Long-term performance of activated carbon air cathodes with different diffusion layer porosities in microbial fuel cells.

PubMed

Zhang, Fang; Pant, Deepak; Logan, Bruce E

2011-12-15

Activated carbon (AC) air-cathodes are inexpensive and useful alternatives to Pt-catalyzed electrodes in microbial fuel cells (MFCs), but information is needed on their long-term stability for oxygen reduction. AC cathodes were constructed with diffusion layers (DLs) with two different porosities (30% and 70%) to evaluate the effects of increased oxygen transfer on power. The 70% DL cathode initially produced a maximum power density of 1214±123 mW/m(2) (cathode projected surface area; 35±4 W/m(3) based on liquid volume), but it decreased by 40% after 1 year to 734±18 mW/m(2). The 30% DL cathode initially produced less power than the 70% DL cathode, but it only decreased by 22% after 1 year (from 1014±2 mW/m(2) to 789±68 mW/m(2)). Electrochemical tests were used to examine the reasons for the degraded performance. Diffusion resistance in the cathode was found to be the primary component of the internal resistance, and it increased over time. Replacing the cathode after 1 year completely restored the original power densities. These results suggest that the degradation in cathode performance was due to clogging of the AC micropores. These findings show that AC is a cost-effective material for oxygen reduction that can still produce ~750 mW/m(2) after 1 year. Copyright © 2011 Elsevier B.V. All rights reserved.

One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

PubMed Central

Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

2015-01-01

Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

DOEpatents

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Mesoporous Nitrogen Doped Carbon-Glass Ceramic Cathode for High Performance Lithium-Oxygen Battery

DTIC Science & Technology

2012-06-01

dry room with controlled moisture content. Composite 3 films on nickel foam were used as working cathodes along with lithium metal as anode and the...cathode formulation [6,7,8,9,10], efficient oxygen reduction catalysts [11,12], electrolyte compositions [13,14], effect of moisture [15], etc...specimens. Structure and purity of these materials were performed by powder X-ray diffraction (XRD) on a Rigaku D/MAX-2250 diffractometer fitted with CuKα

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

Promotional Effect of Molten Carbonates on Proton Conductivity and Oxygen Reduction Reaction - an Experimental and Computational Study

NASA Astrophysics Data System (ADS)

Xiong, Xiaolei

Recent research of Solid oxide fuel cells (SOFCs) is aimed to lower the operating temperature to an intermediate temperature (IT) range of 500 to 700°C, while maintaining a proper performance. This Ph.D. research project investigates the promotional effects of alkaline carbonate eutectics on the proton conductivity of proton conducting electrolytes and cathodic ORR reactivity in SOFCs by both experimental and computational methods. The ionic conductivity of the MC-BZY composite above 500°C increases with the higher loading of MC. The sample exhibited nearly a factor of two higher conductivity in H2-containing atmosphere than in air. First-principles DFT modeling further investigated proton transfer at the interface of BaZrO 3 and molten carbonate. With the presence of carbonate ion, the energy barrier for proton migration becomes as low as 0.332 eV. The modeling indicates the reduction of energy barrier is resulted from the change of rate-determining step from proton transfer between oxygen atoms to proton rotation around oxygen atom. Infiltration of MC into porous cathode can reduce the polarization of resistance (Rp), i.e., enhance the oxygen reduction reaction (ORR) activity. The EIS analysis shows that MC has a beneficial effect on reducing Rp for different cathodes including Au, La0.8Sr 0.2MnO3-delta(LSM), La0.6Sr0.4Co 0.2Fe0.8O3-delta(LSCF) and La2NiO 4+delta (LNO). Specifically, the study on MC loading effect was carried out on LSCF cathode. It shows that a higher loading makes a greater reduction on Rp and the degree of reduction is the same from 500 to 600°C. As the loading increases to 1.4 wt%, the degree of Rp reduction tends to reach a limit. First-principles DFT modeling was further used to investigate the incorporation of oxygen into MC. The formation of CO 52- in molten carbonate was considered as a chemisorption of gas oxygen on the surface of MC infiltrated cathodes. After the formation of CO52-, it reacts with another CO3 2- to form two CO42-, which is a rate-limiting step on potential energy surface. After dissociation, oxygen atoms migrate in molten carbonate, which is energetically favor by intermolecular pathways. An O-O-O linkage is formed between carbonate ions, which facilitates the oxygen migration between carbonate ions.

Influences of dissolved oxygen concentration on biocathodic microbial communities in microbial fuel cells.

PubMed

Rago, Laura; Cristiani, Pierangela; Villa, Federica; Zecchin, Sarah; Colombo, Alessandra; Cavalca, Lucia; Schievano, Andrea

2017-08-01

Dissolved oxygen (DO) at cathodic interface is a critical factor influencing microbial fuel cells (MFC) performance. In this work, three MFCs were operated with cathode under different DO conditions: i) air-breathing (A-MFC); ii) water-submerged (W-MFC) and iii) assisted by photosynthetic microorganisms (P-MFC). A plateau of maximum current was reached at 1.06±0.03mA, 1.48±0.06mA and 1.66±0.04mA, increasing respectively for W-MFC, P-MFC and A-MFC. Electrochemical and microbiological tools (Illumina sequencing, confocal microscopy and biofilm cryosectioning) were used to explore anodic and cathodic biofilm in each MFC type. In all cases, biocathodes improved oxygen reduction reaction (ORR) as compared to abiotic condition and A-MFC was the best performing system. Photosynthetic cultures in the cathodic chamber supplied high DO level, up to 16mg O2 L -1 , which sustained aerobic microbial community in P-MFC biocathode. Halomonas, Pseudomonas and other microaerophilic genera reached >50% of the total OTUs. The presence of sulfur reducing bacteria (Desulfuromonas) and purple non-sulfur bacteria in A-MFC biocathode suggested that the recirculation of sulfur compounds could shuttle electrons to sustain the reduction of oxygen as final electron acceptor. The low DO concentration limited the cathode in W-MFC. A model of two different possible microbial mechanisms is proposed which can drive predominantly cathodic ORR. Copyright © 2017 Elsevier B.V. All rights reserved.

Promotion on electrochemical performance of a cation deficient SrCo0.7Nb0.1Fe0.2O3-δ perovskite cathode for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ding, Liming; Wang, Lixi; Ding, Dong; Zhang, Shihua; Ding, Xifeng; Yuan, Guoliang

2017-06-01

Solid oxide fuel cells (SOFCs) offer great promise for the most efficient and cost-effective conversion to electricity of a wide variety of fuels. The cathode materials with high electro-catalytic activity for oxygen reduction reaction is vital to the development of commercially-viable SOFCs to be operated at reduced temperatures. In present study, cobalt-based perovskite oxides SrxCo0.7Nb0.1Fe0.2O3-δ (SCNF, x = 0.95 and 1) were comparatively investigated as promising cathode materials for intermediate-temperature SOFCs. The SCNF compounds with a slight Sr deficiency (S0.95CNF) exhibited single phase of primitive cubic structure with Pm-3m symmetry. A small Sr deficiency is demonstrated to greatly enhance the electrochemical performance of stoichiometric SCNF cathode due to significantly increased oxygen vacancy. The polarization resistance of S0.95CNF at 700 °C was 0.11 Ω cm2, only about 61% of SCNF. The rate limiting step for oxygen reduction reaction (ORR) is demonstrated to be oxygen ion transfer within the bulk electrode and/or from electrode to electrolyte through the triple phase boundary. Full cells with the SCNF cathode present good performance and stable output at reduced temperatures, indicating the great potential for enhanced performance of Co-based cathodes with A-site deficiency.

Ultrahigh-Capacity Lithium-Oxygen Batteries Enabled by Dry-Pressed Holey Graphene Air Cathodes.

PubMed

Lin, Yi; Moitoso, Brandon; Martinez-Martinez, Chalynette; Walsh, Evan D; Lacey, Steven D; Kim, Jae-Woo; Dai, Liming; Hu, Liangbing; Connell, John W

2017-05-10

Lithium-oxygen (Li-O 2 ) batteries have the highest theoretical energy density of all the Li-based energy storage systems, but many challenges prevent them from practical use. A major obstacle is the sluggish performance of the air cathode, where both oxygen reduction (discharge) and oxygen evolution (charge) reactions occur. Recently, there have been significant advances in the development of graphene-based air cathode materials with a large surface area and catalytically active for both oxygen reduction and evolution reactions, especially with additional catalysts or dopants. However, most studies reported so far have examined air cathodes with a limited areal mass loading rarely exceeding 1 mg/cm 2 . Despite the high gravimetric capacity values achieved, the actual (areal) capacities of those batteries were far from sufficient for practical applications. Here, we present the fabrication, performance, and mechanistic investigations of high-mass-loading (up to 10 mg/cm 2 ) graphene-based air electrodes for high-performance Li-O 2 batteries. Such air electrodes could be easily prepared within minutes under solvent-free and binder-free conditions by compression-molding holey graphene materials because of their unique dry compressibility associated with in-plane holes on the graphene sheet. Li-O 2 batteries with high air cathode mass loadings thus prepared exhibited excellent gravimetric capacity as well as ultrahigh areal capacity (as high as ∼40 mAh/cm 2 ). The batteries were also cycled at a high curtailing areal capacity (2 mAh/cm 2 ) and showed a better cycling stability for ultrathick cathodes than their thinner counterparts. Detailed post-mortem analyses of the electrodes clearly revealed the battery failure mechanisms under both primary and secondary modes, arising from the oxygen diffusion blockage and the catalytic site deactivation, respectively. These results strongly suggest that the dry-pressed holey graphene electrodes are a highly viable architectural platform for high-capacity, high-performance air cathodes in Li-O 2 batteries of practical significance.

Fundamental understanding of oxygen reduction and reaction behavior and developing high performance and stable hetero-structured cathodes

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

Liu, Xingbo

2016-11-14

New unique hetero-structured cathode has been developed in this project. La 2NiO 4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La 0.6Sr 0.4) 0.95Co 0.2Fe 0.8O 3-δ (LSCF) cathode to enhance the surface-limited ORR kinetics on SOFC cathode. Furthermore, the hetero-structured cathode surface maintains high activity under electrode polarization with much less negative effects from surface cation segregation of Sr, which is known to cause degradation issues for conventional LSCF and LSC cathodes, thus improving the cathode long-term stability. The interface chemistry distribution and oxygen transport properties have been studied to prove themore » enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO 2 & La 2-xNiO 4+δ (x=0-0.2) co-infiltration is a simple and cost-effective method to improve both performance and stability of LSCF cathode by limiting nano-particles growth/delamination and further improve the surface stability. For the first time, a physical model is proposed to illustrate how unique interstitial species on hetero-structured cathode surface work to regulate the exchange rate of the incorporation reaction. Meanwhile, fundamental investigation of the surface oxygen exchange and bulk oxygen transport properties under over-potential conditions across cathode materials have been carried out in this project, which were discussed and compared to the Nernst equation that is generally applied to treat any oxide electrodes under equilibrium.« less

PTFE effect on the electrocatalysis of the oxygen reduction reaction in membraneless microbial fuel cells.

PubMed

Guerrini, Edoardo; Grattieri, Matteo; Faggianelli, Alessio; Cristiani, Pierangela; Trasatti, Stefano

2015-12-01

Influence of PTFE in the external Gas Diffusion Layer (GDL) of open-air cathodes applied to membraneless microbial fuel cells (MFCs) is investigated in this work. Electrochemical measurements on cathodes with different PTFE contents (200%, 100%, 80% and 60%) were carried out to characterize cathodic oxygen reduction reaction, to study the reaction kinetics. It is demonstrated that ORR is not under diffusion-limiting conditions in the tested systems. Based on cyclic voltammetry, an increase of the cathodic electrochemical active area took place with the decrease of PTFE content. This was not directly related to MFC productivity, but to the cathode wettability and the biocathode development. Low electrodic interface resistances (from 1 to 1.5 Ω at the start, to near 0.1 Ω at day 61) indicated a negligible ohmic drop. A decrease of the Tafel slopes from 120 to 80 mV during productive periods of MFCs followed the biological activity in the whole MFC system. A high PTFE content in the cathode showed a detrimental effect on the MFC productivity, acting as an inhibitor of ORR electrocatalysis in the triple contact zone.

Ionic Conductivity and its Role in Oxidation Reactions

NASA Astrophysics Data System (ADS)

Tamimi, Mazin Abdulla

In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the combination of a reference catalyst for the oxidative coupling of methane with a support with very high oxygen conductivity demonstrated a small increase in performance at low temperatures.

Impact of electrode sequence on electrochemical removal of trichloroethylene from aqueous solution

PubMed Central

Rajic, Ljiljana; Fallahpour, Noushin; Alshawabkeh, Akram N.

2015-01-01

The electrode sequence in a mixed flow-through electrochemical cell is evaluated to improve the hydrodechlorination (HDC) of trichloroethylene (TCE) in aqueous solutions. In a mixed (undivided) electrochemical cell, oxygen generated at the anode competes with the transformation of target contaminants at the cathode. In this study, we evaluate the effect of placing the anode downstream from the cathode and using multiple electrodes to promote TCE reduction. Experiments with a cathode followed by an anode (C→A) and an anode followed by a cathode (A→C) were conducted using mixed metal oxide (MMO) and iron as electrode materials. The TCE removal rates when the anode is placed downstream of the cathode (C→A) were 54% by MMO→MMO, 64% by MMO→Fe and 87% by Fe→MMO sequence. Removal rates when the anode is placed upstream of the cathode (A→C) were 38% by MMO→MMO, 58% by Fe→MMO and 69% by MMO→Fe sequence. Placing the anode downstream of the cathode positively improves (by 26%) the degradation of aqueous TCE in a mixed flow-through cell as it minimizes the influence of oxygen generated at the MMO anode on TCE reduction at the cathode. Furthermore, placing the MMO anode downstream of the cathode neutralizes pH and redox potential of the treated solution. Higher flow velocity under the C→A setup increases TCE mass flux reduction rate. Using multiple cathodes and an iron foam cathode up stream of the anode increase the removal rate by 1.6 and 2.4 times, respectively. More than 99% of TCE was removed in the presence of Pd catalyst on carbon and as an iron foam coating. Enhanced reaction rates found in this study imply that a mixed flow-through electrochemical cell with multiple cathodes up stream of an anode is an effective method to promote the reduction of TCE in groundwater. PMID:25931774

Recent advances in the design of tailored nanomaterials for efficient oxygen reduction reaction

DOE PAGES

Lv, Haifeng; Li, Dongguo; Strmcnik, Dusan; ...

2016-04-11

In the past decade, polymer electrolyte membrane fuels (PEMFCs) have been evaluated for both automotive and stationary applications. One of the main obstacles for large scale commercialization of this technology is related to the sluggish oxygen reduction reaction that takes place on the cathode side of fuel cell. Consequently, ongoing research efforts are focused on the design of cathode materials that could improve the kinetics and durability. Majority of these efforts rely on novel synthetic approaches that provide control over the structure, size, shape and composition of catalytically active materials. This article highlights the most recent advances that have beenmore » made to tailor critical parameters of the nanoscale materials in order to achieve more efficient performance of the oxygen reduction reaction (ORR).« less

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-02-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

DOE PAGES

Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.; ...

2017-10-17

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

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

Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molten carbonate fuel cell reduction of nickel deposits

DOEpatents

Smith, James L.; Zwick, Stanley A.

1987-01-01

A molten carbonate fuel cell with anode and cathode electrodes and an eleolyte formed with two tile sections, one of the tile sections being adjacent the anode and limiting leakage of fuel gas into the electrolyte with the second tile section being adjacent the cathode and having pores sized to permit the presence of oxygen gas in the electrolyte thereby limiting the formation of metal deposits caused by the reduction of metal compositions migrating into the electrolyte from the cathode.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

2012-11-13

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav [East Setauket, NY; Zhang, Junliang [Stony Brook, NY; Vukmirovic, Miomir [Port Jefferson Station, NY

2011-11-22

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Multiscale Transient and Steady-State Study of the Influence of Microstructure Degradation and Chromium Oxide Poisoning on Solid Oxide Fuel Cell Cathode Performance

NASA Astrophysics Data System (ADS)

Li, Guanchen; von Spakovsky, Michael R.; Shen, Fengyu; Lu, Kathy

2018-01-01

Oxygen reduction in a solid oxide fuel cell cathode involves a nonequilibrium process of coupled mass and heat diffusion and electrochemical and chemical reactions. These phenomena occur at multiple temporal and spatial scales, making the modeling, especially in the transient regime, very difficult. Nonetheless, multiscale models are needed to improve the understanding of oxygen reduction and guide cathode design. Of particular importance for long-term operation are microstructure degradation and chromium oxide poisoning both of which degrade cathode performance. Existing methods are phenomenological or empirical in nature and their application limited to the continuum realm with quantum effects not captured. In contrast, steepest-entropy-ascent quantum thermodynamics can be used to model nonequilibrium processes (even those far-from equilibrium) at all scales. The nonequilibrium relaxation is characterized by entropy generation, which can unify coupled phenomena into one framework to model transient and steady behavior. The results reveal the effects on performance of the different timescales of the varied phenomena involved and their coupling. Results are included here for the effects of chromium oxide concentrations on cathode output as is a parametric study of the effects of interconnect-three-phase-boundary length, oxygen mean free path, and adsorption site effectiveness. A qualitative comparison with experimental results is made.

Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

2015-03-01

Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

Simultaneous Wastewater Treatment, Algal Biomass Production and Electricity Generation in Clayware Microbial Carbon Capture Cells.

PubMed

Jadhav, Dipak A; Jain, Sumat C; Ghangrekar, Makarand M

2017-11-01

Performance of microbial carbon capture cells (MCCs), having a low-cost clayware separator, was evaluated in terms of wastewater treatment and electricity generation using algae Chlorella pyrenoidosa in MCC-1 and Anabaena ambigua in MCC-2 and without algae in a cathodic chamber of MCC-3. Higher power production was achieved in MCC-1 (6.4 W/m 3 ) compared to MCC-2 (4.29 W/m 3 ) and MCC-3 (3.29 W/m 3 ). Higher coulombic efficiency (15.23 ± 1.30%) and biomass production (66.4 ± 4.7 mg/(L*day)) in MCC-1 indicated the superiority of Chlorella over Anabaena algae for carbon capture and oxygen production to facilitate the cathodic reduction. Algal biofilm formation on the cathode surface of MCC-1 increased dissolved oxygen in the catholyte and decreased the cathodic charge transfer resistance with increase in reduction current. Electrochemical analyses revealed slow cathodic reactions and increase in internal resistance in MCC-2 (55 Ω) than MCC-1 (30 Ω), due to lower oxygen produced by Anabaena algae. Thus, biomass production in conjunction with wastewater treatment, CO 2 sequestration and electricity generation can be achieved using Chlorella algal biocathode in MCC.

Oxygen reduction reaction: A framework for success

DOE PAGES

Allendorf, Mark D.

2016-05-06

Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

PubMed Central

Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

2016-01-01

Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

The performance of spinel bulk-like oxygen-deficient CoGa2O4 as an air-cathode catalyst in microbial fuel cell

NASA Astrophysics Data System (ADS)

Liu, Di; Mo, Xiaoping; Li, Kexun; Liu, Yi; Wang, Junjie; Yang, Tingting

2017-08-01

Nano spinel bulk-like CoGa2O4 prepared via a facile hydrothermal method is used as a high efficient electrochemical catalyst in activated carbon (AC) air-cathode microbial fuel cell (MFC). The maximum power density of the modified MFC is 1911 ± 49 mW m-2, 147% higher than the MFC of untreated AC cathode. Transmission electron microscope (TEM) and X-ray diffraction (XRD) exhibit the morphology and crystal structure of CoGa2O4. Rotating disk electrode (RDE) confirms the four-electron pathway at the cathode during the oxygen reduction reaction (ORR). Thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) illustrate that the high rate oxygen vacancy exist in the CoGa2O4. The oxygen vacancy of CoGa2O4 plays an important role in catalytic activity. In a word, the prepared nano spinel bulk-like CoGa2O4 provides an alternative to the costly Pt in air-cathode for power output.

Polyaniline/β-MnO2 nanocomposites as cathode electrocatalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Zhou, Xinxing; Xu, Yunzhi; Mei, Xiaojie; Du, Ningjie; Jv, Rongmao; Hu, Zhaoxia; Chen, Shouwen

2018-05-01

An efficient and inexpensive catalyst for oxygen reduction reaction (ORR), polyaniline (PANI) and β-MnO 2 nanocomposites (PANI/β-MnO 2 ), was developed for air-cathode microbial fuel cells (MFCs). The PANI/β-MnO 2 , β-MnO 2 , PANI and β-MnO 2 mixture modified graphite felt electrodes were fabricated as air-cathodes in double-chambered MFCs and their cell performances were compared. At a dosage of 6 mg cm -2 , the maximum power densities of MFCs with PANI/β-MnO 2 , β-MnO 2 , PANI and β-MnO 2 mixture cathodes reached 248, 183 and 204 mW m -2 , respectively, while the cathode resistances were 38.4, 45.5 and 42.3 Ω, respectively, according to impedance analysis. Weak interaction existed between the rod-like β-MnO 2 and surficial growth granular PANI, this together with the larger specific surface area and PANI electric conducting nature enhanced the electrochemical activity for ORR and improved the power generation. The PANI/β-MnO 2 nanocomposites are a promising cathode catalyst for practical application of MFCs. Copyright © 2018. Published by Elsevier Ltd.

Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

PubMed

Cheng, Fangyi; Chen, Jun

2012-03-21

Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

Solid oxide fuel cells fueled with reducible oxides

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

Chuang, Steven S.; Fan, Liang Shih

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

Hydrothermal Synthesis of Nanostructured Manganese Oxide as Cathodic Catalyst in a Microbial Fuel Cell Fed with Leachate

PubMed Central

Haoran, Yuan; Lifang, Deng; Tao, Lu; Yong, Chen

2014-01-01

Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM) was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM), accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m2 was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment. PMID:24723824

Nickel oxide and carbon nanotube composite (NiO/CNT) as a novel cathode non-precious metal catalyst in microbial fuel cells.

PubMed

Huang, Jianjian; Zhu, Nengwu; Yang, Tingting; Zhang, Taiping; Wu, Pingxiao; Dang, Zhi

2015-10-15

Comparing with the precious metal catalysts, non-precious metal catalysts were preferred to use in microbial fuel cells (MFCs) due to the low cost and high oxygen reduction reaction (ORR) efficiency. In this study, the transmission electron microscope and X-ray diffraction as well as Raman investigation revealed that the prepared nanoscale NiO was attached on the surface of CNT. Cyclic voltammogram and rotating ring-disk electrode tests showed that the NiO/CNT composite catalyst had an apparent oxygen reduction peak and 3.5 electron transfer pathway was acquired under oxygen atmosphere. The catalyst performance was highly dependent on the percentage of NiO in the CNT nanocomposites. When 77% NiO/CNT nano-sized composite was applied as cathode catalyst in membrane free single-chamber air cathode MFC, a maximum power density of 670 mW/m(2) and 0.772 V of OCV was obtained. Moreover, the MFC with pure NiO (control) could not achieve more than 0.1 V. All findings suggested that NiO/CNT could be a potential cathode catalyst for ORR in MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

Potential of porous Co3O4 nanorods as cathode catalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Kumar, Ravinder; Singh, Lakhveer; Zularisam, A W; Hai, Faisal I

2016-11-01

This study aims to investigate the potential of porous Co3O4 nanorods as the cathode catalyst for oxygen reduction reaction (ORR) in aqueous air cathode microbial fuel cells (MFCs). The porous Co3O4 nanorods were synthesized by a facile and cost-effective hydrothermal method. Three different concentrations (0.5mg/cm(2), 1mg/cm(2), and 2mg/cm(2)) of Co3O4 nanorods coated on graphite electrodes were used to test its performance in MFCs. The results showed that the addition of porous Co3O4 nanorods enhanced the electrocatalytic activity and ORR kinetics significantly and the overall resistance of the system was greatly reduced. Moreover, the MFC with a higher concentration of the catalyst achieved a maximum power density of 503±16mW/m(2), which was approximately five times higher than the bare graphite electrode. The improved catalytic activity of the cathodes could be due to the porous properties of Co3O4 nanorods that provided the higher number of active sites for oxygen. Copyright © 2016 Elsevier Ltd. All rights reserved.

Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

PubMed Central

Li, Yong; Wang, Shijie; Su, Pei-Chen

2016-01-01

An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode. PMID:26928192

The excellent performance of nest-like oxygen-deficient Cu1.5Mn1.5O4 applied in activated carbon air-cathode microbial fuel cell.

PubMed

Wang, Junjie; Tian, Pei; Li, Kexun; Ge, Baochao; Liu, Di; Liu, Yi; Yang, Tingting; Ren, Rong

2016-12-01

This study investigated the performance of nano spinel nest-like oxygen-deficient Cu 1.5 Mn 1.5 O 4 doping activated carbon (AC) as air cathode in microbial fuel cell (MFC). The Cu 1.5 Mn 1.5 O 4 was synthesized via hydrothermal method and subsequent annealed. The maximum power density (MPD) of MFC with oxygen-deficient Cu 1.5 Mn 1.5 O 4 modified cathode was 1928±18mWm -2 , which was 1.53 times higher than the bare cathode. The electrochemical studies showed that Cu 1.5 Mn 1.5 O 4 doping AC exhibited higher kinetic activity and lower resistance. The mechanism of oxygen reduction for the catalyst was a four electron pathway. The oxygen deficient of Cu 1.5 Mn 1.5 O 4 played an important role in catalytic activity. So Cu 1.5 Mn 1.5 O 4 would be an excellent promising catalyst for ORR in MFC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Porous nitrogen-doped carbon nanosheet on graphene as metal-free catalyst for oxygen reduction reaction in air-cathode microbial fuel cells.

PubMed

Wen, Qing; Wang, Shaoyun; Yan, Jun; Cong, Lijie; Chen, Ye; Xi, Hongyuan

2014-02-01

Porous nitrogen-doped carbon nanosheet on graphene (PNCN) was used as an alternative cathode catalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). Here we report a novel, low-cost, scalable, synthetic method for preparation of PNCN via the carbonization of graphite oxide-polyaniline hybrid (GO-PANI), subsequently followed by KOH activation treatment. Due to its high concentration of nitrogen and high specific surface area, PNCN exhibited an excellent catalytic activity for ORR. As a result, the maximum power density of 1159.34mWm(-2) obtained with PNCN catalyst was higher than that of Pt/C catalyst (858.49mWm(-2)) in a MFC. Therefore, porous nitrogen-doped carbon nanosheet could be a good alternative to Pt catalyst in MFCs. © 2013.

Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

NASA Astrophysics Data System (ADS)

Strom, Matthew James

Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled out the enzymatic catalysis of ORR and supported the catalysis by MnO2. Sustainable redox reactions at the cathode were evaluated by monitoring the cathodic current of biofilm coated stainless steel for a year under different polarization intensities. The results showed that sustainable cathodic reactions were present in marine biofilms but their influence on the cathodic current was negligible until a potential was reached where the ORR could take place. Additionally seasonal variability was observed in the enhanced cathodic current in Delaware Bay biofilms. This was attributed to the seasonal variability of manganese in the water column.

MnO2-x nanosheets on stainless steel felt as a carbon- and binder-free cathode for non-aqueous lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Wei, Z. H.; Zhao, T. S.; Zhu, X. B.; Tan, P.

2016-02-01

Manganese dioxide (MnO2) has been recognized as an effective catalyst for the oxygen reduction and oxygen evolution reactions in non-aqueous lithium-oxygen batteries. However, a further improvement in battery performance with the MnO2 catalyst is limited by its low electronic conductivity and catalytic activity, which strongly depend on the morphology and composition. In this work, we develop a carbon- and binder-free MnO2-x nanosheets/stainless steel (SS) cathode via a simple and effective electrodeposition-solvothermal route. The created Mn(III) and oxygen vacancy in MnO2-x nanosheets allows an significant increase in the electronic conductivity and catalytic activity. It is experimentally shown that the use of the present nanostructure MnO2-x/SS cathode in a non-aqueous lithium-oxygen battery results in a rechargeable specific capacity of 7300 mAh g-1 at a current density of 200 mA g-1, which is 39% higher than that with the MnO2/SS cathode. In addition, the specific capacities at 400 mA g-1 and 800 mA g-1 reach 5249 mAh g-1 and 2813 mAh g-1, respectively, which are over 30% higher than that with the MnO2/SS cathode. Furthermore, the discharge/charge cycle test shows no degradation for 120 cycles. All the results show that the present nanostructure MnO2-x/SS cathode is a promising candidate for high-performance lithium-oxygen batteries.

New electrocatalysts for hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Cattabriga, R. A.; Giner, J.; Parry, J.; Swette, L. L.

1970-01-01

Platinum-silver, palladium-gold, and platinum-gold alloys serve as oxygen reduction catalysts in high-current-density cells. Catalysts were tested on polytetrafluoroethylene-bonded cathodes and a hydrogen anode at an operating cell temperature of 80 degrees C.

Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

PubMed

Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

2011-04-01

Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

Reactive Black 5 as electron donor and/or electron acceptor in dual chamber of solar photocatalytic fuel cell.

PubMed

Khalik, Wan Fadhilah; Ho, Li-Ngee; Ong, Soon-An; Voon, Chun-Hong; Wong, Yee-Shian; Yusuf, Sara Yasina; Yusoff, NikAthirah; Lee, Sin-Li

2018-07-01

The role of azo dye Reactive Black 5 (RB5) as an electron donor and/or electron acceptor could be distinguished in dual chamber of photocatalytic fuel cell (PFC). The introduction of RB5 in anode chamber increased the voltage generation in the system since degradation of RB5 might produce electrons which also would transfer through external circuit to the cathode chamber. The removal efficiency of RB5 with open and closed circuit was 8.5% and 13.6%, respectively and removal efficiency for open circuit was low due to the fact that recombination of electron-hole pairs might happen in anode chamber since without connection to the cathode, electron cannot be transferred. The degradation of RB5 in cathode chamber with absence of oxygen showed that electrons from anode chamber was accepted by dye molecules to break its azo bond. The presence of oxygen in cathode chamber would improve the oxygen reduction rate which occurred at Platinum-loaded carbon (Pt/C) cathode electrode. The V oc , J sc and P max for different condition of ultrapure water at cathode chamber also affected their fill factor. The transportation of protons to cathode chamber through Nafion membrane could decrease the pH of ultrapure water in cathode chamber and undergo hydrogen evolution reaction in the absence of oxygen which then increased degradation rate of RB5 as well as its electricity generation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Improved fuel-cell-type hydrogen sensor

NASA Technical Reports Server (NTRS)

Rudek, F. P.; Rutkowski, M. D.

1968-01-01

Modified hydrogen sensor replaces oxygen cathode with a cathode consisting of a sealed paste of gold hydroxide and a pure gold current collector. The net reaction which occurs during cell operation is the reduction of the gold hydroxide to gold and water, with a half-cell potential of 1.4 volts.

Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

DOE PAGES

St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

2016-01-05

A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

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

St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

Palladium-cobalt particles as oxygen-reduction electrocatalysts

DOEpatents

Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

2009-12-15

The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

Tracking Oxygen Vacancies in Thin Film SOFC Cathodes

NASA Astrophysics Data System (ADS)

Leonard, Donovan; Kumar, Amit; Jesse, Stephen; Kalinin, Sergei; Shao-Horn, Yang; Crumlin, Ethan; Mutoro, Eva; Biegalski, Michael; Christen, Hans; Pennycook, Stephen; Borisevich, Albina

2011-03-01

Oxygen vacancies have been proposed to control the rate of the oxygen reduction reaction and ionic transport in complex oxides used as solid oxide fuel cell (SOFC) cathodes [1,2]. In this study oxygen vacancies were tracked, both dynamically and statically, with the combined use of scanned probe microscopy (SPM) and scanning transmission electron microscopy (STEM). Epitaxial films of La 0.8 Sr 0.2 Co O3 (L SC113) and L SC113 / LaSrCo O4 (L SC214) on a GDC/YSZ substrate were studied, where the latter showed increased electrocatalytic activity at moderate temperature. At atomic resolution, high angle annular dark field STEM micrographs revealed vacancy ordering in L SC113 as evidenced by lattice parameter modulation and EELS studies. The evolution of oxygen vacancy concentration and ordering with applied bias and the effects of bias cycling on the SOFC cathode performance will be discussed. Research is sponsored by the of Materials Sciences and Engineering Division, U.S. DOE.

Preventing Corrosion by Controlling Cathodic Reaction Kinetics

DTIC Science & Technology

2016-03-25

electrochemical reaction rates of processes that drive corrosion, e.g. the oxygen reduction reaction (ORR). To this end, we have used reactive...elements on the kinetics of oxygen reduction reaction catalyzed on titanium oxide in order to develop new approaches for controlling galvanic corrosion... consumption of anions in reactions with metal cations can deplete the electrolyte. However, in the atmospheric electrolyte, the electrolyte

Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

ERIC Educational Resources Information Center

Duong, Hung Tuan

2009-01-01

The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

Electricity generation from banana peels in an alkaline fuel cell with a Cu2O-Cu modified activated carbon cathode.

PubMed

Liu, Peng; Liu, Xianhua; Dong, Feng; Lin, Qingxia; Tong, Yindong; Li, Yang; Zhang, Pingping

2018-08-01

Low-cost and highly active catalyst for oxygen reduction reaction is of great importance in the design of alkaline fuel cells. In this work, Cu 2 O-Cu composite catalyst has been fabricated by a facile laser-irradiation method. The addition of Cu 2 O-Cu composite in activated carbon air-cathode greatly improves the performance of the cathode. Our results indicate the enhanced performance is likely attributed to the synergistic effect of high conductivity of Cu and the catalytic activity of Cu 2 O towards the oxygen reduction reaction. Furthermore, an alkaline fuel cell equipped with the composite air-cathode has been built to turn banana peels into electricity. Peak power density of 16.12Wm -2 is obtained under the condition of 3M KOH and 22.04gL -1 reducing sugar, which is higher than other reported low-temperature direct biomass alkaline fuel cells. HPLC results indicate the main oxidation products in the alkaline fuel cell were small organic acids. Copyright © 2018 Elsevier B.V. All rights reserved.

Pressurized air cathodes for enhanced stability and power generation by microbial fuel cells

NASA Astrophysics Data System (ADS)

He, Weihua; Yang, Wulin; Tian, Yushi; Zhu, Xiuping; Liu, Jia; Feng, Yujie; Logan, Bruce E.

2016-11-01

Large differences between the water and air pressure in microbial fuel cells (MFCs) can deform and damage cathodes. To avoid deformation, the cathode air pressure was controlled to balance pressure differences between the air and water. Raising the air pressures from 0 to 10 kPa at a set cathode potential of -0.3 V (versus Ag/AgCl) enhanced cathode performance by 17%, but pressures ≥25 kPa decreased current and resulted in air leakage into the solution. Matching the air pressure with the water pressure avoided cathode deformation and improved performance. The maximum power density increased by 15%, from 1070 ± 20 to 1230 ± 70 mW m-2, with balanced air and water pressures of 10-25 kPa. Oxygen partial pressures ≥12.5 kPa in the cathode compartment maintained the oxygen reduction rate to be within 92 ± 1% of that in ambient air. The use of pressurized air flow through the cathode compartments can enable closer spacing of the cathodes compared to passive gas transfer systems, which could make the reactor design more compact. The energy cost of pressurizing the cathodes was estimated to be smaller than the increase in power that resulted from the use of pressurized cathodes.

Assisting cultivation of photosynthetic microorganisms by microbial fuel cells to enhance nutrients recovery from wastewater.

PubMed

Colombo, Alessandra; Marzorati, Stefania; Lucchini, Giorgio; Cristiani, Pierangela; Pant, Deepak; Schievano, Andrea

2017-08-01

Spirulina was cultivated in cathodic compartments of photo-microbial fuel cells (P-MFC). Anodic compartments were fed with swine-farming wastewater, enriched with sodium acetate (2.34g COD L -1 ). Photosynthetic oxygen generation rates were sufficient to sustain cathodic oxygen reduction, significantly improving P-MFC electrochemical performances, as compared to water-cathode control experiments. Power densities (0.8-1Wm -2 ) approached those of air-cathode MFCs, run as control. COD was efficiently removed and only negligible fractions leaked to the cathodic chamber. Spirulina growth rates were comparable to those of control (MFC-free) cultures, while pH was significantly (0.5-1unit) higher in P-MFCs, due to cathodic reactions. Alkaliphilic photosynthetic microorganisms like Spirulina might take advantage of these selective conditions. Electro-migration along with diffusion to the cathodic compartment concurred for the recovery of most nutrients. Only P and Mg were retained in the anodic chamber. A deeper look into electro-osmotic mechanisms should be addressed in future studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cubic PdNP-based air-breathing cathodes integrated in glucose hybrid biofuel cells

NASA Astrophysics Data System (ADS)

Faggion Junior, D.; Haddad, R.; Giroud, F.; Holzinger, M.; Maduro de Campos, C. E.; Acuña, J. J. S.; Domingos, J. B.; Cosnier, S.

2016-05-01

Cubic Pd nanoparticles (PdNPs) were synthesized using ascorbic acid as a reducing agent and were evaluated for the catalytic oxygen reduction reaction. PdNPs were confined with multiwalled carbon nanotube (MWCNT) dispersions to form black suspensions and these inks were dropcast onto glassy carbon electrodes. Different nanoparticle sizes were synthesized and investigated upon oxygen reduction capacities (onset potential and electrocatalytic current densities) under O2 saturated conditions at varying pH values. Strong evidence of O2 diffusion limitation was demonstrated. In order to overcome oxygen concentration and diffusion limitations in solution, we used a gas diffusion layer to create a PdNP-based air-breathing cathode, which delivered -1.5 mA cm-2 at 0.0 V with an onset potential of 0.4 V. This air-breathing cathode was combined with a specially designed phenanthrolinequinone/glucose dehydrogenase-based anode to form a complete glucose/O2 hybrid bio-fuel cell providing an open circuit voltage of 0.554 V and delivering a maximal power output of 184 +/- 21 μW cm-2 at 0.19 V and pH 7.0.Cubic Pd nanoparticles (PdNPs) were synthesized using ascorbic acid as a reducing agent and were evaluated for the catalytic oxygen reduction reaction. PdNPs were confined with multiwalled carbon nanotube (MWCNT) dispersions to form black suspensions and these inks were dropcast onto glassy carbon electrodes. Different nanoparticle sizes were synthesized and investigated upon oxygen reduction capacities (onset potential and electrocatalytic current densities) under O2 saturated conditions at varying pH values. Strong evidence of O2 diffusion limitation was demonstrated. In order to overcome oxygen concentration and diffusion limitations in solution, we used a gas diffusion layer to create a PdNP-based air-breathing cathode, which delivered -1.5 mA cm-2 at 0.0 V with an onset potential of 0.4 V. This air-breathing cathode was combined with a specially designed phenanthrolinequinone/glucose dehydrogenase-based anode to form a complete glucose/O2 hybrid bio-fuel cell providing an open circuit voltage of 0.554 V and delivering a maximal power output of 184 +/- 21 μW cm-2 at 0.19 V and pH 7.0. Electronic supplementary information (ESI) available: Physical characterization, Fig. S1-S4 electrochemical experiments Fig. S5-S11. See DOI: 10.1039/c6nr01245k

Three-electrode metal oxide reduction cell

DOEpatents

Dees, Dennis W.; Ackerman, John P.

2008-08-12

A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

Three-Electrode Metal Oxide Reduction Cell

DOEpatents

Dees, Dennis W.; Ackerman, John P.

2005-06-28

A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries

NASA Astrophysics Data System (ADS)

Zhang, Jian; Luan, Yanping; Lyu, Zhiyang; Wang, Liangjun; Xu, Leilei; Yuan, Kaidi; Pan, Feng; Lai, Min; Liu, Zhaolin; Chen, Wei

2015-09-01

A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery.A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02983j

Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

PubMed Central

Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

2016-01-01

Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH− oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion. PMID:27199009

Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

PubMed

Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

2015-03-11

Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

A Membrane-Free Neutral pH Formate Fuel Cell Enabled by a Selective Nickel Sulfide Oxygen Reduction Catalyst.

PubMed

Yan, Bing; Concannon, Nolan M; Milshtein, Jarrod D; Brushett, Fikile R; Surendranath, Yogesh

2017-06-19

Polymer electrolyte membranes employed in contemporary fuel cells severely limit device design and restrict catalyst choice, but are essential for preventing short-circuiting reactions at unselective anode and cathode catalysts. Herein, we report that nickel sulfide Ni 3 S 2 is a highly selective catalyst for the oxygen reduction reaction in the presence of 1.0 m formate. We combine this selective cathode with a carbon-supported palladium (Pd/C) anode to establish a membrane-free, room-temperature formate fuel cell that operates under benign neutral pH conditions. Proof-of-concept cells display open circuit voltages of approximately 0.7 V and peak power values greater than 1 mW cm -2 , significantly outperforming the identical device employing an unselective platinum (Pt) cathode. The work establishes the power of selective catalysis to enable versatile membrane-free fuel cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward Stabilizing Co 3O 4 Nanoparticles as an Oxygen Reduction Reaction Catalyst for Intermediate-Temperature SOFCs

DOE PAGES

Ren, Yaoyu; Cheng, Yuan; Gorte, Raymond J.; ...

2017-04-05

The oxygen reduction reaction (ORR) activity of a series of composite cathodes consisting of a porous Gd 0.20Ce 0.80O 2-δ (GDC) scaffold infiltrated with Sr-, Co-, and Y-nitrate solutions has been systematically investigated in this study. The results show that such infiltrated cathodes if calcined at low temperatures such as 350°C exhibit low polarization resistance (RP) in the temperature range of 450–700°C, even though XRD analysis reveals that the calcined product is virtually a mixture of Co 3O 4 and SrCO 3. A further study by design-of-experiment suggests that the true ORR-active species is Co 3O 4, whereas SrCO 3more » serves as a sintering inhibitor to preserve the high surface area of Co 3O 4. The findings and understanding in this study present a new strategy for future development of active cathodes for intermediate-temperature solid oxide fuel cells (SOFCs).« less

Toward Stabilizing Co 3O 4 Nanoparticles as an Oxygen Reduction Reaction Catalyst for Intermediate-Temperature SOFCs

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

Ren, Yaoyu; Cheng, Yuan; Gorte, Raymond J.

The oxygen reduction reaction (ORR) activity of a series of composite cathodes consisting of a porous Gd 0.20Ce 0.80O 2-δ (GDC) scaffold infiltrated with Sr-, Co-, and Y-nitrate solutions has been systematically investigated in this study. The results show that such infiltrated cathodes if calcined at low temperatures such as 350°C exhibit low polarization resistance (RP) in the temperature range of 450–700°C, even though XRD analysis reveals that the calcined product is virtually a mixture of Co 3O 4 and SrCO 3. A further study by design-of-experiment suggests that the true ORR-active species is Co 3O 4, whereas SrCO 3more » serves as a sintering inhibitor to preserve the high surface area of Co 3O 4. The findings and understanding in this study present a new strategy for future development of active cathodes for intermediate-temperature solid oxide fuel cells (SOFCs).« less

Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

DOEpatents

Xing, Weibing; Buettner-Garrett, Josh

2017-04-18

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

Electrochemical Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

2010-01-01

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

NASA Astrophysics Data System (ADS)

Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

2016-02-01

Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

CoMn2O4-supported functionalized carbon nanotube: efficient catalyst for oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Nengwu; Lu, Yu; Liu, Bowen; Zhang, Taiping; Huang, Jianjian; Shi, Chaohong; Wu, Pingxiao; Dang, Zhi; Wang, Ruixin

2017-10-01

Recently, the synthesis of nonprecious metal catalysts with low cost and high oxygen reduction reaction (ORR) efficiency is paid much attention in field of microbial fuel cells (MFCs). Transition metal oxides (AMn2O4, A = Co、Ni, and Zn) supported on carbon materials such as graphene and carbon nanotube exhibit stronger electroconductivity and more active sites comparing to bare AMn2O4. Herein, we demonstrate an easy operating Hummer's method to functionalize carbon nanotubes (CNTs) with poly (diallyldimethylammonium chloride) in order to achieve effective loading of CoMn2O4 nanoparticles, named CoMn2O4/PDDA-CNTs (CMODT). After solvothermal treatment, nanoscale CoMn2O4 particles ( 80 nm) were successfully attached on the noncovalent functionalized carbon nanotube. Results show that such composites possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in neutral media. Electrochemical detections as cyclic voltammogram (CV) and rotating ring-disk electrode tests (RRDE) showed that the potential of oxygen reduction peak of 30% CMODT was at - 0.3 V (vs Ag/AgCl), onset potential was at + 0.4 V. Among them, 30% CMODT composite appeared the best candidate of oxygen reduction via 3.9 electron transfer pathway. When 30% CMODT composite was utilized as cathode catalyst in air cathode MFC, the reactor obtained 1020 mW m-2 of the highest maximum power density and 0.781 V of open circuit voltage. The excellent activity and low cost (0.2 g-1) of the hybrid materials demonstrate the potential of transition metal oxide/carbon as effective cathode ORR catalyst for microbial fuel cells. [Figure not available: see fulltext.

