOM affects the dynamic exchange and reactivity between particles and gas-phase molecules. Dicarboxylic acids are ubiquitous in ambient atmosphere and the uptake of which may lead to substantial changes in hygroscopicity, absorption property, and light scattering of aerosol particles. This study investigates the diffusivity of dicarboxylic acids to the matrix of SOM particles. SOM was generated from dark ozonolysis of a-pinene in Harvard Environmental Chamber. The produced SOM particles were passed through an ozone scrubber to remove gas-phase chemistry before being led into a flask reactor, where gas-phase dicarboxylic acid was injected continuously and RH was varied from 5% to 85%. The probe dicarboxylic acids molecules including malonic acid and a-ketoglutaric acid have been investigated for the uptake to SOM particles. Organic composition in the outflow of the flask was measured with a high-resolution time-of-flight aerosol mass spectrometer. The mass fractions of tracer ions in total organic mass for both malonic acid and a-ketoglutaric acid increased substantially with the increase of RH values. The tracer ions of malonic acid were also more abundant in a-pinene SOM particles with increased gas-phase concentrations. These results suggest that the diffusion of the studied dicarboxylic acids molecules to a-pinene SOM particles was enhanced at increased RH values, which is possibly due to the phase transition of a-pinene SOM particles from non-liquid to liquid states. Therefore, particle phase state may be an important factor governing the diffusivity of dicarboxylic acids molecules to a-pinene SOM. Further dicarboxylic acids with various functional groups will be investigated to understand the effects of volatility and structure on their diffusivity.

Equivalence of two approaches for modeling ion permeation through a transmembrane channel with an internal binding site

NASA Astrophysics Data System (ADS)

Zhou, Huan-Xiang

2011-04-01

Ion permeation through transmembrane channels has traditionally been modeled using two different approaches. In one approach, the translocation of the permeant ion through the channel pore is modeled as continuous diffusion and the rate of ion transport is obtained from solving the steady-state diffusion equation. In the other approach, the translocation of the permeant ion through the pore is modeled as hopping along a discrete set of internal binding sites and the rate of ion transport is obtained from solving a set of steady-state rate equations. In a recent work [Zhou, J. Phys. Chem. Lett. 1, 1973 (2010)], the rate constants for binding to an internal site were further calculated by modeling binding as diffusion-influenced reactions. That work provided the foundation for bridging the two approaches. Here we show that, by representing a binding site as an energy well, the two approaches indeed give the same result for the rate of ion transport.

Impedance and dielectric relaxation spectroscopy studies on the calcium modified Na0.5Bi0.44Ca0.06TiO2.97 ceramics

NASA Astrophysics Data System (ADS)

Wang, W. G.; Li, X. Y.

2017-12-01

Na0.5Bi0.44Ca0.06TiO2.97 ceramics were synthetized by conventional solid-state reaction. XRD measurement analysis shows that the Na0.5Bi0.44Ca0.06TiO2.97 sample is the single perovskite structures. The oxide ion conductivity of the Na0.5Bi0.44Ca0.06TiO2.97 sample was investigated by AC impedance spectroscopy measurement. The bulk conductivity of Na0.5Bi0.44Ca0.06TiO2.97 sample can arrive at 2.22×10-4 S/cm at 573 K in air atmosphere. By changing measuring temperature of dielectric frequency spectroscopy measurement, the activation energy E and pre-exponential factor τ0 are E= 0.81 eV, τ0=1.5×10-13 s for Na0.5Bi0.44Ca0.06TiO2.97 sample, respectively. Judging from the relaxation parameters, the dielectric loss peaks correspond to oxide ion via vacancies diffusion in Na0.5Bi0.44Ca0.06TiO2.97 sample. Compared with the same dopant amount Na0.5Bi0.5Ti0.94Mg0.06O2.94 compound, the better oxygen vacancy mobility and larger specific free volume Vsf might be responsible for the favourable oxide ion conductivity in the Na0.5Bi0.44Ca0.06TiO2.97 sample, indicating that calcium modified Na0.5Bi0.5TiO3 materials are promising for intermediate-temperature solid electrochemical devices.

Design-for-manufacture of gradient-index optical systems using time-varying boundary condition diffusion

NASA Astrophysics Data System (ADS)

Harkrider, Curtis Jason

2000-08-01

The incorporation of gradient-index (GRIN) material into optical systems offers novel and practical solutions to lens design problems. However, widespread use of gradient-index optics has been limited by poor correlation between gradient-index designs and the refractive index profiles produced by ion exchange between glass and molten salt. Previously, a design-for- manufacture model was introduced that connected the design and fabrication processes through use of diffusion modeling linked with lens design software. This project extends the design-for-manufacture model into a time- varying boundary condition (TVBC) diffusion model. TVBC incorporates the time-dependent phenomenon of melt poisoning and introduces a new index profile control method, multiple-step diffusion. The ions displaced from the glass during the ion exchange fabrication process can reduce the total change in refractive index (Δn). Chemical equilibrium is used to model this melt poisoning process. Equilibrium experiments are performed in a titania silicate glass and chemically analyzed. The equilibrium model is fit to ion concentration data that is used to calculate ion exchange boundary conditions. The boundary conditions are changed purposely to control the refractive index profile in multiple-step TVBC diffusion. The glass sample is alternated between ion exchange with a molten salt bath and annealing. The time of each diffusion step can be used to exert control on the index profile. The TVBC computer model is experimentally verified and incorporated into the design- for-manufacture subroutine that runs in lens design software. The TVBC design-for-manufacture model is useful for fabrication-based tolerance analysis of gradient-index lenses and for the design of manufactureable GRIN lenses. Several optical elements are designed and fabricated using multiple-step diffusion, verifying the accuracy of the model. The strength of multiple-step diffusion process lies in its versatility. An axicon, imaging lens, and curved radial lens, all with different index profile requirements, are designed out of a single glass composition.

Enhanced Oxygen Diffusion Within the Internal Oxidation Zone of Alloy 617 in Controlled Impurity Helium Environments from 1023 K to 1123 K (750 °C to 850 °C)

NASA Astrophysics Data System (ADS)

Gulsoy, Gokce; Was, Gary S.

2015-04-01

Alloy 617 was exposed to He-CO-CO2 environments with of either 9 or 1320 at temperatures from 1023 K to 1123 K (750 °C to 850 °C) to determine the oxygen diffusion coefficients within the internal oxidation zone of the alloy. The oxygen diffusion coefficients determined based on both intergranular and transgranular oxidation rates were several orders of magnitude greater than those reported in pure nickel and in nickel-based binary alloys, indicating that the rapid internal aluminum oxidation of Alloy 617 was primarily due to enhanced oxygen diffusion along the incoherent Al2O3-alloy interfaces. The range of activation energy values determined for oxygen diffusion associated with the intergranular aluminum oxidation was from 149.6 to 154.7 kJ/mol, and that associated with the transgranular aluminum oxidation was from 244.7 to 283.5 kJ/mol.