Electro-catalytic oxidation device for removing carbon from a fuel reformate

DOEpatents

Liu, Di-Jia [Naperville, IL

2010-02-23

An electro-catalytic oxidation device (ECOD) for the removal of contaminates, preferably carbonaceous materials, from an influent comprising an ECOD anode, an ECOD cathode, and an ECOD electrolyte. The ECOD anode is at a temperature whereby the contaminate collects on the surface of the ECOD anode as a buildup. The ECOD anode is electrically connected to the ECOD cathode, which consumes the buildup producing electricity and carbon dioxide. The ECOD anode is porous and chemically active to the electro-catalytic oxidation of the contaminate. The ECOD cathode is exposed to oxygen, and made of a material which promotes the electro-chemical reduction of oxygen to oxidized ions. The ECOD electrolyte is non-permeable to gas, electrically insulating and a conductor to oxidized. The ECOD anode is connected to the fuel reformer and the fuel cell. The ECOD electrolyte is between and in ionic contact with the ECOD anode and the ECOD cathode.

Microstructure-scaled active sites imaging of a solid oxide fuel cell composite cathode

NASA Astrophysics Data System (ADS)

Nagasawa, Tsuyoshi; Hanamura, Katsunori

2017-11-01

Active sites for oxygen reduction reaction in strontium-doped lanthanum manganite (LSM)/scandia-stabilized zirconia (ScSZ) composite cathode of solid oxide fuel cell (SOFC) is visualized in microstructure scale by oxygen isotope labeling. In order to quench a reaction, a SOFC power generation equipment with a nozzle for direct helium gas impinging jet to the cell is prepared. A typical electrolyte-supported cell is operated by supplying 18O2 at 1073 K and abruptly quenched to room temperature. During the quench, the temperature of the cell is decreased from 1073 K to 673 K in 1 s. The 18O concentration distribution in the cross section of the quenched cathode is obtained by secondary ion mass spectrometry (SIMS) with a spatial resolution of 50 nm. The obtained 18O mapping gives the first visualization of highly distributed active sites in the composite cathode both in macroscopic and particle scales.

Cyanide oxidation by singlet oxygen generated via reaction between H2O2 from cathodic reduction and OCl(-) from anodic oxidation.

PubMed

Tian, Shichao; Li, Yibing; Zeng, Huabin; Guan, Wei; Wang, Yan; Zhao, Xu

2016-11-15

Cyanide is widely present in electroplating wastewater or metallurgical effluents. In the present study, the electrochemical destruction of cyanide with various anode and cathode compositions under alkaline conditions was investigated. The results indicated that the electrochemical system using RuO2/Ti as anode and activated carbon fiber (ACF) as cathode in the presence of sodium chloride was efficient for the cyanide removal. In this system, in situ generation of HClO by anodic oxidation of Cl(-) at RuO2/Ti anode occurred with the H2O2 generation by O2 reduction at ACF cathode. As confirmed by the electron spin resonance technique, the reaction between HClO and H2O2 led to the generation of singlet oxygen, which was responsible for the cyanide removal. Further experiment indicated that the cyanide removal efficiency increased with the increase of the current density or the sodium chloride concentration. Cyanate was identified as main product in the system. Besides, the system exhibited good stability for the cyanide removal, which was beneficial to its practical application. Copyright © 2016. Published by Elsevier Inc.

Isolation and bioelectrochemical characterization of novel fungal sources with oxidasic activity applied in situ for the cathodic oxygen reduction in microbial fuel cells.

PubMed

Morant, Kyriale Vasconcelos; da Silva, Paulo Henrique; de Campos-Takaki, Galba Maria; Hernández, Camilo Enrique La Rotta

2014-11-01

Brazilian filamentous fungi Rhizopus sp. (SIS-31), Aspergillus sp. (SIS-18) and Penicillium sp. (SIS-21), sources of oxidases were isolated from Caatinga's soils and applied during the in situ cathodic oxygen reduction in fuel cells. All strains were cultivated in submerged cultures using an optimized saline medium enriched with 10 g L(-1) of glucose, 3.0 g L(-1) of peptone and 0.0005 g L(-1) of CuSO4 as enzyme inducer. Parameters of oxidase activity, glucose consumption and microbial growth were evaluated. In-cell experiments evaluated by chronoamperometry were performed and two different electrode compositions were also compared. Maximum current densities of 125.7, 98.7 and 11.5 μA cm(-2) were observed before 24 h and coulombic efficiencies of 56.5, 46.5 and 23.8% were obtained for SIS-31, SIS-21 and SIS-18, respectively. Conversely, maximum power outputs of 328.73, 288.80 and 197.77 mW m(-3) were observed for SIS-18, SIS-21 and SIS-31, respectively. This work provides the primary experimental evidences that fungi isolated from the Caatinga region in Brazil can serve as efficient biocatalysts during the oxygen reduction in air-cathodes to improve electricity generation in MFCs. Copyright © 2014 Elsevier Inc. All rights reserved.

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

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.

Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

2015-06-01

Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

A Glucose Fuel Cell for Implantable Brain–Machine Interfaces

PubMed Central

Rapoport, Benjamin I.; Kedzierski, Jakub T.; Sarpeshkar, Rahul

2012-01-01

We have developed an implantable fuel cell that generates power through glucose oxidation, producing steady-state power and up to peak power. The fuel cell is manufactured using a novel approach, employing semiconductor fabrication techniques, and is therefore well suited for manufacture together with integrated circuits on a single silicon wafer. Thus, it can help enable implantable microelectronic systems with long-lifetime power sources that harvest energy from their surrounds. The fuel reactions are mediated by robust, solid state catalysts. Glucose is oxidized at the nanostructured surface of an activated platinum anode. Oxygen is reduced to water at the surface of a self-assembled network of single-walled carbon nanotubes, embedded in a Nafion film that forms the cathode and is exposed to the biological environment. The catalytic electrodes are separated by a Nafion membrane. The availability of fuel cell reactants, oxygen and glucose, only as a mixture in the physiologic environment, has traditionally posed a design challenge: Net current production requires oxidation and reduction to occur separately and selectively at the anode and cathode, respectively, to prevent electrochemical short circuits. Our fuel cell is configured in a half-open geometry that shields the anode while exposing the cathode, resulting in an oxygen gradient that strongly favors oxygen reduction at the cathode. Glucose reaches the shielded anode by diffusing through the nanotube mesh, which does not catalyze glucose oxidation, and the Nafion layers, which are permeable to small neutral and cationic species. We demonstrate computationally that the natural recirculation of cerebrospinal fluid around the human brain theoretically permits glucose energy harvesting at a rate on the order of at least 1 mW with no adverse physiologic effects. Low-power brain–machine interfaces can thus potentially benefit from having their implanted units powered or recharged by glucose fuel cells. PMID:22719888

Significant advantages of sulfur-doped graphene in neutral media as electrocatalyst for oxygen reduction comparing with Pt/C

NASA Astrophysics Data System (ADS)

Shi, Xinxin; Zhang, Jiaona; Huang, Tinglin

2018-02-01

Sulfur-doped graphene (SDG) has been found to be an efficient electrocatalyst for oxygen reduction reaction. However, previous studies on the catalytic activity of SDG have been mainly confined to O2-saturated alkaline media which is a typical alkaline fuel cell environment. Air-cathode microbial fuel cells (ACMFCs), as a novel energy conversion and wastewater treatment technology, use the oxygen from air as cathodic reactant in neutral media with low concentration of O2. Thus, it is meaningful to explore the catalytic performance of SDG in such ACMFC environment. The result showed that in ACMFC environment, the peak current density of SDG in CV test was surprisingly 4.5 times higher than that of Pt/C, indicating a much stronger catalytic activity of SDG. Moreover, SDG exhibited a stronger tolerance against the crossover of glucose (a typical anodic fuel in ACMFC) and better stability than Pt/C in neutral media.

Graphene/graphene-tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O₂ batteries.

PubMed

Li, Qing; Xu, Ping; Gao, Wei; Ma, Shuguo; Zhang, Guoqi; Cao, Ruiguo; Cho, Jaephil; Wang, Hsing-Lin; Wu, Gang

2014-03-05

Nitrogen-doped graphene/graphene-tube nanocomposites are prepared by a hightemperature approach using a newly designed cage-containing metal-organic framework (MOF) to template nitrogen/carbon (dicyandiamide) and iron precursors. The resulting N-Fe-MOF catalysts universally exhibit high oxygen-reduction activity in acidic, alkaline, and non-aqueous electrolytes and superior cathode performance in Li-O2 batteries. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrolyzed binuclear-cobalt-phthalocyanine as electrocatalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Li, Baitao; Wang, Mian; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

2015-10-01

A novel platinum (Pt)-free cathodic materials binuclear-cobalt-phthalocyanine (Bi-CoPc) pyrolyzed at different temperatures (300-1000 °C) were examined as the oxygen reduction reaction (ORR) catalysts, and compared with unpyrolyzed Bi-CoPc/C and Pt cathode in single chamber microbial fuel cells (SCMFCs). The results showed that the pyrolysis process increased the nitrogen abundance on Bi-CoPc and changed the nitrogen types. The Bi-CoPc pyrolyzed at 800 °C contained a significant amount of pyrrolic-N, and exhibited a high electrochemical catalytic activity. The power density and current density increased with temperature: Bi-CoPc/C-800 > Bi-CoPc/C-1000 > Bi-CoPc/C-600 > Bi-CoPc/C-300 > Bi-CoPc/C. The SCMFC with Bi-CoPc/C-800 cathode had a maximum power density of 604 mW m(-2). The low cost Bi-CoPc compounds developed in this study showed a potential in air-breathing MFC systems, with the proper pyrolysis temperature being chosen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells.

PubMed

Kuklja, M M; Kotomin, E A; Merkle, R; Mastrikov, Yu A; Maier, J

2013-04-21

Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,Fe)O3 (BSCF). Special attention is paid to a critical evaluation of advantages and disadvantages of BSCF, which shows the best cathode kinetics known so far for oxides. We demonstrate that it is the combined experimental and theoretical analysis of all major elementary steps of the oxygen reduction reaction which allows us to predict the rate determining steps for a given material under specific operational conditions and thus control and improve SOFC performance.

Methods and apparatus for the on-site production of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Buschmann, Wayne E. (Inventor); James, Patrick I. (Inventor)

2010-01-01

Methods, apparatus, and applications for the on-site production of hydrogen peroxide are described. An embodiment of the apparatus comprises at least one anolyte chamber coupled to at least one anode, at least one catholyte chamber, wherein the at least one catholyte chamber is coupled to at least one cathode, at least one anode membrane and at least one cathode membrane, wherein the anode membrane is adjacent to the at least one anode, wherein the cathode membrane is adjacent to the at least one cathode, at least one central chamber disposed between the at least one anolyte chamber and the at least one catholyte chamber. Hydrogen peroxide is produced by reduction of an oxygen-containing gas at the cathode.

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy.

PubMed

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Kubicek, Markus; Götsch, Thomas; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Klötzer, Bernhard; Fleig, Jürgen

2017-10-18

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO 2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H 2 ) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO 3-δ and (La,Sr)CrO 3-δ based perovskite-type electrodes was studied during electrochemical CO 2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO 2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO 2 reduction. In contrast to water splitting, the CO 2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view.

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy

PubMed Central

2017-01-01

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H2) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO3−δ and (La,Sr)CrO3−δ based perovskite-type electrodes was studied during electrochemical CO2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO2 reduction. In contrast to water splitting, the CO2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view. PMID:28933825

Characterization of SrFe0.75Mo0.25O3-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ composite cathodes prepared by infiltration

NASA Astrophysics Data System (ADS)

Meng, Xie; Han, Da; Wu, Hao; Li, Junliang; Zhan, Zhongliang

2014-01-01

This paper describes the structure and electrochemical properties of composite cathodes for solid oxide fuel cells fabricated by infiltration of aqueous solutions corresponding to SrFe0.75Mo0.25O3-δ (SFMO) into porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) backbones. XRD measurement confirms the predominance of the perovskite SFMO oxides in the infiltrates together with some minor impurities of SrMoO4 after calcinations at 850-1100 °C. The cathode polarization resistance as obtained from impedance measurement on symmetric cathode fuel cells exhibits a pronounced increase as a function of calcinations temperature due to increased SFMO particle sizes, e.g., 0.04 Ω cm2 for 70 nm-sized catalysts calcinated at 850 °C versus 0.11 Ω cm2 for 400 nm-sized catalysts calcinated at 1100 °C. Oxygen partial pressure and temperature dependence of impedance data shows that oxygen reduction kinetics is largely determined by ionization of adsorbed oxygen atoms on the SFMO catalysts.

Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

DOEpatents

Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

2010-04-27

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

Ordered WO3-x nanorods: facile synthesis and their electrochemical properties for aluminum-ion batteries.

PubMed

Tu, Jiguo; Lei, Haiping; Yu, Zhijing; Jiao, Shuqiang

2018-02-01

In this work, we have synthesized ordered WO 3 nanorods via a facile hydrothermal process. And the series WO 3-x nanorods with oxygen vacancies are obtained via a subsequent thermal reduction process. The formation mechanisms of WO 3-x nanorods with different oxygen vacancies are proposed. And the electrochemical results reveal that the WO 3-x nanorods exhibit the improved specific capacity due to the oxygen vacancies caused by the thermal reduction. More importantly, the reaction mechanism of the WO 3-x nanorods as cathodes for aluminum-ion batteries has been proved.

Metal-Organic-Framework-Derived Dual Metal- and Nitrogen-Doped Carbon as Efficient and Robust Oxygen Reduction Reaction Catalysts for Microbial Fuel Cells.

PubMed

Tang, Haolin; Cai, Shichang; Xie, Shilei; Wang, Zhengbang; Tong, Yexiang; Pan, Mu; Lu, Xihong

2016-02-01

A new class of dual metal and N doped carbon catalysts with well-defined porous structure derived from metal-organic frameworks (MOFs) has been developed as a high-performance electrocatalyst for oxygen reduction reaction (ORR). Furthermore, the microbial fuel cell (MFC) device based on the as-prepared Ni/Co and N codoped carbon as air cathode catalyst achieves a maximum power density of 4335.6 mW m -2 and excellent durability.

Hybrid binuclear-cobalt-phthalocyanine as oxygen reduction reaction catalyst in single chamber microbial fuel cells

NASA Astrophysics Data System (ADS)

Li, Baitao; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

2014-12-01

A novel hybrid binuclear-cobalt-phthalocyanine (Bi-CoPc) is developed as the cathode catalyst to replace the costly platinum (Pt) in single chamber microbial fuel cells (SCMFCs). Bi-CoPc/C is integrated with metal oxides (NiO and CoO) to form macrocyclic complex for enhanced oxygen reduction rate (ORR). The characteristics of hybrid catalysts (Bi-CoPc/C-CoO and Bi-CoPc/C-NiO) are compared with Co-contained catalysts (CoPc/C and Bi-CoPc/C) and metal oxide catalysts (NiO and CoO). The increase in O and N functional groups indicates the benefits of NiO and CoO to the cathode catalysts. The cyclic voltammetry (CV) shows the reduction peak for Bi-CoPc/C-NiO and Bi-CoPc/C-CoO at -0.12 V and -0.22 V, respectively. The power densities (368 mW m-2 and 400 mW m-2) of SCMFCs with Bi-CoPc/C-CoO and Bi-CoPc-NiO/C are the highest among the cathodes tested, and close to that of Pt (450 mW m-2). This study demonstrates that hybrid Bi-CoPc/C with metal oxides has a great potential as a cost-effective catalyst in MFCs.

A micro-nano porous oxide hybrid for efficient oxygen reduction in reduced-temperature solid oxide fuel cells

PubMed Central

Da Han; Liu, Xuejiao; Zeng, Fanrong; Qian, Jiqin; Wu, Tianzhi; Zhan, Zhongliang

2012-01-01

Tremendous efforts to develop high-efficiency reduced-temperature (≤ 600°C) solid oxide fuel cells are motivated by their potentials for reduced materials cost, less engineering challenge, and better performance durability. A key obstacle to such fuel cells arises from sluggish oxygen reduction reaction kinetics on the cathodes. Here we reported that an oxide hybrid, featuring a nanoporous Sm0.5Sr0.5CoO3−δ (SSC) catalyst coating bonded onto the internal surface of a high-porosity La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) backbone, exhibited superior catalytic activity for oxygen reduction reactions and thereby yielded low interfacial resistances in air, e.g., 0.021 Ω cm2 at 650°C and 0.043 Ω cm2 at 600°C. We further demonstrated that such a micro-nano porous hybrid, adopted as the cathode in a thin LSGM electrolyte fuel cell, produced impressive power densities of 2.02 W cm−2 at 650°C and 1.46 W cm−2 at 600°C when operated on humidified hydrogen fuel and air oxidant. PMID:22708057

Highly exposed Fe-N4 active sites in porous poly-iron-phthalocyanine based oxygen reduction electrocatalyst with ultrahigh performance for air cathode.

PubMed

Anandhababu, Ganesan; Abbas, Syed Comail; Lv, Jiangquan; Ding, Kui; Liu, Qin; Babu, Dickson D; Huang, Yiyin; Xie, Jiafang; Wu, Maoxiang; Wang, Yaobing

2017-02-14

Progress in the development of efficient electrocatalysts for oxygen reduction reactions is imperative for various energy systems such as metal-air batteries and fuel cells. In this paper, an innovative porous two-dimensional (2D) poly-iron-phthalocyanine (PFe-Pc) based oxygen reduction electrocatalyst created with a simple solid-state chemical reaction without pyrolysis is reported. In this strategy, silicon dioxide nanoparticles play a pivotal role in preserving the Fe-N 4 structure during the polymerization process and thereby assist in the development of a porous structure. The new polymerized phthalocyanine electrocatalyst with tuned porous structure, improved specific surface area and more exposed catalytic active sites via the 2D structure shows an excellent performance towards an oxygen reduction reaction in alkaline media. The onset potential (E = 1.033 V) and limiting current density (I = 5.58 mA cm -2 ) are much better than those obtained with the commercial 20% platinum/carbon electrocatalyst (1.046 V and 4.89 mA cm -2 ) and also show better stability and tolerance to methanol crossover. For practical applications, a zinc-air (Zn-air) battery and methanol fuel cell equipped with the PFe-Pc electrocatalyst as an air cathode reveal a high open circuit voltage and maximum power output (1.0 V and 23.6 mW cm -2 for a methanol fuel cell, and 1.6 V and 192 mW cm -2 for the liquid Zn-air battery). In addition, using the PFe-Pc electrocatalyst as an air cathode in a flexible cable-type Zn-air battery exhibits excellent performance with an open-circuit voltage of 1.409 V. This novel porous 2D PFe-Pc has been designed logically using a new, simple strategy with ultrahigh electrochemical performances in Zn-air batteries and methanol fuel cell applications.

Nano-scale investigations of electric-dipole-layer enhanced field and thermionic emission from high current density cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios

Cesium iodide coated graphitic fibers and scandate cathodes are two important electron emission technologies. The coated fibers are utilized as field emitters for high power microwave sources. The scandate cathodes are promising thermionic cathode materials for pulsed power vacuum electron devices. This work attempts to understand the fundamental physical and chemical relationships between the atomic structure of the emitting cathode surfaces and the superior emission characteristics of these cathodes. Ab initio computational modeling in conjunction with experimental investigations was performed on coated fiber cathodes to understand the origin of their very low turn on electric field, which can be reduced by as much as ten-fold compared to uncoated fibers. Copious amounts of cesium and oxygen were found co-localized on the fiber, but no iodine was detected on the surface. Additional ab initio studies confirmed that cesium oxide dimers could lower the work function significantly. Surface cesium oxide dipoles are therefore proposed as the source of the observed reduction in the turn on electric field. It is also proposed that emission may be further enhanced by secondary electrons from cesium oxide during operation. Thermal conditioning of the coated cathode may be a mechanism by which surface cesium iodide is converted into cesium oxide, promoting the depletion of iodine by formation of volatile gas. Ab initio modeling was also utilized to investigate the stability and work functions of scandate structures. The work demonstrated that monolayer barium-scandium-oxygen surface structures on tungsten can dramatically lower the work function of the underlying tungsten substrate from 4.6 eV down to 1.16 eV, by the formation of multiple surface dipoles. On the basis of this work, we conclude that high temperature kinetics force conventional dispenser cathodes (barium-oxygen monolayers on tungsten) to operate in a non-equilibrium compositional steady state with higher than optimal work functions of ˜2 eV. We hypothesize that scandium enables the barium-oxygen surface monolayer kinetics to access a more thermodynamically stable phase with reported work functions as low as ˜1.3 eV.

Effect of oxygen incorporation on the structure and elasticity of Ti-Al-O-N coatings synthesized by cathodic arc and high power pulsed magnetron sputtering

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

Hans, M., E-mail: hans@mch.rwth-aachen.de; Baben, M. to; Music, D.

2014-09-07

Ti-Al-O-N coatings were synthesized by cathodic arc and high power pulsed magnetron sputtering. The chemical composition of the coatings was determined by means of elastic recoil detection analysis and energy dispersive X-ray spectroscopy. The effect of oxygen incorporation on the stress-free lattice parameters and Young's moduli of Ti-Al-O-N coatings was investigated by X-ray diffraction and nanoindentation, respectively. As nitrogen is substituted by oxygen, implications for the charge balance may be expected. A reduction in equilibrium volume with increasing O concentration is identified by X-ray diffraction and density functional theory calculations of Ti-Al-O-N supercells reveal the concomitant formation of metal vacancies.more » Hence, the oxygen incorporation-induced formation of metal vacancies enables charge balancing. Furthermore, nanoindentation experiments reveal a decrease in elastic modulus with increasing O concentration. Based on ab initio data, two causes can be identified for this: First, the metal vacancy-induced reduction in elasticity; and second, the formation of, compared to the corresponding metal nitride bonds, relatively weak Ti-O and Al-O bonds.« less

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

PubMed

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

2015-09-07

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

Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction.

PubMed

Wang, Jing; Huang, Zhengqing; Liu, Wei; Chang, Chunran; Tang, Haolin; Li, Zhijun; Chen, Wenxing; Jia, Chunjiang; Yao, Tao; Wei, Shiqiang; Wu, Yuen; Li, Yadong

2017-12-06

We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E onset , 1.06 vs 1.03 V) and half-wave potential (E 1/2 , 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H 2 /O 2 and H 2 /air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H 2 /air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Insight into the structure and functional application of the Sr0.95Ce0.05CoO3-δ cathode for solid oxide fuel cells.

PubMed

Yang, Wei; Zhang, Huairuo; Sun, Chunwen; Liu, Lilu; Alonso, J A; Fernández-Díaz, M T; Chen, Liquan

2015-04-06

A new perovskite cathode, Sr0.95Ce0.05CoO3-δ, performs well for oxygen-reduction reactions in solid oxide fuel cells (SOFCs). We gain insight into the crystal structure of Sr1-xCexCoO3-δ (x = 0.05, 0.1) and temperature-dependent structural evolution of Sr0.95Ce0.05CoO3-δ by X-ray diffraction, neutron powder diffraction, and scanning transmission electron microscopy experiments. Sr0.9Ce0.1CoO3-δ shows a perfectly cubic structure (a = a0), with a large oxygen deficiency in a single oxygen site; however, Sr0.95Ce0.05CoO3-δ exhibits a tetragonal perovskite superstructure with a double c axis, defined in the P4/mmm space group, that contains two crystallographically different cobalt positions, with distinct oxygen environments. The structural evolution of Sr0.95Ce0.05CoO3-δ at high temperatures was further studied by in situ temperature-dependent NPD experiments. At 1100 K, the oxygen atoms in Sr0.95Ce0.05CoO3-δ show large and highly anisotropic displacement factors, suggesting a significant ionic mobility. The test cell with a La0.8Sr0.2Ga0.83Mg0.17O3-δ-electrolyte-supported (∼300 μm thickness) configuration yields peak power densities of 0.25 and 0.48 W cm(-2) at temperatures of 1023 and 1073 K, respectively, with pure H2 as the fuel and ambient air as the oxidant. The electrochemical impedance spectra evolution with time of the symmetric cathode fuel cell measured at 1073 K shows that the Sr0.95Ce0.05CoO3-δ cathode possesses superior ORR catalytic activity and long-term stability. Mixed ionic-electronic conduction properties of Sr0.95Ce0.05CoO3-δ account for its good performance as an oxygen-reduction catalyst.

Phase transition of a cobalt-free perovskite as a high-performance cathode for intermediate-temperature solid oxide fuel cells.

PubMed

Jiang, Shanshan; Zhou, Wei; Niu, Yingjie; Zhu, Zhonghua; Shao, Zongping

2012-10-01

It is generally recognized that the phase transition of a perovskite may be detrimental to the connection between cathode and electrolyte. Moreover, certain phase transitions may induce the formation of poor electronic and ionic conducting phase(s), thereby lowering the electrochemical performance of the cathode. Here, we present a study on the phase transition of a cobalt-free perovskite (SrNb(0.1)Fe(0.9)O(3-δ), SNF) and evaluate its effect on the electrochemical performance of the fuel cell. SNF exists as a primitive perovskite structure with space group P4mm (99) at room temperature. As evidenced by in situ high-temperature X-ray diffraction measurements over the temperature range of 600 to 1000 °C, SNF undergoes a transformation to a tetragonal structure with a space group I4/m (87). This phase transition is accompanied by a moderate change in the volume, allowing a good cathode/electrolyte interface on thermal cycling. According to the electrochemical impedance spectroscopy evaluation, the I4/m phase exhibits positive effects on the cathode's performance, showing the highest oxygen reduction reaction activity of cobalt-free cathodes reported so far. This activity improvement is attributed to enhanced oxygen surface processes. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking Electron Uptake from a Cathode into Shewanella Cells: Implications for Energy Acquisition from Solid-Substrate Electron Donors

PubMed Central

Rajeev, Pournami; Jain, Abhiney; Pirbadian, Sahand; Okamoto, Akihiro; Gralnick, Jeffrey A.; El-Naggar, Mohamed Y.; Nealson, Kenneth H.

2018-01-01

ABSTRACT While typically investigated as a microorganism capable of extracellular electron transfer to minerals or anodes, Shewanella oneidensis MR-1 can also facilitate electron flow from a cathode to terminal electron acceptors, such as fumarate or oxygen, thereby providing a model system for a process that has significant environmental and technological implications. This work demonstrates that cathodic electrons enter the electron transport chain of S. oneidensis when oxygen is used as the terminal electron acceptor. The effect of electron transport chain inhibitors suggested that a proton gradient is generated during cathode oxidation, consistent with the higher cellular ATP levels measured in cathode-respiring cells than in controls. Cathode oxidation also correlated with an increase in the cellular redox (NADH/FMNH2) pool determined with a bioluminescence assay, a proton uncoupler, and a mutant of proton-pumping NADH oxidase complex I. This work suggested that the generation of NADH/FMNH2 under cathodic conditions was linked to reverse electron flow mediated by complex I. A decrease in cathodic electron uptake was observed in various mutant strains, including those lacking the extracellular electron transfer components necessary for anodic-current generation. While no cell growth was observed under these conditions, here we show that cathode oxidation is linked to cellular energy acquisition, resulting in a quantifiable reduction in the cellular decay rate. This work highlights a potential mechanism for cell survival and/or persistence on cathodes, which might extend to environments where growth and division are severely limited. PMID:29487241

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Cusick, Robert J.

1988-01-01

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

The removal of low level inorganics via electrogenerated hydrogen peroxide in the presence of catalytic amounts of Fe2+.

PubMed

Marrosu, G; Petrucci, R; Trazza, A

2001-01-01

Low level phosphites and hypophosphites were completely converted into phosphates, via hydrogen peroxide generated by cathodic reduction of oxygen in acidic aqueous medium at a reticulated vitreous carbon electrode, in the presence of little amounts of Fe2+. The contemporary regeneration of Fe2+ by cathodic reduction of Fe3+, produced by the well known Fenton reaction, furnishes an excellent way to continuously produce little amounts of the Fenton reactive and, as a consequence, of the powerful oxidant hydroxyl radical HO.. The best conditions for the complete removal of phosphorous as phosphites and hypophosphites are reported.

Fuel cell development for transportation: Catalyst development

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

Doddapaneni, N.

1996-04-01

Fuel cells are being considered as alternate power sources for transportation and stationary applications. With proton exchange membrane (PEM) fuel cells the fuel crossover to cathodes causes severe thermal management and cell voltage drop due to oxidation of fuel at the platinized cathodes. The main goal of this project was to design, synthesize, and evaluate stable and inexpensive transition metal macrocyclic catalysts for the reduction of oxygen and be electrochemically inert towards anode fuels such as hydrogen and methanol.

Praseodymium Cuprate Thin Film Cathodes for Intermediate Temperature Solid Oxide Fuel Cells: Roles of Doping, Orientation, and Crystal Structure.

PubMed

Mukherjee, Kunal; Hayamizu, Yoshiaki; Kim, Chang Sub; Kolchina, Liudmila M; Mazo, Galina N; Istomin, Sergey Ya; Bishop, Sean R; Tuller, Harry L

2016-12-21

Highly textured thin films of undoped, Ce-doped, and Sr-doped Pr 2 CuO 4 were synthesized on single crystal YSZ substrates using pulsed laser deposition to investigate their area-specific resistance (ASR) as cathodes in solid-oxide fuel cells (SOFCs). The effects of T' and T* crystal structures, donor and acceptor doping, and a-axis and c-axis orientation on ASR were systematically studied using electrochemical impedance spectroscopy on half cells. The addition of both Ce and Sr dopants resulted in improvements in ASR in c-axis oriented films, as did the T* crystal structure with the a-axis orientation. Pr 1.6 Sr 0.4 CuO 4 is identified as a potential cathode material with nearly an order of magnitude faster oxygen reduction reaction kinetics at 600 °C compared to thin films of the commonly studied cathode material La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ . Orientation control of the cuprate films on YSZ was achieved using seed layers, and the anisotropy in the ASR was found to be less than an order of magnitude. The rare-earth doped cuprate was found to be a versatile system for study of relationships between bulk properties and the oxygen reduction reaction, critical for improving SOFC performance.

Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

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

Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

2012-01-01

Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes formore » nonaqueous Li-air batteries.« less

Paper-Based Analytical Devices Relying on Visible-Light-Enhanced Glucose/Air Biofuel Cells.

PubMed

Wu, Kaiqing; Zhang, Yan; Wang, Yanhu; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-11-04

A strategy that combines visible-light-enhanced biofuel cells (BFCs) and electrochemical immunosensor into paper-based analytical devices was proposed for sensitive detection of the carbohydrate antigen 15-3 (CA15-3). The gold nanoparticle modified paper electrode with large surface area and good conductibility was applied as an effective matrix for primary antibodies. The glucose dehydrogenase (GDH) modified gold-silver bimetallic nanoparticles were used as bioanodic biocatalyst and signal magnification label. Poly(terthiophene) (pTTh), a photoresponsive conducting polymer, served as catalyst in cathode for the reduction of oxygen upon illumination by visible light. In the bioanode, electrons were generated through the oxidation of glucose catalyzed by GDH. The amount of electrons is determined by the amount of GDH, which finally depended on the amount of CA15-3. In the cathode, electrons from the bioanode could combine with the generated holes in the HOMO energy level of cathode catalysts pTTh. Meanwhile, the high energy level photoexcited electrons were generated in the LUMO energy level and involved in the oxygen reduction reaction, finally resulting in an increasing current and a decreasing overpotential. According to the current signal, simple and efficient detection of CA15-3 was achieved.

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

PubMed

Yang, Zehui; Nakashima, Naotoshi

2015-07-20

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance.

Metal-air flow batteries using oxygen enriched electrolyte

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

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Metal-air flow batteries using oxygen enriched electrolyte

DOEpatents

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh; Chen, Xujie

2017-08-01

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Light-dependent processes on the cathode enhance the electrical outputs of sediment microbial fuel cells.

PubMed

Bardarov, Ivo; Mitov, Mario; Ivanova, Desislava; Hubenova, Yolina

2018-02-27

In this study, we explored in details the influence of the light irradiation on the SMFCs electrical outputs. The experiments at both natural and artificial illumination firmly show that during the photoperiods the current grows up. The intensity of the current increase depends on the duration of the photoperiod as well as on the wavelength of the monochromatic light source applied. The highest influence of the light irradiation has been obtained at wavelengths, corresponding to the absorption peaks of essential pigments in the light-harvesting system of oxygenic photosynthesizing microorganisms. The decreased values as well as the discontinued fluctuations of the current as a result of suppressed illumination or substitution of the biocathode with a new one suggest that photosynthesizing microorganisms, co-existing in the cathodic biofilm consortium, contribute to the overall SMFC performance. The microscopic observations confirm the existence of chlorophyll-containing microorganisms on the cathode surface. Though the performed metagenomics DNA analysis has not certified a dominance of photosynthesizing microorganisms, all other results support the hypothesis that the current enhance during the photoperiods is due to the in situ bio-oxygen production on the cathode surface, thus lowering the mass transport limitations for the oxygen reduction reaction. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of alkaline exchange membrane fuel cells performance at different operating conditions using DC and AC methods

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana; Odgaard, Madeleine; Schlueter, Debbie; Serov, Alexey

2018-01-01

Membrane electrode assemblies (MEAs) for anion exchange membrane fuel cells (AEMFCs) were manufactured from commercial materials: Pt/C catalyst, A201 AEM and AS4 ionomer by using an industrial mass-production digital printing method. The MEA designs selected are close to those recommended by US Department of Energy, including low loading of platinum on the cathode side (0.2 mg cm-2). Polarization curves and electrochemical impedance spectroscopy (EIS) were applied for MEA evaluation in fuel cell conditions with variation of gas humidification and oxygen partial pressure (air vs oxygen). The typical impedance curves recorded at H2/O2 gas configuration consist of high- and medium-frequency arcs responsible for hydrogen oxidation and oxygen reduction, respectively. Operation with air as a cathode feed gas resulted in a decrease in AEMFC performance due to possible CO2 poisoning and mass transfer losses. At the same time, EIS demonstrated formation of a low frequency loop due to diffusion limitations. Despite the low loading of platinum on the cathode (0.2 mg cm-2), a peak power density of ∼330 mW cm-2 was achieved (at 50/50% of RH on anode and cathode), which is substantially higher performance than for AEMFC MEAs tested at similar conditions.

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Study of Electrocatalytic Properties of Metal–Organic Framework PCN-223 for the Oxygen Reduction Reaction

DOE PAGES

Usov, Pavel M.; Huffman, Brittany; Epley, Charity C.; ...

2017-03-27

Here, a highly robust metal–organic framework (MOF) constructed from Zr 6 oxo clusters and Fe(III) porphyrin linkers, PCN-223-Fe was investigated as a heterogeneous catalyst for oxygen reduction reaction (ORR). Films of the framework were grown on a conductive FTO substrate and showed a high catalytic current upon application of cathodic potentials and achieved high H 2O/H 2O 2 selectivity. In addition, the effect of the proton source on the catalytic performance was also investigated.

Synthesis of low cost organometallic-type catalysts for their application in microbial fuel cell technology.

PubMed

Zerrouki, A; Salar-García, M J; Ortiz-Martínez, V M; Guendouz, S; Ilikti, H; de Los Ríos, A P; Hernández-Fernández, F J; Kameche, M

2018-03-05

Microbial fuel cells (MFCs) are a promising technology that generates electricity from several biodegradable substrates and wastes. The main drawback of these devices is the need of using a catalyst for the oxygen reduction reaction at the cathode, which makes the process relatively expensive. In this work, two low cost materials are tested as catalysts in MFCs. A novel iron complex based on the ligand n-phenyledenparaethoxy aniline has been synthesized and its performance as catalyst in single chamber MFCs containing ionic liquids has been compared with a commercial inorganic material such as Raney nickel. The results show that both materials are suitable for bioenergy production and wastewater treatment in the systems. Raney nickel cathodes allow MFCs to reach a maximum power output of 160 mW.m -3 anode , while the iron complex offers lower values. Regarding the wastewater treatment capacity, MFCs working with Raney nickel-based cathodes reach higher values of chemical oxygen demand removal (76%) compared with the performance displayed by the cathodes based on Fe-complex (56%).

The Effect of Potassium Impurities Deliberately Introduced into Activated Carbon Cathodes on the Performance of Lithium-Oxygen Batteries

DOE PAGES

Zhai, Dengyun; Lau, Kah Chun; Wang, Hsien-Hau; ...

2015-12-02

Rechargeable lithium-air (Li-O 2) batteries have drawn much interest owing to their high energy density. We report on the effect of deliberately introducing potassium impurities into the cathode material on the electrochemical performance of a Li-O 2 battery. Small amounts of potassium introduced into the activated carbon (AC) cathode material in the synthesis process are found to have a dramatic effect on the performance of the Li-O 2 cell. An increased amount of potassium significantly increases capacity, cycle life, and round-trip efficiency. This improved performance is probably due to a larger amount of LiO 2 in the discharge product, whichmore » is a mixture of LiO 2 and Li 2O 2, resulting from the increase in the amount of potassium present. No substantial correlation with porosity or surface area in an AC cathode is found. Lastly, experimental and computational studies indicate that potassium can act as an oxygen reduction catalyst, which can account for the dependence of performance on the amount of potassium.« less

Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

NASA Astrophysics Data System (ADS)

Ou, Shiqi; Zhao, Yi; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

2016-10-01

This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions in a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.

Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

DOE PAGES

Ou, Shiqi; Zhao, Yi; Aaron, Douglas S.; ...

2016-08-15

This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions inmore » a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Lastly, simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.« less

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Performance and microbial ecology of air-cathode microbial fuel cells with layered electrode assemblies.

PubMed

Butler, Caitlyn S; Nerenberg, Robert

2010-05-01

Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the performance and microbial community structure of MFCs with layered assemblies, addressing the effect of materials and oxygen crossover on the community structure. Four MFCs with layered assemblies were constructed using Nafion or Ultrex PEMs and a plain carbon cloth electrode or a cathode with an oxygen-resistant polytetrafluoroethylene diffusion layer. The MFC with Nafion PEM and cathode diffusion layer achieved the highest power density, 381 mW/m(2) (20 W/m(3)). The rates of oxygen diffusion from cathode to anode were three times higher in the MFCs with plain cathodes compared to those with diffusion-layer cathodes. Microsensor studies revealed little accumulation of oxygen within the anode cloth. However, the abundance of bacteria known to use oxygen as an electron acceptor, but not known to have exoelectrogenic activity, was greater in MFCs with plain cathodes. The MFCs with diffusion-layer cathodes had high abundance of exoelectrogenic bacteria within the genus Geobacter. This work suggests that cathode materials can significantly influence oxygen crossover and the relative abundance of exoelectrogenic bacteria on the anode, while PEM materials have little influence on anode community structure. Our results show that oxygen crossover can significantly decrease the performance of air-cathode MFCs with layered assemblies, and therefore limiting crossover may be of particular importance for these types of MFCs.

Evaluating the Passivation of Corrosion of API-X100 Steel with Cyclic Voltammetry

NASA Astrophysics Data System (ADS)

Eliyan, Faysal Fayez; Alfantazi, Akram

2017-10-01

In this research, cyclic voltammetry, in oxygen-free low bicarbonate-carbonate solutions, was used to study the corrosion reactions of a high-strength steel, API-X100. With cycles of different scan ranges, the effects of cycling, transpassivation, and cathodic reduction on the electrochemistry of the passive films were analyzed. It was found that carbonate in higher concentrations reduces the anodic activity and the cathodic reactions of the surface. Bicarbonate in small concentrations in solutions that contained low carbonate concentrations catalyzed dissolution and disrupted the formation of the passive films, in reference to the measured anodic currents. From the experiments, there was electrochemical evidence that with more cycles, the passive films were growing thicker, the transpassivation deteriorated the passive films, and during the cathodic reduction, the dissolution was occurring at lower potentials to facilitate later the passivation at higher potentials.

Stabilizing nanostructured solid oxide fuel cell cathode with atomic layer deposition.

PubMed

Gong, Yunhui; Palacio, Diego; Song, Xueyan; Patel, Rajankumar L; Liang, Xinhua; Zhao, Xuan; Goodenough, John B; Huang, Kevin

2013-09-11

We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.

Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

NASA Astrophysics Data System (ADS)

Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-04-01

The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

DOE PAGES

Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; ...

2015-07-14

Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable thanmore » conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.« less

Durable rechargeable zinc-air batteries with neutral electrolyte and manganese oxide catalyst

NASA Astrophysics Data System (ADS)

Sumboja, Afriyanti; Ge, Xiaoming; Zheng, Guangyuan; Goh, F. W. Thomas; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2016-11-01

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm-2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Platinum-Coated Hollow Graphene Nanocages as Cathode Used in Lithium-Oxygen Batteries

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

Wu, Feng; Xing, Yi; Zeng, Xiaoqiao

2016-08-31

One of the formidable challenges facing aprotic lithium-oxygen (Li-O-2) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt-coated hollow graphene nano cages as cathode in Li-O-2 batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g(-1), even maintain below 3.5 V when the current density increased to 500 mA g(-1). The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri-phase regions as active sites for efficient oxygen reduction, but alsomore » offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic-level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li2O2 growth. The Li2O2 is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene-metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt-decorated graphene nanocage cathode exhibits enhanced electrochemical performances.« less

An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

2016-07-25

The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance comparison of protonic and sodium phosphomolybdovanadate polyoxoanion catholytes within a chemically regenerative redox cathode polymer electrolyte fuel cell

NASA Astrophysics Data System (ADS)

Ward, David B.; Gunn, Natasha L. O.; Uwigena, Nadine; Davies, Trevor J.

2018-01-01

The direct reduction of oxygen in conventional polymer electrolyte fuel cells (PEFCs) is seen by many researchers as a key challenge in PEFC development. Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells offer an alternative approach via the indirect reduction of oxygen, improving durability and reducing cost. These systems substitute gaseous oxygen for a liquid catalyst that is reduced at the cathode then oxidised in a regeneration vessel via air bubbling. A key component of a CRRC system is the liquid catalyst or catholyte. To date, phosphomolybdovanadium polyoxometalates with empirical formula H3+nPVnMo12-nO40 have shown the most promise for CRRC PEFC systems. In this work, four catholyte formulations are studied and compared against each other. The catholytes vary in vanadium content, pH and counter ion, with empirical formulas H6PV3Mo9O40, H7PV4Mo8O40, Na3H3PV3Mo9O40 and Na4H3PV4Mo8O40. Thermodynamic properties, cell performance and regeneration rates are measured, generating new insights into how formulation chemistry affects the components of a CRRC system. The results include the best CRRC PEFC performance reported to date, with noticeable advantages over conventional PEFCs. The optimum catholyte formulation is then determined via steady state tests, the results of which will guide further optimization of the catholyte formulation.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Design of Ultrathin Pt-Based Multimetallic Nanostructures for Efficient Oxygen Reduction Electrocatalysis.

PubMed

Lai, Jianping; Guo, Shaojun

2017-12-01

Nanocatalysts with high platinum (Pt) utilization efficiency are attracting extensive attention for oxygen reduction reactions (ORR) conducted at the cathode of fuel cells. Ultrathin Pt-based multimetallic nanostructures show obvious advantages in accelerating the sluggish cathodic ORR due to their ultrahigh Pt utilization efficiency. A focus on recent important developments is provided in using wet chemistry techniques for making/tuning the multimetallic nanostructures with high Pt utilization efficiency for boosting ORR activity and durability. First, new synthetic methods for multimetallic core/shell nanoparticles with ultrathin shell sizes for achieving highly efficient ORR catalysts are reviewed. To obtain better ORR activity and stability, multimetallic nanowires or nanosheets with well-defined structure and surface are further highlighted. Furthermore, ultrathin Pt-based multimetallic nanoframes that feature 3D molecularly accessible surfaces for achieving more efficient ORR catalysis are discussed. Finally, the remaining challenges and outlooks for the future will be provided for this promising research field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound.