A Highly Hydroxide Conductive, Chemically Stable Anion Exchange Membrane, Poly(2,6 dimethyl 1,4 phenylene oxide)- b -Poly(vinyl benzyl trimethyl ammonium), for Electrochemical Applications

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

Pandey, Tara P.; Sarode, Himanshu N.; Yang, Yating

A chemically stable copolymer [poly(2,6 dimethyl 1,4 phenylene oxide)-b-poly(vinyl benzyl trimethyl ammonium)] with two ion exchange capacities, 3.2 and 2.9 meq g-1, was prepared as anion exchange membranes (AEM-3.2 and AEM-2.9). These materials showed high OH- conductivities of 138 mS.cm-1 and 106 mS.cm-1, for AEM-3.2 and AEM-2.9 respectively, at 60°C, and 95% RH. The OH- conductivity = 45 mS.cm-1 for AEM-3.2 at 60% RH and 60°C in the absence of CO2. Amongst the ions studied, only OH- is fully dissociated at high RH. The lower Ea = 10–13 kJ.mol-1 for OH- compared to F- ~ 20 kJ.mol-1 in conductivity measurements,more » and of H2O from self-diffusion coefficients suggests the presence of a Grotthuss hopping transport mechanism in OH- transport. PGSE-NMR of H2O and F- show that the membranes have low tortuosity, 1.8 and 1.2, and high water self-diffusion coefficients, 0.66 and 0.26 × 10-5 cm2.s-1, for AEM-3.2 and AEM-2.9 respectively. SAXS and TEM show that the membrane has several different sized water environments, ca. 62 nm, 20 nm, and 3.5 nm. The low water uptake, λ = 9–12, reduced swelling, and high OH- conductivity, with no chemical degradation over two weeks, suggests that the membrane is a strong candidate for electrochemical applications.« less

Li4SiO4-Based Artificial Passivation Thin Film for Improving Interfacial Stability of Li Metal Anodes.

PubMed

Kim, Ji Young; Kim, A-Young; Liu, Guicheng; Woo, Jae-Young; Kim, Hansung; Lee, Joong Kee

2018-03-14

An amorphous SiO 2 (a-SiO 2 ) thin film was developed as an artificial passivation layer to stabilize Li metal anodes during electrochemical reactions. The thin film was prepared using an electron cyclotron resonance-chemical vapor deposition apparatus. The obtained passivation layer has a hierarchical structure, which is composed of lithium silicide, lithiated silicon oxide, and a-SiO 2 . The thickness of the a-SiO 2 passivation layer could be varied by changing the processing time, whereas that of the lithium silicide and lithiated silicon oxide layers was almost constant. During cycling, the surface of the a-SiO 2 passivation layer is converted into lithium silicate (Li 4 SiO 4 ), and the portion of Li 4 SiO 4 depends on the thickness of a-SiO 2 . A minimum overpotential of 21.7 mV was observed at the Li metal electrode at a current density of 3 mA cm -2 with flat voltage profiles, when an a-SiO 2 passivation layer of 92.5 nm was used. The Li metal with this optimized thin passivation layer also showed the lowest charge-transfer resistance (3.948 Ω cm) and the highest Li ion diffusivity (7.06 × 10 -14 cm 2 s -1 ) after cycling in a Li-S battery. The existence of the Li 4 SiO 4 artificial passivation layer prevents the corrosion of Li metal by suppressing Li dendritic growth and improving the ionic conductivity, which contribute to the low charge-transfer resistance and high Li ion diffusivity of the electrode.

Coupled diffusion and mechanics in battery electrodes

NASA Astrophysics Data System (ADS)

Eshghinejad, Ahmadreza

We are living in a world with continuous production and consumption of energy. The energy production in the past decades has started to move away from petrochemical sources toward sustainable sources such as solar, wind and geothermal. Also, the energy consumption is further adapting to the sustainable sources. For instance, in recent years electric vehicles are growing fast that can consume sustainable electric energy stored in their batteries. In this direction, in order to further move toward sustainable energy, materials are becoming increasingly important for storing electric energy. Although, currently the technologies such as Li-ion batteries and solid-oxide fuel cells are commercially available for energy applications, improvements are crucial for the next generation of many other technologies producing or consuming sustainable energies. A critical aspect of the electrochemical activities involved in energy storage technologies such as Li-ion batteries and solid-oxide fuel cells is the diffusion of ions into the electrode materials. This process ultimately governs various functional properties of the batteries such as capacity and charging/discharging rates. The first goal of this dissertation is to develop mathematical tools to analyze the ionic diffusion and investigate its coupling with mechanics in electrodes. For this purpose, a thermodynamics-based modeling framework is developed and numerically solved using two numerical methods to analyze ionic diffusion in heterogeneous and structured electrodes. The next goal of this dissertation is to develop and analyze characterization techniques to probe the electrochemical processes at the nano-scale. To this end, the mathematical models are first employed to model a previously developed Atomic Force Microscopy based technique to probe local electrochemical activities called Electrochemical Strain Microscopy (ESM). This method probes the activities by inducing AC electric field to perturb ionic activities and measuring the surface vibrations. Different aspects of this technique are analyzed and the limitations are discussed. Such limitations moves the dissertation toward development of a new technique for probing the electrochemical activities, to overcome the previous limitations, called Scanning Thermo-ionic Microscopy (STIM). In this method, the local activities are probed by inducing AC temperature oscillations to perturb ionic activities and measuring the surface vibrations. The principle mathematical analysis of the coupled governing equations and the method of probing electrochemical activities are discussed in detail. Also, the method is implemented into the AFM hardware/software and the STIM response is confirmed using experiments on LiFePO4 and Sm-doped Ceria as well-known battery and fuel cell electrodes. The STIM method provides a clean method for analyzing energy storage materials and designing novel nano-structured materials for improved performance. Finally, conclusion of the presented work is discussed in the last chapter and the future works to continue the development of the modeling and experiments are listed.

Irradiation-induced Ag nanocluster nucleation in silicate glasses: Analogy with photography

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

Espiau de Lamaestre, R.; Fontainebleau Research Center, Corning SA, 77210 Avon; Bea, H.

2007-11-15

The synthesis of Ag nanoclusters in soda lime silicate glasses and silica was studied by optical absorption and electron spin resonance experiments under both low (gamma ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution--notably via their interaction with defects--are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: Irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolvedmore » noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which, in turn, leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence but also--and primarily--on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag{sup +} to Ag{sup 0}) as compared to gamma photon irradiation.« less

Hierarchically-structured hollow NiO nanospheres/nitrogen-doped graphene hybrid with superior capacity retention and enhanced rate capability for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chen, Jiayuan; Wu, Xiaofeng; Liu, Ya; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Tan, Qiangqiang; Chen, Yunfa

2017-12-01

A facile template-free synthesis strategy is demonstrated to fabricate nanostructured NiO/N-doped graphene hybrid, in which NiO hollow nanospheres with hierarchically mesoporous structure are tightly anchored on N-doped graphene matrix. The mesoporous shell of NiO can not only provide sufficient electrode/electrolyte contact areas to accelerate ion diffusion and electron exchange, but also efficiently mitigate the volume change that occurs during long-time reactions. Simultaneously, the reduced graphene oxide with doping nitrogen atoms are employed as effectively conductive backbone, further enhancing the electrochemical performances. When used as anodic material for lithium ion batteries, the synergistic system delivers a reversible capacity up to 1104.6 mAh g-1 after 150 cycles at a current density of 0.08 A g-1 and 422.3 mAh g-1 at a high charging rate of 4 A g-1, which is better than those of the bare counterparts and most other NiO-based materials reported in the previous literatures. The hierarchically hollow NiO nanostructure combined with N-doped graphene matrix provides a promising candidate applied in advanced anode materials for lithium ion batteries.

Solid-Solution Anion-Enhanced Electrochemical Performances of Metal Sulfides/Selenides for Sodium-Ion Capacitors: The Case of FeS2- xSe x.

PubMed

Long, Yaqiong; Yang, Jing; Gao, Xin; Xu, Xuena; Fan, Weiliu; Yang, Jian; Hou, Shifeng; Qian, Yitai

2018-04-04

Transition-metal sulfides/selenides are explored as advanced electrode materials for nonaqueous sodium-ion capacitors, using FeS 2- x Se x as an example. A solid solution of S/Se in FeS 2- x Se x allows it to combine the high capacity of FeS 2 and the good diffusion kinetics of FeSe 2 together, thereby exhibiting excellent cycle stability (∼220 mA h g -1 after 6000 cycles at 2 A g -1 ) and superior rate capability (∼210 mA h g -1 at 40 A g -1 ) within 0.8-3.0 V. These results are much better than those of FeS 2 and FeSe 2 , confirming the advantages of S/Se solid solution, as supported by EIS spectra, DFT calculations, and electronic conductivity. As FeS 2- x Se x is paired with the activated carbon (AC) as Na-ion capacitors, this device is also better than sodium-ion batteries of FeS 2- x Se x //Na 3 V 2 (PO 4 ) 3 and sodium-ion capacitors of metal oxides//AC, particularly at high rates. These results open a new door for the applications of sulfides/selenides in another device of electrochemical energy storage.