PubMed

González-García, José; Banks, Craig E; Sljukić, Biljana; Compton, Richard G

2007-04-01

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.

A novel metal organic framework-derived carbon-based catalyst for oxygen reduction reaction in a microbial fuel cell

NASA Astrophysics Data System (ADS)

Zhang, Lihua; Hu, Yongyou; Chen, Junfeng; Huang, Wantang; Cheng, Jianhua; Chen, Yuancai

2018-04-01

To improve the power generation of microbial fuel cell (MFC), the cathode is modified to increase its oxygen reduction reaction (ORR) activity by using a Cu, N-incorporated carbon-based material as catalyst, which obtained from pyrolyzing ORR active Cu (II)-based metal organic framework (MOF; Cu-bipy-BTC, bipy = 2,2‧-bipyridine, BTC = 1,3,5-tricarboxylate). MOF-800 (the product of pyrolyzing Cu-bipy-BTC at 800 °C) shows porous structure with micropores ranging from 0.5 to 1.3 nm and mesopores ranging from 27 to 46 nm. It also exhibits improved ORR electrocatalytic activity with a higher current density of -3.06 mA cm-2 compared to Cu-bipy-BTC. Moreover, the charge transfer resistance of MOF-800 cathode (1.38 Ω) is much smaller than that of Cu-bipy-BTC cathode (176.8 Ω). A maximum power density of 326 ± 11 mW m-2 is achieved by MOF-800-MFC, which is 2.6 times of that of Cu-bipy-BTC-MFC and comparable with Pt/C-MFC (402 ± 17 mW m-2). The results imply the enhancements of ORR catalytic activity and electrical conductivity of MOF-800 are due to the enhanced porous structure and abundant active sites (C-N, Cu-Nχ), which result in the improved power generation of MFC. This study provides technical and theoretical validation for the MFC performance improvement by ORR active MOF-derived catalysts modified cathodes.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

Electrochemical approach for passivating steel and other metals and for the simultaneous production of a biocide to render water potable

NASA Technical Reports Server (NTRS)

1972-01-01

Potentiostatic polarization curves indicated that the cathodic reactions in deaerated KI-I2 water solutions were due to iodine reduction and hydrogen evolution. In the presence of oxygen an additional reduction wave appeared. Anodic polarization curves revealed that iodine could be produced in the region of potential from +600 to +1000 nv vs. SCE.

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum

PubMed Central

Yang, Zehui; Nakashima, Naotoshi

2015-01-01

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance. PMID:26192397

High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

2016-09-01

Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

Dynamic Octahedral Breathing in Oxygen-Deficient Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) Perovskite Performing as a Cathode in Intermediate-Temperature SOFC.

PubMed

Gong, Yudong; Sun, Chunwen; Huang, Qiu-an; Alonso, Jose Antonio; Fernández-Díaz, Maria Teresa; Chen, Liquan

2016-03-21

Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) outperforms as a cathode in solid-oxide fuel cells (SOFC), at temperatures as low as 700-750 °C. The microscopical reason for this performance was investigated by temperature-dependent neutron powder diffraction (NPD) experiments. In the temperature range of 25-800 °C, Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) shows a perfectly cubic structure (a = a0), with a significant oxygen deficiency in a single oxygen site, that substantially increases at the working temperatures of a SOFC. The anisotropic thermal motion of oxygen atoms considerably rises with T, reaching B(eq) ≈ 5 Å(2) at 800 °C, with prolate cigar-shaped, anisotropic vibration ellipsoids that suggest a dynamic breathing of the octahedra as oxygen ions diffuse across the structure by a vacancies mechanism, thus implying a significant ionic mobility that could be described as a molten oxygen sublattice. The test cell with a La(0.8)Sr(0.2)Ga(0.83)Mg(0.17)O(3-δ) electrolyte (∼300 μm in thickness)-supported configuration yields a peak power density of 0.20 and 0.40 W cm(-2) at temperatures of 700 and 750 °C, respectively, with pure H2 as fuel and ambient air as oxidant. The electrochemical impedance spectra (EIS) evolution with time of the symmetric cathode fuel cell measured at 750 °C shows that the Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) cathode possesses a superior ORR catalytic activity and long-term stability. The mixed electronic-ionic conduction properties of Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) account for its good performance as an oxygen-reduction catalyst.

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

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

Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

NASA Astrophysics Data System (ADS)

Orellana, Walter

2012-07-01

The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

A novel family of Nb-doped Bi0.5Sr0.5FeO3-δ perovskite as cathode material for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Gao, Lei; Li, Qiang; Sun, Liping; Zhang, Xianfa; Huo, Lihua; Zhao, Hui; Grenier, Jean-Claude

2017-12-01

Cobalt-free provskite oxides Bi0.5Sr0.5Fe1-xNbxO3-δ (BSFNx, x = 0.05, 0.10 and 0.15) were prepared and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). In particular, the effects of Nb substitution on phase evolution, thermal expansion behavior and electrochemical performance were systematically investigated. The average thermal expansion coefficient (TEC) of BSFNx decreases from 13.3 × 10-6 K-1 at x = 0.05 to 12.6 × 10-6 K-1 at x = 0.15 within a temperature range of 50-800 °C. Among the BSFNx materials, Bi0.5Sr0.5Fe0.9Nb0.1O3-δ (BSFN0.10) oxide shows the best electrochemical performance. The polarization resistances (Rp) of BSFN0.10 cathode on CGO electrolyte are 0.038, 0.075 and 0.156 Ω cm2 at 700, 650 and 600 °C, respectively. Meanwhile the maximum power densities of the anode-supported single cells are 1.28, 1.54 and 1.34 W cm-2 at 700 °C for BSFNx cathodes with x = 0.05, 0.10, and 0.15, respectively. Furthermore, the relationship study of oxygen partial pressure dependence on Rp indicates that the oxygen reduction reaction (ORR) rate-limiting step is the oxygen adsorption-dissociation on the electrode surface. The desirable electrochemical performance demonstrates that BSFNx oxides are potential cathode materials for IT-SOFCs.

Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

PubMed Central

Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

2016-01-01

A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

PubMed

Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

2006-05-04

The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

In-situ Electrodeposition of Highly Active Silver Catalyst on Carbon Fiber Papers as Binder Free Cathodes for Aluminum-air Battery.

PubMed

Hong, Qingshui; Lu, Huimin

2017-06-13

Carbon fiber papers supported Ag catalysts (Ag/CFP) with different coverage of electro-active site are prepared by electrochemical deposition and used as binder free cathodes in primary aluminum-air (Al-air) battery. Scanning Electron Microscopy and X-ray Diffraction studies are carried out to characterize the as-prepared Ag/CFP air cathodes. Oxygen reduction reaction (ORR) activities on these air cathodes in alkaline solutions are systematic studied. A newly designed aluminum-air cell is used to further determine the cathodes performance under real operation condition and during the test, the Ag/CFP electrodes show outstanding catalytic activity for ORR in concentrated alkaline electrolyte, and no obvious activity degradation is observed after long-time discharge. The electrochemical test results display the dependence of coverage of the electro-active Ag on the catalytic performance of the air cathodes. The resulting primary Al-air battery made from the best-performing cathode shows an impressive discharge peak power density, outperforming that of using commercial nano-manganese catalyst air electrodes.

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.

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

NASA Astrophysics Data System (ADS)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

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

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

Promotion of Oxygen Reduction by Exsolved Silver Nanoparticles on a Perovskite Scaffold for Low-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Ran, Ran; Chen, Yubo; Shao, Zongping; Liu, Meilin

2016-01-13

Solid oxide fuel cells (SOFCs) have potential to be the cleanest and most efficient electrochemical energy conversion devices with excellent fuel flexibility. To make SOFC systems more durable and economically competitive, however, the operation temperature must be significantly reduced, which depends sensitively on the development of highly active electrocatalysts for oxygen reduction reaction (ORR) at low temperatures. Here we report a novel silver nanoparticle-decorated perovskite oxide, prepared via a facile exsolution process from a Sr0.95Ag0.05Nb0.1Co0.9O3-δ (SANC) perovskite precursor, as a highly active and robust ORR electrocatalyst for low-temperature SOFCs. The exsolved Sr0.95Ag0.05Nb0.1Co0.9O3-δ (denoted as e-SANC) electrode is very active for ORR, achieving a very low area specific resistance (∼0.214 Ω cm(2) at 500 °C). An anode-supported cell with the new heterostructured cathode demonstrates very high peak power density (1116 mW cm(-2) at 500 °C) and stable operation for 140 h at a current density of 625 mA cm(-2). The superior ORR activity and stability are attributed to the fast oxygen surface exchange kinetics and the firm adhesion of the Ag nanoparticles to the Sr0.95Nb0.1Co0.9O3-δ (SNC0.95) support. Moreover, the e-SANC cathode displays improved tolerance to CO2. These unique features make the new heterostructured material a highly promising cathode for low-temperature SOFCs.

Oxygen transport in the internal xenon plasma of a dispenser hollow cathode

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

Capece, Angela M., E-mail: acapece@pppl.gov; Shepherd, Joseph E.; Polk, James E.

2014-04-21

Reactive gases such as oxygen and water vapor modify the surface morphology of BaO dispenser cathodes and degrade the electron emission properties. For vacuum cathodes operating at fixed temperature, the emission current drops rapidly when oxygen adsorbs on top of the low work function surface. Previous experiments have shown that plasma cathodes are more resistant to oxygen poisoning and can operate with O{sub 2} partial pressures one to two orders of magnitude higher than vacuum cathodes before the onset of poisoning occurs. Plasma cathodes used for electric thrusters are typically operated with xenon; however, gas phase barium, oxygen, and tungstenmore » species may be found in small concentrations. The densities of these minor species are small compared with the plasma density, and thus, their presence in the discharge does not significantly alter the xenon plasma parameters. It is important, however, to consider the transport of these minor species as they may deposit on the emitter surface and affect the electron emission properties. In this work, we present the results of a material transport model used to predict oxygen fluxes to the cathode surface by solving the species conservation equations in a cathode with a 2.25 mm diameter orifice operated at a discharge current of 15 A, a Xe flow rate of 3.7 sccm, and 100 ppm of O{sub 2}. The dominant ionization process for O{sub 2} is resonant charge exchange with xenon ions. Ba is effectively recycled in the plasma; however, BaO and O{sub 2} are not. The model shows that the oxygen flux to the surface is not diffusion-limited; therefore, the high resistance to oxygen poisoning observed in plasma cathodes likely results from surface processes not considered here.« less

High-Performance Direct Methanol Fuel Cells with Precious-Metal-Free Cathode.

PubMed

Li, Qing; Wang, Tanyuan; Havas, Dana; Zhang, Hanguang; Xu, Ping; Han, Jiantao; Cho, Jaephil; Wu, Gang

2016-11-01

Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

NASA Astrophysics Data System (ADS)

Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

2016-09-01

The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

Manganese dioxide as a new cathode catalyst in microbial fuel cells

NASA Astrophysics Data System (ADS)

Li, Xiang; Hu, Boxun; Suib, Steven; Lei, Yu; Li, Baikun

This study focused on manganese oxides with a cryptomelane-type octahedral molecular sieve (OMS-2) structure to replace platinum as a cathode catalyst in microbial fuel cells (MFCs). Undoped (ud-OSM-2) and three catalysts doped with cobalt (Co-OMS-2), copper (Cu-OMS-2), and cerium (Ce-OMS-2) to enhance their catalytic performances were investigated. The novel OMS-2 cathodes were examined in granular activated carbon MFC (GACMFC) with sodium acetate as the anode reagent and oxygen in air as the cathode reagent. The results showed that after 400 h of operation, the Co-OMS-2 and Cu-OMS-2 exhibited good catalytic performance in an oxygen reduction reaction (ORR). The voltage of the Co-OMS-2 GACMFC was 217 mV, and the power density was 180 mW m -2. The voltage of the Cu-OMS-2 GACMFC was 214 mV and the power density was 165 mW m -2. The internal resistance (R in) of the OMS-2 GACMFCs (18 ± 1 Ω) was similar to that of the platinum GACMFCs (17 Ω). Furthermore, the degradation rates of organic substrates in the OMS-2 GACMFCs were twice those in the platinum GACMFCs, which enhance their wastewater treatment efficiencies. This study indicated that using OMS-2 manganese oxides to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Fully reversible current driven by a dual marine photosynthetic microbial community.

PubMed

Darus, Libertus; Lu, Yang; Ledezma, Pablo; Keller, Jürg; Freguia, Stefano

2015-11-01

The electrochemical activity of two seawater microbial consortia were investigated in three-electrode bioelectrochemical cells. Two seawater inocula - from the Sunshine Coast (SC) and Gold Coast (GC) shores of Australia - were enriched at +0.6 V vs. SHE using 12/12 h day/night cycles. After re-inoculation, the SC consortium developed a fully-reversible cathodic/anodic current, with a max. of -62 mA m(-2) during the day and +110 mA m(-2) at night, while the GC exhibited negligible daytime output but +98 mA m(-2) at night. Community analysis revealed that both enrichments were dominated by cyanobacteria, indicating their potential as biocatalysts for indirect light conversion to electricity. Moreover, the presence of γ-proteobacterium Congregibacter in SC biofilm was likely related to the cathodic reductive current, indicating its effectiveness at catalysing cathodic oxygen reduction at a surprisingly high potential. For the first time a correlation between a dual microbial community and fully reversible current is reported. Copyright © 2015 Elsevier Ltd. All rights reserved.

Immobilization of a Metal-Nitrogen-Carbon Catalyst on Activated Carbon with Enhanced Cathode Performance in Microbial Fuel Cells.

PubMed

Yang, Wulin; Logan, Bruce E

2016-08-23

Applications of microbial fuel cells (MFCs) are limited in part by low power densities mainly due to cathode performance. Successful immobilization of an Fe-N-C co-catalyst on activated carbon (Fe-N-C/AC) improved the oxygen reduction reaction to nearly a four-electron transfer, compared to a twoelectron transfer achieved using AC. With acetate as the fuel, the maximum power density was 4.7±0.2 W m(-2) , which is higher than any previous report for an air-cathode MFC. With domestic wastewater as a fuel, MFCs with the Fe-N-C/AC cathode produced up to 0.8±0.03 W m(-2) , which was twice that obtained with a Pt-catalyzed cathode. The use of this Fe-N-C/AC catalyst can therefore substantially increase power production, and enable broader applications of MFCs for renewable electricity generation using waste materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Sorption of Oxygen Dissolved in Water on Copper Nanoparticles in an Ion Exchange Matrix

NASA Astrophysics Data System (ADS)

Vakhnin, D. D.; Pridorogina, V. E.; Polyanskii, L. N.; Kravchenko, T. A.; Gorshkov, V. S.

2018-01-01

The redox sorption of molecular oxygen from water by a thin granular layer of a copper-ion exchanger nanocomposite in the currentless mode and under cathodic polarization is studied. The speed of propagation of the boundaries of the chemical reaction of stepwise oxidation of copper nanoparticles under the conditions of polarization slows considerably. At the same time, the amount of electrochemically regenerated copper from the resulting oxides that is capable of interacting with oxygen again grows. The stationarity of the redox sorption of oxygen is due to the equality of the rates of oxidation and reduction of the metallic component of the composite.

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

DOE PAGES

Ogawa, S.; Komini Babu, S.; Chung, H. T.; ...

2016-08-22

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

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

Ogawa, S.; Komini Babu, S.; Chung, H. T.

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Solar Powered CO.Sub.2 Conversion

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor)

2016-01-01

Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.

Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell.

PubMed

Lei, M; Wang, J; Li, J R; Wang, Y G; Tang, H L; Wang, W J

2014-08-11

Replacing precious and nondurable Pt catalysts with cheap materials is a key issue for commercialization of fuel cells. In the case of oxygen reduction reaction (ORR) catalysts for direct methanol fuel cell (DMFC), the methanol tolerance is also an important concern. Here, we develop AlN nanowires with diameters of about 100-150 nm and the length up to 1 mm through crystal growth method. We find it is electrochemically stable in methanol-contained alkaline electrolyte. This novel material exhibits pronounced electrocatalytic activity with exchange current density of about 6.52 × 10(-8) A/cm(2). The single cell assembled with AlN nanowire cathodic electrode achieves a power density of 18.9 mW cm(-2). After being maintained at 100 mA cm(-2) for 48 h, the AlN nanowire-based single cell keeps 92.1% of the initial performance, which is in comparison with 54.5% for that assembled with Pt/C cathode. This discovery reveals a new type of metal nitride ORR catalyst that can be cheaply produced from crystal growth method.

Self-Supported Mesostructured Pt-Based Bimetallic Nanospheres Containing an Intermetallic Phase as Ultrastable Oxygen Reduction Electrocatalysts.

PubMed

Kim, Ho Young; Cho, Seonghun; Sa, Young Jin; Hwang, Sun-Mi; Park, Gu-Gon; Shin, Tae Joo; Jeong, Hu Young; Yim, Sung-Dae; Joo, Sang Hoon

2016-10-01

Developing highly active and stable cathode catalysts is of pivotal importance for proton exchange membrane fuel cells (PEMFCs). While carbon-supported nanostructured Pt-based catalysts have so far been the most active cathode catalysts, their durability and single-cell performance are yet to be improved. Herein, self-supported mesostructured Pt-based bimetallic (Meso-PtM; M = Ni, Fe, Co, Cu) nanospheres containing an intermetallic phase are reported, which can combine the beneficial effects of transition metals (M), an intermetallic phase, a 3D interconnected framework, and a mesoporous structure. Meso-PtM nanospheres show enhanced oxygen reduction reaction (ORR) activity, compared to Pt black and Pt/C catalysts. Notably, Meso-PtNi containing an intermetallic phase exhibits ultrahigh stability, showing enhanced ORR activity even after 50 000 potential cycles, whereas Pt black and Pt/C undergo dramatic degradation. Importantly, Meso-PtNi with an intermetallic phase also demonstrated superior activity and durability when used in a PEMFC single-cell, with record-high initial mass and specific activities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic states of carbon alloy catalysts and nitrogen substituent effects on catalytic activity

NASA Astrophysics Data System (ADS)

Hata, Tomoyuki; Ushiyama, Hiroshi; Yamashita, Koichi

2013-03-01

In recent years, Carbon Alloy Catalysts (CACs) are attracting attention as a candidate for non-platinum-based cathode catalysts in fuel cells. Oxygen reduction reactions at the cathode are divided into two elementary processes, electron transfer and oxygen adsorption. The electron transfer reaction is the rate-determining, and by comparison of energy levels, catalytic activity can be evaluated quantitatively. On the other hand, to begin with, adsorption mechanism is obscure. The purpose of this study is to understand the effect of nitrogen substitution and oxygen adsorption mechanism, by first-principle electronic structure calculations for nitrogen substituted models. To reproduce the elementary processes of oxygen adsorption, we assumed that the initial structures are formed based on the Pauling model, a CACs model and nitrogen substituted CACs models in which various points are replaced with nitrogen. When we try to focus only on the DOS peaks of oxygen, in some substituted model that has high adsorption activity, a characteristic partial occupancy state was found. We conclude that this state will affect the adsorption activity, and discuss on why partially occupied states appear with simplification by using an orbital correlation diagram.

Nitrogen, Fluorine, and Boron Ternary Doped Carbon Fibers as Cathode Electrocatalysts for Zinc-Air Batteries.

PubMed

Wang, Lei; Wang, Yueqing; Wu, Mingguang; Wei, Zengxi; Cui, Chunyu; Mao, Minglei; Zhang, Jintao; Han, Xiaopeng; Liu, Quanhui; Ma, Jianmin

2018-05-01

Zinc-air batteries with high-density energy are promising energy storage devices for the next generation of energy storage technologies. However, the battery performance is highly dependent on the efficiency of oxygen electrocatalyst in the air electrode. Herein, the N, F, and B ternary doped carbon fibers (TD-CFs) are prepared and exhibited higher catalytic properties via the efficient 4e - transfer mechanism for oxygen reduction in comparison with the single nitrogen doped CFs. More importantly, the primary and rechargeable Zn-air batteries using TD-CFs as air-cathode catalysts are constructed. When compared to batteries with Pt/C + RuO 2 and Vulcan XC-72 carbon black catalysts, the TD-CFs catalyzed batteries exhibit remarkable battery reversibility and stability over long charging/discharging cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cathodic and anodic biofilms in Single Chamber Microbial Fuel Cells.

PubMed

Cristiani, P; Carvalho, M L; Guerrini, E; Daghio, M; Santoro, C; Li, B

2013-08-01

The oxygen reduction due to microaerophilic biofilms grown on graphite cathodes (biocathodes) in Single Chamber Microbial Fuel Cells (SCMFCs) is proved and analysed in this paper. Pt-free cathode performances are compared with those of different platinum-loaded cathodes, before and after the biofilm growth. Membraneless SCMFCs were operating in batch-mode, filled with wastewater. A substrate (fuel) of sodium acetate (0.03 M) was periodically added and the experiment lasted more than six months. A maximum of power densities, up to 0.5 W m(-2), were reached when biofilms developed on the electrodes and the cathodic potential decreased (open circuit potential of 50-200 mV vs. SHE). The power output was almost constant with an acetate concentration of 0.01-0.05 M and it fell down when the pH of the media exceeded 9.5, independently of the Pt-free/Pt-loading at the cathodes. Current densities varied in the range of 1-5 Am(-2) (cathode area of 5 cm(2)). Quasi-stationary polarization curves performed with a three-electrode configuration on cathodic and anodic electrodes showed that the anodic overpotential, more than the cathodic one, may limit the current density in the SCMFCs for a long-term operation. Copyright © 2012 Elsevier B.V. All rights reserved.

Oxygen-reducing biocathodes operating with passive oxygen transfer in microbial fuel cells.

PubMed

Xia, Xue; Tokash, Justin C; Zhang, Fang; Liang, Peng; Huang, Xia; Logan, Bruce E

2013-02-19

Oxygen-reducing biocathodes previously developed for microbial fuel cells (MFCs) have required energy-intensive aeration of the catholyte. To avoid the need for aeration, the ability of biocathodes to function with passive oxygen transfer was examined here using air cathode MFCs. Two-chamber, air cathode MFCs with biocathodes produced a maximum power density of 554 ± 0 mW/m(2), which was comparable to that obtained with a Pt cathode (576 ± 16 mW/m(2)), and 38 times higher than that produced without a catalyst (14 ± 3 mW/m(2)). The maximum current density with biocathodes in this air-cathode MFC was 1.0 A/m(2), compared to 0.49 A/m(2) originally produced in a two-chamber MFC with an aqueous cathode (with cathode chamber aeration). Single-chamber, air-cathode MFCs with the same biocathodes initially produced higher voltages than those with Pt cathodes, but after several cycles the catalytic activity of the biocathodes was lost. This change in cathode performance resulted from direct exposure of the cathodes to solutions containing high concentrations of organic matter in the single-chamber configuration. Biocathode performance was not impaired in two-chamber designs where the cathode was kept separated from the anode solution. These results demonstrate that direct-air biocathodes can work very well, but only under conditions that minimize heterotrophic growth of microorganisms on the cathodes.

Effect of the nanosized TiO2 particles in Pd/C catalysts as cathode materials in direct methanol fuel cells.

PubMed

Choi, Mahnsoo; Han, Choonsoo; Kim, In-Tae; Lee, Ji-Jung; Lee, Hong-Ki; Shim, Joongpyo

2011-07-01

Pd-TiO2/C catalysts were prepared by impregnating titanium dioxide (TiO2) on carbon-supported Pd (Pd/C) for use as the catalyst for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFCs). Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried to confirm the distribution, morphology and structure of Pd and TiO2 on the carbon support. In fuel cell test, we confirmed that the addition of TiO2 nanoparticles make the improved catalytic activity of oxygen reduction. The electrochemical characterization of the Pd-TiO2/C catalyst for the ORR was carried out by cyclic voltammetry (CV) in the voltage window of 0.04 V to 1.2 V with scan rate of 25 mV/s. With the increase in the crystallite size of TiO2, the peak potential for OH(ads) desorption on the surface of Pd particle shifted to higher potential. This implies that TiO2 might affect the adsorption and desorption of oxygen molecules on Pd catalyst. The performance of Pd-TiO2/C as a cathode material was found to be similar to or better performance than that of Pt/C.

Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

PubMed

Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

2015-11-18

Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

Protons accumulation during anodic phase turned to advantage for oxygen reduction during cathodic phase in reversible bioelectrodes.

PubMed

Blanchet, Elise; Pécastaings, Sophie; Erable, Benjamin; Roques, Christine; Bergel, Alain

2014-12-01

Reversible bioelectrodes were designed by alternating acetate and oxygen supply. It was demonstrated that the protons produced and accumulated inside the biofilm during the anodic phase greatly favored the oxygen reduction reaction when the electrode was switched to become the biocathode. Protons accumulation, which hindered the bioanode operation, thus became an advantage for the biocathode. The bioanodes, formed from garden compost leachate under constant polarization at -0.2 V vs. SCE, were able to support long exposure to forced aeration, with only a slight alteration of their anodic efficiency. They produced a current density of 16±1.7 A/m2 for acetate oxidation and up to -0.4 A/m2 for oxygen reduction. Analysis of the microbial communities by 16S rRNA pyrosequencing revealed strong selection of Chloroflexi (49±1%), which was not observed for conventional bioanodes not exposed to oxygen. Chloroflexi were found as the dominant phylum of electroactive biofilms for the first time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Highly active nitrogen-doped nanocarbon electrocatalysts for alkaline direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Kruusenberg, Ivar; Ratso, Sander; Vikkisk, Merilin; Kanninen, Petri; Kallio, Tanja; Kannan, Arunachala M.; Tammeveski, Kaido

2015-05-01

Direct methanol fuel cells are assembled and evaluated using Fumatech FAA3 alkaline anion exchange membrane. Two novel metal-free cathode catalysts are synthesised, investigated and compared with the commercial Pt-based catalyst. In this work nitrogen-doped few-layer graphene/multi-walled carbon nanotube (N-FLG/MWCNT) composite and nitrogen-doped MWCNT (N-MWCNT) catalyst are prepared by pyrolysing the mixture of dicyandiamide (DCDA) and carbon nanomaterials at 800 °C. The resulting cathode catalyst material shows a remarkable electrocatalytic activity for oxygen reduction reaction (ORR) in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. Fuel cell tests are performed by using 1 M methanol as anode and pure oxygen gas cathode feed. The maximum power density obtained with the N-FLG/MWCNT material (0.72 mW cm-2) is similar to that of the Pt/C catalyst (0.72 mW cm-2), whereas the N-MWCNT material shows higher peak power density (0.92 mW cm-2) than the commercial Pt/C catalyst.

Oxygen Generation from Carbon Dioxide for Advanced Life Support

NASA Technical Reports Server (NTRS)

Bishop, s. R.; Duncan, K. L.; Hagelin-Weaver, H. E.; Neal, L.; Paul, H. L.; Wachsman, E. D.

2007-01-01

The partial electrochemical reduction of CO2 using ceramic oxygen generators (COGs) is well known and has been studied. Conventional COGs use yttria-stabilized zirconia (YSZ) electrolytes and operate at temperatures greater than 700 C (1, 2). Operating at a lower temperature has the advantage of reducing the mass of the ancillary components such as insulation. Moreover, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight if the oxygen can be recovered. Recently, the University of Florida developed ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth oxide (ESB) for NASA s future exploration of Mars (3). The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal is an issue. This strategy for CO2 removal in advanced life support systems employs a catalytic layer combined with a COG so that the CO2 is reduced completely to solid carbon and oxygen. First, to reduce the COG operating temperature, a thin, bilayer electrolyte was employed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, a catalytic carbon deposition layer was designed and the cathode utilized materials shown to be coke resistant. Third, a composite anode was used consisting of bismuth ruthenate (BRO) and ESB that has been shown to have high performance (4). The inset of figure 1 shows the conceptual design of the tubular COG and the rest of the figure shows schematically the test apparatus. Figure 2 shows the microstructure of a COG tube prior to testing. During testing, current is applied across the cell and initially CuO is reduced to copper metal by electrochemical pumping. Then the oxygen source becomes the CO/CO2. This presentation details the results of testing the COG.

Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

NASA Astrophysics Data System (ADS)

Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

2013-12-01

Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

The effects of minor elements in La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes on oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Oishi, Junya; Otomo, Junichiro; Oshima, Yoshito; Koyama, Michihisa

2015-03-01

It is known that the minor elements affect the performance of solid oxide fuel cell (SOFC). In this study, we focus on the influence of minor elements on the SOFC cathode properties. The Ca, Ba, Al, and Si, which originate from raw materials and production processes for SOFC cathodes, are investigated as minor elements that may have effect on the properties of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode. To examine the effects of minor elements on the cathode properties, Ca, Ba, Al, and Si with a controlled concentration are added to the LSCF reference sample. Conductivity relaxation measurements are conducted to determine the chemical diffusion coefficient (Dchem) and surface exchange coefficient (ktr), which governs the overpotential characteristics of the LSCF cathode. The results show that Al and Si have negative effects on both Dchem and ktr while Ca and Ba do not alter Dchem and show weakly positive effects on ktr. The effects of Ca and Ba for the cathode properties are discussed on the basis of XPS measurements.

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

PubMed

Mao, Xuhui; Yuan, Songhu; Fallahpour, Noushin; Ciblak, Ali; Howard, Joniqua; Padilla, Ingrid; Loch-Caruso, Rita; Alshawabkeh, Akram N

2012-11-06

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

The effect of oxygen pressure on volatility and morphology of LaB6 single crystal cathodes

NASA Technical Reports Server (NTRS)

Davis, P. R.; Schwind, G. A.; Swanson, L. W.

1986-01-01

The effect of oxygen pressure on the volatility and morphology of single crystal LaB6 cathodes, heated to different temperatures, was investigated. At a temperature of 1600 K, an increase of oxygen pressure from 1 x 10 to the -8th torr to 1 x 10 to the -6th torr has led to a 100-fold enhancement in cathode volatility. The enhancement effect of oxygen pressure diminished with increasing temperature: at a cathode operating temperature of 1900 K, the volatility enhancement due to the same oxygen pressure was negligible. It was shown that the faceting frequently observed during evaporation of conically shaped emitters is due to a crystallograpic anisotropy of the oxidation rate of LaB6. No facet formation occurs during evaporation at oxygen pressures below -110 to the -8th torr.

Oxygen Reduction Reaction Affected by Sulfate-Reducing Bacteria: Different Roles of Bacterial Cells and Metabolites.

PubMed

Wu, Jiajia; Liu, Huaiqun; Wang, Peng; Zhang, Dun; Sun, Yan; Li, Ee

2017-09-01

Sulfate-reducing bacteria (SRB) were found to be capable of tolerating a certain amount of oxygen (O 2 ), but how they affect oxygen reduction reaction (ORR) has not been clear. The present work investigated the impact of SRB on ORR in 3.5 wt% sodium chloride solution with the cyclic voltammetry method. The addition of SRB culture solution hampered both the reduction of O 2 to superoxide (O 2 ·- ) and hydrogen peroxide (H 2 O 2 ) to water (H 2 O), and the influence of SRB metabolites was much larger than that of bacterial cells. Sulfide and extracellular polymeric substances (EPS), typical inorganic and organic metabolic products, had great impact on ORR. Sulfide played an important role in the decrease of cathodic current for H 2 O 2 reduction due to its hydrolysis and chemical reaction activity with H 2 O 2 . EPS were sticky, easy to adsorb on the electrode surface and abundant in functional groups, which hindered the transformation of O 2 into O 2 ·- and favored the reduction of H 2 O 2 to H 2 O.

Metal-Organic Framework-Derived Reduced Graphene Oxide-Supported ZnO/ZnCo2O4/C Hollow Nanocages as Cathode Catalysts for Aluminum-O2 Batteries.

PubMed

Liu, Yisi; Jiang, Hao; Hao, Jiayu; Liu, Yulong; Shen, Haibo; Li, Wenzhang; Li, Jie

2017-09-20

Aluminum-air battery is a promising candidate for large-scale energy applications because of its low cost and high energy density. Remarkably, tremendous efforts have been concentrated on developing efficient and stable cathode electrocatalysts toward the oxygen reduction reaction. In this work, a hydrothermal-calcination approach was utilized to prepare novel reduced graphene oxide (rGO)-supported hollow ZnO/ZnCo 2 O 4 nanoparticle-embedded carbon nanocages (ZnO/ZnCo 2 O 4 /C@rGO) using a zeolitic imidazolate framework (ZIF-67)/graphene oxide/zinc nitrate composite as the precursor. The ZnO/ZnCo 2 O 4 /C@rGO hybrid exhibits remarkable electrocatalytic performance for oxygen reduction reaction under alkaline conditions and superior stability and methanol tolerance to those of the commercial Pt/C catalyst. Furthermore, novel and simple Al-air coin cells were first fabricated using the hybrid materials as cathode catalysts under ambient air conditions to further investigate their catalytic performance. The coin cell with the ZnO/ZnCo 2 O 4 /C@rGO cathode catalyst displays a higher open circuit voltage and discharge voltage and more sluggish potential drop than those of the cell with the ZnO/ZnCo 2 O 4 /C cathode catalyst, which confirms that rGO can enhance the electrocatalytic activity and stability of the catalyst system. The excellent electrocatalytic performance of the ZnO/ZnCo 2 O 4 /C@rGO hybrid is attributed to the prominent conductivity and high specific surface area resulting from rGO, the more accessible catalytic active sites induced by the unique porous hollow nanocage structure, and synergic covalent coupling between rGO sheets and ZnO/ZnCo 2 O 4 /C nanocages.

Metal molybdate nanorods as non-precious electrocatalysts for the oxygen reduction

NASA Astrophysics Data System (ADS)

Wu, Tian; Zhang, Lieyu

2015-12-01

Development of non-precious electrocatalysts with applicable electrocatalytic activity towards the oxygen reduction reaction (ORR) is important to fulfill broad-based and large-scale applications of metal/air batteries and fuel cells. Herein, nickel and cobalt molybdates with uniform nanorod morphology are synthesized using a facile one-pot hydrothermal method. The ORR activity of the prepared metal molybdate nanorods in alkaline media are investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperomety in rotating disk electrode (RDE) techniques. The present study suggests that the prepared metal molybdate nanorods exhibit applicable electrocatalytic activities towards the ORR in alkaline media, promising the applications as non-precious cathode in fuel cells and metal-air batteries.

Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells

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

Chong, Lina; Goenaga, Gabriel A.; Williams, Kia

We demonstrated that the oxygen reduction reaction (ORR) activity over the catalysts derived from pyrolyzed cobalt zeolitic imidazolate frameworks depends strongly on the imidazole ligand structure and cobalt content. The activity and durability of these catalysts were tested in the proton exchange membrane fuel cell for the first time. The membrane electrode assembly containing a catalyst derived from Co/Zn bimetallic ZIF at cathode achieved an open circuit voltage of 0.93 V, a current density of 28 mA cm-2 at 0.8 ViR-free and a peak power density of 374 mW cm-2.

Liquid-Feed Methanol Fuel Cell With Membrane Electrolyte

NASA Technical Reports Server (NTRS)

Surampudi, Subbarao; Narayanan, S. R.; Halpert, Gerald; Frank, Harvey; Vamos, Eugene

1995-01-01

Fuel cell generates electricity from direct liquid feed stream of methanol/water solution circulated in contact with anode, plus direct gaseous feed stream of air or oxygen in contact with cathode. Advantages include relative simplicity and elimination of corrosive electrolytic solutions. Offers potential for reductions in size, weight, and complexity, and for increases in safety of fuel-cell systems.

Evaluation of pulsed laser deposited SrNb0.1Co0.9O3-δ thin films as promising cathodes for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Chen, Dengjie; Chen, Chi; Gao, Yang; Zhang, Zhenbao; Shao, Zongping; Ciucci, Francesco

2015-11-01

SrNb0.1Co0.9O3-δ (SNC) thin films prepared on single-crystal yttria-stabilized zirconia (YSZ) electrolytes are evaluated as promising cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Geometrically well-defined polycrystalline SNC thin films with low surface roughness and high surface oxygen vacancy concentration are successfully fabricated by pulsed laser deposition. The thin films are characterized by basic techniques, e.g., X-ray diffraction for phase structure identification, scanning electron microscopy and atomic force microscopy for microstructures measurement, and X-ray photoelectron spectroscopy for elements quantification. Electrochemical impedance spectroscopy (EIS) is used to investigate oxygen reduction reaction activities of SNC thin films in symmetric electrochemical cells. Current collectors (Ag paste, Ag strip, and Au strip) are found to have negligible impact on polarization resistances. A slight decrease of the electrode polarization resistances is observed after adding a samarium doped ceria (SDC) buffer layer between SNC and YSZ. SNC thin-film electrodes exhibit low electrode polarization resistances, e.g., 0.237 Ω cm2 (SNC/SDC/YSZ/SDC/SNC) and 0.274 Ω cm2 (SNC/YSZ/SNC) at 700 °C and 0.21 atm, demonstrating the promise of SNC materials for IT-SOFCs. An oxygen reduction reaction mechanism of SNC thin films is also derived by analyzing EIS at temperature of 550-700 °C under oxygen partial pressure range of 0.04-1 atm.

Effect of cathode cooling efficiency and oxygen plasma gas pressure on the hafnium cathode wall temperature

NASA Astrophysics Data System (ADS)

Ashtekar, Koustubh; Diehl, Gregory; Hamer, John

2012-10-01

The hafnium cathode is widely used in DC plasma arc cutting (PAC) under an oxygen gas environment to cut iron and iron alloys. The hafnium erosion is always a concern which is controlled by the surface temperature. In this study, the effect of cathode cooling efficiency and oxygen gas pressure on the hafnium surface temperature are quantified. The two layer cathode sheath model is applied on the refractive hafnium surface while oxygen species (O2, O, O+, O++, e-) are considered within the thermal dis-equilibrium regime. The system of non-linear equations comprising of current density balance, heat flux balance at both the cathode surface and the sheath-ionization layer is coupled with the plasma gas composition solver. Using cooling heat flux, gas pressure and current density as inputs; the cathode wall temperature, electron temperature, and sheath voltage drop are calculated. Additionally, contribution of emitted electron current (Je) and ions current (Ji) to the total current flux are estimated. Higher gas pressure usually reduces Ji and increases Je that reduces the surface temperature by thermionic cooling.

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-stage Electrolysis Stack

NASA Technical Reports Server (NTRS)

Setlock, John A (Inventor); Green, Robert D (Inventor); Farmer, Serene (Inventor)

2016-01-01

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O.sup.2-) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-Stage Electrolysis Stack

NASA Technical Reports Server (NTRS)

Setlock, John A (Inventor); Green, Robert D (Inventor); Farmer, Serene (Inventor)

2017-01-01

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O(2-)) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

Linking Initial Microstructure to ORR Related Property Degradation in SOFC Cathode: A Phase Field Simulation

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

Lei, Y.; Cheng, T. -L.; Wen, Y. H.

Microstructure evolution driven by thermal coarsening is an important factor for the loss of oxygen reduction reaction rates in SOFC cathode. In this work, the effect of an initial microstructure on the microstructure evolution in SOFC cathode is investigated using a recently developed phase field model. Specifically, we tune the phase fraction, the average grain size, the standard deviation of the grain size and the grain shape in the initial microstructure, and explore their effect on the evolution of the grain size, the density of triple phase boundary, the specific surface area and the effective conductivity in LSM-YSZ cathodes. Itmore » is found that the degradation rate of TPB density and SSA of LSM is lower with less LSM phase fraction (with constant porosity assumed) and greater average grain size, while the degradation rate of effective conductivity can also be tuned by adjusting the standard deviation of grain size distribution and grain aspect ratio. The implication of this study on the designing of an optimal initial microstructure of SOFC cathodes is discussed.« less

Linking Initial Microstructure to ORR Related Property Degradation in SOFC Cathode: A Phase Field Simulation

DOE PAGES

Lei, Y.; Cheng, T. -L.; Wen, Y. H.

2017-07-05

Microstructure evolution driven by thermal coarsening is an important factor for the loss of oxygen reduction reaction rates in SOFC cathode. In this work, the effect of an initial microstructure on the microstructure evolution in SOFC cathode is investigated using a recently developed phase field model. Specifically, we tune the phase fraction, the average grain size, the standard deviation of the grain size and the grain shape in the initial microstructure, and explore their effect on the evolution of the grain size, the density of triple phase boundary, the specific surface area and the effective conductivity in LSM-YSZ cathodes. Itmore » is found that the degradation rate of TPB density and SSA of LSM is lower with less LSM phase fraction (with constant porosity assumed) and greater average grain size, while the degradation rate of effective conductivity can also be tuned by adjusting the standard deviation of grain size distribution and grain aspect ratio. The implication of this study on the designing of an optimal initial microstructure of SOFC cathodes is discussed.« less

High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

PubMed

Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

2018-02-26

The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution

NASA Astrophysics Data System (ADS)

Suo, Ni; Huang, Hao; Wu, Aimin; Cao, Guozhong; Hou, Xiaoduo; Zhang, Guifeng

2018-05-01

Porous boron doped diamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the boron doped diamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous boron doped diamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics

DOE PAGES

Pant, Lalit M.; Weber, Adam Z.

2017-04-14

A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.

Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

DOEpatents

Chlistunoff, Jerzy B [Los Alamos, NM; Lipp, Ludwig [Brookfield, CT; Gottesfeld, Shimshon [Niskayuna, NY

2006-08-01

Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

Hierarchical nanostructured hollow spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange membrane fuel cell.

PubMed

Fang, Baizeng; Kim, Jung Ho; Kim, Minsik; Kim, Minwoo; Yu, Jong-Sung

2009-03-07

Hierarchical nanostructured spherical carbon with hollow macroporous core in combination with mesoporous shell has been explored to support Pt cathode catalyst with high metal loading in proton exchange membrane fuel cell (PEMFC). The hollow core-mesoporous shell carbon (HCMSC) has unique structural characteristics such as large specific surface area and mesoporous volume, ensuring uniform dispersion of the supported high loading (60 wt%) Pt nanoparticles with small particle size, and well-developed three-dimensionally interconnected hierarchical porosity network, facilitating fast mass transport. The HCMSC-supported Pt(60 wt%) cathode catalyst has demonstrated markedly enhanced catalytic activity toward oxygen reduction and greatly improved PEMFC polarization performance compared with carbon black Vulcan XC-72 (VC)-supported ones. Furthermore, the HCMSC-supported Pt(40 wt%) or Pt(60 wt%) outperforms the HCMSC-supported Pt(20 wt%) even at a low catalyst loading of 0.2 mg Pt cm(-2) in the cathode, which is completely different from the VC-supported Pt catalysts. The capability of supporting high loading Pt is supposed to accelerate the commercialization of PEMFC due to the anticipated significant reduction in the amount of catalyst support required, diffusion layer thickness and fabricating cost of the supported Pt catalyst electrode.

Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey

2018-01-01

In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

Element- and charge-state-resolved ion energies in the cathodic arc plasma from composite AlCr cathodes in argon, nitrogen and oxygen atmospheres

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

Franz, Robert; Polcik, Peter; Anders, André

The energy distribution functions of ions in the cathodic arc plasma using composite AlCr cathodes were measured as a function of the background gas pressure in the range 0.5 to 3.5 Pa for different cathode compositions and gas atmospheres. The most abundant aluminium ions were Al+ regardless of the background gas species, whereas Cr 2+ ions were dominating in Ar and N 2 and Cr + in O 2 atmospheres. The energy distributions of the aluminium and chromium ions typically consisted of a high-energy fraction due to acceleration in the expanding plasma plume from the cathode spot and thermalised ionsmore » that were subjected to collisions in the plasma cloud. The fraction of the latter increased with increasing background gas pressure. Atomic nitrogen and oxygen ions showed similar energy distributions as the aluminium and chromium ions, whereas the argon and molecular nitrogen and oxygen ions were formed at greater distance from the cathode spot and thus less subject to accelerating gradients. In addition to the positively charged metal and gas ions, negatively charged oxygen and oxygen-containing ions were observed in O 2 atmosphere. The obtained results are intended to provide a comprehensive overview of the ion energies and charge states in the arc plasma of AlCr composite cathodes in different gas atmospheres as such plasmas are frequently used to deposit thin films and coatings.« less

Element- and charge-state-resolved ion energies in the cathodic arc plasma from composite AlCr cathodes in argon, nitrogen and oxygen atmospheres

DOE PAGES

Franz, Robert; Polcik, Peter; Anders, André

2015-06-01

The energy distribution functions of ions in the cathodic arc plasma using composite AlCr cathodes were measured as a function of the background gas pressure in the range 0.5 to 3.5 Pa for different cathode compositions and gas atmospheres. The most abundant aluminium ions were Al+ regardless of the background gas species, whereas Cr 2+ ions were dominating in Ar and N 2 and Cr + in O 2 atmospheres. The energy distributions of the aluminium and chromium ions typically consisted of a high-energy fraction due to acceleration in the expanding plasma plume from the cathode spot and thermalised ionsmore » that were subjected to collisions in the plasma cloud. The fraction of the latter increased with increasing background gas pressure. Atomic nitrogen and oxygen ions showed similar energy distributions as the aluminium and chromium ions, whereas the argon and molecular nitrogen and oxygen ions were formed at greater distance from the cathode spot and thus less subject to accelerating gradients. In addition to the positively charged metal and gas ions, negatively charged oxygen and oxygen-containing ions were observed in O 2 atmosphere. The obtained results are intended to provide a comprehensive overview of the ion energies and charge states in the arc plasma of AlCr composite cathodes in different gas atmospheres as such plasmas are frequently used to deposit thin films and coatings.« less

A hierarchically honeycomb-like carbon via one-step surface and pore adjustment with superior capacity for lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Li, Jing; Zhang, Yining; Zhou, Wei; Nie, Hongjiao; Zhang, Huamin

2014-09-01

Li-O2 batteries have attracted considerable attention due to their high energy density. The critical challenges that limit the practical applications include effective utilization of electrode space for solid products deposition and acceptable cycling performance. In the present work, a nitrogen-doped micron-sized honeycomb-like carbon is developed for use as a cathode material for Li-O2 batteries. This novel material is obtained by using nano-CaCO3 particles as hard template and sucrose as the carbon source, followed by thermal annealing at 800 °C in ammonia. With one-step ammonia activation, surface nitrogenation and further pore structure optimization are realized simultaneously. The material exhibits enhanced activity for oxygen reduction reaction and oxygen transfer ability. Surprisingly, an improved cycling stability is also obtained. As a result, a superior discharge capacity up to 12,600 mAh g-1 is achieved, about 4 times that of commercial Ketjenblack carbon. The results provide a novel route to construct effective non-metal carbon-based cathodes for high performance of Li-O2 batteries.

High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

PubMed

Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

2016-08-09

Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strategies toward High-Performance Cathode Materials for Lithium-Oxygen Batteries.

PubMed

Wang, Kai-Xue; Zhu, Qian-Cheng; Chen, Jie-Sheng

2018-05-11

Rechargeable aprotic lithium (Li)-O 2 batteries with high theoretical energy densities are regarded as promising next-generation energy storage devices and have attracted considerable interest recently. However, these batteries still suffer from many critical issues, such as low capacity, poor cycle life, and low round-trip efficiency, rendering the practical application of these batteries rather sluggish. Cathode catalysts with high oxygen reduction reaction (ORR) and evolution reaction activities are of particular importance for addressing these issues and consequently promoting the application of Li-O 2 batteries. Thus, the rational design and preparation of the catalysts with high ORR activity, good electronic conductivity, and decent chemical/electrochemical stability are still challenging. In this Review, the strategies are outlined including the rational selection of catalytic species, the introduction of a 3D porous structure, the formation of functional composites, and the heteroatom doping which succeeded in the design of high-performance cathode catalysts for stable Li-O 2 batteries. Perspectives on enhancing the overall electrochemical performance of Li-O 2 batteries based on the optimization of the properties and reliability of each part of the battery are also made. This Review sheds some new light on the design of highly active cathode catalysts and the development of high-performance lithium-O 2 batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite cathode materials development for intermediate temperature solid oxide fuel cell systems

NASA Astrophysics Data System (ADS)

Qin, Ya

Solid oxide fuel cell (SOFC) systems are of particular interest as electrochemical power systems that can operate on various hydrocarbon fuels with high fuel-to-electrical energy conversion efficiency. Within the SOFC stack, La0.8Sr 0.2Ga0.8Mg0.115Co0.085O3-delta (LSGMC) has been reported as an optimized composition of lanthanum gallate based electrolytes to achieve higher oxygen ionic conductivity at intermediate temperatures, i.e., 500-700°C. The electrocatalytic properties of interfaces between LSGMC electrolytes and various candidate intermediate-temperature SOFC cathodes have been investigated. Sm0.5Sr0.5CoO 3-delta (SSC), and La0.6Sr0.4Co0.2Fe 0.8O3-delta (LSCF), in both pure and composite forms with LSGMC, were investigated with regards to both oxygen reduction and evolution, A range of composite cathode compositions, having ratios of SSC (in wt.%) with LSGMC (wt.%) spanning the compositions 9:1, 8:2, 7:3, 6:4 and 5:5, were investigated to determine the optimal cathode-electrolyte interface performance at intermediate temperatures. All LSGMC electrolyte and cathode powders were synthesized using the glycine-nitrate process (GNP). Symmetrical electrochemical cells were investigated with three-electrode linear dc polarization and ac impedance spectroscopy to characterize the kinetics of the interfacial reactions in detail. Composite cathodes were found to perform better than the single phase cathodes due to significantly reduced polarization resistances. Among those composite SSC-LSGMC cathodes, the 7:3 composition has demonstrated the highest current density at the equivalent overpotential values, indicating that 7:3 is an optimal mixing ratio of the composite cathode materials to achieve the best performance. For the composite SC-LSGMC cathode/LSGMC interface, the cathodic overpotential under 1 A/cm2 current density was as low as 0.085 V at 700°C, 0.062V at 750°C and 0.051V at 800°C in air. Composite LSCF-LSGMC cathode/LSGMC interfaces were found to have about twice the exchange current density of composite SSC-LSGMC/LSGMC interfaces at 700°C. In this research effort, it has been found that: (1) the glycine-nitrate combustion process is favorable to produce perovskite-type oxide powders with good phase purity and negligible intermediate or contaminant phases; (2) The electrochemical performance for both the SSC-LSGMC and LSCF-LSGMC composite electrode materials on LSGMC confirm their potential for use in intermediate temperature SOFC applications; (3) The composite LSCF-LSGMC electrode exhibited much higher current density than the composite SSC-LSGMC electrode in the current dc polarization measurements; and (4) Primary market study results showed promising commercialization feasibility of these new materials sets, provided production is scaled up (with dramatic cost reductions).

A detailed study of Au-Ni bimetal synthesized by the phase separation mechanism for the cathode of low-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Yang, Tao; Rodrigues de Almeida, Carlos Manuel; Ramasamy, Devaraj; Almeida Loureiro, Francisco José

2014-12-01

A facile co-reduction and annealing synthesis route of nanospheric particles of Au-Ni bimetal with adjustable composition was developed. In a typical synthesis, a direct co-reduction of HAuCl4.4H2O and NiCl2 in aqueous solution was performed with the assistance of reductive NaBH4 and an anionic surfactant sodium dodecyl sulfate (SDS) functioned as the structure-directing agent. Ultrasonic mixing was used at the same time to control the size of the particles. The morphology, microstructure and the state of the surface atoms were analyzed in detail. These nanospheres showed enhanced electrocatalytic activity towards oxygen reduction reaction than that of pure Au nanoparticles, demonstrated in the low temperature SOFC as cathode. The maximum power density generated is 810 mW cm-2 at 550 °C. This is a promising route of taking advantages the Phase Separation Mechanism to greatly reduce the use of noble metals in the ORR field without sacrificing the electrocatalytic activity.

Inhibition of microbial growth on air cathodes of single chamber microbial fuel cells by incorporating enrofloxacin into the catalyst layer.

PubMed

Liu, Weifeng; Cheng, Shaoan; Sun, Dan; Huang, Haobin; Chen, Jie; Cen, Kefa

2015-10-15

The inevitable growth of aerobic bacteria on the surface of air cathodes is an important factor reducing the performance stability of air cathode single-chamber membrane-free microbial fuel cells (MFCs). Thus searching for effective methods to inhibit the cathodic microbial growth is critical for the practical application of MFCs. In this study, enrofloxacin (ENR), a broad spectrum fluoroquinolone antibiotic, was incorporated into the catalyst layer of activated carbon air cathodes (ACACs) to inhibit the cathodic microbial growth. The biomass content on ACACs was substantially reduced by 60.2% with ENR treatment after 91 days of MFCs operation. As a result of the inhibited microbial growth, the oxygen reduction catalytic performance of the ENR treated ACACs was much stable compared to the fast performance decline of the untreated control. Consequently, a quite stable electricity production was obtained for the MFCs with the ENR treated ACACs, in contrast with a 22.5% decrease in maximum power density of the MFCs with the untreated cathode. ENR treatment of ACACs showed minimal effects on the anode performance. These results indicate that incorporating antibiotics into ACACs should be a simple and effective strategy to inhibit the microbial growth and improve the long-term stability of the performance of air cathode and the electricity production of MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

Inkjet-Printed Porous Silver Thin Film as a Cathode for a Low-Temperature Solid Oxide Fuel Cell.

PubMed

Yu, Chen-Chiang; Baek, Jong Dae; Su, Chun-Hao; Fan, Liangdong; Wei, Jun; Liao, Ying-Chih; Su, Pei-Chen

2016-04-27

In this work we report a porous silver thin film cathode that was fabricated by a simple inkjet printing process for low-temperature solid oxide fuel cell applications. The electrochemical performance of the inkjet-printed silver cathode was studied at 300-450 °C and was compared with that of silver cathodes that were fabricated by the typical sputtering method. Inkjet-printed silver cathodes showed lower electrochemical impedance due to their porous structure, which facilitated oxygen gaseous diffusion and oxygen surface adsorption-dissociation reactions. A typical sputtered nanoporous silver cathode became essentially dense after the operation and showed high impedance due to a lack of oxygen supply. The results of long-term fuel cell operation show that the cell with an inkjet-printed cathode had a more stable current output for more than 45 h at 400 °C. A porous silver cathode is required for high fuel cell performance, and the simple inkjet printing technique offers an alternative method of fabrication for such a desirable porous structure with the required thermal-morphological stability.

A proposed physical model for the impregnated tungsten cathode based on Auger surface studies of the Ba-O-W system

NASA Technical Reports Server (NTRS)

Forman, R.

1979-01-01

Auger spectra and work function measurements are used to study the surface reactions between tungsten surface and adsorbed layers of barium, and barium and oxygen. The barium on an impregnated tungsten cathod seems to be an intermediate state, probably a coadsorbed barium-oxygen layer on tungsten. A slightly revised version of the previously suggested (1976) impregnated tungsten cathode model is proposed. This revised model assumes that the cathode surface during life has an adsorbed surface layer of a monolayer or less of both barium and oxygen on the surface. At end of life, steep drop in electron emission and resultant cathode failure occur. Recent NASA life test results on TWT type tubes are reported and explained by the proposed model.

Co3O4 nanoparticles decorated carbon nanofiber mat as binder-free air-cathode for high performance rechargeable zinc-air batteries

NASA Astrophysics Data System (ADS)

Li, Bing; Ge, Xiaoming; Goh, F. W. Thomas; Hor, T. S. Andy; Geng, Dongsheng; Du, Guojun; Liu, Zhaolin; Zhang, Jie; Liu, Xiaogang; Zong, Yun

2015-01-01

An efficient, durable and low cost air-cathode is essential for a high performance metal-air battery for practical applications. Herein, we report a composite bifunctional catalyst, Co3O4 nanoparticles-decorated carbon nanofibers (CNFs), working as an efficient air-cathode in high performance rechargeable Zn-air batteries (ZnABs). The particles-on-fibers nanohybrid materials were derived from electrospun metal-ion containing polymer fibers followed by thermal carbonization and a post annealing process in air at a moderate temperature. Electrochemical studies suggest that the nanohybrid material effectively catalyzes oxygen reduction reaction via an ideal 4-electron transfer process and outperforms Pt/C in catalyzing oxygen evolution reactions. Accordingly, the prototype ZnABs exhibit a low discharge-charge voltage gap (e.g. 0.7 V, discharge-charge at 2 mA cm-2) with higher stability and longer cycle life compared to their counterparts constructed using Pt/C in air-cathode. Importantly, the hybrid nanofiber mat readily serves as an integrated air-cathode without the need of any further modification. Benefitting from its efficient catalytic activities and structural advantages, particularly the 3D architecture of highly conductive CNFs and the high loading density of strongly attached Co3O4 NPs on their surfaces, the resultant ZnABs show significantly improved performance with respect to the rate capability, cycling stability and current density, promising good potential in practical applications.An efficient, durable and low cost air-cathode is essential for a high performance metal-air battery for practical applications. Herein, we report a composite bifunctional catalyst, Co3O4 nanoparticles-decorated carbon nanofibers (CNFs), working as an efficient air-cathode in high performance rechargeable Zn-air batteries (ZnABs). The particles-on-fibers nanohybrid materials were derived from electrospun metal-ion containing polymer fibers followed by thermal carbonization and a post annealing process in air at a moderate temperature. Electrochemical studies suggest that the nanohybrid material effectively catalyzes oxygen reduction reaction via an ideal 4-electron transfer process and outperforms Pt/C in catalyzing oxygen evolution reactions. Accordingly, the prototype ZnABs exhibit a low discharge-charge voltage gap (e.g. 0.7 V, discharge-charge at 2 mA cm-2) with higher stability and longer cycle life compared to their counterparts constructed using Pt/C in air-cathode. Importantly, the hybrid nanofiber mat readily serves as an integrated air-cathode without the need of any further modification. Benefitting from its efficient catalytic activities and structural advantages, particularly the 3D architecture of highly conductive CNFs and the high loading density of strongly attached Co3O4 NPs on their surfaces, the resultant ZnABs show significantly improved performance with respect to the rate capability, cycling stability and current density, promising good potential in practical applications. Electronic supplementary information (ESI) available: TGA curves of as electrospun Co(ii)-PAN fiber and C-CoPAN900 EDX and XPS spectra of the C-CoPAN900 photo of a home-built Zn-air cell and the preparation method of conventional catalyst electrode; polarization curves and corresponding power density plots of the battery using conventional type cathode of C-CoPN900 and commercial Pt/C catalyst; the electrocatalytic properties of hybrid CNFs obtained from varied weight ratios of PAN to cobalt acetate, e.g. 16 : 1 and 8 : 1, and their corresponding TGA curves; a comparison of the Zn-air battery performance of this work with recent literatures. See DOI: 10.1039/c4nr05988c

Enhancing CO2 electrolysis through synergistic control of non-stoichiometry and doping to tune cathode surface structures

PubMed Central

Ye, Lingting; Zhang, Minyi; Huang, Ping; Guo, Guocong; Hong, Maochun; Li, Chunsen; Irvine, John T. S.; Xie, Kui

2017-01-01

Sustainable future energy scenarios require significant efficiency improvements in both electricity generation and storage. High-temperature solid oxide cells, and in particular carbon dioxide electrolysers, afford chemical storage of available electricity that can both stabilize and extend the utilization of renewables. Here we present a double doping strategy to facilitate CO2 reduction at perovskite titanate cathode surfaces, promoting adsorption/activation by making use of redox active dopants such as Mn linked to oxygen vacancies and dopants such as Ni that afford metal nanoparticle exsolution. Combined experimental characterization and first-principle calculations reveal that the adsorbed and activated CO2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The dual doping strategy provides optimal performance with no degradation being observed after 100 h of high-temperature operation and 10 redox cycles, suggesting a reliable cathode material for CO2 electrolysis. PMID:28300066

Investigation of nanoporous platinum thin films fabricated by reactive sputtering: Application as micro-SOFC electrode

NASA Astrophysics Data System (ADS)

Jung, WooChul; Kim, Jae Jin; Tuller, Harry L.

2015-02-01

Highly porous Pt thin films, with nano-scale porosity, were fabricated by reactive sputtering. The strategy involved deposition of thin film PtOx at room temperature, followed by the subsequent decomposition of the oxide by rapid heat treatment. The resulting films exhibited percolating Pt networks infiltrated with interconnected nanosized pores, critical for superior solid oxide fuel cell cathode performance. This approach is particularly attractive for micro-fabricated solid oxide fuel cells, since it enables fabrication of the entire cell stack (anode/electrolyte/cathode) within the sputtering chamber, without breaking vacuum. In this work, the morphological, crystallographic and chemical properties of the porous electrode were systematically varied by control of deposition conditions. Oxygen reduction reaction kinetics were investigated by means of electrochemical impedance spectroscopy, demonstrating the critical role of nano-pores in achieving satisfactory micro-SOFC cathode performance.

Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

NASA Astrophysics Data System (ADS)

Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

2017-02-01

The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

Air breathing lithium power cells

DOEpatents

Farmer, Joseph C.

2014-07-15

A cell suitable for use in a battery according to one embodiment includes a catalytic oxygen cathode; a stabilized zirconia electrolyte for selective oxygen anion transport; a molten salt electrolyte; and a lithium-based anode. A cell suitable for use in a battery according to another embodiment includes a catalytic oxygen cathode; an electrolyte; a membrane selective to molecular oxygen; and a lithium-based anode.

Molten carbonate fuel cell cathode with mixed oxide coating

DOEpatents

Hilmi, Abdelkader; Yuh, Chao-Yi

2013-05-07

A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

Solid oxide fuel cell cathode infiltrate particle size control and oxygen surface exchange resistance determination

NASA Astrophysics Data System (ADS)

Burye, Theodore E.

Over the past decade, nano-sized Mixed Ionic Electronic Conducting (MIEC) -- micro-sized Ionic Conducting (IC) composite cathodes produced by the infiltration method have received much attention in the literature due to their low polarization resistance (RP) at intermediate (500-700°C) operating temperatures. Small infiltrated MIEC oxide nano-particle size and low intrinsic MIEC oxygen surface exchange resistance (Rs) have been two critical factors allowing these Nano-Micro-Composite Cathodes (NMCCs) to achieve high performance and/or low temperature operation. Unfortunately, previous studies have not found a reliable method to control or reduce infiltrated nano-particle size. In addition, controversy exists on the best MIEC infiltrate composition because: 1) Rs measurements on infiltrated MIEC particles are presently unavailable in the literature, and 2) bulk and thin film Rs measurements on nominally identical MIEC compositions often vary by up to 3 orders of magnitude. Here, two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, were developed to systematically produce a reduction in the average La0.6Sr0.4Co0.8Fe 0.2O3-delta (LSCF) infiltrated nano-particle size from 50 nm to 22 nm. This particle size reduction reduced the SOFC operating temperature, (defined as the temperature where RP=0.1 Ocm 2) from 650°C to 540°C. In addition, Rs values for infiltrated MIEC particles were determined for the first time through finite element modeling calculations on 3D Focused Ion Beam-Scanning Electron Microscope (FIB-SEM) reconstructions of electrochemically characterized infiltrated electrodes.

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

NASA Technical Reports Server (NTRS)

Miller, R. O.

1975-01-01

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

An oxygen-independent and membrane-less glucose biobattery/supercapacitor hybrid device.

PubMed

Xiao, Xinxin; Conghaile, Peter Ó; Leech, Dónal; Ludwig, Roland; Magner, Edmond

2017-12-15

Enzymatic biofuel cells can generate electricity directly from the chemical energy of biofuels in physiological fluids, but their power density is significantly limited by the performance of the cathode which is based on oxygen reduction for in vivo applications. An oxygen-independent and membrane-less glucose biobattery was prepared that consists of a dealloyed nanoporous gold (NPG) supported glucose dehydrogenase (GDH) bioanode, immobilised with the assistance of conductive polymer/Os redox polymer composites, and a solid-state NPG/MnO 2 cathode. In a solution containing 10mM glucose, a maximum power density of 2.3µWcm -2 at 0.21V and an open circuit voltage (OCV) of 0.49V were registered as a biobattery. The potential of the discharged MnO 2 could be recovered, enabling a proof-of-concept biobattery/supercapacitor hybrid device. The resulting device exhibited a stable performance for 50 cycles of self-recovery and galvanostatic discharge as a supercapacitor at 0.1mAcm -2 over a period of 25h. The device could be discharged at current densities up to 2mAcm -2 supplying a maximum instantaneous power density of 676 μW cm -2 , which is 294 times higher than that from the biobattery alone. A mechanism for the recovery of the potential of the cathode, analogous to that of RuO 2 (Electrochim. Acta 42(23), 3541-3552) is described. Copyright © 2017 Elsevier B.V. All rights reserved.

Palladium nanoparticles functionalized graphene nanosheets for Li-O2 batteries: enhanced performance by tailoring the morphology of discharge product

NASA Astrophysics Data System (ADS)

Wang, Liangjun; Chen, Wei; SSL Team

Lithium oxygen (Li-O2) batteries represent a promising candidate for the next generation electric vehicle.1-3 Despite the attractive prospect, some issues including large overpotentials, poor recyclability and unstable electrolyte4-6 limit the wide applications of Li-O2 batteries. Due to the insoluble and non-conductive nature of discharge product Li2O2, it has been widely accepted that the performance of oxygen evolution reaction (OER) process is not only determined by the catalyst itself but also close linked to morphology and electronic conductivity of Li2O2 formed during oxygen reduction reaction (ORR) process. Herein, we report a strategy to improve the battery performance by tailoring the morphology of discharge product. By using graphene nanosheets (GNSs) functionalized with Pd nanoparticles (NPs) as cathode catalyst, the growth and morphology of the discharge products of Li2O2 can be effectively tailored, thereby leading to the improved Li-O2 battery performance. Surprisingly, on bare GNSs cathode, the discharge product showed widely observed large-sized toroidal morphology. While for Pd NPs functionalized GNSs, the discharge product was homogenously distributed on the cathode in the form of small nanoparticles with an average diameter of 25 nm. As a result, Pd NPs functionalized GNSs exhibited a high discharge capacity of 7690 mAh g-1. Meanwhile, the battery with tailored morphology exhibits lower charge overpotential.

Metal | polypyrrole battery with the air regenerated positive electrode

NASA Astrophysics Data System (ADS)

Grgur, Branimir N.

2014-12-01

Recharge characteristics of the battery based on the electrochemically synthesized polypyrrole cathode and aluminum, zinc, or magnesium anode in 2 M NH4Cl are investigated. It is shown that polypyrrole electrode can be regenerated by the reoxidation with the dissolved oxygen from the air. Using the polypyrrole synthesized on high surface graphite-felt electrode under modest discharge conditions, stable discharge voltage of 1.1 V is obtained. Such behavior is explained by the complex interaction of polypyrrole and hydrogen peroxide produced by the oxygen reduction reaction. The electrochemical characteristics are compared with the zinc-manganese dioxide and zinc-air systems.

Atmospheric pressure cold plasma as an antifungal therapy

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

Sun Peng; Wu Haiyan; Sun Yi

2011-01-10

A microhollow cathode based, direct-current, atmospheric pressure, He/O{sub 2} (2%) cold plasma microjet was used to inactive antifungal resistants Candida albicans, Candida krusei, and Candida glabrata in air and in water. Effective inactivation (>90%) was achieved in 10 min in air and 1 min in water. Antifungal susceptibility tests showed drastic reduction of the minimum inhibitory concentration after plasma treatment. The inactivation was attributed to the reactive oxygen species generated in plasma or in water. Hydroxyl and singlet molecular oxygen radicals were detected in plasma-water system by electron spin resonance spectroscopy. This approach proposed a promising clinical dermatology therapy.

Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes

DOE PAGES

Hu, E.; Lyu, Y.; Xin, H.; ...

2016-09-26

Li- and Mn-rich (LMR) cathode materials have been considered as promising candidates for energy storage applications due to high energy density. However, these materials suffer from a serious problem of voltage fade. Oxygen loss and the layer to spinel phase transition are two major contributors of such voltage fade. In this paper, using a combination of x-ray diffraction (XRD), pair distribution function (PDF), x-ray absorption (XAS) techniques and aberration-corrected scanning transmission electron microscopy (STEM), we studied the effects of micro structural defects, especially the grain boundaries on the oxygen loss and layered-to-spinel phase transition through prelithiation of a model compoundmore » Li2Ru0.5Mn0.5O3. It is found that the nano-sized micro structural defects, especially the large amount of grain boundaries created by the prelithiation can greatly accelerate the oxygen loss and voltage fade. Defects (such as nano-sized grain boundaries) and oxygen release form a positive feedback loop, promote each other during cycling, and accelerate the two major voltage fade contributors: the transition metal reduction and layered-to-spinel phase transition. These results clearly demonstrate the important relationships among the oxygen loss, microstructural defects and voltage fade. The importance of maintaining good crystallinity and protecting the surface of LMR material are also suggested.« less

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

PubMed

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Construction and operation of microbial fuel cell with Chlorella vulgaris biocathode for electricity generation.

PubMed

Wu, Xia-yuan; Song, Tian-shun; Zhu, Xu-jun; Wei, Ping; Zhou, Charles C

2013-12-01

In this study, a modified microbial fuel cell (MFC) with a tubular photobioreactor (PHB) configuration as a cathode compartment was constructed by introducing Chlorella vulgaris to the cathode chamber used to generate oxygen in situ. Two types of cathode materials and light/dark cycles were used to test the effect on MFC with algae biocathode. Results showed that the use of algae is an effective approach because these organisms can act as efficient in situ oxygenators, thereby facilitating the cathodic reaction. Dissolved oxygen and voltage output displayed a clear light positive response and were drastically enhanced compared with the abiotic cathode. In particular, carbon paper-coated Pt used as a cathode electrode increased voltage output at a higher extent than carbon felt used as an electrode. The maximum power density of 24.4 mW/m2 was obtained from the MFC with algae biocathode which utilized the carbon paper-coated Pt as the cathode electrode under intermittent illumination. This density was 2.8 times higher than that of the abiotic cathode. Continuous illumination shortened the algal lifetime. These results demonstrated that intermittent illumination and cathode material-coated catalyst are beneficial to a more efficient and prolonged operation of MFC with C. vulgaris biocathode.

Construction and operation of microbial fuel cell with Chlorella vulgaris biocathode for electricity generation.

PubMed

Wu, Xia-yuan; Song, Tian-shun; Zhu, Xu-jun; Wei, Ping; Zhou, Charles C

2013-12-01

In this study, a modified microbial fuel cell (MFC) with a tubular photobioreactor (PHB) configuration as a cathode compartment was constructed by introducing Chlorella vulgaris to the cathode chamber used to generate oxygen in situ. Two types of cathode materials and light/dark cycles were used to test the effect on MFC with algae biocathode. Results showed that the use of algae is an effective approach because these organisms can act as efficient in situ oxygenators, thereby facilitating the cathodic reaction. Dissolved oxygen and voltage output displayed a clear light positive response and were drastically enhanced compared with the abiotic cathode. In particular, carbon paper-coated Pt used as a cathode electrode increased voltage output at a higher extent than carbon felt used as an electrode. The maximum power density of 24.4 mW/m(2) was obtained from the MFC with algae biocathode which utilized the carbon paper-coated Pt as the cathode electrode under intermittent illumination. This density was 2.8 times higher than that of the abiotic cathode. Continuous illumination shortened the algal lifetime. These results demonstrated that intermittent illumination and cathode material-coated catalyst are beneficial to a more efficient and prolonged operation of MFC with C. vulgaris biocathode.

Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

NASA Astrophysics Data System (ADS)

Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

2014-01-01

Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

NASA Astrophysics Data System (ADS)

Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

2015-10-01

We propose a new strategy for alleviating the reverse current phenomenon using a unique ;atmospheric resistive switching mechanism; (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

Pt-decorated PdCo@Pd/C core-shell nanoparticles with enhanced stability and electrocatalytic activity for the oxygen reduction reaction.

PubMed

Wang, Deli; Xin, Huolin L; Yu, Yingchao; Wang, Hongsen; Rus, Eric; Muller, David A; Abruña, Hector D

2010-12-22

A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications.

Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction

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

Wang, Deli; Xin, Huolin L.; Yu, Yingchao

2010-11-24

A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuelmore » cell applications.« less

In-situ diagnostic tools for hydrogen transfer leak characterization in PEM fuel cell stacks part II: Operational applications

NASA Astrophysics Data System (ADS)

Niroumand, Amir M.; Homayouni, Hooman; DeVaal, Jake; Golnaraghi, Farid; Kjeang, Erik

2016-08-01

This paper describes a diagnostic tool for in-situ characterization of the rate and distribution of hydrogen transfer leaks in Polymer Electrolyte Membrane (PEM) fuel cell stacks. The method is based on reducing the air flow rate from a high to low value at a fixed current, while maintaining an anode overpressure. At high air flow rates, the reduction in air flow results in lower oxygen concentration in the cathode and therefore reduction in cell voltages. Once the air flow rate in each cell reaches a low value at which the cell oxygen-starves, the voltage of the corresponding cell drops to zero. However, oxygen starvation results from two processes: 1) the electrochemical oxygen reduction reaction which produces current; and 2) the chemical reaction between oxygen and the crossed over hydrogen. In this work, a diagnostic technique has been developed that accounts for the effect of the electrochemical reaction on cell voltage to identify the hydrogen leak rate and number of leaky cells in a fuel cell stack. This technique is suitable for leak characterization during fuel cell operation, as it only requires stack air flow and voltage measurements, which are readily available in an operational fuel cell system.

Conductor of high electrical current at high temperature in oxygen and liquid metal environment

DOEpatents

Powell, IV, Adam Clayton; Pati, Soobhankar; Derezinski, Stephen Joseph; Lau, Garrett; Pal, Uday B.; Guan, Xiaofei; Gopalan, Srikanth

2016-01-12

In one aspect, the present invention is directed to apparatuses for and methods of conducting electrical current in an oxygen and liquid metal environment. In another aspect, the invention relates to methods for production of metals from their oxides comprising providing a cathode in electrical contact with a molten electrolyte, providing a liquid metal anode separated from the cathode and the molten electrolyte by a solid oxygen ion conducting membrane, providing a current collector at the anode, and establishing a potential between the cathode and the anode.

Effect of electrochemical redox reaction on growth and metabolism of Saccharomyces cerevisiae as an environmental factor.

PubMed

Na, Kwan Byung; Hwang, Tae Sik; Lee, Sung Hun; Ahn, Dae Hee; Park, Doo Hyun

2007-03-01

The effect of an electrochemically generated oxidation-reduction potential and electric pulse on ethanol production and growth of Saccharomyces cerevisiae ATCC 26603 was experimented and compared with effects of electron mediators (neutral red, benzyl viologen, and thionine), chemical oxidants (hydrogen peroxide and hypochlorite), chemical reductants (sulfite and nitrite), oxygen, and hydrogen. The oxidation (anodic) and reduction (cathodic) potential and electric pulse activated ethanol production and growth, and changed the total soluble protein pattern of the test strain. Neutral red electrochemically reduced activated ethanol production and growth of the test strain, but benzyl viologen and thionine did not. Nitrite inhibited ethanol production but did not influence growth of the test strain. Hydrogen peroxide, hypochlorite, and sulfite did not influence ethanol production and growth of the test strain. Hydrogen and oxygen also did not influence the growth and ethanol production. It shows that the test strain may perceive electrochemically generated oxidation-reduction potential and electric pulse as an environmental factor.

Development of a high-performance composite cathode for LT-SOFC

NASA Astrophysics Data System (ADS)

Lee, Byung Wook

Solid Oxide Fuel Cell (SOFC) has drawn considerable attention for decades due to its high efficiency and low pollution, which is made possible since chemical energy is directly converted to electrical energy through the system without combustion. However, successful commercialization of SOFC has been delayed due to its high production cost mainly related with using high cost of interconnecting materials and the other structural components required for high temperature operation. This is the reason that intermediate (IT) or low temperature (LT)-SOFC operating at 600~800°C or 650°C and below, respectively, is of particular significance because it allows the wider selection of cheaper materials such as stainless steel for interconnects and the other structural components. Also, extended lifetime and system reliability are expected due to less thermal stress through the system with reduced temperature. More rapid start-up/shut-down procedure is another advantage of lowering the operating temperatures. As a result, commercialization of SOFC will be more viable. However, there exists performance drop with reduced operating temperature due to increased polarization resistances from the electrode electrochemical reactions and decreased electrolyte conductivity. Since ohmic polarization of the electrolyte can be significantly reduced with state-of-the art thin film technology and cathode polarization has more drastic effect on total SOFC electrochemical performance than anode polarization as temperature decreases, development of the cathode with high performance operating at IT or LT range is thus essential. On the other hand, chemical stability of the cathode and its chemical compatibility with the electrolyte should also be considered for cathode development since instability and incompatibility of the cathode will also cause substantial performance loss. Based on requirements of the cathode mentioned above, in this study, several chemico-physical approaches were carried out to develop a high-performance composite cathode, in particular, for LT-SOFC operating 650°C and below since stability and compatibility of the materials in interest are secured at low temperatures. First, a nano-sized pyrochlore bismuth ruthenate (Bi2Ru 2O7 or BRO7 shortly), one of the promising cathode materials, was successfully synthesized using glycine-nitrate combustion (GNC) route. Stoichiometric Bi2Ru2O7 without any impurity phase was achieved with considerably improved processing condition, leading to the crystallite size of ~24nm in diameter. Even though the resulting powder tends to agglomerate, resulting in overall 200~400nm size range, it still showed better quality than the one prepared by solid state (SS) reaction route followed by extra milling steps such as vibro-milling and sonication for further particle size reduction. Glycine-to-nitrate (G/N) ratio was found to play a critical role in determining the reaction temperature and reaction duration, thus phase purity and particle morphology (particle size, shape, and agglomeration etc). Composite cathodes of such prepared BRO7 (GNC BRO7) combined with SS erbia-stabilized bismuth oxide, Bi1.6Er0.4O3 or ESB, showed better electrochemical performance than vibro-milled BRO7 (VM BRO7)-SS ESB. ASR values of 0.123Ocm2 at 700°C and 4.59cOm 2 at 500°C, respectively, were achieved, which follows well the trend of particle size effect on performance of composite cathodes. Additionally, the number of processing steps (thus time) was reduced by GNC route. Several issues in regard to synthesis process and characteristics of BRO7 material itself will be addressed in this dissertation. Secondly, a unique in-situ composite cathode synthesis was successfully developed and applied for BRO7-ESB composite cathodes to improve percolation and to reduce agglomeration of each phase inside the cathode so that the effective triple phase boundary (TPB) length was extended. To disperse and stabilize ESB powder in de-ionized (DI) water, zeta potential profile of ESB powder in DI water as a function of pH was first achieved. The effect of a dispersant (ammonium citrate dibasic) on the stability of ESB powder dispersed in DI water was also investigated. Knowledge of BRO7 wet chemical synthesis from previous study was utilized for final product of in-situ BRO7-ESB composite cathodes. Such prepared composite particles were characterized and the electrochemical performance of in-situ BRO7-ESB composite cathodes was examined as well. Performance enhancement was observed so that ASR values of 0.097Ocm2 and 3.58Ocm2 were achieved at 700°C and 500°C, respectively, which were 19% and 22% improvement, respectively compared to those of conventionally mixed composite cathodes of BRO7-ESB. Finally, a highly controlled nanostructured BRO7-ESB composite cathode was developed by infiltration of BRO7 onto ESB scaffolds to maximize the effective TPB length, to improve the connectivity of ESB phase inside the cathode for better oxygen-ion diffusion, and to minimize delamination between the electrolyte and cathode layers. ESB scaffolds were first established by adding a graphite pore-former and controlling heat treatment condition. Nano-sized BRO7 particles were successfully created on the surface of previously formed ESB scaffold by infiltration of concentrated (Bi, Ru) nitrate solution followed by the optimized heat treatment. Such prepared composite cathodes exhibited superior electrochemical performance to conventionally made BRO7-ESB composite cathodes and even better than GNC BRO7-SS ESB developed in this dissertation, e.g. 0.073Ocm2 at 700°C and 1.82Ocm2 at 500°C, respectively. This cathode system was revealed to be highly competitive among all the reported composite cathodes consisting of the same or different materials prepared by various processing techniques. It was demonstrated that the extended TPB length from continuous network of BRO7 nanoparticles and better connectivity of ESB scaffolds enabled the outstanding performance. Moreover, de-lamination of cathode from the electrolyte was prevented thanks to improved adhesion between ESB scaffolds and ESB electrolyte. Dissociative adsorption of oxygen gas were proposed to be the dominant rate-determining process for the overall oxygen reduction reaction at low temperatures (500-600°C) whereas all of the constituting sub-reactions such as oxygen gas dissociative adsorption, oxygen ion diffusion towards TPB region, and oxygen ion incorporation were found to play roles competitively in the overall reaction at relatively high operating temperature (650-700°C) based on analysis of impedance spectra.

Solid oxide fuel cell cathode with oxygen-reducing layer

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

Surdoval, Wayne A.; Berry, David A.; Shultz, Travis

The disclosure provides a SOFC comprised of an electrolyte, anode, and cathode, where the cathode comprises an MIEC and an oxygen-reducing layer. The oxygen-reducing layer is in contact with the MIEC, and the MIEC is generally between and separating the oxygen-reducing layer and the electrolyte. The oxygen-reducing layer is comprised of single element oxides, single element carbonates, or mixtures thereof, and has a thickness of less than about 30 nm. In a particular embodiment, the thickness is less than 5 nm. In another embodiment, the thickness is about 3 monolayers or less. The oxygen-reducing layer may be a continuous filmmore » or a discontinuous film with various coverage ratios. The oxygen-reducing layer at the thicknesses described may be generated on the MIEC surface using means known in the art such as, for example, ALD processes.« less

Modular cathode assemblies and methods of using the same for electrochemical reduction

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

Wiedmeyer, Stanley G.; Barnes, Laurel A.; Williamson, Mark A.

Modular cathode assemblies are useable in electrolytic reduction systems and include a basket through which fluid electrolyte may pass and exchange charge with a material to be reduced in the basket. The basket can be divided into upper and lower sections to provide entry for the material. Example embodiment cathode assemblies may have any shape to permit modular placement at any position in reduction systems. Modular cathode assemblies include a cathode plate in the basket, to which unique and opposite electrical power may be supplied. Example embodiment modular cathode assemblies may have standardized electrical connectors. Modular cathode assemblies may bemore » supported by a top plate of an electrolytic reduction system. Electrolytic oxide reduction systems are operated by positioning modular cathode and anode assemblies at desired positions, placing a material in the basket, and charging the modular assemblies to reduce the metal oxide.« less

Modular cathode assemblies and methods of using the same for electrochemical reduction

DOEpatents

Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L

2014-12-02

Modular cathode assemblies are useable in electrolytic reduction systems and include a basket through which fluid electrolyte may pass and exchange charge with a material to be reduced in the basket. The basket can be divided into upper and lower sections to provide entry for the material. Example embodiment cathode assemblies may have any shape to permit modular placement at any position in reduction systems. Modular cathode assemblies include a cathode plate in the basket, to which unique and opposite electrical power may be supplied. Example embodiment modular cathode assemblies may have standardized electrical connectors. Modular cathode assemblies may be supported by a top plate of an electrolytic reduction system. Electrolytic oxide reduction systems are operated by positioning modular cathode and anode assemblies at desired positions, placing a material in the basket, and charging the modular assemblies to reduce the metal oxide.

Materials characterization of impregnated W and W-Ir cathodes after oxygen poisoning

NASA Astrophysics Data System (ADS)

Polk, James E.; Capece, Angela M.

2015-05-01

Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten-iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W-Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W-Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W-Ir. However, the W-Ir emitter exhibited less erosion and redeposition at the upstream end than the pure W emitter.

Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode.

PubMed

Savych, Iuliia; Subianto, Surya; Nabil, Yannick; Cavaliere, Sara; Jones, Deborah; Rozière, Jacques

2015-07-14

Novel platinum-catalysed, corrosion-resistant, loose-tube-structured electrocatalysts for proton exchange membrane fuel cells have been obtained using single-needle electrospinning associated with a microwave-assisted polyol method. Monodisperse platinum particles supported on Nb-SnO2 demonstrated higher electrochemical stability than conventional Pt/C electrodes during ex situ potential cycling and comparable activity in the oxygen reduction reaction. In situ fuel cell operation under accelerated stress test conditions of a membrane electrode assembly elaborated using a Pt/C anode and Pt/Nb-SnO2 cathode confirmed that the voltage loss is significantly lower for the novel cathode than for an MEA prepared using conventional Pt/C supported electrocatalysts. Furthermore, the Nb-SnO2 stabilised the supported platinum nanoparticles against dissolution, migration and reprecipitation in the membrane. Pt/Nb-SnO2 loose-tubes constitute a mitigation strategy for two known degradation mechanisms in PEMFC: corrosion of the carbon support at the cathode, and dissolution of Pt at high cell voltages.

An Overview of Electron Acceptors in Microbial Fuel Cells

PubMed Central

Ucar, Deniz; Zhang, Yifeng; Angelidaki, Irini

2017-01-01

Microbial fuel cells (MFC) have recently received increasing attention due to their promising potential in sustainable wastewater treatment and contaminant removal. In general, contaminants can be removed either as an electron donor via microbial catalyzed oxidization at the anode or removed at the cathode as electron acceptors through reduction. Some contaminants can also function as electron mediators at the anode or cathode. While previous studies have done a thorough assessment of electron donors, cathodic electron acceptors and mediators have not been as well described. Oxygen is widely used as an electron acceptor due to its high oxidation potential and ready availability. Recent studies, however, have begun to assess the use of different electron acceptors because of the (1) diversity of redox potential, (2) needs of alternative and more efficient cathode reaction, and (3) expanding of MFC based technologies in different areas. The aim of this review was to evaluate the performance and applicability of various electron acceptors and mediators used in MFCs. This review also evaluated the corresponding performance, advantages and disadvantages, and future potential applications of select electron acceptors (e.g., nitrate, iron, copper, perchlorate) and mediators. PMID:28469607

A novel cobalt-free layered GdBaFe 2O 5+ δ cathode for proton conducting solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xue, Xingjian

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO 2 and high thermal expansion coefficients. In this research, a cobalt-free layered GdBaFe 2O 5+ δ (GBF) perovskite was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton conducting electrolyte of stable BaZr 0.1Ce 0.7Y 0.2O 3- δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBF were fabricated and characterized using complex impedance technique from 600 to 700 °C. An open-circuit potential of 1.007 V, maximum power density of 417 mW cm -2, and a low electrode polarization resistance of 0.18 Ω cm 2 were achieved at 700 °C. The results indicate that layered GBF perovskite is a good candidate for cobalt-free cathode material, while the developed Ni-BZCY7|BZCY7|GBF cell is a promising functional material system for solid oxide fuel cells.

Report on Carbon Nano Material Workshop: Challenges and Opportunities

DTIC Science & Technology

2013-01-22

trolyte fuel cells ( PEMFCs ) utilize the ability of the catalysts to initiate and maintain the oxygen reduction reaction on the cathode and the fuel...oxidation reaction on the anode. In order to increase the efficiency of the PEMFC catalysts, high-surface-area mesoporous carbons, carbon blacks, carbon...mechanical and thermal properties derived from a three-dimensional intercon- nected nanonetwork structure. The exceptional properties of CAs for PEMFC

Activated carbon derived from chitosan as air cathode catalyst for high performance in microbial fuel cells

NASA Astrophysics Data System (ADS)

Liu, Yi; Zhao, Yong; Li, Kexun; Wang, Zhong; Tian, Pei; Liu, Di; Yang, Tingting; Wang, Junjie

2018-02-01

Chitosan with rich of nitrogen is used as carbon precursor to synthesis activated carbon through directly heating method in this study. The obtained carbon is activated by different amount of KOH at different temperatures, and then prepared as air cathodes for microbial fuel cells. Carbon sample treated with double amount of KOH at 850 °C exhibits maximum power density (1435 ± 46 mW m-2), 1.01 times improved, which ascribes to the highest total surface area, moderate micropore and mesoporous structure and the introduction of nitrogen. The electrochemical impedance spectroscopy and powder resistivity state that carbon treated with double amount of KOH at 850 °C possesses lower resistance. The other electrochemical measurements demonstrate that the best kinetic activity make the above treated sample to show the best oxygen reduction reaction activity. Besides, the degree of graphitization of samples increases with the activated temperature increasing, which is tested by Raman. According to elemental analysis and X-ray photoelectron spectroscopy, all chitosan samples are nitrogen-doped carbon, and high content nitrogen (pyridinic-N) improves the electrochemical activity of carbon treated with KOH at 850 °C. Thus, carbon materials derived from chitosan would be an optimized catalyst for oxygen reduction reaction in microbial fuel cell.

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-08-15

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

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

Investigation of antioxidant capacity of the extracts of bilberry (VACCINUM MYRTILLIS L.) by voltammetry

NASA Astrophysics Data System (ADS)

Vtorushina, A. N.; Nikonova, E. D.

2016-02-01

This paper deals with the urgent issue of the search of new drugs based on plant raw materials that have an influence on various stages of oxidation processes occurring in the human body. The aim of this paper is to determine the antioxidant activity of the bilberry extracts that are used in the medicine practice by a cathodic voltammetry method. We consider the influence of water and alcohol bilberry extracts on the process of oxygen electroreduction. From these extracts the most activity relation to the process of cathodic oxygen reduction showed alcohol (40%) bilberry extract. It was also stated that the alcohol extract of bilberry has a greater antioxidant activity than other known antioxidants such as ascorbic acid, glucose, dihydroquercetin. Thus, after consideration of a number of plant objects, we showed the possibility of applying the method of cathodic voltammetry for the determination of total antioxidant activity of plant material and identifying and highlighting the most perspective sources of biologically active substances (BAS), as well as the ability of identifying extractants that fully extract BAS from plant raw materials. The activity data of extracts of plant raw materials gives an opportunity of establishing an effective yield phytopreparation based on bilberry that has an antioxidant effect.

Treatment of high-strength sulfate wastewater using an autotrophic biocathode in view of elemental sulfur recovery.

PubMed

Blázquez, Enric; Gabriel, David; Baeza, Juan Antonio; Guisasola, Albert

2016-11-15

Treatment of high-strength sulfate wastewaters is becoming a research issue not only for its optimal management but also for the possibility of recovering elemental sulfur. Moreover, sulfate-rich wastewater production is expected to grow due to the increased SO 2 emission contained in flue gases which are treated by chemical absorption in water. Bioelectrochemical systems (BESs) are a promising alternative for sulfate reduction with a lack of electron donor, since hydrogen can be generated in situ from electricity. However, complete sulfate reduction leads to hydrogen sulfide as final sulfur compound. This work is the first to demonstrate that, in addition to an efficient sulfate-rich wastewater treatment, elemental sulfur could be recovered in a biocathode of a BES under oxygen limiting conditions. The key of the process is the biological oxidation of sulfide to elemental sulfur simultaneously to the sulfate reduction in the cathode using the oxygen produced in the anode that diffuses through the membrane. High sulfate reduction rates (up to 388 mg S-SO 4 2-  L -1  d -1 ) were observed linked to a low production of sulfide. Accumulation of elemental sulfur over graphite fibers of the biocathode was demonstrated by energy dispersive spectrometry, discarding the presence of metal sulfides. Microbial community analysis of the cathode biofilm demonstrated the presence of sulfate-reducing bacteria (mainly Desulfovibrio sp.) and sulfide-oxidizing bacteria (mainly Sulfuricurvum sp.). Hence, this biocathode allows simultaneous biological sulfate reduction and biological sulfide oxidation to elemental sulfur, opening up a novel process for recovering sulfur from sulfate-rich wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Survey of Alternative Oxygen Production Technologies

NASA Technical Reports Server (NTRS)

Lueck, Dale E.; Parrish, Clyde F.; Buttner, William J.; Surma, Jan M.; Delgado, H. (Technical Monitor)

2001-01-01

Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Metallofullerenes as fuel cell electrocatalysts: a theoretical investigation of adsorbates on C59Pt.

PubMed

Gabriel, Margaret A; Genovese, Luigi; Krosnicki, Guillaume; Lemaire, Olivier; Deutsch, Thierry; Franco, Alejandro A

2010-08-28

Nano-structured electrode degradation in state-of-the-art polymer electrolyte membrane fuel cells (PEMFCs) is one of the main shortcomings that limit the large-scale development and commercialization of this technology. During normal operating conditions of the fuel cell, the PEMFC lifetime tends to be limited by coarsening of the cathode's Pt-based catalyst and by corrosion of the cathode's carbon black support. Because of their chemical properties, metallofullerenes such as C(59)Pt may be more electrochemically stable than the Pt/C mixture. In this paper we investigate, by theoretical methods, the stability of oxygen reduction reaction (ORR) adsorbates on the metallofullerene C(59)Pt and evaluate its potential as a PEMFC fuel cell catalyst.

Outlook for benefits of sediment microbial fuel cells with two bio‐electrodes

PubMed Central

De Schamphelaire, Liesje; Rabaey, Korneel; Boeckx, Pascal; Boon, Nico; Verstraete, Willy

2008-01-01

Summary The benefits of sediment microbial fuel cells (SMFCs) go beyond energy generation for low‐power applications. Aside from producing electrical energy, SMFCs can enhance the oxidation of reduced compounds at the anode, thus bringing about the removal of excessive or unwanted reducing equivalents from submerged soils. Moreover, an SMFC could be applied to control redox‐dependent processes in sediment layers. Several cathodic reactions that may drive these sediment oxidation reactions are examined. Special attention is given to two biologically mediated cathodic reactions, respectively employing an oxygen reduction and a manganese cycle. Both reactions imply a low cost and a high electrode potential and are of interest for reactor‐type MFCs as well as for SMFCs. PMID:21261866

Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

NASA Technical Reports Server (NTRS)

Srinivasan, Vakula S.; Singer, Joseph

1986-01-01

This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

Pluronic F127 as auxiliary template for preparing nitrogen and oxygen dual doped mesoporous carbon cathode of lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Wu, Junwei; Liu, Yanchen; Cui, Yanhui; Ouyang, Jue; Baker, Andrew P.; Li, Zuohua; Zhang, Huayu

2018-02-01

Two mesoporous carbon foam (MCF) with nitrogen and oxygen dual doped are fabricated through facile templated hydrothermal process. One using fumed silica as single template is named S-MCF, and another using fumed silica and Pluronic F127 as double templates is named D-MCF. When using Pluronic F127 as an auxiliary template, the D-MCF shows different porous architecture and surface chemical nature from S-MCF, thus they behave differently as cathode materials in Li-O2 batteries. The D-MCF electrode exhibits a slight lower discharge capacity and an increased overpotential than that of S-SCF due to the decreased surface area and oxygen content. However, a better cycle stability was proved for the D-MCF electrode because of its higher nitrogen and lower oxygen content. When further composited with RuO2 nanoparticles, the RuO2/D-MCF cathode can operate 160 cycles with capacity cutoff of 500 mAh g-1, and this prolonged cycle life, compared to the 102 cycles of S-MCF cathode, verifies the superior electrochemical stability of D-MCF further and illuminates the crucial role of carbon substrate in the cathodes of Li-O2 batteries.

The influence of oxygen additions on argon-shielded gas metal arc welding processes

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

Joensson, P.G.; Murphy, A.B.; Szekely, J.

1995-02-01

It has been observed experimentally that small additions of oxygen to the argon shielding gas affect the general operation of GMAW processes. By theoretically modeling the arc column, it is shown that the addition of 2 to 5% oxygen to argon has an insignificant effect on the arc characteristics. This corresponds to the minor changes in the thermophysical transport and thermodynamic properties caused by the oxygen addition. Therefore, it is concluded that the addition of oxygen to the argon shielding gas mainly affects the anode and the cathode regions. From the literature, it was found that the formation of oxidesmore » initiates arcing at the cathode and decreases the movement of the cathode spots. These oxides can also improve the wetting conditions at the workpiece and the electrode. Finally, oxygen is found to affect the surface tension gradient and thereby the convective flow of liquid metal in the weld pool.« less

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1996-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1997-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways.

PubMed

Xu, Shaomao; Yao, Yonggang; Guo, Yuanyuan; Zeng, Xiaoqiao; Lacey, Steven D; Song, Huiyu; Chen, Chaoji; Li, Yiju; Dai, Jiaqi; Wang, Yanbin; Chen, Yanan; Liu, Boyang; Fu, Kun; Amine, Khalil; Lu, Jun; Hu, Liangbing

2018-01-01

The lithium-air (Li-O 2 ) battery has been deemed one of the most promising next-generation energy-storage devices due to its ultrahigh energy density. However, in conventional porous carbon-air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile-based air cathode is developed with a triple-phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile-based Li-O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm -2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile-based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

PubMed

Liu, Pan; Han, Jiuhui; Guo, Xianwei; Ito, Yoshikazu; Yang, Chuchu; Ning, Shoucong; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2018-02-16

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O 2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li 2 O 2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li 2 O 2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

PubMed Central

Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

2013-01-01

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

DOE PAGES

Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; ...

2015-07-22

The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC). Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared Pt MLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability ofmore » the Pt MLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.« less

Situ treatment of contaminated groundwater

DOEpatents

McNab, Jr., Walt W.; Ruiz, Roberto; Pico, Tristan M.

2001-01-01

A system for treating dissolved halogenated organic compounds in groundwater that relies upon electrolytically-generated hydrogen to chemically reduce the halogenated compounds in the presence of a suitable catalyst. A direct current is placed across at least a pair, or an array, of electrodes which are housed within groundwater wells so that hydrogen is generated at the cathode and oxygen at the anode. A pump is located within the well housing in which the cathode(s) is(are) located and draws in groundwater where it is hydrogenated via electrolysis, passes through a well-bore treatment unit, and then transported to the anode well(s) for reinjection into the ground. The well-bore treatment involves a permeable cylinder located in the well bore and containing a packed bed of catalyst material that facilitates the reductive dehalogenation of the halogenated organic compounds by hydrogen into environmentally benign species such as ethane and methane. Also, electro-osmatic transport of contaminants toward the cathode also contributes to contaminant mass removal. The only above ground equipment required are the transfer pipes and a direct circuit power supply for the electrodes. The electrode wells in an array may be used in pairs or one anode well may be used with a plurality of cathode wells. The DC current flow between electrode wells may be periodically reversed which controls the formation of mineral deposits in the alkaline cathode well-bore water, as well as to help rejuvenate the catalysis.

Characterization of bacterial and archaeal communities in air-cathode microbial fuel cells, open circuit and sealed-off reactors.

PubMed

Shehab, Noura; Li, Dong; Amy, Gary L; Logan, Bruce E; Saikaly, Pascal E

2013-11-01

A large percentage of organic fuel consumed in a microbial fuel cell (MFC) is lost as a result of oxygen transfer through the cathode. In order to understand how this oxygen transfer affects the microbial community structure, reactors were operated in duplicate using three configurations: closed circuit (CC; with current generation), open circuit (OC; no current generation), and sealed off cathodes (SO; no current, with a solid plate placed across the cathode). Most (98 %) of the chemical oxygen demand (COD) was removed during power production in the CC reactor (maximum of 640 ± 10 mW/m(2)), with a low percent of substrate converted to current (coulombic efficiency of 26.5 ± 2.1 %). Sealing the cathode reduced COD removal to 7 %, but with an open cathode, there was nearly as much COD removal by the OC reactor (94.5 %) as the CC reactor. Oxygen transfer into the reactor substantially affected the composition of the microbial communities. Based on analysis of the biofilms using 16S rRNA gene pyrosequencing, microbes most similar to Geobacter were predominant on the anodes in the CC MFC (72 % of sequences), but the most abundant bacteria were Azoarcus (42 to 47 %) in the OC reactor, and Dechloromonas (17 %) in the SO reactor. Hydrogenotrophic methanogens were most predominant, with sequences most similar to Methanobacterium in the CC and SO reactor, and Methanocorpusculum in the OC reactors. These results show that oxygen leakage through the cathode substantially alters the bacterial anode communities, and that hydrogenotrophic methanogens predominate despite high concentrations of acetate. The predominant methanogens in the CC reactor most closely resembled those in the SO reactor, demonstrating that oxygen leakage alters methanogenic as well as general bacterial communities.

Fast turn-on osmium coated cathode

NASA Astrophysics Data System (ADS)

Marrian, C. R. K.; Haas, G. A.; Shih, A.

1984-03-01

This abstract discloses a fast turn-on refractory coated cathode comprising a porous tungsten metal matrix impregnated with barium calcium aluminate and coated with osmium. The osmium coating has a planned series of interruptions with each interruption being on the order of several microns in width to thereby expose the tungsten. These interruptions permit the barium and oxygen from the impregnant to rise to the cathode surface during activation or reactivation to form a desired near monolayer of barium and oxygen to enhance electron emission. Thus, this cathode design provides a fast turn-on characteristic even after shelf storage.

[Advanced treatment of coking wastewater with a novel heterogeneous electro-Fenton technology].

PubMed

Li, Hai-Tao; Li, Yu-Ping; Zhang, An-Yang; Cao, Hong-Bin; Li, Xin-Gang; Zhang, Yi

2011-01-01

A novel electro-catalytic reactor, with oxygen-reduction cathode (PAQ/GF), dimensionally stable anode (IrO2-RuO2 -TiO2/ Ti) and heterogeneous catalysts, is developed for advanced treatment of coking wastewater after biological process, integrating cathodic and anodic simultaneous oxidation processes. A PAQ/GF electrode was synthesized by the electro-polymerization of 2-ethyl anthraquinone on graphite felt, which was characterized with cyclic voltametry measurements; the results indicated that the PAQ/GF electrode showed high reversibility for oxidation-reduction reaction of anthraquinone and catalytic activity for O2 reduction to H2O2; 13.5 mmol/L H2O2 was obtained after electrolysis for 6 h at -0.7 V (vs. SCE) and pH 6 with a current efficiency of 50% in a membrane reactor. Fe-Cu/Y350 catalysts, prepared by impregnation method, could catalyze the production of hydroxyl radicals (*OH) from H2O2, which was confirmed both by fading reaction of crystal violet and oxidation of *OH-probe compound (p-chlorobenzoic acid); Fe-Cu/Y350 also showed high catalytic-activity for the oxidation of organics by hypochlorous sodium, because COD removal of coking wastewater reached 26% in the catalytic process while only 11% of COD removal was obtained in the absence of Fe-Cu/Y350. COD removal of coking wastewater reached 49.4% (26.0% and 23.4% in cathodic system and anodic system, respectively) in the developed electrolytic-reactor, which was higher than that of conventional cathodic-anodic-oxidation process (29.8%). At optimal reaction condition of initial COD = 192 mg/L, I = 10A x m(-2) and pH 4-5, more than 50% COD were removed after electrolysis for 1 h. The mechanism might be as follows: in cathodic system, H2O2 is generated from reduction of O2 on PAQ/GF cathode, and catalyzed by Fe-Cu/Y350 for production of *OH, which causes mineralization and degradation of organic pollutants; in anodic system, Cl2 and HClO are generated from Cl- oxidation on IrO2-RuO2-TiO2/Ti anode and the organic pollutants are oxidized by Cl2, and HClO with Fe-Cu/Y350 catalysts or by direct anodic oxidation.

Sustainable green technology on wastewater treatment: The evaluation of enhanced single chambered up-flow membrane-less microbial fuel cell.

PubMed

Thung, Wei-Eng; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Ridwan, Fahmi; Oon, Yoong-Ling; Oon, Yoong-Sin; Lehl, Harvinder Kaur

2018-04-01

This study demonstrated the potential of single chamber up-flow membrane-less microbial fuel cell (UFML-MFC) in wastewater treatment and power generation. The purpose of this study was to evaluate and enhance the performance under different operational conditions which affect the chemical oxygen demand (COD) reduction and power generation, including the increase of KCl concentration (MFC1) and COD concentration (MFC2). The results showed that the increase of KCl concentration is an important factor in up-flow membrane-less MFC to enhance the ease of electron transfer from anode to cathode. The increase of COD concentration in MFC2 could led to the drop of voltage output due to the prompt of biofilm growth in MFC2 cathode which could increase the internal resistance. It also showed that the COD concentration is a vital issue in up-flow membrane-less MFC. Despite the COD reduction was up to 96%, the power output remained constrained. Copyright © 2017. Published by Elsevier B.V.

Designer interphases for the lithium-oxygen electrochemical cell

PubMed Central

Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I.; Tu, Zhengyuan; Lau, Sampson; Zachman, Michael J.; Kourkoutis, Lena F.; Archer, Lynden A.

2017-01-01

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells. PMID:28439557

Electrode Modification and Optimization in Air-Cathode Single-Chamber Microbial Fuel Cells.

PubMed

Wang, Yanhua; Wu, Jiayan; Yang, Shengke; Li, Huihui; Li, Xiaoping

2018-06-27

Due to the known problems of microbial fuel cells (MFCs), such as low electricity generation performance and high cost of operation, we modified the electrode with graphene and polyaniline (PANI) is a single-chamber air-cathode MFC and then evaluated the effects of electrode modification on MFC electricity generation performance. Carbon cloth electrodes (unmodified, CC; graphene-modified, G/CC; and polyaniline-graphene-modified, PANI-G/CC) were prepared using the impregnation method. Sulfonated cobalt phthalocyanine (CoPcS) was then introduced as a cathode catalyst. The Co-PANI-G/CC cathode showed higher catalytic activity toward oxygen reduction compared with other electrodes. The maximum power density of the MFC with Co-PANI-G/CC cathode was 32.2 mW/m², which was 1.8 and 6.1 times higher than the value obtained with Co-G/CC and Co/CC cathodes, respectively. This indicates a significant improvement in the electricity generation of single-chamber MFCs and provides a simple, effective cathode modification method. Furthermore, we constructed single-chamber MFCs using the modified anode and cathode and analyzed electricity generation and oxytetracycline (OTC) degradation with different concentrations of OTC as the fuel. With increasing added OTC concentration, the MFC performance in both electricity generation and OTC degradation gradually decreased. However, when less than 50 mg/L OTC was added, the 5-day degradation rate of OTC reached more than 90%. It is thus feasible to process OTC-containing wastewater and produce electricity using single-chamber MFCs, which provides a new concept for wastewater treatment.

Fusion Welding Research.

DTIC Science & Technology

1983-04-30

contaminants from the surface. Further studies of this effect of oxygen on cathodic cleaning of aluminum are being held pending further results of GMAW of...oxygen on cathodic cleaning of aluminum has resulted from these tests, but much more information on the fundamentals of metal transfer in pulsed GMAW

Density functional theory study of oxygen migration in molten carbonate

NASA Astrophysics Data System (ADS)

Lei, Xueling; Haines, Kahla; Huang, Kevin; Qin, Changyong

2016-02-01

The process of oxygen migration in alkali molten carbonate salts has been examined using density functional theory method. All geometries were optimized at the B3LYP/6-31G(d) level, while single point energy corrections were performed using MP4 and CCSD(T). At TS, a O-O-O linkage is formed and O-O bond forming and breaking is concerted. A cooperative ;cogwheel; mechanism as described in the equation of CO42- + CO32- →CO32- ⋯O ⋯CO32- →CO32- + CO42- is involved. The energy barrier is calculated to be 103.0, 136.3 and 127.9 kJ/mol through an intra-carbonate pathway in lithium, sodium and potassium carbonate, respectively. The reliability and accuracy of B3LYP/6-31G(d) were confirmed by CCSD(T). The calculated low values of activation energy indicate that the oxygen transfer in molten carbonate salts is fairly easy. In addition, it is found that lithium carbonate is not only a favorable molten carbonate salt for better cathode kinetics, but also it is widely used for reducing the melting point of Li/Na and Li/K eutectic MC mixtures. The current results imply that the process of oxygen reduction in MC modified cathodes is facilitated by the presence of MC, resulting in an enhancement of cell performance at low operating temperatures.

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

DOE PAGES

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan; ...

2017-10-28

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

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

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Unsupported Pt-Ni Aerogels with Enhanced High Current Performance and Durability in Fuel Cell Cathodes.

PubMed

Henning, Sebastian; Ishikawa, Hiroshi; Kühn, Laura; Herranz, Juan; Müller, Elisabeth; Eychmüller, Alexander; Schmidt, Thomas J

2017-08-28

Highly active and durable oxygen reduction catalysts are needed to reduce the costs and enhance the service life of polymer electrolyte fuel cells (PEFCs). This can be accomplished by alloying Pt with a transition metal (for example Ni) and by eliminating the corrodible, carbon-based catalyst support. However, materials combining both approaches have seldom been implemented in PEFC cathodes. In this work, an unsupported Pt-Ni alloy nanochain ensemble (aerogel) demonstrates high current PEFC performance commensurate with that of a carbon-supported benchmark (Pt/C) following optimization of the aerogel's catalyst layer (CL) structure. The latter is accomplished using a soluble filler to shift the CL's pore size distribution towards larger pores which improves reactant and product transport. Chiefly, the optimized PEFC aerogel cathodes display a circa 2.5-fold larger surface-specific ORR activity than Pt/C and maintain 90 % of the initial activity after an accelerated stress test (vs. 40 % for Pt/C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rational design of novel cathode materials in solid oxide fuel cells using first-principles simulations

NASA Astrophysics Data System (ADS)

Choi, YongMan; Lin, M. C.; Liu, Meilin

The search for clean and renewable sources of energy represents one of the most vital challenges facing us today. Solid oxide fuel cells (SOFCs) are among the most promising technologies for a clean and secure energy future due to their high energy efficiency and excellent fuel flexibility (e.g., direct utilization of hydrocarbons or renewable fuels). To make SOFCs economically competitive, however, development of new materials for low-temperature operation is essential. Here we report our results on a computational study to achieve rational design of SOFC cathodes with fast oxygen reduction kinetics and rapid ionic transport. Results suggest that surface catalytic properties are strongly correlated with the bulk transport properties in several material systems with the formula of La 0.5Sr 0.5BO 2.75 (where B = Cr, Mn, Fe, or Co). The predictions seem to agree qualitatively with available experimental results on these materials. This computational screening technique may guide us to search for high-efficiency cathode materials for a new generation of SOFCs.

Performance of mixed-species biocathode microbial fuel cells using saline mustard tuber wastewater as self-buffered catholyte.

PubMed

Guo, Fei; Fu, Guokai; Zhang, Zhi

2015-03-01

Mixed-species biocathode microbial fuel cells (MFCs) were constructed. Mustard tuber wastewater (MTWW) was used as catholyte. Simultaneous organic matters and nitrogen removal at the cathode was observed, and majority of contaminants reduced were accomplished within acclimating period (AP). Concerning nitrogen removal, aerobic and anaerobic microenvironment could be formed within the cathodic biofilms, and both heterotrophic denitrification and bioelectrochemical denitrification were involved. Also, it was demonstrated that organic matters and ammonium could have detrimental effects on voltage output, but it could retrieve finally. Similar maximum power densities were obtained during stage1 (1.20Wm(-3)), stage2 (1.24Wm(-3)) and stage3 (1.32Wm(-3)). However, overpotential for oxygen reduction was investigated due to lower bacteria activity at cathode, which could major limitation for energy recovery. Considering similar performance of MFCs during different stages, it could be concluded that MTWW was adequately self-buffered when used as catholyte at mixed-species biocathodes. Copyright © 2015. Published by Elsevier Ltd.

Erythrocyte-like hollow carbon capsules and their application in proton exchange membrane fuel cells.

PubMed

Kim, Jung Ho; Yu, Jong-Sung

2010-12-14

Hierarchical nanostructured erythrocyte-like hollow carbon (EHC) with a hollow hemispherical macroporous core of ca. 230 nm in diameter and 30-40 nm thick mesoporous shell was synthesized and explored as a cathode catalyst support in a proton exchange membrane fuel cell (PEMFC). The morphology control of EHC was successfully achieved using solid core/mesoporous shell (SCMS) silica template and different styrene/furfuryl alcohol mixture compositions by a nanocasting method. The EHC-supported Pt (20 wt%) cathodes prepared have demonstrated markedly enhanced catalytic activity towards oxygen reduction reactions (ORRs) and greatly improved PEMFC polarization performance compared to carbon black Vulcan XC-72 (VC)-supported ones, probably due to the superb structural characteristics of the EHC such as uniform size, well-developed porosity, large specific surface area and pore volume. In particular, Pt/EHC cathodes exhibited ca. 30-60% higher ORR activity than a commercial Johnson Matthey Pt catalyst at a low catalyst loading of 0.2 mg Pt cm(-2).

Molten salt applications in materials processing

NASA Astrophysics Data System (ADS)

Mishra, Brajendra; Olson, David L.

2005-02-01

The science of molten salt electrochemistry for electrowinning of reactive metals, such as calcium, and its in situ application in pyro-reduction has been described. Calcium electrowinning has been performed in a 5 10 wt% calcium oxide calcium chloride molten salt by the electrolytic dissociation of calcium oxide. This electrolysis requires the use of a porous ceramic sheath around the anode to keep the cathodically deposited calcium and the anodic gases separate. Stainless steel cathode and graphite anode have been used in the temperature range of 850 950 °C. This salt mixture is produced as a result of the direct oxide reduction (DOR) of reactive metal oxides by calcium in a calcium chloride bath. The primary purpose of this process is to recover the expensive calcium reductant and to recycle calcium chloride. Experimental data have been included to justify the suitability as well as limitations of the electrowinning process. Transport of oxygen ions through the sheath is found to be the rate controlling step. Under the constraints of the reactor design, a calcium recovery rate of approx. 150 g/h was achieved. Feasibility of a process to produce metals by pyrometallurgical reduction, using the calcium reductant produced electrolytically within the same reactor, has been shown in a hybrid process. Several processes are currently under investigation to use this electrowon calcium for in situ reduction of metal oxides.

Efficient reversible electrodes for solid oxide electrolyzer cells

DOEpatents

Elangovan, Singaravelu [South Jordan, UT; Hartvigsen, Joseph J [Kaysville, UT

2011-07-12

An electrolyzer cell is disclosed which includes a cathode to reduce an oxygen-containing molecule, such as H2O, CO2, or a combination thereof, to produce an oxygen ion and a fuel molecule, such as H2, CO, or a combination thereof. An electrolyte is coupled to the cathode to transport the oxygen ion to an anode. The anode is coupled to the electrolyte to receive the oxygen ion and produce oxygen gas therewith. In one embodiment, the anode may be fabricated to include an electron-conducting phase having a perovskite crystalline structure or structure similar thereto. This perovskite may have a chemical formula of substantially (Pr(1-x)Lax)(z-y)A'yBO(3-.differential.), wherein 0.ltoreq.x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.5, and 0.8.ltoreq.z.ltoreq.1.1. In another embodiment, the cathode includes an electron-conducting phase that contains nickel oxide intermixed with magnesium oxide.

Methods and systems for fuel production in electrochemical cells and reactors

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

Marina, Olga A.; Pederson, Larry R.

Methods and systems for fuel, chemical, and/or electricity production from electrochemical cells are disclosed. A voltage is applied between an anode and a cathode of an electrochemical cell. The anode includes a metal or metal oxide electrocatalyst. Oxygen is supplied to the cathode, producing oxygen ions. The anode electrocatalyst is at least partially oxidized by the oxygen ions transported through an electrolyte from the cathode to the anode. A feed gas stream is supplied to the anode electrocatalyst, which is converted to a liquid fuel. The anode electrocatalyst is re-oxidized to higher valency oxides, or a mixture of oxide phases,more » by supplying the oxygen ions to the anode. The re-oxidation by the ions is controlled or regulated by the amount of voltage applied.« less

Effect of sintering temperature on the electrolysis of TiO2

NASA Astrophysics Data System (ADS)

Li, Ze-quan; Ru, Li-yue; Bai, Cheng-guang; Zhang, Na; Wang, Hai-hua

2012-07-01

The effects of sintering temperature on the microstructure and the conductivity of TiO2 cathodes were studied by examining the phase composition, microstructure, and element contents of the sintered cathodes and the cathodic products using X-ray diffraction and scanning electronic microscopy-energy dispersive spectrometry. The oxygen vacancy, conductivity, average pore diameter, and specific surface area of the sintered cathodes were detected by X-ray photoelectron spectroscopy, four-point probe, and ASPA 2010. The results showed that TiO2 phase transformations occurred, and oxygen vacancies formed with the increase of sintering temperature. The cathodic conductivity improved, but the average pore diameter and the effective response area of the TiO2 cathode were reduced when the sintering temperature increased. These phenomena could weaken the contact between reaction ions and electrons and also had the same effect on the cathodes and the molten salt. Moreover, they were disadvantageous to ion migration, so a lower sintering temperature was favorable for the microstructure of electrolysis. Consequently, the cathodic conductivity may be improved, but the microstructure became compact with the increase of sintering temperature. The cathodic products at different temperatures indicated that the cathodic conductivity was more important for electrolysis.

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, D.; Yeager, E.; Shingler, M.; Aldred, W.; Wang, C.

1990-01-01

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Development and Long-Term Stability of a Novel Microbial Fuel Cell BOD Sensor with MnO2 Catalyst

PubMed Central

Kharkwal, Shailesh; Tan, Yi Chao; Lu, Min; Ng, How Yong

2017-01-01

A novel microbial fuel cell (MFC)-based biosensor was designed for continuous monitoring of biochemical oxygen demand (BOD) in real wastewater. To lower the material cost, manganese dioxide (MnO2) was tested as an innovative cathode catalyst for oxygen reduction in a single chamber air-cathode MFC, and two different crystalline structures obtained during synthesis of MnO2 (namely β- and γ-MnO2) were compared. The BOD sensor was studied in a comprehensive way, using both sodium acetate solution and real domestic wastewater (DWW). The optimal performance of the sensor was obtained with a β-MnO2 catalyst, with R2 values of 0.99 and 0.98 using sodium acetate solution and DWW, respectively. The BOD values predicted by the β-MnO2 biosensor for DWW were in agreement with the BOD5 values, determined according to standard methods, with slight variations in the range from 3% to 12%. Finally, the long-term stability of the BOD biosensor was evaluated over 1.5 years. To the best of our knowledge, this is the first report of an MFC BOD sensor using an MnO2 catalyst at the cathode; the feasibility of using a low-cost catalyst in an MFC for online measurement of BOD in real wastewater broadens the scope of applications for such devices. PMID:28134838

Advanced characterization of lithium battery materials with positrons

NASA Astrophysics Data System (ADS)

Barbiellini, Bernardo; Kuriplach, Jan

2017-01-01

Cathode materials are crucial to improved battery performance, in part because there are not yet materials that can maintain high power and stable cycling with a capacity comparable to that of anode materials. Our parameter-free, gradient-corrected model for electron-positron correlations predicts that spectroscopies based on positron annihilation can be deployed to study the effect of lithium intercalation in the oxide matrix of the cathode. The positron characteristics in oxides can be reliably computed using methods based on first-principles. Thus, we can enable a fundamental characterization of lithium battery materials involving positron annihilation spectroscopy and first-principles calculations. The detailed information one can extract from positron experiments could be useful for understanding and optimizing both battery materials and bi-functional catalysts for oxygen reduction and evolution.

Synthesis and application of polypyrrole/carrageenan nano-bio composite as a cathode catalyst in microbial fuel cells.

PubMed

Esmaeili, Chakavak; Ghasemi, Mostafa; Heng, Lee Yook; Hassan, Sedky H A; Abdi, Mahnaz M; Daud, Wan Ramli Wan; Ilbeygi, Hamid; Ismail, Ahmad Fauzi

2014-12-19

A novel nano-bio composite polypyrrole (PPy)/kappa-carrageenan(KC) was fabricated and characterized for application as a cathode catalyst in a microbial fuel cell (MFC). High resolution SEM and TEM verified the bud-like shape and uniform distribution of the PPy in the KC matrix. X-ray diffraction (XRD) has approved the amorphous structure of the PPy/KC as well. The PPy/KC nano-bio composites were then studied as an electrode material, due to their oxygen reduction reaction (ORR) ability as the cathode catalyst in the MFC and the results were compared with platinum (Pt) as the most common cathode catalyst. The produced power density of the PPy/KC was 72.1 mW/m(2) while it was 46.8 mW/m(2) and 28.8 mW/m(2) for KC and PPy individually. The efficiency of the PPy/KC electrode system is slightly lower than a Pt electrode (79.9 mW/m(2)) but due to the high cost of Pt electrodes, the PPy/KC electrode system has potential to be an alternative electrode system for MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Carbon-Free CoO Mesoporous Nanowire Array Cathode for High-Performance Aprotic Li-O2 Batteries.

PubMed

Wu, Baoshan; Zhang, Hongzhang; Zhou, Wei; Wang, Meiri; Li, Xianfeng; Zhang, Huamin

2015-10-21

Although various kinds of catalysts have been developed for aprotic Li-O2 battery application, the carbon-based cathodes are still vulnerable to attacks from the discharge intermediates or products, as well as the accompanying electrolyte decomposition. To ameliorate this problem, the free-standing and carbon-free CoO nanowire array cathode was purposely designed for Li-O2 batteries. The single CoO nanowire formed as a special mesoporous structure, owing even comparable specific surface area and pore volume to the typical Super-P carbon particles. In addition to the highly selective oxygen reduction/evolution reactions catalytic activity of CoO cathodes, both excellent discharge specific capacity and cycling efficiency of Li-O2 batteries were obtained, with 4888 mAh gCoO(-1) and 50 cycles during 500 h period. Owing to the synergistic effect between elaborate porous structure and selective intermediate absorption on CoO crystal, a unique bimodal growth phenomenon of discharge products was occasionally observed, which further offers a novel mechanism to control the formation/decomposition morphology of discharge products in nanoscale. This research work is believed to shed light on the future development of high-performance aprotic Li-O2 batteries.

Electrophoretic deposition of multi-walled carbon nanotube on a stainless steel electrode for use in sediment microbial fuel cells.

PubMed

Song, Tian-Shun; Peng-Xiao; Wu, Xia-Yuan; Zhou, Charles C

2013-07-01

Sediment microbial fuel cells (SMFCs) could be used as power sources and one type of new technology for the removal of organic matters in sediments. In order to improve electrode materials and enhance their effect on the performance, we deposited multi-walled carbon nanotube (MWNT) on stainless steel net (SSN). Electrophoretic deposition technique as a method with low cost, process simplicity, and thickness control was used for this electrode modification and produced this novel SSN-MWNT electrode. The performances of SMFCs with SSN-MWNT as electrode were investigated. The results showed that the maximum power density of SMFC with SSN-MWNT cathode was 31.6 mW m(-2), which was 3.2 times that of SMFC with an uncoated stainless steel cathode. However, no significant increase in the maximum power density of SMFC with SSN-MWNT anode was detected. Further electrochemical analysis showed that when SSN-MWNT was used as the cathode, the cathodic electrochemical activity and oxygen reduction rate were significantly improved. This study demonstrates that the electrophoretic deposition of carbon nanotubes on conductive substrate can be applied for improving the performance of SMFC.

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

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

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

DOE PAGES

Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin; ...

2018-01-24

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, anmore » atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.« less

Simultaneous NOx and hydrocarbon emissions control for lean-burn engines using low-temperature solid oxide fuel cell at open circuit.

PubMed

Huang, Ta-Jen; Hsu, Sheng-Hsiang; Wu, Chung-Ying

2012-02-21

The high fuel efficiency of lean-burn engines is associated with high temperature and excess oxygen during combustion and thus is associated with high-concentration NO(x) emission. This work reveals that very high concentration of NO(x) in the exhaust can be reduced and hydrocarbons (HCs) can be simultaneously oxidized using a low-temperature solid oxide fuel cell (SOFC). An SOFC unit is constructed with Ni-YSZ as the anode, YSZ as the electrolyte, and La(0.6)Sr(0.4)CoO(3) (LSC)-Ce(0.9)Gd(0.1)O(1.95) as the cathode, with or without adding vanadium to LSC. SOFC operation at 450 °C and open circuit can effectively treat NO(x) over the cathode at a very high concentration in the simulated exhaust. Higher NO(x) concentration up to 5000 ppm can result in a larger NO(x) to N(2) rate. Moreover, a higher oxygen concentration promotes NO conversion. Complete oxidation of HCs can be achieved by adding silver to the LSC current collecting layer. The SOFC-based emissions control system can treat NO(x) and HCs simultaneously, and can be operated without consuming the anode fuel (a reductant) at near the engine exhaust temperature to eliminate the need for reductant refilling and extra heating.

Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

PubMed

Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

2017-05-09

An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Xiao Xia; Cullen, David A; Pan, Yung-Tin; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Wang, Jingyun; Engelhard, Mark H; Zhang, Hanguang; He, Yanghua; Shao, Yuyan; Su, Dong; More, Karren L; Spendelow, Jacob S; Wu, Gang

2018-03-01

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Performance of Highly Mesoporous Nitrogen Doped Carbon Cathode in Lithium-Oxygen Batteries (Postprint)

DTIC Science & Technology

2011-03-01

concentrations. Cathode capacity approaching 000mAhg−1 for a Mn based catalyst [7] and cathode capac- ty 5360mAhg−1 for cell employing a hydrophobic ionic ... liquid nd lithium salt were reported [8]. A gravimetric capacity of 813mAhg−1 was achieved using a novel lithium–oxygen cath- de architecture without...andNafion (tetrafluoroethy- ene based fluoropolymer-copolymer) solution in one case and -KB and Nafion in another were prepared and spread on graphite

Solid oxide fuel cells having porous cathodes infiltrated with oxygen-reducing catalysts

DOEpatents

Liu, Meilin; Liu, Ze; Liu, Mingfei; Nie, Lifang; Mebane, David Spencer; Wilson, Lane Curtis; Surdoval, Wayne

2014-08-12

Solid-oxide fuel cells include an electrolyte and an anode electrically coupled to a first surface of the electrolyte. A cathode is provided, which is electrically coupled to a second surface of the electrolyte. The cathode includes a porous backbone having a porosity in a range from about 20% to about 70%. The porous backbone contains a mixed ionic-electronic conductor (MIEC) of a first material infiltrated with an oxygen-reducing catalyst of a second material different from the first material.

Assessment of electrochemical properties of a biogalvanic system for tissue characterisation

PubMed Central

Chandler, J.H.; Culmer, P.R.; Jayne, D.G.; Neville, A.

2015-01-01

Biogalvanic characterisation is a promising method for obtaining health-specific tissue information. However, there is a dearth of understanding in the literature regarding the underlying galvanic cell, electrode reactions and their controlling factors which limits the application of the technique. This work presents a parametric electrochemical investigation into a zinc–copper galvanic system using salt (NaCl) solution analogues at physiologically-relevant concentrations (1.71, 17.1 & 154 mM). The potential difference at open cell, closed cell maximum current and the internal resistance (based on published characterisation methods) were measured. Additionally, independent and relative polarisation scans of the electrodes were performed to improve understanding of the system. Our findings suggest that the prominent reaction at the cathode is that of oxygen-reduction, not hydrogen-evolution. Results indicate that cell potentials are influenced by the concentration of dissolved oxygen at low currents and maximum closed cell currents are limited by the rate of oxygen diffusion to the cathode. Characterised internal resistance values for the salt solutions did not correspond to theoretical values at the extremes of concentration (1.71 and 154 mM) due to electrode resistance and current limitation. Existing biogalvanic models do not consider these phenomena and should be improved to advance the technique and its practical application. PMID:25460609

Some reflections on the understanding of the oxygen reduction reaction at Pt(111)

PubMed Central

Gómez-Marín, Ana M; Rizo, Ruben

2013-01-01

Summary The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments. PMID:24455454

Some reflections on the understanding of the oxygen reduction reaction at Pt(111).

PubMed

Gómez-Marín, Ana M; Rizo, Ruben; Feliu, Juan M

2013-12-27

The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments.

Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

NASA Astrophysics Data System (ADS)

Stolbov, Sergey; Alcántara Ortigoza, Marisol

2012-02-01

The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

Modeling Joule Heating Effect on Lunar O2 Generation via Electrolytic Reduction.

NASA Technical Reports Server (NTRS)

Dominquez, Jesus; Poizeau, Sophie; Sibille, Laurent

2009-01-01

Kennedy Space Center is leading research work on lunar O2 generation via electrolytic reduction of regolith; the metal oxide present in the regolith is dissociated in oxygen anions and metal cations leading to the generation of gaseous oxygen at the anode and liquid metal at the cathode. Electrical resistance of molten regolith is high, leading to heating of the melt when electrical current is applied between the electrodes (Joule heating). The authors have developed a 3D model using a rigorous approach for two coupled physics (thermal and electrical potential) to not only study the effect of Joule heating on temperature distribution throughout the molten regolith but also to evaluate and optimize the design of the electrolytic cells. This paper presents the results of the thermal analysis performed on the model and used to validate the design of the electrolytic cell.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

Sequential reductive and oxidative biodegradation of chloroethenes stimulated in a coupled bioelectro-process.

PubMed

Lohner, Svenja T; Becker, Dirk; Mangold, Klaus-Michael; Tiehm, Andreas

2011-08-01

This article for the first time demonstrates successful application of electrochemical processes to stimulate sequential reductive/oxidative microbial degradation of perchloroethene (PCE) in mineral medium and in contaminated groundwater. In a flow-through column system, hydrogen generation at the cathode supported reductive dechlorination of PCE to cis-dichloroethene (cDCE), vinyl chloride (VC), and ethene (ETH). Electrolytically generated oxygen at the anode allowed subsequent oxidative degradation of the lower chlorinated metabolites. Aerobic cometabolic degradation of cDCE proved to be the bottleneck for complete metabolite elimination. Total removal of chloroethenes was demonstrated for a PCE load of approximately 1.5 μmol/d. In mineral medium, long-term operation with stainless steel electrodes was demonstrated for more than 300 days. In contaminated groundwater, corrosion of the stainless steel anode occurred, whereas DSA (dimensionally stable anodes) proved to be stable. Precipitation of calcareous deposits was observed at the cathode, resulting in a higher voltage demand and reduced dechlorination activity. With DSA and groundwater from a contaminated site, complete degradation of chloroethenes in groundwater was obtained for two months thus demonstrating the feasibility of the sequential bioelectro-approach for field application.

Transport studies in polymer electrolyte fuel cell with porous metallic flow field at ultra high current density

NASA Astrophysics Data System (ADS)

Srouji, Abdul-Kader

Achieving cost reduction for polymer electrolyte fuel cells (PEFC) requires a simultaneous effort in increasing power density while reducing precious metal loading. In PEFCs, the cathode performance is often limiting due to both the slow oxygen reduction reaction (ORR), and mass transport limitation caused by limited oxygen diffusion and liquid water flooding at high current density. This study is motivated by the achievement of ultra-high current density through the elimination of the channel/land (C/L) paradigm in PEFC flow field design. An open metallic element (OME) flow field capable of operating at unprecedented ultra-high current density (3 A/cm2) introduces new advantages and limitations for PEFC operation. The first part of this study compares the OME with a conventional C/L flow field, through performance and electrochemical diagnostic tools such as electrochemical impedance spectroscopy (EIS). The results indicate the uniqueness of the OME's mass transport improvement. No sign of operation limitation due to flooding is noted. The second part specifically examines water management at high current density using the OME flow field. A unique experimental setup is developed to measure steady-state and transient net water drag across the membrane, in order to characterize the fundamental aspects of water transport at high current density with the OME. Instead of flooding, the new limitation is identified to be anode side dry-out of the membrane, caused by electroosmotic drag. The OME improves water removal from the cathode, which immediately improves oxygen transport and performance. However, the low water content in the cathode reduces back diffusion of water to the membrane, and electroosmotic drag dominates at high current density, leading to dry-out. The third part employs the OME flow field as a tool that avoids C/L effects endemic to a typical flow field, in order to study oxygen transport resistance at the catalyst layer of a PEFC. In open literature, a resistance of unknown origin, was shown to directly or indirectly scale with Pt loading. A lack of understanding of the mechanism responsible for such resistance is noted, and several possible theories have been proposed. This lack of fundamental understanding of the origins of this resistance adds complexity to computational models which are designed to capture performance behavior with ultra-low loading electrodes. By employing the OME flow field as a tool to study this phenomena, the origins of the transport resistance appearing at ultra-low Platinum (Pt) loading is proposed to be an increase in oxygen dilution resistance through water film.