H2 Production Under Visible Light Irradiation from Aqueous Methanol Solution on CaTiO3:Cu Prepared by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Lim, Sung Nam; Song, Shin Ae; Jeong, Yong-Cheol; Kang, Hyun Woo; Park, Seung Bin; Kim, Ki Young

2017-10-01

Perovskite-type photocatalysts of CaCu x Ti1- x O3 (0 ≤ x ≤ 0.02) powder were prepared by spray pyrolysis of aqueous solution or aqueous solution with polymeric additive. The effects of the amount of copper ions doped in the photocatalyst and the precursor type on the photocatalytic activity under visible-light irradiation were investigated. The crystal structure, oxidation state, and light adsorption properties of the prepared photocatalysts were analyzed using x-ray diffraction, x-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy, respectively. The doping of copper ions in CaTiO3 allowed visible-light absorption owing to a narrowing of the band gap energy of the host material through the formation of a new donor level for copper ions. Among the doped samples prepared from the aqueous precursor, CaTiO3 doped with 1 mol.% copper ions had the highest hydrogen evolution rate (140.7 μmol g-1 h-1). Notably, the hydrogen evolution rate of the photocatalyst doped with 1 mol.% copper ions prepared from the aqueous precursor with polymeric additive (295.0 μmol g-1 h-1) was two times greater than that prepared from the aqueous precursor, due to the morphology effect.

Interconnected V2O5 nanoporous network for high-performance supercapacitors.

PubMed

Saravanakumar, B; Purushothaman, Kamatchi K; Muralidharan, G

2012-09-26

Vanadium pentoxide (V(2)O(5)) has attracted attention for supercapcitor applications because of its extensive multifunctional properties. In the present study, V(2)O(5) nanoporous network was synthesized via simple capping-agent-assisted precipitation technique and it is further annealed at different temperatures. The effect of annealing temperature on the morphology, electrochemical and structural properties, and stability upon oxidation-reduction cycling has been analyzed for supercapacitor application. We achieved highest specific capacitance of 316 F g(-1) for interconnected V(2)O(5) nanoporous network. This interconnected nanoporous network creates facile nanochannels for ion diffusion and facilitates the easy accessibility of ions. Moreover, after six hundred consecutive cycling processes the specific capacitance has changed only by 24%. A simple cost-effective preparation technique of V(2)O(5) nanoporous network with excellent capacitive behavior, energy density, and stability encourages its possible commercial exploitation for the development of high-performance supercapacitors.

Entropic contributions enhance polarity compensation for CeO2(100) surfaces

NASA Astrophysics Data System (ADS)

Capdevila-Cortada, Marçal; López, Núria

2017-03-01

Surface structure controls the physical and chemical response of materials. Surface polar terminations are appealing because of their unusual properties but they are intrinsically unstable. Several mechanisms, namely metallization, adsorption, and ordered reconstructions, can remove thermodynamic penalties rendering polar surfaces partially stable. Here, for CeO2(100), we report a complementary stabilization mechanism based on surface disorder that has been unravelled through theoretical simulations that: account for surface energies and configurational entropies; show the importance of the ion distribution degeneracy; and identify low diffusion barriers between conformations that ensure equilibration. Disordered configurations in oxides might also be further stabilized by preferential adsorption of water. The entropic stabilization term will appear for surfaces with a high number of empty sites, typically achieved when removing part of the ions in a polar termination to make the layer charge zero. Assessing the impact of surface disorder when establishing new structure-activity relationships remains a challenge.

Role of oxygen diffusion at Ni/Cr2O3 interface in intergranular oxidation of Ni-Cr alloy

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Sushko, Maria; Schreiber, Daniel; Rosso, Kevin; Bruemmer, Stephen

Certain Ni-Cr alloys used in nuclear systems experience intergranular oxidation and stress corrosion cracking when exposed to high-temperature water leading to their degradation and unexpected failure. To develop a mechanistic understanding of grain boundary oxidation processes, we proposed a mesoscale metal alloy oxidation model that combines quantum Density Functional Theory (DFT) with mesoscopic Poisson-Nernst-Planck/classical DFT. This framework encompasses the chemical specificity of elementary diffusion processes and mesoscale reactive dynamics, and allows modeling oxidation processes on experimentally relevant length scales from first principles. As a proof of concept, a preliminary model was previously employed that limited oxygen diffusion pathways to those through the oxide phase and did not allow oxygen diffusion in the alloy or across oxide/alloy interfaces. In this work, we expand the model to include oxygen diffusion pathways along Ni/Cr2O3 interfaces and demonstrate the increasing importance of such pathways for intergranular oxidation of Ni-Cr alloys with high Cr content. This work is supported by the U.S. Dept. of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Simulations are performed using PNNL Institutional Computing facility.

Breaking The Ion Frozen-in Condition Via The Non-gyrotropic Pressure Effect In Magnetic Reconnection

NASA Astrophysics Data System (ADS)

Dai, L.; Wang, C.; Angelopoulos, V.; Glassmeier, K. H.

2016-12-01

For magnetic reconnection to proceed, the frozen-in condition for both ion fluid and electron fluid in a localized diffusion region must be violated. In the framework of fluid, the frozen-in can be broken by inertial effects, thermal pressure effects, or inter-species collisions. An essential question in reconnection physics is what effect breaks the ion/electron frozen-in in the diffusion region. We present clear in-situ evidence that the off-diagonal pressure tensor, which corresponds to a non-gyrotropic pressure effect, is mainly responsible for breaking the ion frozen-in condition in reconnection. The non-gyrotropic pressure tensor is a fluid manifestation of ion demagnetization in reconnection. As our experiences indicate, we feel the need to clarify several conceptual points regarding the approach to studying diffusion region. 1) Conceptually, the ion/electron momentum equations ("ion/electron Ohm's law"), rather than the generalized Ohm's law (Rossi and Olbert,1970, equation [12.25] ), are appropriate for investigating the fronzen-in or decoupling of individual fluid species. 2) The reconnection electric field is equally explainable in terms of ion momentum or electron momentum equation.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling

NASA Astrophysics Data System (ADS)

Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Donohoe, Gregory C.; Valentine, Stephen J.

2016-03-01

Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H]2- ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H]3- ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H]2- ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H]3- ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

Oxygen Diffusion and Reaction Kinetics in Continuous Fiber Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Eckel, Andrew J.; Cawley, James D.

1999-01-01

Previous stressed oxidation tests of C/SiC composites at elevated temperatures (350 C to 1500 C) and sustained stresses (69 MPa and 172 MPa) have led to the development of a finite difference cracked matrix model. The times to failure in the samples suggest oxidation occurred in two kinetic regimes defined by the rate controlling mechanisms (i.e. diffusion controlled and reaction controlled kinetics). Microstructural analysis revealed preferential oxidation along as-fabricated, matrix microcracks and also suggested two regimes of oxidation kinetics dependent on the oxidation temperature. Based on experimental results, observation, and theory, a finite difference model was developed. The model simulates the diffusion of oxygen into a matrix crack bridged by carbon fibers. The model facilitates the study of the relative importance of temperature, the reaction rate constant, and the diffusion coefficient on the overall oxidation kinetics.

Analysis techniques for tracer studies of oxidation. M. S. Thesis Final Report

NASA Technical Reports Server (NTRS)

Basu, S. N.