Cathodic Deposition of Mg(OH)2 Coatings on Pure mg in Three mg Salts Aqueous Solutions

NASA Astrophysics Data System (ADS)

Yongjun, Zhang; Xiaomeng, Pei; Shugong, Jia

Film-forming effects of cathodic deposition on pure Mg substrate at constant DC in aqueous solutions of magnesium nitrate (Mg(NO3)2ṡ6H2O), magnesium chloride (MgCl2ṡ6H2O) and magnesium sulfate (MgSO4ṡ7H2O) respectively were investigated systematically. Typical processes were studied by potentiodynamic cathodic polarization and galvanostatic polarization and typical samples were analyzed by SEM and XRD. The results indicate that the depositing efficiency is not only the highest but stablest, and deposited coatings show the best uniformity with Mg(NO3)2ṡ6H2O solution employed as depositing medium and applied current density ≥1.0mA cm-2. Cathodic deposition leads to regular mass loss of Mg substrate. The cathodic polarization curve of pure Mg in magnesium nitrate solution shows more obvious pseudo-passivation, several Tafel regions with different slopes appearing before diffusion-limited current density region, and oxygen consumption is the major cathodic reduction reaction under specified current density. However, hydrogen evolution reaction is dominant in both Mg chloride and Mg sulfate solutions. The deposition coatings are all composed of continuous and uniform mesh-like “basic layer” adjacent to substrate and discrete distributed snowball-like particles on the microscopic scale. The phase compositions are all crystal Mg(OH)2, and the coatings deposited in Mg chloride solution have (011) preferred orientation.

Concurrent CO2 Control and O2 Generation for Advanced Life Support

NASA Technical Reports Server (NTRS)

Paul, Heather L.; Duncan, Keith L.; Hagelin-Weaver, Helena E.; Bishop, Sean R.; Wachsman, Eric D.

2007-01-01

The electrochemical reduction of carbon dioxide (CO2) using ceramic oxygen generators (COGs) is well known and widely studied, however, conventional devices using yttria-stabilized zirconia (YSZ) electrolytes operate at temperatures greater than 700 C. Operating at such high temperatures increases system mass compared to lower temperature systems because of increased energy overhead to get the COG up to operating temperature and the need for heavier insulation and/or heat exchangers to reduce the COG oxygen (O2) output temperature for comfortable inhalation. Recently, the University of Florida developed novel ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth for NASA's future exploration of Mars. To reduce landed mass and operation expenditures during the mission, in-situ resource utilization was proposed using these COGs to obtain both lifesupporting oxygen and oxidant/propellant fuel, by converting CO2 from the Mars atmosphere. The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal was an issue. The strategy proposed for CO2 removal for advanced life support systems employs a catalytic layer combined with a COG so that it is reduced all the way to solid carbon and oxygen. Hence, a three-phased approach was used for the development of a viable low weight COG for CO2 removal. First, to reduce the COG operating temperature a high oxide ion conductivity electrolyte was developed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, novel cathodes and a removable catalytic carbon deposition layer were designed. Third, to improve efficiency, a pre-stage for CO2 absorption was used to concentrate CO2 from the exhalate before sending it to the COG. These subsystems were then integrated into a single CO2 removal system. This paper describes our progress to date on these tasks.

Oxygen Reduction Reaction on Graphene in an Electro-Fenton System: In Situ Generation of H2 O2 for the Oxidation of Organic Compounds.

PubMed

Chen, Chen-Yu; Tang, Cheng; Wang, Hao-Fan; Chen, Cheng-Meng; Zhang, Xiaoyuan; Huang, Xia; Zhang, Qiang

2016-05-23

Fenton oxidation using an aqueous mixture of Fe(2+) and H2 O2 is a promising environmental remediation strategy. However, the difficulty of storage and shipment of concentrated H2 O2 and the generation of iron sludge limit its broad application. Therefore, highly efficient and cost-effective electrocatalysts are in great need. Herein, a graphene catalyst is proposed for the electro-Fenton process, in which H2 O2 is generated in situ by the two-electron reduction of the dissolved O2 on the cathode and then decomposes to generate (.) OH in acidic solution with Fe(2+) . The π bond of the oxygen is broken whereas the σ bond is generally preserved on the metal-free reduced graphene oxide owing to the high free energy change. Consequently, the oxygen is reduced to H2 O2 through a two-electron pathway. The thermally reduced graphene with a high specific surface area (308.8 m(2)  g(-1) ) and a large oxygen content (10.3 at %) exhibits excellent reactivity for the two-electron oxygen reduction reaction to H2 O2 . A highly efficient peroxide yield (64.2 %) and a remarkable decolorization of methylene blue (12 mg L(-1) ) of over 97 % in 160 min are obtained. The degradation of methylene blue with hydroxyl radicals generated in situ is described by a pseudo first-order kinetics model. This provides a proof-of-concept of an environmentally friendly electro-Fenton process using graphene for the oxygen reduction reaction in an acidic solution to generate H2 O2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ formation of oxygen vacancy in perovskite Sr0.95Ti0.8Nb0.1M0.1O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis

PubMed Central

Zhang, Jun; Xie, Kui; Wei, Haoshan; Qin, Qingqing; Qi, Wentao; Yang, Liming; Ruan, Cong; Wu, Yucheng

2014-01-01

In this work, redox-active Mn or Cr is introduced to the B site of redox stable perovskite Sr0.95Ti0.9Nb0.1O3.00 to create oxygen vacancies in situ after reduction for high-temperature CO2 electrolysis. Combined analysis using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis confirms the change of the chemical formula from oxidized Sr0.95Ti0.9Nb0.1O3.00 to reduced Sr0.95Ti0.9Nb0.1O2.90 for the bare sample. By contrast, a significant concentration of oxygen vacancy is additionally formed in situ for Mn- or Cr-doped samples by reducing the oxidized Sr0.95Ti0.8Nb0.1M0.1O3.00 (M = Mn, Cr) to Sr0.95Ti0.8Nb0.1M0.1O2.85. The ionic conductivities of the Mn- and Cr-doped titanate improve by approximately 2 times higher than bare titanate in an oxidizing atmosphere and 3–6 times higher in a reducing atmosphere at intermediate temperatures. A remarkable chemical accommodation of CO2 molecules is achieved on the surface of the reduced and doped titanate, and the chemical desorption temperature reaches a common carbonate decomposition temperature. The electrical properties of the cathode materials are investigated and correlated with the electrochemical performance of the composite electrodes. Direct CO2 electrolysis at composite cathodes is investigated in solid-oxide electrolyzers. The electrode polarizations and current efficiencies are observed to be significantly improved with the Mn- or Cr-doped titanate cathodes. PMID:25403738

Fundamental Impact of Humidity on SOFC Cathode ORR

DOE PAGES

Huang, Y. L.; Pellegrinelli, C.; Wachsman, E. D.

2015-12-17

Although solid oxide fuel cells (SOFC) have demonstrated excellent performance, the durability of SOFCs under real working conditions is still an issue for commercial deployment. In particular cathode exposure to atmospheric air contaminants, such as humidity, can result in long-term performance degradation issues. Therefore, a fundamental understanding of the interaction between water molecules and cathodes is essential to resolve this issue and further enhance cathode durability. In order to study the effects of humidity on the oxygen reduction reaction (ORR), we used in-situ 18O isotope exchange techniques to probe the exchange of water with two of themost common SOFC cathodemore » materials, (La 0.8Sr 0.2) 0.95MnO 3±δ (LSM) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF). In this experiment, heavy water, D 2O (with a mass/charge ratio of m/z = 20), is used to avoid the overlapping of H 2O and the 18O 2 cracking fraction, which both provide a peak at m/z = 18. A series of temperature programmed isotope exchange measurements were performed to comprehensively study the interaction of water with the cathode surface as a function of temperature, oxygen partial pressure, and water vapor concentration. The results suggest that water and O 2 share the same surface exchange sites, leading to competitive adsorption. Our findings show that water prefers to exchange with LSCF at lower temperatures, around 300–450°C. For LSM, O 2 is more favorable than water to be adsorbed on the surface and the presence of O 2 limits water exchange. The experimental data are summarized in a Temperature-PO 2 diagram to help visualize how the exchange of water on each material depends on the operating conditions.« less

Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells

DOE PAGES

Sebastian, David; Serov, Alexey; Matanovic, Ivana; ...

2017-02-21

Direct alcohol fuel cells (DAFCs) represent the best alternative to batteries for portable and auxiliary power units application due to the high energy density of short chain alcohols. Currently, the utilization of the best platinum group metal (PGM) cathode catalysts is limited, not only by a high cost and scarce resources, but also by the inefficient oxygen reduction reaction (ORR) when permeated alcohols adsorb on the catalytic active sites. In this work, a highly active Fe-N-C catalyst derived from the pyrolysis of nicarbazin (a nitrogen charge transfer organic salt) and an iron precursor has been investigated to get insights onmore » the extraordinary tolerance to the presence of alcohols (methanol and ethanol) of such a PGM-free catalyst. Density functional theory (DFT) calculations demonstrate for the first time that Fe-N 4 and Fe-N 2C 2 active sites preferentially adsorb oxygen with much higher energy than methanol, ethanol and products of partial ethanol oxidation (0.73–1.16 eV stronger adsorption), while nitrogen-carbon related sites (pyridinic and graphitic nitrogen) are much less selective towards ORR. Half-cell electrochemical characterization showed that the Fe-N-C catalyst overcomes Pt ORR activity in acidic medium with methanol or ethanol concentrations as low as 0.01 M. The feasibility of DAFCs operation based on high methanol (up to 17 M) and ethanol (up to 5 M) concentration thanks to the utilization of Fe-N-C cathode catalyst is demonstrated. Lastly, a new strategy is proposed for DAFCs where using Pt only at the anode and Fe-N-C at the cathode allows extending the device energy density compared to PGM-based catalysts at both electrodes.« less

Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells

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

Sebastian, David; Serov, Alexey; Matanovic, Ivana

Direct alcohol fuel cells (DAFCs) represent the best alternative to batteries for portable and auxiliary power units application due to the high energy density of short chain alcohols. Currently, the utilization of the best platinum group metal (PGM) cathode catalysts is limited, not only by a high cost and scarce resources, but also by the inefficient oxygen reduction reaction (ORR) when permeated alcohols adsorb on the catalytic active sites. In this work, a highly active Fe-N-C catalyst derived from the pyrolysis of nicarbazin (a nitrogen charge transfer organic salt) and an iron precursor has been investigated to get insights onmore » the extraordinary tolerance to the presence of alcohols (methanol and ethanol) of such a PGM-free catalyst. Density functional theory (DFT) calculations demonstrate for the first time that Fe-N 4 and Fe-N 2C 2 active sites preferentially adsorb oxygen with much higher energy than methanol, ethanol and products of partial ethanol oxidation (0.73–1.16 eV stronger adsorption), while nitrogen-carbon related sites (pyridinic and graphitic nitrogen) are much less selective towards ORR. Half-cell electrochemical characterization showed that the Fe-N-C catalyst overcomes Pt ORR activity in acidic medium with methanol or ethanol concentrations as low as 0.01 M. The feasibility of DAFCs operation based on high methanol (up to 17 M) and ethanol (up to 5 M) concentration thanks to the utilization of Fe-N-C cathode catalyst is demonstrated. Lastly, a new strategy is proposed for DAFCs where using Pt only at the anode and Fe-N-C at the cathode allows extending the device energy density compared to PGM-based catalysts at both electrodes.« less

High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

PubMed Central

2015-01-01

Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

Theoretical Design and Experimental Evaluation of Molten Carbonate Modified LSM Cathode for Low Temperature Solid Oxide Fuel Cells

DTIC Science & Technology

2015-01-07

Min Lee, Kevin Huang. Mixed Oxide-Ion and Carbonate-Ion Conductors (MOCCs) as Electrolyte Materials for Solid Oxide Fuel Cells, 218th ECS Meeting... Solid Oxide Fuel Cells The views, opinions and/or findings contained in this report are those of the author(s) and should not contrued as an official...ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 Solid Oxide Fuel Cell, Oxygen Reduction, Molten Carbonate

Electrodeposited Mn-Sn-X Alloys for Corrosion Protection Coatings

DTIC Science & Technology

2002-09-30

amount of tin and oxygen (Figure 7, right), and possess an amorphous structure. The addition of tartrate , EDTA or gluconate suppresses Mn reduction...pH 6.4-6.6 and 2.6-2.8, and at different cupric ion concentrations is conducted by using cathodic potentiodynamic and cyclic voltammetry methods...in the form of MnOx(OH)2-x⋅nH2O, where x increases and n decreases with depth. The effect of the variation of cupric ion concentration ([Cu2+]) on

Molecular Level Understanding of Electrocatalysis in High pH Environment

DTIC Science & Technology

2015-07-08

consisting of alkali metal hydroxide doped PBI membrane with 2.0 mgPtRu cm-2 anode and 1.0 mgPt cm-2 loadings at the anode and cathode, respectively...Direct!ethanol!fuel!cells!using!an!anion! exchange!membrane.!J!Power!Sources.!2008;185:621*6.! [4]!Hou!H,!Sun!G,!He!R,!Wu!Z,!Sun!B.!Alkali! doped ...electrocatalysts! for!oxygen!reduction! derived!from!polyaniline,!iron,!and! cobalt .!Science!(Washington,!DC,!U!S).!2011;332:443*7.! [17]! Zagal! JH

A high-performance, cobalt-free cathode for intermediate-temperature solid oxide fuel cells with excellent CO2 tolerance

NASA Astrophysics Data System (ADS)

Bu, Yun-fei; Zhong, Qin; Chen, Dong-Chang; Chen, Yu; Lai, Samson Yuxiu; Wei, Tao; Sun, Hai-bin; Ding, Dong; Liu, Meilin

2016-07-01

Compared with some cobalt-rich cathodes which have been proven to yield high performance in SOFCs, interest in cobalt-free cathodes has increased due to their reduced thermal expansion coefficients (TECs), high structural stability, and CO2 tolerance. In this report, a new robust Co-free complex perovskite oxide PrLa0.4Ba0.6Fe0.8Zn0.2O5+δ (PLBFZ) has been synthesized and evaluated. The TEC is 14.4 × 10-6 K-1. With the introduction of Sm0.2Ce0.8O2 (SDC), the composite cathode PLBFZ-SDC with a mass ratio of 7:3 (PLBFZ-SDC 73) exhibited the best electrocatalytic activity for oxygen reduction under OCV conditions, with polarization values of 0.044, 0.079, 0.124, 0.251, 0.572, and 1.297 Ω cm-2 at 800, 750, 700, 650, 600, and 550 °C, respectively. The power densities of the cell were 1309, 1079, 788 and 586 mW cm-2 at 750, 700, 650, and 600 °C, respectively. Moreover, it appears to have good stability in air containing 1% CO2 (volume ratio) for 150 h based on Raman and polarization resistance (Rp) analysis. These results suggest that PLBFZ and its SDC composite are promising cathodes for IT-SOFCs.

La0.8Sr0.2Fe0.8Cu0.2O3-δ as “cobalt-free” cathode for La0.8Sr0.2Ga0.8Mg0.2O3-δ electrolyte

NASA Astrophysics Data System (ADS)

Zurlo, Francesca; Di Bartolomeo, Elisabetta; D'Epifanio, Alessandra; Felice, Valeria; Natali Sora, Isabella; Tortora, Luca; Licoccia, Silvia

2014-12-01

A "cobalt-free" cathode material with stoichiometric composition La0.8Sr0.2Fe0.8Cu0.2O3-δ (LSFCu) was specifically developed for use with La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) electrolyte in intermediate temperature solid oxide fuel cell (IT-SOFC) systems. The chemical stability of LSFCu in contact with LSGM electrolyte was investigated by structural and morphological analysis. The electrochemical properties of LSFCu dense pellets were investigated in the temperature range 600-750 °C by electrochemical impedance spectroscopy (EIS). LSFCu|LSGM|LSFCu symmetrical cells were prepared and area specific resistance (ASR) values, directly depending on the rate limiting step of the oxygen reduction reaction, were evaluated. Fuel cells were prepared using LSFCu as cathode material on a LSGM pellet and electrochemical tests were performed in the 700-800 °C temperature range and compared to similar fuel cells prepared by using commercial La0.6Sr0.4Fe0.8Co0.2O3-δ (LSFCo) as a cathode. The maximum current density and power density recorded for LSFCu and LSFCo were similar. This fact demonstrates that Cu can be used as Co substitute in perovskite cathode materials.

Chrysanthemum flower-like NiCo2O4-nitrogen doped graphene oxide composite: an efficient electrocatalyst for lithium-oxygen and zinc-air batteries.

PubMed

Moni, Prabu; Hyun, Suyeon; Vignesh, Ahilan; Shanmugam, Sangaraju

2017-07-06

Chrysanthemum flower-like NiCo 2 O 4 -nitrogen doped graphene oxide composite material has been explored as a bifunctional cathode electrocatalyst for aqueous zinc-air and non-aqueous lithium-oxygen batteries. This cathode exhibits maximum discharge capacities of 712 and 15 046 mA h g -1 for zinc-air and lithium-oxygen batteries, respectively, with stable cycling over 50 cycles.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-02-14

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-12-05

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

2016-01-12

Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

2014-01-28

Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Efficient reversible electrodes for solid oxide electrolyzer cells

DOEpatents

Elangovan, S.; Hartvigsen, Joseph J.; Zhao, Feng

2013-01-15

An electrolyzer cell is disclosed which includes a cathode to reduce an oxygen-containing molecule, such as H2O, CO.sub.2, or a combination thereof, to produce an oxygen ion and a fuel molecule, such as H.sub.2, CO, or a combination thereof. An electrolyte is coupled to the cathode to transport the oxygen ion to an anode. The anode is coupled to the electrolyte to receive the oxygen ion and produce oxygen gas therewith. In one embodiment, the anode may be fabricated to include an electron-conducting phase having a perovskite crystalline structure or structure similar thereto. This perovskite may have a chemical formula of substantially (Pr(.sub.1-x)La.sub.x)(z-y)A'.sub.yBO(3-.differential.), wherein 0

Vertically aligned carbon nanotubes as anode and air-cathode in single chamber microbial fuel cells

NASA Astrophysics Data System (ADS)

Amade, R.; Moreno, H. A.; Hussain, S.; Vila-Costa, M.; Bertran, E.

2016-10-01

Electrode optimization in microbial fuel cells is a key issue to improve the power output and cell performance. Vertically aligned carbon nanotubes (VACNTs) grown on low cost stainless-steel mesh present an attractive approach to increase the cell performance while avoiding the use of expensive Pt-based materials. In comparison with non-aligned carbon nanotubes (NACNTs), VACNTs increase the oxygen reduction reaction taking place at the cathode by a factor of two. In addition, vertical alignment also increases the power density up to 2.5 times with respect to NACNTs. VACNTs grown at the anode can further improve the cell performance by increasing the electrode surface area and thus the electron transfer between bacteria and the electrode. The maximum power density obtained using VACNTs was 14 mW/m2 and 160 mV output voltage.

Computational Interpretation of the Relation Between Electric Field and the Applied Current for Cathodic Protection Under Different Conductivity Environments

NASA Astrophysics Data System (ADS)

Kim, Yong-Sang; Ko, Sang-Jin; Lee, Sangkyu; Kim, Jung-Gu

2018-03-01

An interpretation of the relation between the electric field and the applied current for cathodic protection is investigated using a boundary element method simulation. Also, a conductivity-difference environment is set for the interface influence. The variation of the potential distribution is increased with the increase of the applied current and the conductivity difference due to the rejection of the current at the interface. In the case of the electric field, the tendencies of the increasing rate and the applied currents are similar, but the interface influence is different according to the directional component and field type (decrease of E z and increases of E x and E y) due to the directional difference between the electric fields. Also, the change tendencies of the electric fields versus the applied current plots are affected by the polarization curve tendency regarding the polarization type (activation and concentration polarizations in the oxygen-reduction and hydrogen-reduction reactions). This study shows that the underwater electric signature is determined by the polarization behavior of the materials.

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells.

PubMed

Kongkanand, Anusorn; Mathias, Mark F

2016-04-07

Substantial progress has been made in reducing proton-exchange membrane fuel cell (PEMFC) cathode platinum loadings from 0.4-0.8 mgPt/cm(2) to about 0.1 mgPt/cm(2). However, at this level of cathode Pt loading, large performance loss is observed at high-current density (>1 A/cm(2)), preventing a reduction in the overall stack cost. This next developmental step is being limited by the presence of a resistance term exhibited at these lower Pt loadings and apparently due to a phenomenon at or near the catalyst surface. This issue can be addressed through the design of catalysts with high and stable Pt dispersion as well as through development and implementation of ionomers designed to interact with Pt in a way that does not constrain oxygen reduction reaction rates. Extrapolating from progress made in past decades, we are optimistic that the concerted efforts of materials and electrode designers can resolve this issue, thus enabling a large step toward fuel cell vehicles that are affordable for the mass market.

Low platinum loading cathode modified with Cs3H2PMo10V2O40 for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Renzi, M.; D'Angelo, G.; Marassi, R.; Nobili, F.

2016-09-01

The catalytic activity of commercial Pt nanoparticles mixed with mesoporous polyoxometalate Cs3H2PMo10V2O40 towards oxygen reduction reaction is evaluated. The polyoxometalate co-catalyst is prepared by titration of an aqueous solution of phosphovanadomolibdic acid. SEM micrography shows reduction particle size to less than 300 nm, while XRD confirms that the resulting salt maintains the Kegging structure. The composite catalyst is prepared by mixing the POM salt with Pt/C by sonication. RRDE studies show better kinetics for ORR with low Pt loading at the electrode surface. A MEA is assembled by using a Pt/POM-based cathode, in order to assess performance in a working fuel cell. Current vs. potential curves reveals comparable or better performances at 100%, 62% and 17% relative humidity for the POM-modified MEA with respect to a commercial MEA with higher Pt loading at the cathode. Electrochemical impedance spectroscopy (EIS) confirms better kinetics at low relative humidity. Finally, an accelerated stress test (AST) with square wave (SW) between 0.4 V and 0.8 V is performed to evaluate MEA stability for at least 100 h and make predictions about lifetime, showing that after initial losses the catalytic system can retain stable performance and good morphological stability.

Microbial fuel cell operation using monoazo and diazo dyes as terminal electron acceptor for simultaneous decolourisation and bioelectricity generation.

PubMed

Oon, Yoong-Sin; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Oon, Yoong-Ling; Lehl, Harvinder Kaur; Thung, Wei-Eng; Nordin, Noradiba

2017-03-05

Monoazo and diazo dyes [New coccine (NC), Acid orange 7 (AO7), Reactive red 120 (RR120) and Reactive green 19 (RG19)] were employed as electron acceptors in the abiotic cathode of microbial fuel cell. The electrons and protons generated from microbial organic oxidation at the anode which were utilized for electrochemical azo dye reduction at the cathodic chamber was successfully demonstrated. When NC was employed as the electron acceptor, the chemical oxygen demand (COD) removal and dye decolourisation efficiencies obtained at the anodic and cathodic chamber were 73±3% and 95.1±1.1%, respectively. This study demonstrated that the decolourisation rates of monoazo dyes were ∼50% higher than diazo dyes. The maximum power density in relation to NC decolourisation was 20.64mW/m 2 , corresponding to current density of 120.24mA/m 2 . The decolourisation rate and power output of different azo dyes were in the order of NC>AO7>RR120>RG19. The findings revealed that the structure of dye influenced the decolourisation and power performance of MFC. Azo dye with electron-withdrawing group at para substituent to azo bond would draw electrons from azo bond; hence the azo dye became more electrophilic and more favourable for dye reduction. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

NASA Astrophysics Data System (ADS)

Zeller, Robert August

Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm + cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.

Sintered wire cathode

DOEpatents

Falce, Louis R [San Jose, CA; Ives, R Lawrence [Saratoga, CA

2009-06-09

A porous cathode structure is fabricated from a plurality of wires which are placed in proximity to each other in elevated temperature and pressure for a sintering time. The sintering process produces the porous cathode structure which may be divided into a plurality of individual porous cathodes, one of which may be placed into a dispenser cathode support which includes a cavity for containing a work function reduction material such as BaO, CaO, and Al.sub.2O.sub.3. The work function reduction material migrates through the pores of the porous cathode from a work replenishment surface adjacent to the cavity of the dispenser cathode support to an emitting cathode surface, thereby providing a dispenser cathode which has a uniform work function and therefore a uniform electron emission.

Electrolytic oxide reduction system

DOEpatents

Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L; Berger, John F

2015-04-28

An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies, a plurality of cathode assemblies, and a lift system configured to engage the anode and cathode assemblies. The cathode assemblies may be alternately arranged with the anode assemblies such that each cathode assembly is flanked by two anode assemblies. The lift system may be configured to selectively engage the anode and cathode assemblies so as to allow the simultaneous lifting of any combination of the anode and cathode assemblies (whether adjacent or non-adjacent).

Investigation of a chemically regenerative redox cathode polymer electrolyte fuel cell using a phosphomolybdovanadate polyoxoanion catholyte

NASA Astrophysics Data System (ADS)

Gunn, Natasha L. O.; Ward, David B.; Menelaou, Constantinos; Herbert, Matthew A.; Davies, Trevor J.

2017-04-01

Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells (PEFCs), where the direct reduction of oxygen is replaced by an in-direct mechanism occurring outside of the cell, are attractive to study as they offer a solution to the cost and durability problems faced by conventional PEFCs. This study reports the first detailed characterization of a high performance complete CRRC PEFC system, where catholyte is circulated between the cathode side of the cell and an air-liquid oxidation reactor called the "regenerator". The catholyte is an aqueous solution of phosphomolybdovanadate polyoxoanion and is assessed in terms of its performance within both a small single cell and corresponding regenerator over a range of redox states. Two methods for determining regeneration rate are proposed and explored. Expressing the regeneration rate as a "chemical" current is suggested as a useful means of measuring re-oxidation rate with respect to the cell. The analysis highlights the present limitations to the technology and provides an indication of the maximum power density achievable, which is highly competitive with conventional PEFC systems.

Enhancing Electrode Performance by Exsolved Nanoparticles: A Superior Cobalt-Free Perovskite Electrocatalyst for Solid Oxide Fuel Cells.

PubMed

Yang, Guangming; Zhou, Wei; Liu, Meilin; Shao, Zongping

2016-12-28

The successful development of low-cost, durable electrocatalysts for oxygen reduction reaction (ORR) at intermediate temperatures is critical for broad commercialization of solid oxide fuel cells. Here, we report our findings in design, fabrication, and characterization of a cobalt-free SrFe 0.85 Ti 0.1 Ni 0.05 O 3-δ cathode decorated with NiO nanoparticles. Exsolved from and well bonded to the parent electrode under well-controlled conditions, the NiO nanoparticles uniformly distributed on the surface of the parent electrode greatly enhance cathode performance, demonstrating ORR activity better than that of the benchmark cobalt-based Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ . Further, a process for regeneration of the NiO nanoparticles was also developed to mitigate potential performance degradation due to coarsening of NiO particles under practical operating conditions. As a general approach, this exsolution-dissolution of electrocatalytically active nanoparticles on an electrode surface may be applicable to the development of other high-performance cobalt-free cathodes for fuel cells and other electrochemical systems.

Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

PubMed Central

Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

2016-01-01

Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945

Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

PubMed

Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

2010-12-14

Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Cell design concepts for aqueous lithium-oxygen batteries: A model-based assessment

NASA Astrophysics Data System (ADS)

Grübl, Daniel; Bessler, Wolfgang G.

2015-11-01

Seven cell design concepts for aqueous (alkaline) lithium-oxygen batteries are investigated using a multi-physics continuum model for predicting cell behavior and performance in terms of the specific energy and specific power. Two different silver-based cathode designs (a gas diffusion electrode and a flooded cathode) and three different separator designs (a porous separator, a stirred separator chamber, and a redox-flow separator) are compared. Cathode and separator thicknesses are varied over a wide range (50 μm-20 mm) in order to identify optimum configurations. All designs show a considerable capacity-rate effect due to spatiotemporally inhomogeneous precipitation of solid discharge product LiOH·H2O. In addition, a cell design with flooded cathode and redox-flow separator including oxygen uptake within the external tank is suggested. For this design, the model predicts specific power up to 33 W/kg and specific energy up to 570 Wh/kg (gravimetric values of discharged cell including all cell components and catholyte except housing and piping).

The hemoglobin system of the serpent eel Ophisurus serpens: structural and functional characterization.

PubMed

Manconi, Barbara; Pellegrini, Mariagiuseppina; Messana, Irene; Sanna, Maria Teresa; Castagnola, Massimo; Iavarone, Federica; Coluccia, Elisabetta; Giardina, Bruno; Olianas, Alessandra

2013-10-01

The hemoglobin system of the serpent eel Ophisurus serpens was structurally and functionally characterized with the aim of comparing it to the hemoglobin system of other fish species, as oxygen loading under the severe habitat conditions experienced by O. serpens could have necessitated specific adaptation mechanisms during evolution. The hemoglobin system of O. serpens includes one cathodic and four anodic components. The molecular mass of the α and β chains of the cathodic component as well as the 2 α and 4 β of the anodic components were determined. Analysis of the intact α and β chains from cathodic hemoglobin and their proteolytic digestion products by high-resolution MS and MS/MS experiments resulted in 92 and 95 % sequence coverage of the α and β globins, respectively. The oxygen binding properties of both hemoglobin components were analyzed with respect to their interactions with their physiological effectors. Stripped cathodic hemoglobin displayed the highest oxygen affinity among Anguilliformes with no significant effect of pH on O2-affinity. In the presence of both chloride and organic phosphates, O2-affinity was strongly reduced, and cooperativity was enhanced; moreover, cathodic hemoglobin contains two indistinguishable GTP-binding sites. Stripped anodic hemoglobins exhibited both low O2-affinity and low cooperativity and a larger Bohr effect than cathodic hemoglobin. The cathodic hemoglobin of O. serpens and the corresponding component of Conger conger share the greatest structural and functional similarity among hemoglobin systems of Anguilliformes studied to date, consistent with their phylogenetic relationship.

A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

PubMed

Abirami, Mari; Hwang, Soo Min; Yang, Juchan; Senthilkumar, Sirugaloor Thangavel; Kim, Junsoo; Go, Woo-Seok; Senthilkumar, Baskar; Song, Hyun-Kon; Kim, Youngsik

2016-12-07

Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn 3 [Co(CN) 6 ] 2 ·nH 2 O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g -1 hard carbon during 100 cycles (energy efficiencies of 74-79%).

Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

DOEpatents

Chen, Fanglin; Wang, Yao

2017-02-21

Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

Oxygen-hydrogen fuel cell with an iodine-iodide cathode - A concept

NASA Technical Reports Server (NTRS)

Javet, P.

1970-01-01

Fuel cell uses a porous cathode through which is fed a solution of iodine in aqueous iodide solution, the anode is a hydrogen electrode. No activation polarization appears on the cathode because of the high exchange-current density of the iodine-iodide electrode.

A simple biofuel cell cathode with human red blood cells as electrocatalysts for oxygen reduction reaction.

PubMed

Ayato, Yusuke; Sakurai, Kenichiro; Fukunaga, Saori; Suganuma, Takuya; Yamagiwa, Kiyofumi; Shiroishi, Hidenobu; Kuwano, Jun

2014-05-15

A red blood cell (RBC) from human exhibited direct electron transfer (DET) activity on a bare indium tin oxide (ITO) electrode. A formal potential of -0.152 V vs. a silver-silver chloride saturated potassium chloride (Ag|AgCl|KCl(satd.)) was estimated for the human RBC (type AB) from a pair of redox peaks at around 0.089 and -0.215 V (vs. Ag|AgCl|KCl(satd.)) on cyclic voltammetric (CV) measurements in a phosphate buffered saline (PBS; 39 mM; pH 7.4) solution. The results agreed well with those of a redox couple for iron-bearing heme groups in hemoglobin molecules (HbFe(II)/HbFe(III)) on the bare ITO electrodes, indicated that DET active species were hemoglobin (Hb) molecules encapsulated by a phospholipid bilayer membrane of the human RBC. The quantity of electrochemically active Hb in the human RBC was estimated to be 30 pmol cm(-2). In addition, the human RBC exhibited oxygen reduction reaction (ORR) activity in the dioxygen (O2) saturated PBS solution at the negative potential from ca. -0.15 V (vs. Ag|AgCl|KCl(satd.)). A single cell test proved that a biofuel cell (BFC) with an O2|RBC|ITO cathode showed the open-circuit voltage (OCV) of ca. 0.43 V and the maximum power density of ca. 0.68 μW cm(-2). © 2013 Published by Elsevier B.V.

Aluminum reduction cell electrode

DOEpatents

Payne, J.R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces. 10 figs.

Aluminum reduction cell electrode

DOEpatents

Payne, John R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces.

Cathode architectures for alkali metal / oxygen batteries

DOEpatents

Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

2015-01-13

Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

2017-09-01

Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Carbon-containing cathodes for enhanced electron emission

DOEpatents

Cao, Renyu; Pan, Lawrence; Vergara, German; Fox, Ciaran

2000-01-01

A cathode has electropositive atoms directly bonded to a carbon-containing substrate. Preferably, the substrate comprises diamond or diamond-like (sp.sup.3) carbon, and the electropositive atoms are Cs. The cathode displays superior efficiency and durability. In one embodiment, the cathode has a negative electron affinity (NEA). The cathode can be used for field emission, thermionic emission, or photoemission. Upon exposure to air or oxygen, the cathode performance can be restored by annealing or other methods. Applications include detectors, electron multipliers, sensors, imaging systems, and displays, particularly flat panel displays.

Nitrogen and Phosphorus Codoped Mesoporous Carbon Derived from Polypyrrole as Superior Metal-Free Electrocatalyst toward the Oxygen Reduction Reaction.

PubMed

Zhang, Zhengping; Sun, Junting; Dou, Meiling; Ji, Jing; Wang, Feng

2017-05-17

To replace high-cost platinum group metal (PGM) electrocatalysts for oxygen reduction reaction (ORR) that is the crucial cathode reaction in fuel cell technology and metal-air battery, the development of low-cost and high-efficiency non-PGM catalysts for ORR has attracted much attention during the past decades. As one of the promising candidates, N-doped carbon is highly desirable for its strong designability and outstanding catalytic activity and stability. In this work, a facile and rational strategy is demonstrated for preparation of N,P-codoped mesoporous carbon (N,P-MC) for ORR by the direct pyrolysis treatment of polypyrrole with phytic acid as P-dopant and polystyrene sphere as template. The resultant N,P-MC exhibits a mesoporous structure with the optimized ORR active sites originating from the N,P-codoping. Owing to these features, N,P-MC exhibits excellent ORR activity, remarkable electrochemical stability, and superior methanol tolerance, comparable or even better than that of commercial Pt/C catalyst. The origin of enhanced ORR performance can be attributed to both the increased active sites and the mesoporous structure, which is expected to guide the future preparation of more capable carbon-based electrocatalysts for oxygen reduction and other electrocatalytic application.

Decolorizing textile wastewater with Fenton's reagent electrogenerated with a solar photovoltaic cell.

PubMed

Figueroa, Sandra; Vázquez, Leticia; Alvarez-Gallegos, A

2009-02-01

In this work it is demonstrated that Fenton's reagent can be electroproduced with abundant and cheap feedstock: oxygen saturated wastewater and solar energy. Experiments were carried out in a divided electrochemical flow cell using two electrodes: a three dimensional reticulated vitreous carbon cathode and stainless steel anode. Fenton's reagent is produced by oxygen reduction on the cathode in the presence of 1mM Fe(2+). The influence of electrolyte nature and its concentration and potential difference on the current efficiency, as well as the rate of Fenton's reagent electroproduction is discussed and it is concluded that over this extended range of conditions the current efficiency, for Fenton's reagent production, fell within the range 50-70%. It is possible to electroproduce a stoichiometric amount of Fenton reagent for the oxidation of 0.061mM Reactive Black 5 (in tap water+0.05M Na(2)SO(4), approximately pH 2.8). Similar results were obtained for solutions containing 0.1mM Acid Green 25. Some practical applications in the field of water treatment are included. The energy required for drive electrochemical reaction is supplied to the flow cell by means of a commercial solar panel.

In situ growth of NiFe alloy nanoparticles embedded into N-doped bamboo-like carbon nanotube as a bifunctional electrocatalyst for Zn-air battery.

PubMed

Bin, Duan; Yang, Beibei; Li, Chao; Liu, Yao; Zhang, Xiao; Wang, Yong-Gang; Xia, Yongyao

2018-06-26

Developing low-cost catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with superior performance in alkaline solution is of significance for large-scale application in aqueous zinc-air batteries (ZABs). Herein, we describe in situ design of embedded NiFe nanoparticles into the N-doped bamboo-like carbon nanotube (NBCNT) with high catalytic performance and stability. The obtained NiFe@NBCNT hybrid exhibits a high electrochemical activity and stability with an unexpectedly low overpotential of ~195 mV for OER at 10 mA cm-2, and an onset potential at 1.03 V for ORR, superior to the state-of-the-art Pt/C and RuO2 catalysts. Additionally, compared to the mixture Pt/C and RuO2 cathode, the ZAB based on the NiFe@NBCNT cathode displays lower overpotential (0.80 V), higher stable round-trip efficiency (58.3%) and improved power density for 200 cycles at 10 mA cm-2. Apparently, the obtained results indicate that NiFe@NBCNT hybird is proven to be one of the best non-noble metal catalysts for achieving commercial implementation of rechargeable ZABs.

Overcoming bottlenecks of enzymatic biofuel cell cathodes: crude fungal culture supernatant can help to extend lifetime and reduce cost.

PubMed

Sané, Sabine; Jolivalt, Claude; Mittler, Gerhard; Nielsen, Peter J; Rubenwolf, Stefanie; Zengerle, Roland; Kerzenmacher, Sven

2013-07-01

Enzymatic biofuel cells (BFCs) show great potential for the direct conversion of biochemically stored energy from renewable biomass resources into electricity. However, enzyme purification is time-consuming and expensive. Furthermore, the long-term use of enzymatic BFCs is hindered by enzyme degradation, which limits their lifetime to only a few weeks. We show, for the first time, that crude culture supernatant from enzyme-secreting microorganisms (Trametes versicolor) can be used without further treatment to supply the enzyme laccase to the cathode of a mediatorless BFC. Polarization curves show that there is no significant difference in the cathode performance when using crude supernatant that contains laccase compared to purified laccase in culture medium or buffer solution. Furthermore, we demonstrate that the oxygen reduction activity of this enzymatic cathode can be sustained over a period of at least 120 days by periodic resupply of crude culture supernatant. This is more than five times longer than control cathodes without the resupply of culture supernatant. During the operation period of 120 days, no progressive loss of potential is observed, which suggests that significantly longer lifetimes than shown in this work may be possible. Our results demonstrate the possibility to establish simple, cost efficient, and mediatorless enzymatic BFC cathodes that do not require expensive enzyme purification procedures. Furthermore, they show the feasibility of an enzymatic BFC with an extended lifetime, in which self-replicating microorganisms provide the electrode with catalytically active enzymes in a continuous or periodic manner. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium-Air Cell Development

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Dobley, Arthur; Seymour, Frasier W.

2014-01-01

Lithium-air (Li-air) primary batteries have a theoretical specific capacity of 11,400 Wh/kg, the highest of any common metal-air system. NASA is developing Li-air technology for a Mobile Oxygen Concentrator for Spacecraft Emergencies, an application which requires an extremely lightweight primary battery that can discharge over 24 hours continuously. Several vendors were funded through the NASA SBIR program to develop Li-air technology to fulfill the requirements of this application. New catalysts and carbon cathode structures were developed to enhance the oxygen reduction reaction and increase surface area to improve cell performance. Techniques to stabilize the lithium metal anode surface were explored. Experimental results for prototype laboratory cells are given. Projections are made for the performance of hypothetical cells constructed from the materials that were developed.

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

NASA Astrophysics Data System (ADS)

Navessin, Titichai

2005-07-01

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

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Microbial fuel cells

DOEpatents

Nealson, Kenneth H; Pirbazari, Massoud; Hsu, Lewis

2013-04-09

A microbial fuel cell includes an anode compartment with an anode and an anode biocatalyst and a cathode compartment with a cathode and a cathode biocatalyst, with a membrane positioned between the anode compartment and the cathode compartment, and an electrical pathway between the anode and the cathode. The anode biocatalyst is capable of catalyzing oxidation of an organic substance, and the cathode biocatalyst is capable of catalyzing reduction of an inorganic substance. The reduced organic substance can form a precipitate, thereby removing the inorganic substance from solution. In some cases, the anode biocatalyst is capable of catalyzing oxidation of an inorganic substance, and the cathode biocatalyst is capable of catalyzing reduction of an organic or inorganic substance.

Promoting formation of noncrystalline Li2O2 in the Li-O2 battery with RuO2 nanoparticles.

PubMed

Yilmaz, Eda; Yogi, Chihiro; Yamanaka, Keisuke; Ohta, Toshiaki; Byon, Hye Ryung

2013-10-09

Low electrical efficiency for the lithium-oxygen (Li-O2) electrochemical reaction is one of the most significant challenges in current nonaqueous Li-O2 batteries. Here we present ruthenium oxide nanoparticles (RuO2 NPs) dispersed on multiwalled carbon nanotubes (CNTs) as a cathode, which dramatically increase the electrical efficiency up to 73%. We demonstrate that the RuO2 NPs contribute to the formation of poorly crystalline lithium peroxide (Li2O2) that is coated over the CNT with large contact area during oxygen reduction reaction (ORR). This unique Li2O2 structure can be smoothly decomposed at low potential upon oxygen evolution reaction (OER) by avoiding the energy loss associated with the decomposition of the more typical Li2O2 structure with a large size, small CNT contact area, and insulating crystals.

Membrane electrode assembly fabricated with the combination of Pt/C and hollow shell structured-Pt-SiO2@ZrO2 sphere for self-humidifying proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Ko, Y. D.; Yang, H. N.; Züttel, Andreas; Kim, S. D.; Kim, W. J.

2017-11-01

The Pt-supported hollow structured Pt-HZrO2 with the shell thickness of 27 nm is successfully synthesized. The water retention ability of Pt-HZrO2 is significantly enhanced compared with that of SiO2@ZrO2 due to the hydrophilic hollow structured HZrO2with high BET surface area. Pt-C and Pt-HZrO2 are combined with different weight fractions to prepare the double catalyst electrode (DCE). The membrane electrode assembly with the DCE is fabricated and applied to both anode and cathode or anode side only. The water flooding and thus rapid voltage drop is affected by the presence/or absence of the DCE at the cathode side. The cell test and visual experiment suggests that the Pt-HZrO2 layer adsorb the water molecules generated by the oxygen reduction reaction (ORR), preventing the water flooding. The power generation under RH 0% strongly suggests the back-diffusion of water molecules generated by the ORR. The flow rate to the cathode significantly affects the water flooding and cell performance. Higher flow rate to the cathode is advantageous to expel the water generated by the ORR, thus preventing water flooding and enhancing the cell performance. Therefore, the weight fraction of Pt-C to Pt-HZrO2 and the flow rate to the cathode should be well balanced.

Electrodeposited-film electrodes derived from a precursor dinitrosyl iron complex for electrocatalytic water splitting.

PubMed

Li, Wei-Liang; Chiou, Tzung-Wen; Chen, Chien-Hong; Yu, Yi-Ju; Chu, Li-Kang; Liaw, Wen-Feng

2018-05-29

In artificial photosynthesis, water splitting plays an important role for the conversion and storage of renewable energy sources. Here, we report a study on the electrocatalytic properties of the electrodeposited-film electrodes derived from irreversible electro-reduction/-oxidation of a molecular dinitrosyl iron complex (DNIC) {Fe(NO)2}9 [(Me6tren)Fe(NO)2]+ (Me6tren = tris[2-(dimethylamino)ethyl]amine) for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solution, individually. For HER, the overpotential and Tafel slope for the electrodeposited-film cathode are lower than those of the equiv.-weight Pt/C electrode. The electrodeposited-film anode for the OER is stable for 139 h. Integration of the electrodeposited-film cathode and anode into a single electrode-pair device for electrocatalytic water splitting exhibits an onset voltage of 1.77 V, achieving a geometrical current density of 10 mA cm-2.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

PubMed Central

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-01-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries. PMID:28393912

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-04-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

PubMed

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2017-04-10

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

PubMed

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Effect of Si on DC arc plasma generation from Al-Cr and Al-Cr-Si cathodes used in oxygen

NASA Astrophysics Data System (ADS)

Zhirkov, I.; Landälv, L.; Göthelid, E.; Ahlgren, M.; Eklund, P.; Rosen, J.

2017-02-01

Al2O3 alloyed with Cr is an important material for the tooling industry. It can be synthesized from an arc discharge using Al-Cr cathodes in an oxygen atmosphere. Due to formation of Al-rich oxide islands on the cathode surface, the arc process stability is highly sensitive to oxygen pressure. For improved stability, the use of Al0.70Cr0.25Si0.05 cathodes has previously been suggested, where Si may reduce island formation. Here, we have investigated the effect of Si by comparing plasma generation and thin film deposition from Al0.7Cr0.3 and Al0.7Cr0.25Si0.05 cathodes. Plasma ion composition, ion energies, ion charge states, neutral species, droplet formation, and film composition have been characterized at different O2 flow rates for arc currents of 60 and 90 A. Si and related compounds are detected in plasma ions and in plasma neutrals. Scanning electron microscopy and energy dispersive X-ray analysis show that the cathode composition and the film composition are the same, with Si present in droplets as well. The effect of Si on the process stability, ion energies, and ion charge states is found to be negligible compared to that of the arc current. The latter is identified as the most relevant parameter for tuning the properties of the reactive discharge. The present work increases the fundamental understanding of plasma generation in a reactive atmosphere, and provides input for the choice of cathode composition and process parameters in reactive DC arc synthesis.

Influence of Pr6O11 on oxygen electroreduction kinetics and electrochemical performance of Sr2Fe1.5Mo0.5O6-δ based cathode

NASA Astrophysics Data System (ADS)

Osinkin, D. A.; Beresnev, S. M.; Bogdanovich, N. M.

2018-07-01

Oxygen electroreduction kinetics and electrochemical performance of the Pr6O11-impregnated Sr2Fe1.5Mo0.5O6-δ - Ce0.8Sm0.2O1.9 (SFM-SDC) cathode have been first studied. By means of distribution of relaxation times and non-linear least squares analysis of impedance spectra were shown that the addition of Pr6O11 into the cathode leads to the increase in the rate of the low-frequency step. It is suggested that the observed phenomenon is associated with the increase in the rate of surface oxygen exchange. It is shown that the introduction of praseodymium oxide into the cathode results in a decrease in the area specific polarization resistances of the cathode at equilibrium potentials from 0.23 to 0.06 Ω cm2 at 800 °C in air. The maximum power density of symmetrical solid oxide fuel cell (SOFC) with impregnated SFM-SDC electrodes and supporting 760 μm La0.85Sr0.15Ga0.85Mg0.15O3-δ electrolyte without buffer/barrier and collector layers under air/wet hydrogen (dry CH4) condition was about 0.5 (0.26) W cm-2 at 800 °C. The overvoltage of the cathode was higher than that of the anode under air/wet hydrogen and vice versa when methane was supplied to the anode. The obtained results elucidate that the impregnated SFM-SDC is a promising cathode for SOFC application.

Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

PubMed Central

Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

2016-01-01

A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries. PMID:27074882

Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

NASA Astrophysics Data System (ADS)

Zhan, Chun; Yao, Zhenpeng; Lu, Jun; Ma, Lu; Maroni, Victor A.; Li, Liang; Lee, Eungje; Alp, Esen E.; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Johnson, Christopher; Thackeray, Michael M.; Chan, Maria K. Y.; Wolverton, Chris; Amine, Khalil

2017-12-01

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.

1984-01-01

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Electrochemical characterisation of air electrodes based on La 0.6Sr 0.4CoO 3 and carbon nanotubes

NASA Astrophysics Data System (ADS)

Thiele, Doreen; Züttel, Andreas

The efficiency of fuel cells suffers from the high activation polarisation at the cathode, where the oxygen reduction reaction takes place. In order to improve the performance, air electrodes composed of carbon nanotubes (CNTs) and the perovskite La 0.6Sr 0.4CoO 3 are produced by two different methods and investigated. In the first method CNTs are directly grown on the perovskite and in the second method CNTs and perovskite are combined by ultrasonic mixing. Their catalytic activity towards oxygen reduction in alkaline solution is evaluated by polarisation curves and electrochemical impedance spectroscopy. Best performance shows the electrode composed of 25 wt% CNTs, 55 wt% La 0.6Sr 0.4CoO 3 and 20 wt% PTFE as binder, produced by ultrasonic mixing. The Nyquist plot of this electrode displays two potential-dependent semi-circles, accounting for processes on the catalyst surface and for processes depending on the morphology of the electrode.

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

PubMed

Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

2017-03-08

Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe 3 O 4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

A highly active hybrid catalyst modified (La0.60Sr0.40)0.95Co0.20Fe0.80O3-δ cathode for proton conducting solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lei, Libin; Tao, Zetian; Hong, Tao; Wang, Xiaoming; Chen, Fanglin

2018-06-01

The sluggish reaction kinetics in the cathode usually leads to considerable cathode polarization resistance, hindering the development of proton conducting solid oxide fuel cells (H-SOFCs) operated at intermediate temperatures (400-650 °C). To address this problem, for the first time, a novel hybrid catalyst consisting of PrNi0.5Mn0.5O3 and PrOx is impregnated in the (La0.60Sr0.40)0.95Co0.20Fe0.80O3-δ (LSCF) cathode of H-SOFCs, resulting in significant enhancement of the cathode reaction kinetics. Single cells with impregnated LSCF cathode and BaZr0.8Y0.2O3 (BZY) electrolyte yield a maximum power density (MPD) of 0.198 W cm-2 at 600 °C, more than doubled of that with blank LSCF cathode (0.083 W cm-2). ECR and EIS studies reveal that the hybrid catalyst can substantially accelerate the oxygen-ion transfer and oxygen dissociation-absorption processes in the cathode, resulting in significantly lower polarization resistance and higher MPD. In addition, the hybrid catalyst possesses good chemical and microstructural stability at 600 °C. Consequently, the single cells with impregnated LSCF cathode show excellent durability. This study shows that the impregnation of this novel hybrid catalyst in the cathode could be a promising approach to improve the performance and stability of H-SOFCs.

Surface-Selective Preferential Production of Reactive Oxygen Species on Piezoelectric Ceramics for Bacterial Killing.

PubMed

Tan, Guoxin; Wang, Shuangying; Zhu, Ye; Zhou, Lei; Yu, Peng; Wang, Xiaolan; He, Tianrui; Chen, Junqi; Mao, Chuanbin; Ning, Chengyun

2016-09-21

Reactive oxygen species (ROS) can be used to kill bacterial cells, and thus the selective generation of ROS from material surfaces is an emerging direction in antibacterial material discovery. We found the polarization of piezoelectric ceramic causes the two sides of the disk to become positively and negatively charged, which translate into cathode and anode surfaces in an aqueous solution. Because of the microelectrolysis of water, ROS are preferentially formed on the cathode surface. Consequently, the bacteria are selectively killed on the cathode surface. However, the cell experiment suggested that the level of ROS is safe for normal mammalian cells.

Metal-air cells comprising collapsible foam members and means for minimizing internal pressure buildup

NASA Technical Reports Server (NTRS)

Putt, Ronald A. (Inventor); Woodruff, Glenn (Inventor)

1994-01-01

This invention provides a prismatic zinc-air cell including, in general, a prismatic container having therein an air cathode, a separator and a zinc anode. The container has one or more oxygen access openings, and the air cathode is disposed in the container in gaseous communication with the oxygen access openings so as to allow access of oxygen to the cathode. The separator has a first side in electrolytic communication with the air cathode and a second side in electrolytic communication with the zinc anode. The separator isolates the cathode and the zinc anode from direct electrical contact and allows passage of electrolyte therebetween. An expansion chamber adjacent to the zinc anode is provided which accommodates expansion of the zinc anode during discharge of the cell. A suitable collapsible foam member generally occupies the expansion space, providing sufficient resistance tending to oppose movement of the zinc anode away from the separator while collapsing upon expansion of the zinc anode during discharge of the cell. One or more vent openings disposed in the container are in gaseous communication with the expansion space, functioning to satisfactorily minimize the pressure buildup within the container by venting gasses expelled as the foam collapses during cell discharge.

In-situ time-of-flight neutron diffraction study of the structure evolution of electrode materials in a commercial battery with LiNi0.8Co0.15Al0.05O2 cathode

NASA Astrophysics Data System (ADS)

Bobrikov, I. A.; Samoylova, N. Yu.; Sumnikov, S. V.; Ivanshina, O. Yu.; Vasin, R. N.; Beskrovnyi, A. I.; Balagurov, A. M.

2017-12-01

A commercial lithium-ion battery with LiNi0.8Co0.15Al0.05O2 (NCA) cathode has been studied in situ using high-intensity and high-resolution neutron diffraction. Structure and phase composition of the battery electrodes have been probed during charge-discharge in different cycling modes. The dependence of the anode composition on the charge rate has been determined quantitatively. Different kinetics of Li (de)intercalation in the graphite anode during charge/discharge process have been observed. Phase separation of the cathode material has not been detected in whole voltage range. Non-linear dependencies of the unit cell parameters, atomic and layer spacing on the lithium content in the cathode have been observed. Measured dependencies of interatomic spacing and interlayer spacing, and unit cell parameters of the cathode structure on the lithium content could be qualitatively explained by several factors, such as variations of oxidation state of cation in oxygen octahedra, Coulomb repulsion of oxygen layers, changes of average effective charge of oxygen layers and van der Waals interactions between MeO2-layers at high level of the NCA delithiation.

Controllable Electrochemical Fabrication of KO2-Decorated Binder-Free Cathodes for Rechargeable Lithium-Oxygen Batteries.

PubMed

Yu, Wei; Wang, Huwei; Qin, Lei; Hu, Junyang; Liu, Liang; Li, Baohua; Zhai, Dengyun; Kang, Feiyu

2018-05-23

Understanding the electrochemical property of superoxides in alkali metal oxygen batteries is critical for the design of a stable oxygen battery with high capacity and long cycle performance. In this work, a KO 2 -decorated binder-free cathode is fabricated by a simple and efficient electrochemical strategy. KO 2 nanoparticles are uniformly coated on the carbon nanotube film (CNT-f) through a controllable discharge process in the K-O 2 battery, and the KO 2 -decorated CNT-f is innovatively introduced into the Li-O 2 battery as the O 2 diffusion electrode. The Li-O 2 battery based on the KO 2 -decorated CNT-f cathode can deliver enhanced discharge capacity, reduced charge overpotential, and more stable cycle performance compared with the battery in the absence of KO 2 . In situ formed KO 2 particles on the surface of CNT-f cathode assist to form Li 2 O 2 nanosheets in the Li-O 2 battery, which contributes to the improvement of discharge capacity and cycle life. Interestingly, the analysis of KO 2 -decorated CNT-f cathodes, after discharge and cycle tests, reveals that the electrochemically synthesized KO 2 seems not a conventional electrocatalyst but a partially dissolvable and decomposable promoter in Li-O 2 batteries.

CuCr2O4@rGO Nanocomposites as High-Performance Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries

NASA Astrophysics Data System (ADS)

Liu, Jiandi; Zhao, Yanyan; Li, Xin; Wang, Chunge; Zeng, Yaping; Yue, Guanghui; Chen, Qiang

2018-06-01

Rechargeable lithium-oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium-oxygen batteries (LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component. Hence, we aim to demonstrate that CuCr2O4@rGO (CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 200 mA g-1. The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.[Figure not available: see fulltext.

Microscale measurements of oxygen concentration across the thickness of diffusion media in operating polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Epting, William K.; Litster, Shawn

2016-02-01

Although polymer electrolyte fuel cells (PEFCs) offer promise as efficient, low emission power sources, the large amount of platinum catalyst used for the cathode's oxygen reduction (ORR) results in high costs. One approach to using less Pt is to increase the oxygen concentration at the catalyst by reducing the oxygen transport resistances. An important resistance is that of the diffusion media (DM). The DM are highly heterogeneous porous carbon fiber substrates with a graded composition of additives across their thickness. In this work we use an oxygen microsensor with a micro-positioning system to measure the oxygen concentration and presence of liquid water in the pores at discrete points across the thickness of a commercial carbon felt DM in operating PEFCs. Under conditions with no liquid water, the DM accounts for 60% of the oxygen depletion, with 60-70% of that depletion being due to the thin microporous layer (MPL) on the catalyst layer (CL) side. Using concentration gradient data, we quantify the non-uniform local transport resistance across the DM and relate it to high resolution 3D X-ray computed tomography of the same DM.

Increasing the Energy Efficiency of Aluminum-Reduction Cells Using Modified Cathodes

NASA Astrophysics Data System (ADS)

Jianping, Peng; Yang, Song; Yuezhong, Di; Yaowu, Wang; Naixiang, Feng

2017-10-01

A cathode with an inclined surface (5°) and increased bar collector height (230 mm high) was incorporated into two 300-kA industrial aluminum-reduction cells. The voltage of the cells with the modified cathode was reduced by approximately 200 mV when compared with that of a conventional cell with a flat cathode. Through the use of simulations, the reduction in the cell voltage was attributed to the cathode modification (40 mV) and a reduced electrolyte level of 0.5 cm (160 mV). As a result of reduced anode cathode distance (ACD), the ledge toe was extended to the anode shadow by 12 cm. This caused a large inverted horizontal current and a velocity increase. The ledge profile returned to the desired position when the cells were insulated more effectively, and the metal velocity and metal crest in the modified cells were reduced accordingly.

Effect of Gas Pressure on Polarization of SOFC Cathode Prepared by Plasma Spray

NASA Astrophysics Data System (ADS)

Li, Cheng-Xin; Wang, Zhun-Zhun; Liu, Shuai; Li, Chang-Jiu

2013-06-01

A cermet-supported tubular SOFC was fabricated using thermal spray. The cell performance was investigated at temperatures from 750 to 900 °C and pressures from 0.1 to 0.5 MPa to examine the effect of operating gas pressure on the cell performance. The influence of gas pressure on the cathodic polarization was studied through the electrochemical impedance approach to examine the controlling electrochemical processes during cell operation. Results show that increasing the operating gas pressure improves the power output performance significantly. When the gas pressure is increased from 0.1 to 0.3 MPa, the maximum power density is increased by a factor of 32% at a temperature of 800 °C. The cathode polarization decreases significantly with the increase of the gas pressure. The electrochemical analysis shows that the main control processes of the cathode reaction are the oxygen species transfer at the three-phase boundary and oxygen diffusion on the surface or in the bulk of the cathode, which are enhanced with increasing gas pressure.

Defect Chemistry, Electrical Properties, and Evaluation of New Oxides Sr2 CoNb1-x Tix O6-δ (0≤x≤1) as Cathode Materials for Solid Oxide Fuel Cells.

PubMed

Azcondo, María Teresa; Yuste, Mercedes; Pérez-Flores, Juan Carlos; Muñoz-Gil, Daniel; García-Martín, Susana; Muñoz-Noval, Alvaro; Orench, Inés Puente; García-Alvarado, Flaviano; Amador, Ulises

2017-07-21

The perovskite series Sr 2 CoNb 1-x Ti x O 6-δ (0≤x≤1) was investigated in the full compositional range to assess its potential as cathode material for solid oxide fuel cell (SOFC). The variation of transport properties and thus, the area specific resistances (ASR) are explained by a detailed investigation of the defect chemistry. Increasing the titanium content from x=0-1 produces both oxidation of Co 3+ to Co 4+ (from 0 up to 40 %) and oxygen vacancies (from 6.0 to 5.7 oxygen atom/formula unit), although each charge compensation mechanism predominates in different compositional ranges. Neutron diffraction reveals that samples with high Ti-contents lose a significant amount of oxygen upon heating above 600 K. Oxygen is partially recovered upon cooling as the oxygen release and uptake show noticeably different kinetics. The complex defect chemistry of these compounds, together with the compositional changes upon heating/cooling cycles and atmospheres, produce a complicated behavior of electrical conductivity. Cathodes containing Sr 2 CoTiO 6-δ display low ASR values, 0,13 Ω cm 2 at 973 K, comparable to those of the best compounds reported so far, being a very promising cathode material for SOFC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elucidating anionic oxygen activity in lithium-rich layered oxides

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

Xu, Jing; Sun, Meiling; Qiao, Ruimin

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

Elucidating anionic oxygen activity in lithium-rich layered oxides

DOE PAGES

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

2018-03-05

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

Predicting the Oxygen-Binding Properties of Platinum Nanoparticle Ensembles by Combining High-Precision Electron Microscopy and Density Functional Theory.

PubMed

Aarons, Jolyon; Jones, Lewys; Varambhia, Aakash; MacArthur, Katherine E; Ozkaya, Dogan; Sarwar, Misbah; Skylaris, Chris-Kriton; Nellist, Peter D

2017-07-12

Many studies of heterogeneous catalysis, both experimental and computational, make use of idealized structures such as extended surfaces or regular polyhedral nanoparticles. This simplification neglects the morphological diversity in real commercial oxygen reduction reaction (ORR) catalysts used in fuel-cell cathodes. Here we introduce an approach that combines 3D nanoparticle structures obtained from high-throughput high-precision electron microscopy with density functional theory. Discrepancies between experimental observations and cuboctahedral/truncated-octahedral particles are revealed and discussed using a range of widely used descriptors, such as electron-density, d-band centers, and generalized coordination numbers. We use this new approach to determine the optimum particle size for which both detrimental surface roughness and particle shape effects are minimized.

Improved cell for water-vapor electrolysis

NASA Technical Reports Server (NTRS)

Aylward, J. R.

1981-01-01

Continuous-flow electrolytic cells decompose water vapor in steam and room air into hydrogen and oxygen. Sintered iridium oxide catalytic anode coating yields dissociation rates hundredfold greater than those obtained using platinum black. Cell consists of two mirror-image cells, with dual cathode sandwiched between two anodes. Gas traverses serpentine channels within cell and is dissociated at anode. Oxygen mingles with gas stream, while hydrogen migrates through porous matrix and is liberated as gas at cathode.

Faradaic reactions in capacitive deionization (CDI) - problems and possibilities: A review.

PubMed

Zhang, Changyong; He, Di; Ma, Jinxing; Tang, Wangwang; Waite, T David

2018-01-01

Capacitive deionization (CDI) is considered to be one of the most promising technologies for the desalination of brackish water with low to medium salinity. In practical applications, Faradaic redox reactions occurring in CDI may have both negative and positive effects on CDI performance. In this review, we present an overview of the types and mechanisms of Faradaic reactions in CDI systems including anodic oxidation of carbon electrodes, cathodic reduction of oxygen and Faradaic ion storage and identify their apparent negative and positive effects on water desalination. A variety of strategies including development of novel electrode materials and use of alternative configurations and/or operational modes are proposed for the purpose of mitigation or elimination of the deterioration of electrodes and the formation of byproducts caused by undesired side Faradaic reactions. It is also recognized that Faradaic reactions facilitate a variety of exciting new applications including i) the incorporation of intercalation electrodes to enhance water desalination or to selectively separate certain ions through reversible Faradaic reactions and ii) the use of particular anodic oxidation and cathodic reduction reactions to realize functions such as water disinfection and contaminant removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical Reduction of Dissolved Oxygen in Alkaline, Solid Polymer Electrolyte Films.

PubMed

Novitski, David; Kosakian, Aslan; Weissbach, Thomas; Secanell, Marc; Holdcroft, Steven

2016-11-30

Mass transport of oxygen through an ionomer contained within the cathode catalyst layer in an anion exchange membrane fuel cell is critical for a functioning fuel cell, yet is relatively unexplored. Moreover, because water is a reactant in the oxygen reduction reaction (ORR) in alkaline media, an adequate supply of water is required. In this work, ORR mass transport behavior is reported for methylated hexamethyl-p-terphenyl polymethylbenzimidazoles (HMT-PMBI), charge balanced by hydroxide ions (IEC from 2.1 to 2.5 mequiv/g), and commercial Fumatec FAA-3 membranes. Electrochemical mass transport parameters are determined by potential step chronoamperometry using a Pt microdisk solid-state electrochemical cell, in air at 60 °C, with relative humidity controlled between 70% and 98%. The oxygen diffusion coefficient (D bO2 ), oxygen concentration (c bO2 ), and oxygen permeability (D bO2 ·c bO2 ) were obtained by nonlinear curve fitting of the current transients using the Shoup-Szabo equation. Mass transport parameters are correlated to water content of the ionomer membrane. It is found that the oxygen diffusion coefficients decreased by 2 orders of magnitude upon reducing the water content of the ionomer membrane by lowering the relative humidity. The limitation of the Shoup-Szabo equation for extracting ORR mass transport parameters using thin ionomer films was evaluated by numerical modeling of the current transients, which revealed that a significant discrepancy (up to 29% under present conditions) was evident for highly hydrated membranes for which the oxygen diffusion coefficient was largest, and in which the oxygen depletion region reached the ionomer/gas interface during the chronoamperometric analysis.

Microbial fuel cells with highly active aerobic biocathodes

NASA Astrophysics Data System (ADS)

Milner, Edward M.; Popescu, Dorin; Curtis, Tom; Head, Ian M.; Scott, Keith; Yu, Eileen H.

2016-08-01

Microbial fuel cells (MFCs), which convert organic waste to electricity, could be used to make the wastewater infrastructure more energy efficient and sustainable. However, platinum and other non-platinum chemical catalysts used for the oxygen reduction reaction (ORR) at the cathode of MFCs are unsustainable due to their high cost and long-term degradation. Aerobic biocathodes, which use microorganisms as the biocatalysts for cathode ORR, are a good alternative to chemical catalysts. In the current work, high-performing aerobic biocathodes with an onset potential for the ORR of +0.4 V vs. Ag/AgCl were enriched from activated sludge in electrochemical half-cells poised at -0.1 and + 0.2 V vs. Ag/AgCl. Gammaproteobacteria, distantly related to any known cultivated gammaproteobacterial lineage, were identified as dominant in these working electrode biofilms (23.3-44.3% of reads in 16S rRNA gene Ion Torrent libraries), and were in very low abundance in non-polarised control working electrode biofilms (0.5-0.7%). These Gammaproteobacteria were therefore most likely responsible for the high activity of biologically catalysed ORR. In MFC tests, a high-performing aerobic biocathode increased peak power 9-fold from 7 to 62 μW cm-2 in comparison to an unmodified carbon cathode, which was similar to peak power with a platinum-doped cathode at 70 μW cm-2.

Hollow-spherical Co/N-C nanoparticle as an efficient electrocatalyst used in air cathode microbial fuel cell.

PubMed

Yang, Tingting; Li, Kexun; Pu, Liangtao; Liu, Ziqi; Ge, Baochao; Pan, Yajun; Liu, Ying

2016-12-15

The hollow-spherical Co/N-C nanoparticle, which is synthesized via a simple hydrothermal reaction followed by heat treatment, is firstly used as electrocatalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cell (MFC). The maximum power density of MFC with 10% Co/N-C air-cathode is as high as 2514±59mWm(-2), which is almost 174% higher than the control. The exchange current density (i0) of cathode equipped with 10% Co/N-C is 238% higher than that of untreated AC. While the total resistance of treated samples decreases from 13.017 to 10.255Ω. The intensity ratio of Raman D to G band (ID/IG) decreases from 0.93 (N-C) to 0.73 (Co/N-C), indicating the catalyst forms graphite structure. Both XRD and XPS testify that Co is bonded to N within graphitic sheets and serves as the active sites in ORR. The four-electron pathway of the Co/N-C also plays a crucial role in electrochemical catalytic activity. As a result, it can be expected that the as-synthesized Co/N-C, with extraordinary electro-catalytic performance towards ORR, will be a promising alternative to the state-of-the-art non-precious metal ORR electro-catalysts for electrochemical energy applications. Copyright © 2016 Elsevier B.V. All rights reserved.

An innovative architectural design to enhance the electrochemical performance of La2NiO4+δ cathodes for solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Sharma, Rakesh K.; Burriel, Mónica; Dessemond, Laurent; Martin, Vincent; Bassat, Jean-Marc; Djurado, Elisabeth

2016-06-01

An architectural design of the cathode microstructure based on combining electrostatic spray deposition (ESD) and screen-printing (SP) techniques has demonstrated to be an innovative strategy to enhance the electrochemical properties of La2NiO4+δ (LNO) as oxygen electrode on Ce0.9Gd0.1O2-δ (CGO) electrolyte for solid oxide fuel cells. For this purpose, the influence of the ESD process parameters on the microstructure has been systematically investigated. Electrochemical performances of four selected cathode microstructures are investigated: (i) 3-D coral nanocrystalline (average particle size ∼ 100 nm) LNO film grown by ESD; (ii) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) grown by ESD with a continuous nanometric dense interface; (iii) porous screen-printed LNO film (average particle size ∼ 400 nm); and (iv) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) with a continuous nanometric dense interface prepared by ESD topped by a LNO current collector prepared by SP. A significant reduction in the polarization resistance (Rpol) is obtained (0.08 Ω cm2 at 700 °C) for 3-D coral topped by the SP layer. Moreover LNO is found to be stable and compatible with CGO up to 800 °C for only 10 days duration in air, making it potentially suitable for SOFCs cathode application.

Bio-inspired Construction of Advanced Fuel Cell Cathode with Pt Anchored in Ordered Hybrid Polymer Matrix.

PubMed

Xia, Zhangxun; Wang, Suli; Jiang, Luhua; Sun, Hai; Liu, Shuang; Fu, Xudong; Zhang, Bingsen; Sheng Su, Dang; Wang, Jianqiang; Sun, Gongquan

2015-11-05

The significant use of platinum for catalyzing the cathodic oxygen reduction reactions (ORRs) has hampered the widespread use of polymer electrolyte membrane fuel cells (PEMFCs). The construction of well-defined electrode architecture in nanoscale with enhanced utilization and catalytic performance of Pt might be a promising approach to address such barrier. Inspired by the highly efficient catalytic processes in enzymes with active centers embedded in charge transport pathways, here we demonstrate for the first time a design that allocates platinum nanoparticles (Pt NPs) at the boundaries with dual-functions of conducting both electrons by aid of polypyrrole and protons via Nafion(®) ionomer within hierarchical nanoarrays. By mimicking enzymes functionally, an impressive ORR activity and stability is achieved. Using this brand new electrode architecture as the cathode and the anode of a PEMFC, a high mass specific power density of 5.23 W mg(-1)Pt is achieved, with remarkable durability. These improvements are ascribed to not only the electron decoration and the anchoring effects from the Nafion(®) ionomer decorated PPy substrate to the supported Pt NPs, but also the fast charge and mass transport facilitated by the electron and proton pathways within the electrode architecture.

Bio-inspired Construction of Advanced Fuel Cell Cathode with Pt Anchored in Ordered Hybrid Polymer Matrix

NASA Astrophysics Data System (ADS)

Xia, Zhangxun; Wang, Suli; Jiang, Luhua; Sun, Hai; Liu, Shuang; Fu, Xudong; Zhang, Bingsen; Sheng Su, Dang; Wang, Jianqiang; Sun, Gongquan

2015-11-01

The significant use of platinum for catalyzing the cathodic oxygen reduction reactions (ORRs) has hampered the widespread use of polymer electrolyte membrane fuel cells (PEMFCs). The construction of well-defined electrode architecture in nanoscale with enhanced utilization and catalytic performance of Pt might be a promising approach to address such barrier. Inspired by the highly efficient catalytic processes in enzymes with active centers embedded in charge transport pathways, here we demonstrate for the first time a design that allocates platinum nanoparticles (Pt NPs) at the boundaries with dual-functions of conducting both electrons by aid of polypyrrole and protons via Nafion® ionomer within hierarchical nanoarrays. By mimicking enzymes functionally, an impressive ORR activity and stability is achieved. Using this brand new electrode architecture as the cathode and the anode of a PEMFC, a high mass specific power density of 5.23 W mg-1Pt is achieved, with remarkable durability. These improvements are ascribed to not only the electron decoration and the anchoring effects from the Nafion® ionomer decorated PPy substrate to the supported Pt NPs, but also the fast charge and mass transport facilitated by the electron and proton pathways within the electrode architecture.

A concise guide to sustainable PEMFCs: recent advances in improving both oxygen reduction catalysts and proton exchange membranes.

PubMed

Scofield, Megan E; Liu, Haiqing; Wong, Stanislaus S

2015-08-21

The rising interest in fuel cell vehicle technology (FCV) has engendered a growing need and realization to develop rational chemical strategies to create highly efficient, durable, and cost-effective fuel cells. Specifically, technical limitations associated with the major constituent components of the basic proton exchange membrane fuel cell (PEMFC), namely the cathode catalyst and the proton exchange membrane (PEM), have proven to be particularly demanding to overcome. Therefore, research trends within the community in recent years have focused on (i) accelerating the sluggish kinetics of the catalyst at the cathode and (ii) minimizing overall Pt content, while simultaneously (a) maximizing activity and durability as well as (b) increasing membrane proton conductivity without causing any concomitant loss in either stability or as a result of damage due to flooding. In this light, as an example, high temperature PEMFCs offer a promising avenue to improve the overall efficiency and marketability of fuel cell technology. In this Critical Review, recent advances in optimizing both cathode materials and PEMs as well as the future and peculiar challenges associated with each of these systems will be discussed.

Combinatorial high-throughput optical screening of high performance Pd alloy cathode for hybrid Li-air battery.

PubMed

Jun, Young Jin; Park, Sung Hyeon; Woo, Seong Ihl

2014-12-08

Combinatorial high-throughput optical screening method was developed to find the optimum composition of highly active Pd-based catalysts at the cathode of the hybrid Li-air battery. Pd alone, which is one-third the cost of Pt, has difficulty in replacing Pt; therefore, the integration of other metals was investigated to improve its performance toward oxygen reduction reaction (ORR). Among the binary Pd-based catalysts, the composition of Pd-Ir derived catalysts had higher performance toward ORR compared to other Pd-based binary combinations. The composition at 88:12 at. % (Pd: Ir) showed the highest activity toward ORR at the cathode of the hybrid Li-air battery. The prepared Pd(88)Ir(12)/C catalyst showed a current density of -2.58 mA cm(-2) at 0.8 V (vs RHE), which was around 30% higher compared to that of Pd/C (-1.97 mA cm(-2)). When the prepared Pd(88)Ir(12)/C catalyst was applied to the hybrid Li-air battery, the polarization of the cell was reduced and the energy efficiency of the cell was about 30% higher than that of the cell with Pd/C.

Concurrent Phosphorus Recovery and Energy Generation in Mediator-Less Dual Chamber Microbial Fuel Cells: Mechanisms and Influencing Factors.

PubMed

Almatouq, Abdullah; Babatunde, Akintunde O

2016-03-29

This study investigated the mechanism and key factors influencing concurrent phosphorus (P) recovery and energy generation in microbial fuel cells (MFC) during wastewater treatment. Using a mediator-less dual chamber microbial fuel cell operated for 120 days; P was shown to precipitate as struvite when ammonium and magnesium chloride solutions were added to the cathode chamber. Monitoring data for chemical oxygen demand (COD), pH, oxidation reduction potential (ORP) and aeration flow rate showed that a maximum 38% P recovery was achieved; and this corresponds to 1.5 g/L, pH > 8, -550 ± 10 mV and 50 mL/min respectively, for COD, pH(cathode), ORP and cathode aeration flow rate. More importantly, COD and aeration flow rate were shown to be the key influencing factors for the P recovery and energy generation. Results further show that the maximum P recovery corresponds to 72 mW/m² power density. However, the energy generated at maximum P recovery was not the optimum; this shows that whilst P recovery and energy generation can be concurrently achieved in a microbial fuel cell, neither can be at the optimal value.

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

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

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li–O 2 Batteries

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

Wu, Feng; Xing, Yi; Li, Li

To improve the electrochemical performance of the high energy Li–O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron–oxygen functional groups linking to the carbon surface or edge serve as additional reaction sitesmore » to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger interactions with Li5O6 clusters, so that B-rGO more effectively activates Li–O bonds to decompose Li2O2 during charge than rGO does. With B-rGO as a catalytic substrate, the Li–O2 battery achieves a high discharge capacity and excellent rate capability. Moreover, catalysts could be added into the B-rGO substrate to further lower the overpotential and enhance the cycling performance in future.« less

A highly active hybrid catalyst modified (La 0.60Sr 0.40) 0.95Co 0.20Fe 0.80O 3-δ cathode for proton conducting solid oxide fuel cells

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

Lei, Libin; Tao, Zetian; Hong, Tao

The sluggish reaction kinetics in the cathode usually leads to considerable cathode polarization resistance, hindering the development of proton conducting solid oxide fuel cells (H-SOFCs) operated at intermediate temperatures (400–650 °C). In this paper, to address this problem, for the first time, a novel hybrid catalyst consisting of PrNi 0.5Mn 0.5O 3 and PrOx is impregnated in the (La 0.60Sr 0.40) 0.95Co 0.20Fe 0.80O 3-δ (LSCF) cathode of H-SOFCs, resulting in significant enhancement of the cathode reaction kinetics. Single cells with impregnated LSCF cathode and BaZr 0.8Y 0.2O 3 (BZY) electrolyte yield a maximum power density (MPD) of 0.198 Wmore » cm -2 at 600 °C, more than doubled of that with blank LSCF cathode (0.083 W cm -2). ECR and EIS studies reveal that the hybrid catalyst can substantially accelerate the oxygen-ion transfer and oxygen dissociation-absorption processes in the cathode, resulting in significantly lower polarization resistance and higher MPD. In addition, the hybrid catalyst possesses good chemical and microstructural stability at 600 °C. Consequently, the single cells with impregnated LSCF cathode show excellent durability. Finally, this study shows that the impregnation of this novel hybrid catalyst in the cathode could be a promising approach to improve the performance and stability of H-SOFCs.« less

A highly active hybrid catalyst modified (La 0.60Sr 0.40) 0.95Co 0.20Fe 0.80O 3-δ cathode for proton conducting solid oxide fuel cells

DOE PAGES

Lei, Libin; Tao, Zetian; Hong, Tao; ...

2018-04-06

The sluggish reaction kinetics in the cathode usually leads to considerable cathode polarization resistance, hindering the development of proton conducting solid oxide fuel cells (H-SOFCs) operated at intermediate temperatures (400–650 °C). In this paper, to address this problem, for the first time, a novel hybrid catalyst consisting of PrNi 0.5Mn 0.5O 3 and PrOx is impregnated in the (La 0.60Sr 0.40) 0.95Co 0.20Fe 0.80O 3-δ (LSCF) cathode of H-SOFCs, resulting in significant enhancement of the cathode reaction kinetics. Single cells with impregnated LSCF cathode and BaZr 0.8Y 0.2O 3 (BZY) electrolyte yield a maximum power density (MPD) of 0.198 Wmore » cm -2 at 600 °C, more than doubled of that with blank LSCF cathode (0.083 W cm -2). ECR and EIS studies reveal that the hybrid catalyst can substantially accelerate the oxygen-ion transfer and oxygen dissociation-absorption processes in the cathode, resulting in significantly lower polarization resistance and higher MPD. In addition, the hybrid catalyst possesses good chemical and microstructural stability at 600 °C. Consequently, the single cells with impregnated LSCF cathode show excellent durability. Finally, this study shows that the impregnation of this novel hybrid catalyst in the cathode could be a promising approach to improve the performance and stability of H-SOFCs.« less

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Jiang, Junhua; Aulich, Ted R; Ignatchenko, Alexey V

2015-04-14

Methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia are disclosed. Embodiments include (1) ammonium nitrate produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source: (3) ammonia produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source or a hydrogen equivalent such as carbon monoxide or a mixture of carbon monoxide and hydrogen at the anode; and (4) urea-ammonium nitrate produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source.

Chemical activation of commercial CNTs with simultaneous surface deposition of manganese oxide nano flakes for the creation of CNTs-graphene supported oxygen reduction ternary composite catalysts applied in air fuel cell

NASA Astrophysics Data System (ADS)

Sun, Ling; Liu, Danxian

2018-07-01

To elevate power performance is crucial for commercally potential metal air fuel cells. Non-precious metal oxide-based oxygen reduction catalytic electrode is much desirable. Rational combination with low-dimension nanomaterials are greatly expected as the supports. Herein, carbon nanotubes (CNTs)-graphene supported manganese oxides composite catalysts (CMnCs) were obtained through activating commercial CNTs, namely, immersing them in acidic KMnO4 solution at room condition. It avoided conventional hydrothermal process and template surfactants. CMnCs-based air cathodes were made via pilot manufacture technology and equipped in fuel cells. Through characterizations, CNTs was found structurally defective and their outer walls suffered cracking into graphene nano pieces during processing, which further enhanced oxygen reduction reaction (ORR). Nano sized manganese oxide flakes were simulataneously grown on the CNTs-graphene surfaces, identified as the manganite. The areal distribution was found closely related to the additive amount of KMnO4 with regard to CNTs, somewhat influencing catalytic performance. The ORR activities of these CMnCs exceeded raw CNTs and referred manganese catalysts under identical conditions, and also the CMnCs air fuel cells were capable of outputting ∼15% more power at 100 mA/cm2. This reseach provided an inspiring pilot evidence for updating air fuel cell power from economical carbon as well as industrialization.

Anode-cathode power distribution systems and methods of using the same for electrochemical reduction

DOEpatents

Koehl, Eugene R; Barnes, Laurel A; Wiedmeyer, Stanley G; Williamson, Mark A; Willit, James L

2014-01-28

Power distribution systems are useable in electrolytic reduction systems and include several cathode and anode assembly electrical contacts that permit flexible modular assembly numbers and placement in standardized connection configurations. Electrical contacts may be arranged at any position where assembly contact is desired. Electrical power may be provided via power cables attached to seating assemblies of the electrical contacts. Cathode and anode assembly electrical contacts may provide electrical power at any desired levels. Pairs of anode and cathode assembly electrical contacts may provide equal and opposite electrical power; different cathode assembly electrical contacts may provide different levels of electrical power to a same or different modular cathode assembly. Electrical systems may be used with an electrolyte container into which the modular cathode and anode assemblies extend and are supported above, with the modular cathode and anode assemblies mechanically and electrically connecting to the respective contacts in power distribution systems.

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

DOE PAGES

Mu, Linqin; Lin, Ruoqian; Xu, Rong; ...

2018-04-18

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

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

Mu, Linqin; Lin, Ruoqian; Xu, Rong

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

High speed municipal sewage treatment in microbial fuel cell integrated with anaerobic membrane filtration system.

PubMed

Lee, Y; Oa, S W

2014-01-01

A cylindrical two chambered microbial fuel cell (MFC) integrated with an anaerobic membrane filter was designed and constructed to evaluate bioelectricity generation and removal efficiency of organic substrate (glucose or domestic wastewater) depending on organic loading rates (OLRs). The MFC was continuously operated with OLRs 3.75, 5.0, 6.25, and 9.38 kg chemical oxygen demand (COD)/(m(3)·d) using glucose as a substrate, and the cathode chamber was maintained at 5-7 mg/L of dissolved oxygen. The optimal OLR was found to be 6.25 kgCOD/(m(3)·d) (hydraulic retention time (HRT) 1.9 h), and the corresponding voltage and power density averaged during the operation were 0.15 V and 13.6 mW/m(3). With OLR 6.25 kgCOD/(m(3)·d) using domestic wastewater as a substrate, the voltage and power reached to 0.13 V and 91 mW/m(3) in the air cathode system. Even though a relatively short HRT of 1.9 h was applied, stable effluent could be obtained by the membrane filtration system and the following air purging. In addition, the short HRT would provide economic benefit in terms of reduction of construction and operating costs compared with a conventional aerobic treatment process.

RuO2 nanoparticles decorated MnOOH/C as effective bifunctional electrocatalysts for lithium-air battery cathodes with long-cycling stability

NASA Astrophysics Data System (ADS)

Kim, Gil-Pyo; Lim, Dongwook; Park, Inyeong; Park, Hyelee; Shim, Sang Eun; Baeck, Sung-Hyeon

2016-08-01

Manganite (MnOOH) is one of the most effective electrocatalysts for oxygen reduction reaction (ORR), and RuO2 nanoparticles exhibit high activity for oxygen evolution reaction (OER). We herein report a facile means of producing well dispersed RuO2/MnOOH on Ketjen black (RuO2/MnOOH/C) as a bifunctional catalyst for lithium-air (Li-air) batteries. RuO2/MnOOH/C was simply synthesized using a hydrothermal/precipitation based method, and was used as a cathode for a Li-air battery using a Swagelok-type cell. The importance of dispersing active catalysts on a carbon support was clearly demonstrated by textural, charge-discharge voltammetric, and electrochemical impedance spectroscopic (EIS) analyses, comparing results with a catalyst produced by physically mixing RuO2/MnOOH with carbon (RuO2/MnOOH + C). RuO2/MnOOH/C showed low overpotential and stable cycleability up to 170th cycles with 1000 mAh g-1 of charge-discharge capacity, which was attributed to its enhanced active surface area and low charge-transfer resistance. The results obtained suggest that this strategy can be widely applied to bifunctional electrocatalysis, such as secondary batteries and regenerative fuel cell (RFC).

Nanotubular MnO2/graphene oxide composites for the application of open air-breathing cathode microbial fuel cells.

PubMed

Gnana Kumar, G; Awan, Zahoor; Suk Nahm, Kee; Xavier, J Stanley

2014-03-15

Nanotubular shaped α-MnO2/graphene oxide nanocomposites were synthesized via a simple, cost and time efficient hydrothermal method. The growth of hollow structured MnO2 nanotubes preferentially occurred along the [001] direction as evidenced from the morphological and structural characterizations. The tunnels of α-MnO2 nanotubes easily accommodated the molecular oxygen and exhibited excellent catalytic activity towards the oxygen reduction reaction over the rod structure and was further enhanced with the effective carbon support graphene oxide. The MnO2 nanotubes/graphene oxide nanocomposite modified electrode exhibited a maximum power density of 3359 mW m(-2) which is 7.8 fold higher than that of unmodified electrode and comparable with the Pt/C modified electrode. The microbial fuel cell equipped with MnO2 nanotubes/graphene oxide nanocomposite modified cathode exhibited quick start up and excellent durability over the studied electrodes and is attributed to the high surface area and number of active sites. These findings not only provide the fundamental studies on carbon supported low-dimensional transition-metal oxides but also open up the new possibilities of their applications in green energy devices. © 2013 Elsevier B.V. All rights reserved.

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, Donald A.; Yeager, E.

1992-01-01

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, Peter C.; Lessing, Paul A.

1995-01-01

A chemical reactor for oxygenating hydrocarbons includes: a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed.

[Treatment of acrylate wastewater by electrocatalytic reduction process].

PubMed

Yu, Li-Na; Song, Yu-Dong; Zhou, Yue-Xi; Zhu, Shu-Quan; Zheng, Sheng-Zhi; Ll, Si-Min

2011-10-01

High-concentration acrylate wastewater was treated by an electrocatalytic reduction process. The effects of the cation exchange membrane (CEM) and cathode materials on acrylate reduction were investigated. It indicated that the acrylate could be reduced to propionate acid efficiently by the electrocatalytic reduction process. The addition of CEM to separator with the cathode and anode could significantly improve current efficiency. The cathode materials had significant effect on the reduction of acrylate. The current efficiency by Pd/Nickel foam, was greater than 90%, while those by nickel foam, the carbon fibers and the stainless steel decreased successively. Toxicity of the wastewater decreased considerably and methane production rate in the biochemical methane potential (BMP) test increased greatly after the electrocatalytic reduction process.

Electrocatalytic activity of Pd-loaded Ti/TiO2 nanotubes cathode for TCE reduction in groundwater.

PubMed

Xie, Wenjing; Yuan, Songhu; Mao, Xuhui; Hu, Wei; Liao, Peng; Tong, Man; Alshawabkeh, Akram N

2013-07-01

A novel cathode, Pd loaded Ti/TiO2 nanotubes (Pd-Ti/TiO2NTs), is synthesized for the electrocatalytic reduction of trichloroethylene (TCE) in groundwater. Pd nanoparticles are successfully loaded on TiO2 nanotubes which grow on Ti plate via anodization. Using Pd-Ti/TiO2NTs as the cathode in an undivided electrolytic cell, TCE is efficiently and quantitatively transformed to ethane. Under conditions of 100 mA and pH 7, the removal efficiency of TCE (21 mg/L) is up to 91% within 120 min, following pseudo-first-order kinetics with the rate constant of 0.019 min(-1). Reduction rates increase from 0.007 to 0.019 min(-1) with increasing the current from 20 to 100 mA, slightly decrease in the presence of 10 mM chloride or bicarbonate, and decline with increasing the concentrations of sulfite or sulfide. O2 generated at the anode slightly influences TCE reduction. At low currents, TCE is mainly reduced by direct electron transfer on the Pd-Ti/TiO2NT cathode. However, the contribution of Pd-catalytic hydrodechlorination, an indirect reduction mechanism, becomes significant with increasing the current. Compared with other common cathodes, i.e., Ti-based mixed metal oxides, graphite and Pd/Ti, Pd-Ti/TiO2NTs cathode shows superior performance for TCE reduction. Copyright © 2013 Elsevier Ltd. All rights reserved.