1984-01-01

Analysis techniques to obtain quantitative diffusion data from tracer concentration profiles were developed. Mass balance ideas were applied to determine the mechanism of oxide growth and to separate the fraction of inward and outward growth of oxide scales. The process of inward oxygen diffusion with exchange was theoretically modelled and the effect of lattice diffusivity, grain boundary diffusivity and grain size on the tracer concentration profile was studied. The development of the tracer concentration profile in a growing oxide scale was simulated. The double oxidation technique was applied to a FeCrAl-Zr alloy using 0-18 as a tracer. SIMS was used to obtain the tracer concentration profile. The formation of lacey oxide on the alloy was discussed. Careful consideration was given to the quality of data required to obtain quantitative information.

Nitric oxide-mediated bystander signal transduction induced by heavy-ion microbeam irradiation

NASA Astrophysics Data System (ADS)

Tomita, Masanori; Matsumoto, Hideki; Funayama, Tomoo; Yokota, Yuichiro; Otsuka, Kensuke; Maeda, Munetoshi; Kobayashi, Yasuhiko

2015-07-01

In general, a radiation-induced bystander response is known to be a cellular response induced in non-irradiated cells after receiving bystander signaling factors released from directly irradiated cells within a cell population. Bystander responses induced by high-linear energy transfer (LET) heavy ions at low fluence are an important health problem for astronauts in space. Bystander responses are mediated via physical cell-cell contact, such as gap-junction intercellular communication (GJIC) and/or diffusive factors released into the medium in cell culture conditions. Nitric oxide (NO) is a well-known major initiator/mediator of intercellular signaling within culture medium during bystander responses. In this study, we investigated the NO-mediated bystander signal transduction induced by high-LET argon (Ar)-ion microbeam irradiation of normal human fibroblasts. Foci formation by DNA double-strand break repair proteins was induced in non-irradiated cells, which were co-cultured with those irradiated by high-LET Ar-ion microbeams in the same culture plate. Foci formation was suppressed significantly by pretreatment with an NO scavenger. Furthermore, NO-mediated reproductive cell death was also induced in bystander cells. Phosphorylation of NF-κB and Akt were induced during NO-mediated bystander signaling in the irradiated and bystander cells. However, the activation of these proteins depended on the incubation time after irradiation. The accumulation of cyclooxygenase-2 (COX-2), a downstream target of NO and NF-κB, was observed in the bystander cells 6 h after irradiation but not in the directly irradiated cells. Our findings suggest that Akt- and NF-κB-dependent signaling pathways involving COX-2 play important roles in NO-mediated high-LET heavy-ion-induced bystander responses. In addition, COX-2 may be used as a molecular marker of high-LET heavy-ion-induced bystander cells to distinguish them from directly irradiated cells, although this may depend on the time after irradiation.

Ion beam nano-engineering of erbium doped silicon for enhanced light emission at 1.54 microns

NASA Astrophysics Data System (ADS)

Naczas, Sebastian

Erbium doped silicon is of great interest as a potential light source in Silicon Photonics research due to its light emission at 1.54 mum, which corresponds to the minimal loss of optical transmission in silica fibers for telecommunications. In this thesis a basic mechanism for excitation and de-excitation of Er in Si is reviewed. Based on such fundamental understanding, an innovative approach is proposed and implemented to improve Er luminescence properties through the formation of metal nanoparticles via impurity gettering in Si nanocavities. The first part of the work demonstrates the use of ion implantation combined with thermal treatments for forming Ag nanoparticles in the vicinity of Er luminescence centers in Si. The utilization of standard semiconductor fabrication equipment and moderate thermal budgets make this approach fully compatible with Si CMOS technologies. The presence of Ag nanoparticles leads to an enhancement in the Er photoluminescence intensity, its excitation cross section and the population of optically active Er, possibly due to the surface plasmon excitation effects related to Ag nanoparticles. The resulting structures were characterized by Hydrogen depth profiling (NRA), Rutherford backscattering spectroscopy (RBS), Photoluminescence (PL), Transmission electron microscopy (TEM). In order to optimize the Er luminescence properties in such a system it is necessary to understand how the sample conditions affect the formation of Ag nanoparticles in Si. Therefore in the second part of this project we investigate the role of surface oxide in point defect generation and recombination, and the consequence on nanocavity formation and defect retention in Si. Investigation of the surface oxide effects on nanocavity formation in hydrogen implanted silicon and the influence of resultant nanocavities on diffusion and gettering of implanted silver atoms. Two sets of Si samples were prepared, depending on whether the oxide layer was etched off before (Group-A) or after (Group-B) post-H-implantation annealing. As evidenced by transmission electron microscopy, Group-A samples exhibited an array of large-sized nanocavities in hexagon-like shape, whereas a narrow band of sphere-shaped nanocavities of small size was present below the surface in Group-B samples. These Si samples with pre-existing nanocavities were further implanted with Ag ions in the surface region and post-Ag-implantation annealing was conducted in the temperature range between 600 and 900 °C. Measurements based on RBS revealed much different behaviors for Ag redistribution and defect accumulation in these two sets of samples. Compared to the case for Group-B Si, Group-A Si exhibited a lower concentration of residual defects and a slower kinetics in Ag diffusion as well. The properties of nanocavities, e.g., their depth distribution, size, and even shape, are believed to be responsible for the observed disparities between the samples with and without surface oxides, including an interesting contrast of surface vs. bulk diffusion phenomena for implanted Ag atoms. Based on this thesis work, we believe that this approach is promising for achieving monolithically integrated room-temperature light emitting devices based on Er-doped Si, if the properties (e.g., density/size/type of nanoparticles) of these novel Si nanostructures could be further optimized in future studies.

Transport of carbon ion test particles and hydrogen recycling in the plasma of the Columbia tokamak HBT'' (High Beta Tokamak)

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

Wang, Jian-Hua.

Carbon impurity ion transport is studied in the Columbia High Beta Tokamak (HBT), using a carbon tipped probe which is inserted into the plasma (n{sub e} {approx} 1 {minus} 5 {times} 10{sup 14} (cm{sup {minus}3}), T{sub e} {approx} 4 {minus} 10 (eV), B{sub t} {approx} 0.2 {minus} 0.4(T)). Carbon impurity light, mainly the strong lines of C{sub II}(4267A, emitted by the C{sup +} ions) and C{sub III} (4647A, emitted by the C{sup ++} ions), is formed by the ablation or sputtering of plasma ions and by the discharge of the carbon probe itself. The diffusion transport of the carbon ionsmore » is modeled by measuring the space-and-time dependent spectral light emission of the carbon ions with a collimated optical beam and photomultiplier. The point of emission can be observed in such a way as to sample regions along and transverse to the toroidal magnetic field. The carbon ion diffusion coefficients are obtained by fitting the data to a diffusion transport model. It is found that the diffusion of the carbon ions is classical'' and is controlled by the high collisionality of the HBT plasma; the diffusion is a two-dimensional problem and the expected dependence on the charge of the impurity ion is observed. The measurement of the spatial distribution of the H{sub {alpha}} emissivity was obtained by inverting the light signals from a 4-channel polychromator, the data were used to calculate the minor-radial influx, the density, and the recycling time of neutral hydrogen atoms or molecules. The calculation shows that the particle recycling time {tau}{sub p} is comparable with the plasma energy confinement time {tau}{sub E}; therefore, the recycling of the hot plasma ions with the cold neutrals from the walls is one of the main mechanisms for loss of plasma energy.« less

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

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

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

Investigation of corrosion caused by constituents of refinery wastewater effluent used as circulating cooling water.

PubMed

Zhang, Zhongzhi; Song, Shaofu; Huang, Jie; Ji, Lin; Wu, Fangyun

2003-01-01

The corrosion rate of steel plate using single-factor, multifactor, and complex water systems was investigated via refinery wastewater effluents used as circulating cooling water. The results show that the primary corrosion factors of steel depend on the characteristics of the ions, the formation of the oxidized coating, the diffusion of dissolved oxygen, and other complex factors, although ions such as chloride, calcium, and carbonate play an important role. The corrosion rate of carbon steel exhibits two trends: The corrosion rate is high at low conductivity, increases to a maximum, and then decreases and becomes stable with increasing conductivity, as is the case with chloride, sulfate, nitrate and calcium ions. On the other hand, the corrosion rate is highest at low conductivity and then decreases and becomes stable with increasing conductivity, as is the case with carbonate, silicate, and sodium nitrate ions. Research results indicate that the anticorrosive ability is minimal at low conductivity; but is excellent at high conductivity. Pretreatment of low-conductivity water using air flotation and clarification to decrease the concentrations of chloride, calcium, and carbonate ions to a suitable level to satisfy the anticorrosion requirements is required. However, it is not necessary to significantly reduce the salt concentration or conductivity of the water by osmosis or ion exchange to obtain an anticorrosion effect when reusing wastewater effluents as circulating cooling water.

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

DOE PAGES

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul; ...

2015-11-17

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

Electrochemical properties of tin oxide anodes for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Lu, Ying Ching; Ma, Chuze; Alvarado, Judith; Kidera, Takafumi; Dimov, Nikolay; Meng, Ying Shirley; Okada, Shigeto

2015-06-01

Few tin (Sn)-oxide based anode materials have been found to have large reversible capacity for both sodium (Na)-ion and lithium (Li)-ion batteries. Herein, we report the synthesis and electrochemical properties of Sn oxide-based anodes for sodium-ion batteries: SnO, SnO2, and SnO2/C. Among them, SnO is the most suitable anode for Na-ion batteries with less first cycle irreversibility, better cycle life, and lower charge transfer resistance. The energy storage mechanism of the above-mentioned Sn oxides was studied, which suggested that the conversion reaction of the Sn oxide anodes is reversible in Na-ion batteries. The better anode performance of SnO is attributed by the better conductivity.

Investigation of heavy-ion fusion with deformed surface diffuseness: Actinide and lanthanide targets

NASA Astrophysics Data System (ADS)

Alavi, S. A.; Dehghani, V.

2017-05-01

By using a deformed Broglia-Winther nuclear interaction potential in the framework of the WKB method, the near- and above-barrier heavy-ion-fusion cross sections of 16O with some lanthanides and actinides have been calculated. The effect of deformed surface diffuseness on the nuclear interaction potential, the effective interaction potential at distinct angle, barrier position, barrier height, cross section at each angles, and fusion cross sections of 16O+147Sm,150Nd,154Sm , and 166Er and 16O+232Th,238U,237Np , and 248Cm have been studied. The differences between the results obtained by using deformed surface diffuseness and those obtained by using constant surface diffuseness were noticeable. Good agreement between experimental data and theoretical calculation with deformed surface diffuseness were observed for 16O+147Sm,154Sm,166Er,238U,237Np , and 248Cm reactions. It has been observed that deformed surface diffuseness plays a significant role in heavy-ion-fusion studies.

Thermal diffusion in partially ionized gases - The case of unequal temperatures. [in solar chromosphere

NASA Technical Reports Server (NTRS)

Geiss, J.; Burgi, A.

1987-01-01

Previous calculations of thermal diffusion coefficients in partially ionized gases are extended to the case of unequal neutral and ion temperatures and/or temperature gradients. Formulas are derived for the general case of a major gas as well as for minor atoms and ions. Strong enhancements of minor-ion thermal diffusion coefficients over their values in the fully ionized gas are found when the degree of ionization in the main gas is relatively low. However, compared to the case of equal temperatures, the enhancements are less strong when the neutrals are cooler than the ions. The specific case of the H-H(+) mixture, which is important in the study of solar and stellar atmospheres, is discussed as an application.

A model for self-diffusion of guanidinium-based ionic liquids: a molecular simulation study.

PubMed

Klähn, Marco; Seduraman, Abirami; Wu, Ping

2008-11-06

We propose a novel self-diffusion model for ionic liquids on an atomic level of detail. The model is derived from molecular dynamics simulations of guanidinium-based ionic liquids (GILs) as a model case. The simulations are based on an empirical molecular mechanical force field, which has been developed in our preceding work, and it relies on the charge distribution in the actual liquid. The simulated GILs consist of acyclic and cyclic cations that were paired with nitrate and perchlorate anions. Self-diffusion coefficients are calculated at different temperatures from which diffusive activation energies between 32-40 kJ/mol are derived. Vaporization enthalpies between 174-212 kJ/mol are calculated, and their strong connection with diffusive activation energies is demonstrated. An observed formation of cavities in GILs of up to 6.5% of the total volume does not facilitate self-diffusion. Instead, the diffusion of ions is found to be determined primarily by interactions with their immediate environment via electrostatic attraction between cation hydrogen and anion oxygen atoms. The calculated average time between single diffusive transitions varies between 58-107 ps and determines the speed of diffusion, in contrast to diffusive displacement distances, which were found to be similar in all simulated GILs. All simulations indicate that ions diffuse by using a brachiation type of movement: a diffusive transition is initiated by cleaving close contacts to a coordinated counterion, after which the ion diffuses only about 2 A until new close contacts are formed with another counterion in its vicinity. The proposed diffusion model links all calculated energetic and dynamic properties of GILs consistently and explains their molecular origin. The validity of the model is confirmed by providing an explanation for the variation of measured ratios of self-diffusion coefficients of cations and paired anions over a wide range of values, encompassing various ionic liquid classes as well as the simulated GILs. The proposed diffusion model facilitates the qualitative a priori prediction of the impact of ion modifications on the diffusive characteristics of new ionic liquids.

A scaled-ionic-charge simulation model that reproduces enhanced and suppressed water diffusion in aqueous salt solutions.

PubMed

Kann, Z R; Skinner, J L

2014-09-14

Non-polarizable models for ions and water quantitatively and qualitatively misrepresent the salt concentration dependence of water diffusion in electrolyte solutions. In particular, experiment shows that the water diffusion coefficient increases in the presence of salts of low charge density (e.g., CsI), whereas the results of simulations with non-polarizable models show a decrease of the water diffusion coefficient in all alkali halide solutions. We present a simple charge-scaling method based on the ratio of the solvent dielectric constants from simulation and experiment. Using an ion model that was developed independently of a solvent, i.e., in the crystalline solid, this method improves the water diffusion trends across a range of water models. When used with a good-quality water model, e.g., TIP4P/2005 or E3B, this method recovers the qualitative behaviour of the water diffusion trends. The model and method used were also shown to give good results for other structural and dynamic properties including solution density, radial distribution functions, and ion diffusion coefficients.

Evaluation Of Ion Exchange For Fabrication Of Rare-Earth Doped Waveguides

NASA Astrophysics Data System (ADS)

Howell, Brian P.; Beerling, Timothy

1987-01-01

Rare earth ions are frequently incorporated into lasers by doping common glasses with the ions in the glass melt. This paper describes the potential of using diffusion of the rare earth ion from molten salt baths to incorporate it in the glass. The paper discusses the molten salts, the rare earths as a group, the diffusion phenomena, the glasses, and finally the interaction of all these to produce the process. General predictions of the waveguide profile and potential problems are presented.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Real-space analysis of diffusion behavior and activation energy of individual monatomic ions in a liquid.

PubMed

Miyata, Tomohiro; Uesugi, Fumihiko; Mizoguchi, Teruyasu

2017-12-01

Investigation of the local dynamic behavior of atoms and molecules in liquids is crucial for revealing the origin of macroscopic liquid properties. Therefore, direct imaging of single atoms to understand their motions in liquids is desirable. Ionic liquids have been studied for various applications, in which they are used as electrolytes or solvents. However, atomic-scale diffusion and relaxation processes in ionic liquids have never been observed experimentally. We directly observe the motion of individual monatomic ions in an ionic liquid using scanning transmission electron microscopy (STEM) and reveal that the ions diffuse by a cage-jump mechanism. Moreover, we estimate the diffusion coefficient and activation energy for the diffusive jumps from the STEM images, which connect the atomic-scale dynamics to macroscopic liquid properties. Our method is the only available means to observe the motion, reactions, and energy barriers of atoms/molecules in liquids.

Diffusion in cementitious materials. 2: Further investigations of chloride and oxygen diffusion in well-cured OPC and OPC/30%PFA pastes

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

Ngala, V.T.; Page, C.L.; Parrott, L.J.

1995-05-01

Steady-state diffusion of dissolved oxygen and chloride ions in hydrated OPC and OPC/30%PFA pastes, hydrated for 2 weeks at 20 C and 10 weeks at 38 C, was studied at water/binder (w/s) ratios 0.4, 0.5, 0.6 and 0.7. Total porosity and a simple measure of capillary porosity, the volume fractions of the water lost in specimens from a saturated surface dry condition to a near-constant weight at 90.7% relative humidity, were also determined. The diffusion rate of chloride ions diminished markedly, to very low values, as the capillary porosity approached zero. For a given w/s ratio or capillary porosity themore » chloride ion diffusion coefficient for OPC/30%PFA pastes was about one order of magnitude smaller than that to OPC pastes. The rate of diffusion of dissolved oxygen also diminished as the capillary porosity reduced but it was still significant as the capillary porosity approached zero. For a given capillary porosity the oxygen diffusion coefficient for OPC/30%PFA pastes was about 30% smaller than that for OPC pastes. The results support the view that chloride ion diffusion in pastes of low capillary porosity is retarded by the surface charge of the hydrated cement gel. In contrast, the hydrated cement gel is much more permeable to the similarly-sized, neutral oxygen molecule.« less

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device.

PubMed

Ida, K; Funaba, H; Kado, S; Narihara, K; Tanaka, K; Takeiri, Y; Nakamura, Y; Ohyabu, N; Yamazaki, K; Yokoyama, M; Murakami, S; Ashikawa, N; deVries, P C; Emoto, M; Goto, M; Idei, H; Ikeda, K; Inagaki, S; Inoue, N; Isobe, M; Itoh, K; Kaneko, O; Kawahata, K; Khlopenkov, K; Komori, A; Kubo, S; Kumazawa, R; Liang, Y; Masuzaki, S; Minami, T; Miyazawa, J; Morisaki, T; Morita, S; Mutoh, T; Muto, S; Nagayama, Y; Nakanishi, H; Nishimura, K; Noda, N; Notake, T; Kobuchi, T; Ohdachi, S; Ohkubo, K; Oka, Y; Osakabe, M; Ozaki, T; Pavlichenko, R O; Peterson, B J; Sagara, A; Saito, K; Sakakibara, S; Sakamoto, R; Sanuki, H; Sasao, H; Sasao, M; Sato, K; Sato, M; Seki, T; Shimozuma, T; Shoji, M; Suzuki, H; Sudo, S; Tamura, N; Toi, K; Tokuzawa, T; Torii, Y; Tsumori, K; Yamamoto, T; Yamada, H; Yamada, I; Yamaguchi, S; Yamamoto, S; Yoshimura, Y; Watanabe, K Y; Watari, T; Hamada, Y; Motojima, O; Fujiwara, M

2001-06-04

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

Highly uniform Co9S8 nanoparticles grown on graphene nanosheets as advanced anode materials for improved Li-storage performance

NASA Astrophysics Data System (ADS)

Liu, Shumin; Wang, Jinxian; Wang, Jianwei; Zhang, Feifei; Wang, Limin

2016-12-01

A Co9S8/GNS (graphene nanosheets) nanocomposites has been synthesized via a facile solvothermal approach followed by thermal treatment in nitrogen at 500 °C using graphite oxide sheets, CoCl2·6H2O and thiourea as the starting materials. Highly uniform Co9S8 nanoparticles with a size of about 80-90 nm are evenly grafted on the surface of GNS, forming a unique Co9S8/GNS hybrid nanostructure. When evaluated as anode materials for lithium ion batteries, impressive electrochemical performances of the as-prepared nanocomposites are achieved compared to that of pure bulk Co9S8, with an high reversible capacity of 1480 mAh g-1. Moreover, the as-synthesized nanocomposites present excellent cycling durability and high-rate capability. The improvement in the electrochemical properties could be attributed to the well-designed structure of the Co9S8/GNS nanocomposite which possesses large number of accessible active sites for lithium-ion insertion, fast ion diffusion rate and good electronic conductivity.

Cr3+-Doped Yb3Ga5O12 Nanophosphor: Synthesis, Optical, EPR, Studies

NASA Astrophysics Data System (ADS)

Singh, Vijay; Sivaramaiah, G.; Rao, J. L.; Singh, N.; Pathak, M. S.; Jirimali, H. D.; Singh, Pramod K.; Srivastava, Anoop K.; Dhoble, S. J.; Mohapatra, M.

2016-08-01

Gallium garnets of lanthanides are multifunctional materials especially known for their complicated structure and magnetic properties. In addition, with a suitable transition metal dopant ion, these matrices have been proved to be excellent materials for lasers. In particular, gallium garnet of ytterbium (Yb3Ga5O12) is known to possess excellent properties with regards to these applications. In this connection, Yb3Ga5O12 doped with Cr3+ nanophosphors were synthesized by a solution combustion route. The synthesized material was characterized by powder x-ray diffraction and scanning electron microscopy for phase purity and homogenous morphology. In order to ascertain the oxidation state of the doped ion, diffuse reflectance (DRF), photoluminescence (PL) and electron paramagnetic resonance (EPR) experiments were performed on the sample. The DRF and PL data suggested the stabilisation of the trivalent Cr ion in the matrix. The EPR spectra exhibited two resonance signals with effective g values at g ≈ 7.6 and 4. The EPR data corroborated the DRF and PL results, suggesting the stabilisation of Cr3+ in the matrix at octahedral-type geometries.

In Situ Chelating Synthesis of Hierarchical LiNi1/3 Co1/3 Mn1/3 O2 Polyhedron Assemblies with Ultralong Cycle Life for Li-Ion Batteries.

PubMed

Zhang, Yue; Jia, Dianzeng; Tang, Yakun; Huang, Yudai; Pang, Weikong; Guo, Zaiping; Zhou, Zhen

2018-06-03

Layered lithium transition-metal oxides, with large capacity and high discharge platform, are promising cathode materials for Li-ion batteries. However, their high-rate cycling stability still remains a large challenge. Herein, hierarchical LiNi 1/3 Co 1/3 Mn 1/3 O 2 polyhedron assemblies are obtained through in situ chelation of transition metal ions (Ni 2+ , Co 2+ , and Mn 2+ ) with amide groups uniformly distributed along the backbone of modified polyacrylonitrile chains to achieve intimate mixing at the atomic level. The assemblies exhibit outstanding electrochemical performances: superior rate capability, high volumetric energy density, and especially ultralong high-rate cyclability, due to the superiority of unique hierarchical structures. The polyhedrons with exposed active crystal facets provide more channels for Li + diffusion, and meso/macropores serve as access shortcuts for fast migration of electrolytes, Li + and electrons. The strategy proposed in this work can be extended to fabricate other mixed transition metal-based materials for advanced batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low Temperature Vacuum Synthesis of Triangular CoO Nanocrystal/Graphene Nanosheets Composites with Enhanced Lithium Storage Capacity

PubMed Central

Guan, Qun; Cheng, Jianli; Li, Xiaodong; Wang, Bin; Huang, Ling; Nie, Fude; Ni, Wei

2015-01-01

CoO nanocrystal/graphene nanosheets (GNS) composites, consisting of a triangular CoO nanocrystal of 2~20 nm on the surface of GNS, are synthesized by a mild synthetic method. First, cobalt acetate tetrahydrate is recrystallized in the alcohol solution at a low temperature. Then, graphene oxide mixed with cobalt-precursor followed by high vacuum annealing to form the CoO nanocrystal/GNS composites. The CoO nanocrystal/GNS composites exhibit a high reversible capacity of 1481.9 m Ah g−1 after 30 cycles with a high Coulombic efficiency of over 96% when used as anode materials for lithium ion battery. The excellent electrochemical performances may be attributed to the special structure of the composites. The well-dispersed triangular CoO nanocrystal on the substrate of conductive graphene can not only have a shorter diffusion length for lithium ions, better stress accommodation capability during the charge-discharge processes and more accessible active sites for lithium-ion storage and electrolyte wetting, but also possess a good conductive network, which can significantly improve the whole electrochemical performance. PMID:25961670

Adsorption and diffusion of mono, di, and trivalent ions on two-dimensional TiS2

NASA Astrophysics Data System (ADS)

Samad, Abdus; Shafique, Aamir; Shin, Young-Han

2017-04-01

A comparative study of the monovalent (Li, Na, and K) and multivalent (Be, Mg, Ca, and Al) metal ion adsorption and diffusion on an electronically semi-metallic two-dimensional nanosheet of 1T structured TiS2 is presented here to contribute to the search for abundant, cheap, and nontoxic ingredients for efficient rechargeable metal ion batteries. The total formation energy of the metal ion adsorption and the Bader charge analysis show that the divalent Mg and Ca ions can have a charge storage density double that of the monovalent Li, Na, and K ions, while the Be and Al ions form metallic clusters even at a low adsorption density because of their high bulk energies. The adsorption of Mg ions shows the lowest averaged open circuit voltage (0.13 V). The activation energy barriers for the diffusion of metal ions on the surface of the monolayer successively decrease from Li to K and Be to Ca. Mg and Ca, being divalent, are capable of storing a higher power density than Li while K and Na have a higher rate capability than the Li ions. Therefore, rechargeable Li ion batteries can be totally or partially replaceable by Mg ion batteries, where high power density and high cell voltage are required, while the abundant, cheap, and fast Na ions can be used for green grid applications.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

PubMed Central

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

Operation of staged membrane oxidation reactor systems

DOEpatents

Repasky, John Michael

2012-10-16

A method of operating a multi-stage ion transport membrane oxidation system. The method comprises providing a multi-stage ion transport membrane oxidation system with at least a first membrane oxidation stage and a second membrane oxidation stage, operating the ion transport membrane oxidation system at operating conditions including a characteristic temperature of the first membrane oxidation stage and a characteristic temperature of the second membrane oxidation stage; and controlling the production capacity and/or the product quality by changing the characteristic temperature of the first membrane oxidation stage and/or changing the characteristic temperature of the second membrane oxidation stage.

Removal of hexavalent chromium in carbonic acid solution by oxidizing slag discharged from steelmaking process in electric arc furnace

NASA Astrophysics Data System (ADS)

Yokoyama, Seiji; Okazaki, Kohei; Sasano, Junji; Izaki, Masanobu

2014-02-01

Hexavalent chromium (Cr(VI)) is well-known to be a strong oxidizer, and is recognized as a carcinogen. Therefore, it is regulated for drinking water, soil, groundwater and sea by the environmental quality standards all over the world. In this study, it was attempted to remove Cr(VI) ion in a carbonic acid solution by the oxidizing slag that was discharged from the normal steelmaking process in an electric arc furnace. After the addition of the slag into the aqueous solution contained Cr(VI) ion, concentrations of Cr(VI) ion and total chromium (Cr(VI) + trivalent chromium (Cr(III)) ions decreased to lower detection limit of them. Therefore, the used slag could reduce Cr(VI) and fix Cr(III) ion on the slag. While Cr(VI) ion existed in the solution, iron did not dissolve from the slag. From the relation between predicted dissolution amount of iron(II) ion and amount of decrease in Cr(VI) ion, the Cr(VI) ion did not react with iron(II) ion dissolved from the slag. Therefore, Cr(VI) ion was removed by the reductive reaction between Cr(VI) ion and the iron(II) oxide (FeO) in the slag. This reaction progressed on the newly appeared surface of iron(II) oxide due to the dissolution of phase composed of calcium etc., which existed around iron(II) oxide grain in the slag.

Diffusion across the modified polyethylene separator GX in the heat-sterilizable AgO-Zn battery

NASA Technical Reports Server (NTRS)

Lutwack, R.

1973-01-01

Models of diffusion across an inert membrane have been studied using the computer program CINDA. The models were constructed to simulate various conditions obtained in the consideration of the diffusion of Ag (OH)2 ions in the AgO-Zn battery. The effects on concentrations across the membrane at the steady state and on the fluxout as a function of time were used to examine the consequences of stepwise reducing the number of sources of ions, of stepwise blocking the source and sink surfaces, of varying the magnitude of the diffusion coefficient for a uniform membrane, of varying the diffusion coefficient across the membrane, and of excluding volumes to diffusion.

Improving the Performance of Layered Oxide Cathode Materials with Football-Like Hierarchical Structure for Na-Ion Batteries by Incorporating Mg2+ into Vacancies in Na-Ion Layers.

PubMed

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

2018-04-09

The development of advanced cathode materials is still a great interest for sodium-ion batteries. The feasible commercialization of sodium-ion batteries relies on the design and exploitation of suitable electrode materials. This study offers a new insight into material design to exploit high-performance P2-type cathode materials for sodium-ion batteries. The incorporation of Mg 2+ into intrinsic Na + vacancies in Na-ion layers can lead to a high-performance P2-type cathode material for sodium-ion batteries. The materials prepared by the coprecipitation approach show a well-defined morphology of secondary football-like hierarchical structures. Neutron power diffraction and refinement results demonstrate that the incorporation of Mg 2+ into intrinsic vacancies can enlarge the space for Na-ion diffusion, which can increase the d-spacing of the (0 0 2) peak and the size of slabs but reduce the chemical bond length to result in an enhanced rate capability and cycling stability. The incorporation of Mg 2+ into available vacancies and a unique morphology make Na 0.7 Mg 0.05 Mn 0.8 Ni 0.1 Co 0.1 O 2 a promising cathode, which can be charged and discharged at an ultra-high current density of 2000 mA g -1 with an excellent specific capacity of 60 mAh g -1 . This work provides a new insight into the design of electrode materials for sodium-ion batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous diffusion of poly(ethylene oxide) in agarose gels.

PubMed

Brenner, Tom; Matsukawa, Shingo

2016-11-01

We report on the effect of probe size and diffusion time of poly(ethylene) oxide in agarose gels. Time-dependence of the diffusion coefficient, reflecting anomalous diffusion, was observed for poly(ethylene) oxide chains with hydrodynamic radii exceeding about 20nm at an agarose concentration of 2%. The main conclusion is that the pore distribution includes pores that are only several nm across, in agreement with scattering reports in the literature. Interpretation of the diffusion coefficient dependence on the probe size based on a model of entangled rigid rods yielded a rod length of 72nm. Copyright © 2016. Published by Elsevier B.V.

Systems and methods for separation and purification of products

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

Weiss, Michael Joseph; Gilliam, Ryan J.; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with an unsaturated hydrocarbon and/or a saturated hydrocarbon to form products. Separation and/or purification of the products as well as of the metal ions in the lower oxidation state and the higher oxidation state, is provided herein.

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

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

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

DOE PAGES

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei; ...

2017-07-17

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

a Plutonium Ceramic Target for Masha

NASA Astrophysics Data System (ADS)

Wilk, P. A.; Shaughnessy, D. A.; Moody, K. J.; Kenneally, J. M.; Wild, J. F.; Stoyer, M. A.; Patin, J. B.; Lougheed, R. W.; Ebbinghaus, B. B.; Landingham, R. L.; Oganessian, Yu. Ts.; Yeremin, A. V.; Dmitriev, S. N.

2005-09-01

We are currently developing a plutonium ceramic target for the MASHA mass separator. The MASHA separator will use a thick plutonium ceramic target capable of tolerating temperatures up to 2000 °C. Promising candidates for the target include oxides and carbides, although more research into their thermodynamic properties will be required. Reaction products will diffuse out of the target into an ion source, where they will then be transported through the separator to a position-sensitive focal-plane detector array. Experiments on MASHA will allow us to make measurements that will cement our identification of element 114 and provide for future experiments where the chemical properties of the heaviest elements are studied.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, J.R.; Thomas, T.M.; Czanderna, A.W.

1984-07-31

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, John R.; Thomas, Terence M.; Czanderna, Alvin W.

1985-01-01

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Advanced detectors and signal processing for bubble memories

NASA Technical Reports Server (NTRS)

Kryder, M. H.; Rasky, P. H. L.; Greve, D. W.

1985-01-01

The feasibility of combining silicon and magnetic bubble technologies is demonstrated. Results of bubble film annealing indicate that a low temperature silicon on garnet technology is the most likely one to succeed commercially. Annealing ambients are also shown to have a major effect on the magnetic properties of bubble films. Functional MOSFETs were fabricated on bubble films coated with thick (approximately 1 micron) SiO2 layers. The two main problems with these silicon on garnet MOSFETs are low electron mobilities and large gate leakage currents. Results indicate that the laser recrystallized silicon and gate oxide (SiO2) layers are contaminated. The data suggest that part of the contaminating ions originate in the sputtered oxide spacer layer and part originates in the bubble film itself. A diffusion barrier, such as silicon nitride, placed between the bubble film and the silicon layer should eliminate the contamination induced problem.

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

PubMed

Becker, J S; Breuer, U; Westheide, J; Saprykin, A I; Holzbrecher, H; Nickel, H; Dietze, H J

1996-06-01

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

Chalcogenide and pnictide nanocrystals from the silylative deoxygenation of metal oxides

DOE PAGES

Lin, Chia-Cheng; Tan, Shannon J.; Vela, Javier

2017-09-11

Transition metal chalcogenide and pnictide nanocrystals are of interest for optoelectronic and catalytic applications. In this paper, we present a generalized route to the synthesis of these materials from the silylative deoxygenation of metal oxides with trimethylsilyl reagents. Specific nanophases produced in this way include Ni 3S 2, Ni 5Se 5, Ni 2P, Co 9S 8, Co 3Se 4, CoP, Co 2P, and heterobimetallic (Ni/Co) 9S 8. The resulting chalcogenide nanocrystals are hollow, likely due to differential rates of ion diffusion during the interfacial phase transformation reaction (Kirkendall-type effect). In contrast, the phosphide nanocrystals are solid, likely because they formmore » at higher reaction temperatures. Finally, in all cases, simultaneous partial decomposition of the deoxygenating silyl reagent produces a coating of amorphous silica around the newly formed nanocrystals, which could impact their stability and recyclability.« less

Timing considerations for preclinical MRgRT: effects of ion diffusion, SNR and imaging times on FXG gel calibration

NASA Astrophysics Data System (ADS)

Welch, M.; Foltz, W. D.; Jaffray, D. A.

2015-01-01

Sub-millimeter resolution images are required for gel dosimeters to be used in preclinical research, which is challenging for MR probed ferrous xylenol-orange (FXG) dosimeters due to ion diffusion and inadequate SNR. A preclinical 7 T MR, small animal irradiator and FXG dosimeters were used in all experiments. Ion diffusion was analyzed using high resolution (0.2 mm/pixel) T1 MR images collected every 5 minutes, post-irradiation, for an hour. Using Fick's second law, ion diffusion was approximated for the first hour post-irradiation. SNR, T1 map precision and calibration fit were determined for two MR protocols: (1) 10 minute acquisition, 0.35mm/pixel and 3mm slices, (2) 45 minute acquisition, 0. 25 mm/pixel and 2 mm slices. SNR and T1 map precision were calculated using a Monte Carlo simulation. Calibration curves were determined by plotting R1 relaxation rates versus depth dose data, and fitting a linear trend line. Ion diffusion was estimated as 0.003mm2 in the first hour post-irradiation. For protocols (1) and (2) respectively, Monte Carlo simulation predicted T1 precisions of 3% and 5% within individual voxels using experimental SNRs; the corresponding measured T1 precisions were 8% and 12%. The linear trend lines reported slopes of 27 ± 3 Gy*s (R2: 0.80 ± 0.04) and 27 ± 4 Gy*s (R2: 0.90 ± 0.04). Ion diffusion is negligible within the first hour post-irradiation, and an accurate and reproducible calibration can be achieved in a preclinical setting with sub-millimeter resolution.

Improved durability of proton exchange membrane fuel cells by introducing Sn (IV) oxide into electrodes using an ion exchange method

NASA Astrophysics Data System (ADS)

Poulsen, M. G.; Larsen, M. J.; Andersen, S. M.

2017-03-01

Electrodes of Proton Exchange Membrane Fuel Cells (PEMFCs), consisting of catalyst-coated gas diffusion layers, were subjected to an optimized ion exchange procedure, in which tin (IV) oxide (SnO2) nanoparticles were introduced into them. Both methanol and sulfuric acid were tested as ion exchange solvents. SnO2 has previously been shown to exhibit radical scavenging abilities towards radicals inside the electrocatalyst layers. Its presence inside the electrodes was confirmed using X-ray photoelectron spectroscopy and X-ray fluorescence. After exposure to an accelerated stress test in a three-electrode setup, the electrodes containing SnO2 were found to have retained approximately 73.0% of their original Pt, while only 53.2% was retained in electrodes treated identically, but without Sn. Similarly, the SnO2-treated electrodes also experienced a smaller loss in electrochemical surface area in comparison to before the accelerated stress test. A membrane electrode assembly (MEA) constructed with a SnO2-containing anode was evaluated over 500 h. The results showed remarkably reduced OCV decay rate and end of test hydrogen crossover compared to the control MEA, indicating that SnO2 aids in impeding membrane thinning and pinhole formation. The results point toward a positive effect of SnO2 on fuel cell durability, by reducing the degradation of the membrane as well as of the ionomer in the electrocatalyst layer.

The genetic basis of energy conservation in the sulfate-reducing bacterium Desulfovibrio alaskensis G20

DOE PAGES

Price, Morgan N.; Ray, Jayashree; Wetmore, Kelly M.; ...

2014-10-31

Sulfate-reducing bacteria play major roles in the global carbon and sulfur cycles, but it remains unclear how reducing sulfate yields energy. To determine the genetic basis of energy conservation, we measured the fitness of thousands of pooled mutants of Desulfovibrio alaskensis G20 during growth in 12 different combinations of electron donors and acceptors. We show that ion pumping by the ferredoxin:NADH oxidoreductase Rnf is required whenever substrate-level phosphorylation is not possible. The uncharacterized complex Hdr/flox-1 (Dde_1207:13) is sometimes important alongside Rnf and may perform an electron bifurcation to generate more reduced ferredoxin from NADH to allow further ion pumping. Similarly,more » during the oxidation of malate or fumarate, the electron-bifurcating transhydrogenase NfnAB-2 (Dde_1250:1) is important and may generate reduced ferredoxin to allow additional ion pumping by Rnf. During formate oxidation, the periplasmic [NiFeSe] hydrogenase HysAB is required, which suggests that hydrogen forms in the periplasm, diffuses to the cytoplasm, and is used to reduce ferredoxin, thus providing a substrate for Rnf. We found that during hydrogen utilization, the transmembrane electron transport complex Tmc is important and may move electrons from the periplasm into the cytoplasmic sulfite reduction pathway. Finally, mutants of many other putative electron carriers have no clear phenotype, which suggests that they are not important under our growth conditions, although we cannot rule out genetic redundancy.« less