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA Technical Reports Server (NTRS)

Anderson, Everett B.; Taylor, E. Jennings; Wilemski, Gerald; Gelb, Alan

1993-01-01

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

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

Kuhn, M., E-mail: kuhnm@mit.edu; Hashimoto, S.; Sato, K.

The oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} has been the topic of various reports in the literature, but has been exclusively measured at high oxygen partial pressures, pO{sub 2}, and/or elevated temperatures. For applications of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}}, such as solid oxide fuel cell cathodes or oxygen permeation membranes, knowledge of the oxygen nonstoichiometry and thermo-chemical stability over a wide range of pO{sub 2} is crucial, as localized low pO{sub 2} could trigger failure of the material and device. By employing coulometric titration combined with thermogravimetry, the oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} was measured at highmore » and intermediate pO{sub 2} until the material decomposed (at log(pO{sub 2}/bar) Almost-Equal-To -4.5 at 1073 K). For a gradually reduced sample, an offset in oxygen content suggests that La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} forms a 'super-reduced' solid solution before decomposing. When the sample underwent alternate reduction-oxidation, a hysteresis-like pO{sub 2} dependence of the oxygen content in the decomposition pO{sub 2} range was attributed to the reversible formation of ABO{sub 3} and A{sub 2}BO{sub 4} phases. Reduction enthalpy and entropy were determined for the single-phase region and confirmed interpolated values from the literature. - Graphical abstract: Oxygen nonstoichiometry (shown as 3-{delta}) of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} as a function of pO{sub 2} at 773-1173 K. The experimental data were obtained by thermogravimetric analysis (TG) and coulometric titration (measured either by a simple reduction (CT1) or a 'two-step-forward one-step-back' reduction-oxidation (CT2) procedure). D1 and D2 denote the decomposition pO{sub 2}. The solid lines are the fit to the thermogravimetry and CT1 data. The dashed lines represent the non-equilibrium region where the sample shows a super-reduced state. Highlights: Black-Right-Pointing-Pointer Oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} at intermediate temperatures and p(O2). Black-Right-Pointing-Pointer Experimental confirmation of previously interpolated reduction enthalpy. Black-Right-Pointing-Pointer Decomposition p(O2) assessed by coulometric titration. Black-Right-Pointing-Pointer Hysteresis-like p(O2) dependence of oxygen content at decomposition p(O2).« less

Substantial Humic Acid Adsorption to Activated Carbon Air Cathodes Produces a Small Reduction in Catalytic Activity.

PubMed

Yang, Wulin; Watson, Valerie J; Logan, Bruce E

2016-08-16

Long-term operation of microbial fuel cells (MFCs) can result in substantial degradation of activated carbon (AC) air-cathode performance. To examine a possible role in fouling from organic matter in water, cathodes were exposed to high concentrations of humic acids (HA). Cathodes treated with 100 mg L(-1) HA exhibited no significant change in performance. Exposure to 1000 mg L(-1) HA decreased the maximum power density by 14% (from 1310 ± 30 mW m(-2) to 1130 ± 30 mW m(-2)). Pore blocking was the main mechanism as the total surface area of the AC decreased by 12%. Minimization of external mass transfer resistances using a rotating disk electrode exhibited only a 5% reduction in current, indicating about half the impact of HA adsorption was associated with external mass transfer resistance and the remainder was due to internal resistances. Rinsing the cathodes with deionized water did not restore cathode performance. These results demonstrated that HA could contribute to cathode fouling, but the extent of power reduction was relatively small in comparison to large mass of humics adsorbed. Other factors, such as biopolymer attachment, or salt precipitation, are therefore likely more important contributors to long-term fouling of MFC cathodes.

Mineralization of aniline in aqueous solution by electrochemical activation of persulfate.

PubMed

Chen, Wen-Shing; Huang, Chi-Pin

2015-04-01

Oxidative degradation of aniline in aqueous solution was carried out by coupling electrolysis with persulfate oxidation, in which a synergistic effect occurred. Experiments were performed under a batch-wise mode to evaluate the influence of various operation parameters on the electrolytic behavior, such as acidity of aqueous solution, temperature, electrode potential, persulfate anion concentration and nitrogen/oxygen gas dosage. The aniline pollutants could be almost entirely mineralized by means of electro-activated persulfate oxidation, wherein sulfate radicals were presumed to be principal oxidizing agents. Besides, electrogenerated hydrogen peroxide originated from cathodic reduction of oxygen, supplied chiefly by anodic oxidation of water, would contribute partially for decomposition of aniline. On the whole, the electro-activated persulfate process is a very promising method for treatment of aniline in wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

α-MnO2 nanorods supported on porous graphitic carbon nitride as efficient electrocatalysts for lithium-air batteries

NASA Astrophysics Data System (ADS)

Hang, Yang; Zhang, Chaofeng; Luo, Xiaoman; Xie, Yingshen; Xin, Sen; Li, Yutao; Zhang, Dawei; Goodenough, John B.

2018-07-01

Synthesis of α-MnO2 nanorods grown on porous graphitic carbon nitride (g-C3N4) sheets via a facile hydrothermal treatment gives a porous composite exhibiting higher activity for an air cathode than the individual component of α-MnO2 or porous g-C3N4 for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The porous g-C3N4/α-MnO2 composite also exhibits better performance in a Li-air battery than pure α-MnO2 or XC-72 carbon catalysts, which includes superior discharge capacity, low voltage gap and high cycle stability. The α-MnO2 nanorods catalyze the OER and the porous g-C3N4 sheets catalyze the ORR.

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen.

PubMed

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Pickup, David M; Liu, Yi-Sheng; Edström, Kristina; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

2016-07-01

During the charging and discharging of lithium-ion-battery cathodes through the de- and reintercalation of lithium ions, electroneutrality is maintained by transition-metal redox chemistry, which limits the charge that can be stored. However, for some transition-metal oxides this limit can be broken and oxygen loss and/or oxygen redox reactions have been proposed to explain the phenomenon. We present operando mass spectrometry of (18)O-labelled Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2, which demonstrates that oxygen is extracted from the lattice on charging a Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2 cathode, although we detected no O2 evolution. Combined soft X-ray absorption spectroscopy, resonant inelastic X-ray scattering spectroscopy, X-ray absorption near edge structure spectroscopy and Raman spectroscopy demonstrates that, in addition to oxygen loss, Li(+) removal is charge compensated by the formation of localized electron holes on O atoms coordinated by Mn(4+) and Li(+) ions, which serve to promote the localization, and not the formation, of true O2(2-) (peroxide, O-O ~1.45 Å) species. The quantity of charge compensated by oxygen removal and by the formation of electron holes on the O atoms is estimated, and for the case described here the latter dominates.

Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell.

PubMed

Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

2014-01-22

Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode.

Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell

PubMed Central

Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

2014-01-01

Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode. PMID:24448514

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Aulich, Ted R.; Olson, Edwin S.; Jiang, Junhua

2013-03-19

The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be solid.

Effect of high donor number solvent and cathode morphology on interfacial processes in Li-air batteries

NASA Astrophysics Data System (ADS)

Kislenko, S. A.

2018-01-01

The work is focused on the investigation of the effect of solvent and carbon cathode morphology on the performance of Li-air batteries. Molecular dynamics simulation was used to explore the interfacial behavior of the main reactants (O2 and Li+) of the oxygen reduction reaction in high donor number solvent dimethyl sulfoxide (DMSO) at the following carbon surfaces: graphene plane, graphene edge, nanotube. It was shown that the adsorption barrier of O2 molecules decreases in the order graphene plane > nanotube > graphene edge, leading to the fastest adsorption kinetics on graphene edges. Strong solvation of Li+ in DMSO prevents ions adsorption on defect-free graphene planes and nanotubes, which is qualitatively different from low donor number solvents, such as acetonitrile. It can be concluded from these results, that nucleation and growth of discharge products in DMSO is shifted from the surface towards the solvent bulk that, in turn, leads to capacity increase of Li-air batteries.

Enhanced Performance of non-PGM Catalysts in Air Operated PEM-Fuel Cells

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary Brian; ...

2016-10-13

Here a non-platinum group metal (non-PGM) oxygen reduction catalyst was prepared from “support-free” zeolitic imidazolate framework (ZIF) precursor and tested in the proton exchange membrane fuel cell with air as the cathode feed. The iron nitrogen and carbon composite (FeeNeC) based catalyst has high specific surface area decorated uniformly with active sites, which redefines the triple phase boundary (TPB) and requires re-optimization of the cathodic membrane electrode fabrication to ensure efficient mass and charge transports to the catalyst surface. This study reports an effort in optimizing catalytic ink formulation for the membrane electrode preparation and its impact to the fuelmore » cell performance under air. Through optimization, the fuel cell areal current density as high as 115.2 mA/cm 2 at 0.8 V or 147.6 mA/cm 2 at 0.8 V iR-free has been achieved under one bar air. We also investigated impacts on fuel cell internal impedance and the water formation.« less

Co-Pt core-shell nanostructured catalyst prepared by selective chemical vapor pulse deposition of Pt on Co as a cathode in polymer electrolyte fuel cells

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

Seo, Sang-Joon; Chung, Ho-Kyoon; Yoo, Ji-Beom

2014-01-15

A new type of PtCo/C catalyst for use as a cathode in polymer electrolyte fuel cells was prepared by selective chemical vapor pulse deposition (CVPD) of Pt on the surface of Co. The activity of the prepared catalyst for oxygen reduction was higher than that of a catalyst prepared by sequential impregnation (IMP) with the two metallic components. This catalytic activity difference occurs because the former catalyst has smaller Pt crystallites that produce stronger Pt-Co interactions and have a larger Pt surface area. Consequently, the CVPD catalyst has a great number of Co particles that are in close contact withmore » the added Pt. The Pt surface was also electronically modified by interactions with Co, which were stronger in the CVPD catalyst than in the IMP catalyst, as indicated by X-ray diffraction, X-ray photoemission spectroscopy, and cyclic voltammetry measurements of the catalysts.« less

Characterization of the Ternary Compound Pd5Pt3Ni2 for PEMFC Cathode Electrocatalysts

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

Jarvis, Karalee; Zhao, J; Allard Jr, Lawrence Frederick

2010-01-01

Research on proton exchange membrane fuel cells (PEMFC) has increased over the last decade due to an increasing demand for alternative energy solutions. Most PEMFCs use Pt on carbon support as electrocatalysts for oxygen reduction reactions (ORR) [1]. Due to the high cost of Pt, there is a strong drive to develop less expensive catalysts that meet or exceed the performance of Pt. Binary and ternary Pt alloys with less expensive metals are a possible route [1]. In this work, a ternary alloy with composition Pd5Pt3Ni2 was studied as a potential cathode material. Preliminary results showed similar catalytic performance tomore » pure Pt in single-cell tests. However, to enhance its performance, it is necessary to understand how this ternary catalyst behaves during fuel cell operation. Various electron microscopy techniques were used to characterize the ternary Pd5Pt3Ni2 catalysts within the membrane-electrode assembly (MEA) both before and after fuel cell operation.« less

Corrosion testing of candidates for the alkaline fuel cell cathode

NASA Technical Reports Server (NTRS)

Singer, Joseph; Fielder, William L.

1989-01-01

Current/voltage data was obtained for specially made corrosion electrodes of some oxides and of gold materials for the purpose of developing a screening test of catalysts and supports for use at the cathode of the alkaline fuel cell. The data consists of measurements of current at fixed potentials and cyclic voltammograms. These data will have to be correlated with longtime performance data in order to fully evaluate this approach to corrosion screening. Corrosion test screening of candidates for the oxygen reduction electrode of the alkaline fuel cell was applied to two substances, the pyrochlore Pb2Ru2O6.5 and the spinel NiCo2O4. The substrate gold screen and a sample of the IFC Orbiter Pt-Au performance electrode were included as blanks. The pyrochlore data indicate relative stability, although nothing yet can be said about long term stability. The spinel was plainly unstable. For this type of testing to be validated, comparisons will have to be made with long term performance tests.

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Photoelectrocatalytic Synthesis of Hydrogen Peroxide by Molecular Copper-Porphyrin Supported on Titanium Dioxide Nanotubes.

PubMed

Apaydin, Dogukan H; Seelajaroen, Hathaichanok; Pengsakul, Orathip; Thamyongkit, Patchanita; Sariciftci, Niyazi Serdar; Kunze-Liebhäuser, Julia; Portenkirchner, Engelbert

2018-04-24

We report on a self-assembled system comprising a molecular copper-porphyrin photoelectrocatalyst, 5-(4-carboxy-phenyl)-10,15,20-triphenylporphyrinatocopper(II) (CuTPP-COOH), covalently bound to self-organized, anodic titania nanotube arrays (TiO 2 NTs) for photoelectrochemical reduction of oxygen. Visible light irradiation of the porphyrin-covered TiO 2 NTs under cathodic polarization up to -0.3 V vs. Normal hydrogen electrode (NHE) photocatalytically produces H 2 O 2 in pH neutral electrolyte, at room temperature and without need of sacrificial electron donors. The formation of H 2 O 2 upon irradiation is proven and quantified by direct colorimetric detection using 4-nitrophenyl boronic acid ( p -NPBA) as a reactant. This simple approach for the attachment of a small molecular catalyst to TiO 2 NTs may ultimately allow for the preparation of a low-cost H 2 O 2 evolving cathode for efficient photoelectrochemical energy storage under ambient conditions.

Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

PubMed

Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

2013-09-01

Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area. Copyright © 2013 Elsevier Ltd. All rights reserved.

Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

NASA Astrophysics Data System (ADS)

Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

2017-07-01

We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

Metagenomic Analysis Indicates Epsilonproteobacteria as a Potential Cause of Microbial Corrosion in Pipelines Injected with Bisulfite

PubMed Central

An, Dongshan; Dong, Xiaoli; An, Annie; Park, Hyung S.; Strous, Marc; Voordouw, Gerrit

2016-01-01

Sodium bisulfite (SBS) is used as an oxygen scavenger to decrease corrosion in pipelines transporting brackish subsurface water used in the production of bitumen by steam-assisted gravity drainage. Sequencing 16S rRNA gene amplicons has indicated that SBS addition increased the fraction of the sulfate-reducing bacteria (SRB) Desulfomicrobium, as well as of Desulfocapsa, which can also grow by disproportionating sulfite into sulfide, sulfur, and sulfate. SRB use cathodic H2, formed by reduction of aqueous protons at the iron surface, or use low potential electrons from iron and aqueous protons directly for sulfate reduction. In order to reveal the effects of SBS treatment in more detail, metagenomic analysis was performed with pipe-associated solids (PAS) scraped from a pipe section upstream (PAS-616P) and downstream (PAS-821TP) of the SBS injection point. A major SBS-induced change in microbial community composition and in affiliated hynL genes for the large subunit of [NiFe] hydrogenase was the appearance of sulfur-metabolizing Epsilonproteobacteria of the genera Sulfuricurvum and Sulfurovum. These are chemolithotrophs, which oxidize sulfide or sulfur with O2 or reduce sulfur with H2. Because O2 was absent, this class likely catalyzed reduction of sulfur (S0) originating from the metabolism of bisulfite with cathodic H2 (or low potential electrons and aqueous protons) originating from the corrosion of steel (Fe0). Overall this accelerates reaction of of S0 and Fe0 to form FeS, making this class a potentially powerful contributor to microbial corrosion. The PAS-821TP metagenome also had increased fractions of Deltaproteobacteria including the SRB Desulfomicrobium and Desulfocapsa. Altogether, SBS increased the fraction of hydrogen-utilizing Delta- and Epsilonproteobacteria in brackish-water-transporting pipelines, potentially stimulating anaerobic pipeline corrosion if dosed in excess of the intended oxygen scavenger function. PMID:26858705

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, P.C.; Lessing, P.A.

1995-06-27

A chemical reactor for oxygenating hydrocarbons includes: (a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; (b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; (c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and (d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed. 4 figs.

Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

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

Gopalan, Srikanth

2017-04-06

This final report for project FE0009656 covers the period from 10/01/2012 to 09/30/2015 and covers research accomplishments on the effects of carbon dioxide on the surface composition and structure of cathode materials for solid oxide fuel cells (SOFCs), specifically La1-xSrxFeyCo1- yO3-δ (LSCF). Epitaxially deposited thin films of LSCF on various single-crystal substrates have revealed the selective segregation of strontium to the surface thereby resulting in a surface enrichment of strontium. The near surface compositional profile in the films have been measured using total x-ray fluorescence (TXRF), and show that the kinetics of strontium segregation are higher at higher partial pressuresmore » of carbon dioxide. Once the strontium segregates to the surface, it leads to the formation of precipitates of SrO which convert to SrCO3 in the presence of even modest concentrations of carbon dioxide in the atmosphere. This has important implications for the performance of SOFCs which is discussed in this report. These experimental observations have also been verified by Density Functional Theory calculations (DFT) which predict the conditions under which SrO and SrCO3 can occur in LSCF. Furthermore, a few cathode compositions which have received attention in the literature as alternatives to LSCF cathodes have been studied in this work and shown to be thermodynamically unstable under the operating conditions of the SOFCs.« less

Modified Gold Electrode and Hollow Mn3O4 Nanoparticles as Electrode Materials for Microbial Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Dhungana, Pramod

Microbial fuel cell (MFC) technology has attracted great attention in the scientific community as it offers the possibility of extraction of electricity from wide range of soluble and dissolved organic waste or renewable biomass, including sludge, waste water and cellulosic biomass. Microbial fuel cells are devices that utilize microbial metabolic processes to convert chemical energy via the oxidation of organic substances to produce electric current. MFCs consist of two chambers, an anode and cathode, separated by ion-permeable materials. The efficiency of producing electricity using the MFC depends on several factors such as immobilization of microorganisms on anode, mode of electron transfer, types of substrate/fuel and effectiveness of cathode materials for oxygen reduction reaction (ORR). In this work, in order to immobilize the microorganisms on anode materials, we have investigated the surface modification of gold electrode (anode) using alkyl dithiol and aryl thiol with glucose. The modification processes were characterized by using contact angle measurements and proton nuclear magnetic resonance (NMR). In order to study the effectiveness of cathode materials for ORR, we have synthesized hollow Mn3O 4 nanoparticles which are electrically very poor. Therefore, the hollow nanoparticles were mixed with electrically conductive multi-walled carbon nanotube as support and optimized the mixing process. This composite material shows enhanced ORR activity in all types of pH conditions. In future, we will focus to integrate anode and cathode in MFC to check its efficiency to produce electricity.

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Jiang, Long; Wang, Jie; Xiong, Xiaolei; ...

2016-01-21

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

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

Jiang, Long; Wang, Jie; Xiong, Xiaolei

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Electrochemical reduction of carbon dioxide. Final report

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

LaConti, A.B.; Molter, T.M.; Zagaja, J.A.

1986-05-01

Many researchers have studied the electrochemical reduction of carbon dioxide and related organic species to form concentrated liquid/gaseous products in laboratory-scale hardware. Hamilton Standard has developed a high pressure SPE electrolysis cell capable of reducing carbon dioxide streams to form pure, concentrated alcohols, carboxylic acids, and other hydrocarbons. The process is unique in that the byproducts of reaction include oxygen and, under some test conditions water. In addition, a relatively simple test system was designed and constructed permitting both batch and semibatch type electrochemical reduction studies. In this study, cathode materials were developed which 1) had a characteristic high hydrogenmore » overvoltage, and 2) possessed the intrinsic affinity for electrochemical reduction of the carbon dioxide species. In addition, suitable anode electrocatalyst materials were identified. Studies involving the electrochemical reduction of carbon dioxide required the ability to identify and quantify reaction products obtained during cell evaluation. Gas chromatographic techniques were developed along with the establishment of ion chromatographic methods permitting the analysis of organic reaction products. Hamilton Standard has evaluated electrochemical carbon dioxide reduction cells under a variety of test conditions.« less

Tuning Nanowires and Nanotubes for Efficient Fuel-Cell Electrocatalysis.

PubMed

Wang, Wei; Lv, Fan; Lei, Bo; Wan, Sheng; Luo, Mingchuan; Guo, Shaojun

2016-12-01

Developing new synthetic methods for the controlled synthesis of Pt-based or non-Pt nanocatalysts with low or no Pt loading to facilitate sluggish cathodic oxygen reduction reaction (ORR) and organics oxidation reactions is the key in the development of fuel-cell technology. Various nanoparticles (NPs), with a range of size, shape, composition, and structure, have shown good potential to catalyze the sluggish cathodic and anodic reactions. In contrast to NPs, one-dimensional (1D) nanomaterials such as nanowires (NWs), and nanotubes (NTs), exhibit additional advantages associated with their anisotropy, unique structure, and surface properties. The prominent characteristics of NWs and NTs include fewer lattice boundaries, a lower number of surface defect sites, and easier electron and mass transport for better electrocatalytic activity and lower vulnerability to dissolution, Ostwald ripening, and aggregation than Pt NPs for enhanced stability. An overview of recent advances in tuning 1D nanostructured Pt-based, Pd-based, or 1D metal-free nanomaterials as advanced electrocatalysts is provided here, for boosting fuel-cell reactions with high activity and stability, including the oxygen reduction reaction (ORR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR). After highlighting the different strategies developed so far for the synthesis of Pt-based 1D nanomaterials with controlled size, shape, and composition, special emphasis is placed on the rational design of diverse NWs and NTs catalysts such as Pt-based NWs or NTs, non-Pt NTs, and carbon NTs with molecular engineering, etc. for enhancing the ORR, MOR, and EOR. Finally, some perspectives are highlighted on the development of more efficient fuel-cell electrocatalysts featuring high stability, low cost, and enhanced performance, which are the key factors in accelerating the commercialization of fuel-cell technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the electrochemical cycling effect, electrolyte exposure also shows non-negligible influence on cathode surface degradation. These chemical and structural changes of the NMC cathode could contribute to the first-cycle coulombic inefficiency, restrict the charge transfer characteristics and ultimately impact the cell capacity.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

NASA Astrophysics Data System (ADS)

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-Ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-04-01

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g-1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g-1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

PubMed

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-04-18

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

Study of oxygen gas production phenomenon during stand and discharge in silver-zinc batteries

NASA Technical Reports Server (NTRS)

1973-01-01

The effects of a number of cell process and performance variables upon the oxygen evolution rate of silver/silver oxide cathodes are studied to predict and measure the conditions which would result in the production of a minimum of oxygen. The following five tasks comprise the study: the design and fabrication of two pilot test cells to be used for electrode testing; the determination of the sensitivity and accuracy of the test cell; the determination of total volumes and rates of generation by cathodes of standard production procedures; the construction of a sequential test plan; and the construction of a series of positive formation cells in which formation process factors can be controlled.

A novel method for effective diffusion coefficient measurement in gas diffusion media of polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Yang, Linlin; Sun, Hai; Fu, Xudong; Wang, Suli; Jiang, Luhua; Sun, Gongquan

2014-07-01

A novel method for measuring effective diffusion coefficient of porous materials is developed. The oxygen concentration gradient is established by an air-breathing proton exchange membrane fuel cell (PEMFC). The porous sample is set in a sample holder located in the cathode plate of the PEMFC. At a given oxygen flux, the effective diffusion coefficients are related to the difference of oxygen concentration across the samples, which can be correlated with the differences of the output voltage of the PEMFC with and without inserting the sample in the cathode plate. Compared to the conventional electrical conductivity method, this method is more reliable for measuring non-wetting samples.

Ab initio investigation of barium-scandium-oxygen coatings on tungsten for electron emitting cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Booske, John H.; Morgan, Dane

2010-02-01

Microwave, x-ray, and radio-frequency radiation sources require a cathode emitting electrons into vacuum. Thermionic B-type dispenser cathodes consist of BaxOz coatings on tungsten (W), where the surface coatings lower the W work function and enhance electron emission. The new and promising class of scandate cathodes modifies the B-type surface through inclusion of Sc, and their superior emissive properties are also believed to stem from the formation of a low work function surface alloy. In order to better understand these cathode systems, density-functional theory (DFT)-based ab initio modeling is used to explore the stability and work function of BaxScyOz on W(001) monolayer-type surface structures. It is demonstrated how surface depolarization effects can be calculated easily using ab initio calculations and fitted to an analytic depolarization equation. This approach enables the rapid extraction of the complete depolarization curve (work function versus coverage relation) from relatively few DFT calculations, useful for understanding and characterizing the emitting properties of novel cathode materials. It is generally believed that the B-type cathode has some concentration of Ba-O dimers on the W surface, although their structure is not known. Calculations suggest that tilted Ba-O dimers are the stable dimer surface configuration and can explain the observed work function reduction corresponding to various dimer coverages. Tilted Ba-O dimers represent a new surface coating structure not previously proposed for the activated B-type cathode. The thermodynamically stable phase of Ba and O on the W surface was identified to be the Ba0.25O configuration, possessing a significantly lower Φ value than any of the Ba-O dimer configurations investigated. The identification of a more stable Ba0.25O phase implies that if Ba-O dimers cover the surface of emitting B-type cathodes, then a nonequilibrium steady state must dominate the emitting surface. The identification of a stable and low work function Ba0.25Sc0.25O structure suggests that addition of Sc to the B-type cathode surface could form this alloy structure under operating conditions, leading to improved cathode performance and stability. Detailed comparison to previous experimental results of BaxScyOz on W surface coatings are made to both validate the modeling and aid in interpretation of experimental data. The studies presented here demonstrate that ab initio methods are powerful for understanding the fundamental physics of electron emitting materials systems and can potentially aid in the development of improved cathodes.

Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode

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

Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang

Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next generation high energy density lithium ion battery. The challenge for using this category of cathode is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the firstmore » time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3M1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling; while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with structural stability and correspondingly a superior performance.« less

COMPUTATIONAL MODELING OF CATHODIC LIMITATIONS ON LOCALIZED CORROSION OF WETTED SS 316L, AT ROOM TEMPERATURE

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

F. Cui; F.J. Presuel-Moreno; R.G. Kelly

2005-10-13

The ability of a SS316L surface wetted with a thin electrolyte layer to serve as an effective cathode for an active localized corrosion site was studied computationally. The dependence of the total net cathodic current, I{sub net}, supplied at the repassivation potential E{sub rp} (of the anodic crevice) on relevant physical parameters including water layer thickness (WL), chloride concentration ([Cl{sup -}]) and length of cathode (Lc) were investigated using a three-level, full factorial design. The effects of kinetic parameters including the exchange current density (i{sub o,c}) and Tafel slope ({beta}{sub c}) of oxygen reduction, the anodic passive current density (i{submore » p}) (on the cathodic surface), and E{sub rp} were studied as well using three-level full factorial designs of [Cl{sup -}] and Lc with a fixed WL of 25 {micro}m. The study found that all the three parameters WL, [Cl{sup -}] and Lc as well as the interactions of Lc x WL and Lc x [Cl{sup -}] had significant impact on I{sub net}. A five-factor regression equation was obtained which fits the computation results reasonably well, but demonstrated that interactions are more complicated than can be explained with a simple linear model. Significant effects on I{sub net} were found upon varying either i{sub o,c}, {beta}{sub c}, or E{sub rp}, whereas i{sub p} in the studied range was found to have little impact. It was observed that I{sub net} asymptotically approached maximum values (I{sub max}) when Lc increased to critical minimum values. I{sub max} can be used to determine the stability of coupled localized corrosion and the critical Lc provides important information for experimental design and corrosion protection.« less

Nb and Pd co-doped La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ as a stable, high performance electrode for barrier-layer-free Y2O3-ZrO2 electrolyte of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Chen, Kongfa; He, Shuai; Li, Na; Cheng, Yi; Ai, Na; Chen, Minle; Rickard, William D. A.; Zhang, Teng; Jiang, San Ping

2018-02-01

La0.6Sr0.2Co0.2Fe0.8O3-δ (LSCF) is the most intensively investigated high performance cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), but strontium segregation and migration at the electrode/electrolyte interface is a critical issue limiting the electrocatalytic activity and stability of LSCF based cathodes. Herein, we report a Nb and Pd co-doped LSCF (La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ, LSCFNPd) perovskite as stable and active cathode on a barrier-layer-free anode-supported yttria-stabilized zirconia (YSZ) electrolyte cell using direct assembly method without pre-sintering at high temperatures. The cell exhibits a peak power density of 1.3 W cm-2 at 750 °C and excellent stability with no degradation during polarization at 500 mA cm-2 and 750 °C for 175 h. Microscopic and spectroscopic analysis show that the electrochemical polarization promotes the formation of electrode/electrolyte interface in operando and exsolution of Pd/PdO nanoparticles. The Nb doping in the B-site of LSCF significantly reduces the Sr surface segregation, enhancing the stability of the cathode, while the exsoluted Pd/PdO nanoparticles increases the electrocatalytic activity for the oxygen reduction reaction. The present study opens up a new route for the development of cobaltite-based perovskite cathodes with high activity and stability for barrier-layer-free YSZ electrolyte based IT-SOFCs.

Gas-Flow Tailoring Fabrication of Graphene-like Co-Nx-C Nanosheet Supported Sub-10 nm PtCo Nanoalloys as Synergistic Catalyst for Air-Cathode Microbial Fuel Cells.

PubMed

Cao, Chun; Wei, Liling; Zhai, Qiran; Ci, Jiliang; Li, Weiwei; Wang, Gang; Shen, Jianquan

2017-07-12

In this work, we presented a novel, facile, and template-free strategy for fabricating graphene-like N-doped carbon as oxygen reduction catalyst in sustainable microbial fuel cells (MFCs) by using an ion-inducing and spontaneous gas-flow tailoring effect from a unique nitrogen-rich polymer gel precursor which has not been reported in materials science. Remarkably, by introduction of trace platinum- and cobalt- precursor in polymer gel, highly dispersed sub-10 nm PtCo nanoalloys can be in situ grown and anchored on graphene-like carbon. The as-prepared catalysts were investigated by a series of physical characterizations, electrochemical measurements, and microbial fuel cell tests. Interestingly, even with a low Pt content (5.13 wt %), the most active Co/N codoped carbon supported PtCo nanoalloys (Co-N-C/Pt) exhibited dramatically improved catalytic activity toward oxygen reduction reaction coupled with superior output power density (1008 ± 43 mW m -2 ) in MFCs, which was 29.40% higher than the state of the art Pt/C (20 wt %). Notability, the distinct catalytic activity of Co-N-C/Pt was attributed to the highly efficient synergistic catalytic effect of Co-Nx-C and PtCo nanoalloys. Therefore, Co-N-C/Pt should be a promising oxygen reduction catalyst for application in MFCs. Further, the novel strategy for graphene-like carbon also can be widely used in many other energy conversion and storage devices.

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

PubMed Central

Li, Haipeng; Sun, Liancheng; Wang, Zhuo; Zhang, Yongguang; Tan, Taizhe; Wang, Gongkai

2018-01-01

A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S) batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide) aerogel (S/AC/GA) cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO) was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D) interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V. PMID:29373525

Thermal and electrochemical behaviour of C/Li xCoO 2 cell during safety test

NASA Astrophysics Data System (ADS)

Doh, Chil-Hoon; Kim, Dong-Hun; Kim, Hyo-Suck; Shin, Hye-Min; Jeong, Young-Dong; Moon, Seong-In; Jin, Bong-Soo; Eom, Seung Wook; Kim, Hyun-Soo; Kim, Ki-Won; Oh, Dae-Hee; Veluchamy, Angathevar

Thermal and electrochemical processes in a 1000 mAh lithium-ion pouch cell with a graphite anode and a Li xCoO 2 cathode during a safety test are examined. In overcharge tests, the forced current shifts the cell voltage to above 4.2 V. This causes a cell charged at the 1 C rate to lose cycleability and a cell charged at the 3 C rate to undergo explosion. In nail penetration and impact tests, a high discharge current passing through the cells gives rise to thermal runaway. These overcharge and high discharge currents promote joule heat within the cells and leads to decomposition and release of oxygen from the de-lithiated Li xCoO 2 and combustion of carbonaceous materials. X-ray diffraction analysis reveals the presence of Co 3O 4 in the cathode material of a 4.5 V cell heated to 400 °C. The major cathode product formed after the combustion process cells abused by forced current is Co 3O 4 and by discharge current the products are LiCoO 2 and Co 3O 4. The formation of a trace quantity of CoO through the reduction of Co 3O 4 by virtue of the reducing power of the organic solvent is also discussed.

Chlorobenzene Poisoning and Recovery of Platinum-Based Cathodes in Proton Exchange Membrane Fuel Cells

PubMed Central

Zhai, Yunfeng; Baturina, Olga; Ramaker, David; Farquhar, Erik; St-Pierre, Jean; Swider-Lyons, Karen

2015-01-01

The platinum electrocatalysts found in proton exchange membrane fuel cells are poisoned both reversibly and irreversibly by air pollutants and residual manufacturing contaminants. In this work, the poisoning of a Pt/C PEMFC cathode was probed by a trace of chlorobenzene in the air feed. Chlorobenzene inhibits the oxygen reduction reaction and causes significant cell performance loss. The performance loss is largely restored by neat air operation and potential cycling between 0.08 V and 1.2 V under H2/N2 (anode/cathode). The analysis of emissions, in situ X-ray absorption spectroscopy and electrochemical impedance spectra show the chlorobenzene adsorption/reaction and molecular orientation on Pt surface depend on the electrode potential. At low potentials, chlorobenzene deposits either on top of adsorbed H atoms or on the Pt surface via the benzene ring and is converted to benzene (ca. 0.1 V) or cyclohexane (ca. 0 V) upon Cl removal. At potentials higher than 0.2 V, chlorobenzene binds to Pt via the Cl atom and can be converted to benzene (less than 0.3 V) or desorbed. Cl− is created and remains in the membrane electrode assembly. Cl− binds to the Pt surface much stronger than chlorobenzene, but can slowly be flushed out by liquid water. PMID:26388963

Bio-inspired Construction of Advanced Fuel Cell Cathode with Pt Anchored in Ordered Hybrid Polymer Matrix

PubMed Central

Xia, Zhangxun; Wang, Suli; Jiang, Luhua; Sun, Hai; Liu, Shuang; Fu, Xudong; Zhang, Bingsen; Sheng Su, Dang; Wang, Jianqiang; Sun, Gongquan

2015-01-01

The significant use of platinum for catalyzing the cathodic oxygen reduction reactions (ORRs) has hampered the widespread use of polymer electrolyte membrane fuel cells (PEMFCs). The construction of well-defined electrode architecture in nanoscale with enhanced utilization and catalytic performance of Pt might be a promising approach to address such barrier. Inspired by the highly efficient catalytic processes in enzymes with active centers embedded in charge transport pathways, here we demonstrate for the first time a design that allocates platinum nanoparticles (Pt NPs) at the boundaries with dual-functions of conducting both electrons by aid of polypyrrole and protons via Nafion® ionomer within hierarchical nanoarrays. By mimicking enzymes functionally, an impressive ORR activity and stability is achieved. Using this brand new electrode architecture as the cathode and the anode of a PEMFC, a high mass specific power density of 5.23 W mg−1Pt is achieved, with remarkable durability. These improvements are ascribed to not only the electron decoration and the anchoring effects from the Nafion® ionomer decorated PPy substrate to the supported Pt NPs, but also the fast charge and mass transport facilitated by the electron and proton pathways within the electrode architecture. PMID:26537781

Oxygen Reduction Kinetics of La2-xSrxNiO 4+delta Electrodes for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Guan, Bo

In the development of intermediate temperature solid oxide fuel cell (IT-SOFC), mixed ionic-electronic conductors (MIEC) have drawn big interests due to their both ionic and electronic species transport which can enlarge the 3-dimension of the cathode network. This thesis presents an investigation of MIEC of Ruddlesden-popper (RP) phases like K2NiF4 type La2NiO4+delta (LNO)-based oxides which have interesting transport, catalytic properties and suitable thermal expansion coefficients. The motivation of this present work is to further understand the fundamental of the effect of Sr doing on the oxygen reduction reaction (ORR) kinetics of LNO cathode. Porous symmetrical cells of La2-xSrxNiO4+delta (0≤x≤0.4) were fabricated and characterized by electrochemical impedance spectroscopy (EIS) in different PO2 from temperature range of 600˜800°C. The spectra were analyzed based on the impedance model introduced by Adler et al. The rate determining steps (RDS) for ORR were proposed and the responsible reasons were discussed. The overall polarization resistances of doped samples increase with Sr level. Surface oxygen exchange and bulk ionic diffusion co-control the ORR kinetics. With high Sr content (x=0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. However for porous symmetrical cells it is hard to associate the resistance from EIS directly to each ORR elementary processes because of the difficulty in describing the microstructure of the porous electrode. The dense electrode configuration was adopted in this thesis. By using the dense electrode, the surface area, the thickness of electrode, the interface between electrode and electrolyte and lastly the 3PB are theoretically well-defined. Through this method, there is a good chance to distinguish the contribution of surface exchange from other processes. Dense and thin electrode layers in thickness of ˜40 mum are fabricated by using a novel spray modified pressing method. Negligible bulk diffusion resistance is confirmed by parallel experiment and EIS analysis, resulting in exclusive focus on the surface process. It is ambiguously proved that Sr doping impairs the surface kinetics of lanthanum nickelates. The interstitial oxygen is suggested to be the key role when the oxygen incorporation is rat determining. For the first time, a physical model is proposed to illustrate how those interstitial species work to regulate the exchange rate of the incorporation reaction. To achieve better surface exchange ability on LNO, Mn is chosen as the doping element substituted for Ni with different levels to improve the surface kinetics because Mn is much active both for adsorption process and for incorporation process due to the high state of Mn leading to the high amount of the interstitial oxygen. Mn is found to substantially promote the surface kinetics, showing highest surface exchange coefficient (k) of 1.57x10-6cm/s at 700°C on composition of La1.8Sr0.2Ni0.9 Mn0.1O4+delta. Such value is ˜80% larger than that of the undoped sample, and is one of the highest k among the currently available R-P phase intermediate temperature (IT) cathode.

Bioelectrochemical ethanol production through mediated acetate reduction by mixed cultures.

PubMed

Steinbusch, Kirsten J J; Hamelers, Hubertus V M; Schaap, Joris D; Kampman, Christel; Buisman, Cees J N

2010-01-01

Biological acetate reduction with hydrogen is a potential method to convert wet biomass waste into ethanol. Since the ethanol concentration and reaction rates are low, this research studies the feasibility of using an electrode, in stead of hydrogen, as an electron donor for biological acetate reduction in conjunction of an electron mediator. Initially, the effect of three selected mediators on metabolic flows during acetate reduction with hydrogen was explored; subsequently, the best performing mediator was used in a bioelectrochemical system to stimulate acetate reduction at the cathode with mixed cultures at an applied cathode potential of -550 mV. In the batch test, methyl viologen (MV) was found to accelerate ethanol production 6-fold and increased ethanol concentration 2-fold to 13.5 +/- 0.7 mM compared to the control. Additionally, MV inhibited n-butyrate and methane formation, resulting in high ethanol production efficiency (74.6 +/- 6%). In the bioelectrochemical system, MV addition to an inoculated cathode led directly to ethanol production (1.82 mM). Hydrogen was coproduced at the cathode (0.0035 Nm(3) hydrogen m(-2) d(-1)), so it remained unclear whether acetate was reduced to ethanol by electrons supplied by the mediator or by hydrogen. As MV reacted irreversibly at the cathode, ethanol production stopped after 5 days.

Highly ordered and ultra-long carbon nanotube arrays as air cathodes for high-energy-efficiency Li-oxygen batteries

NASA Astrophysics Data System (ADS)

Yu, Ruimin; Fan, Wugang; Guo, Xiangxin; Dong, Shaoming

2016-02-01

Carbonaceous air cathodes with rational architecture are vital for the nonaqueous Li-O2 batteries to achieve large energy density, high energy efficiency and long cycle life. In this work, we report the cathodes made of highly ordered and vertically aligned carbon nanotubes grown on permeable Ta foil substrates (VACNTs-Ta) via thermal chemical vapour deposition. The VACNTs-Ta, composed of uniform carbon nanotubes with approximately 240 μm in superficial height, has the super large surface area. Meanwhile, the oriented carbon nanotubes provide extremely outstanding passageways for Li ions and oxygen species. Electrochemistry tests of VACNTs-Ta air cathodes show enhancement in discharge capacity and cycle life compared to those made from short-range oriented and disordered carbon nanotubes. By further combining with the LiI redox mediator that is dissolved in the tetraethylene dimethyl glycol based electrolytes, the batteries exhibit more than 200 cycles at the current density of 200 mA g-1 with a cut-off discharge capacity of 1000 mAh g-1, and their energy efficiencies increase from 50% to 82%. The results here demonstrate the importance of cathode construction for high-energy-efficiency and long-life Li-O2 batteries.

Three-Dimensional Transport Modeling for Proton Exchange Membrane(PEM) Fuel Cell with Micro Parallel Flow Field

PubMed Central

Lee, Pil Hyong; Han, Sang Seok; Hwang, Sang Soon

2008-01-01

Modeling and simulation for heat and mass transport in micro channel are being used extensively in researches and industrial applications to gain better understanding of the fundamental processes and to optimize fuel cell designs before building a prototype for engineering application. In this study, we used a single-phase, fully three dimensional simulation model for PEMFC that can deal with both anode and cathode flow field for examining the micro flow channel with electrochemical reaction. The results show that hydrogen and oxygen were solely supplied to the membrane by diffusion mechanism rather than convection transport, and the higher pressure drop at cathode side is thought to be caused by higher flow rate of oxygen at cathode. And it is found that the amount of water in cathode channel was determined by water formation due to electrochemical reaction plus electro-osmotic mass flux directing toward the cathode side. And it is very important to model the back diffusion and electro-osmotic mass flux accurately since the two flux was closely correlated each other and greatly influenced for determination of ionic conductivity of the membrane which directly affects the performance of fuel cell. PMID:27879774

Turning Waste Chemicals into Wealth-A New Approach To Synthesize Efficient Cathode Material for an Li-O2 Battery.

PubMed

Yao, Ying; Wu, Feng

2017-09-20

An Li-O 2 battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li-O 2 battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing "waste" such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.

Turning Waste Chemicals into Wealth—A New Approach To Synthesize Efficient Cathode Material for an Li–O 2 Battery

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

Yao, Ying; Wu, Feng

An Li–O 2 battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li–O 2more » battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing “waste” such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.« less

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

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

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

SOFC seal and cell thermal management

DOEpatents

Potnis, Shailesh Vijay [Neenah, WI; Rehg, Timothy Joseph [Huntington Beach, CA

2011-05-17

The solid oxide fuel cell module includes a manifold, a plate, a cathode electrode, a fuel cell and an anode electrode. The manifold includes an air or oxygen inlet in communication with divergent passages above the periphery of the cell which combine to flow the air or oxygen radially or inwardly for reception in the center of the cathode flow field. The latter has interconnects providing circuitous cooling passages in a generally radial outward direction cooling the fuel cell and which interconnects are formed of different thermal conductivity materials for a preferential cooling.

All ceramic structure for molten carbonate fuel cell

DOEpatents

Smith, James L.; Kucera, Eugenia H.

1992-01-01

An all-ceramic molten carbonate fuel cell having a composition formed of a multivalent metal oxide or oxygenate such as an alkali metal, transition metal oxygenate. The structure includes an anode and cathode separated by an electronically conductive interconnect. The electrodes and interconnect are compositions ceramic materials. Various combinations of ceramic compositions for the anode, cathode and interconnect are disclosed. The fuel cell exhibits stability in the fuel gas and oxidizing environments. It presents reduced sealing and expansion problems in fabrication and has improved long-term corrosion resistance.

Electrolytic production of neodymium without perfluorinated carbon compounds on the offgases

DOEpatents

Keller, R.; Larimer, K.T.

1998-09-22

A method is described for producing neodymium in an electrolytic cell without formation of perfluorinated carbon gases (PFCs), the method comprising the steps of providing an electrolyte in the electrolytic cell and providing an anode in an anode region of the electrolyte and providing a cathode in a cathode region of the electrolytic cell. Dissolving an oxygen-containing neodymium compound in the electrolyte in the anode region and maintaining a more intense electrolyte circulation in the anode region than in the cathode region. Passing an electrolytic current between said anode and said cathode and depositing neodymium metal at the cathode, preventing the formation of perfluorinated carbon gases by limiting anode over voltage. 4 figs.

Electrolytic production of neodymium without perfluorinated carbon compounds on the offgases

DOEpatents

Keller, Rudolf; Larimer, Kirk T.

1998-01-01

A method of producing neodymium in an electrolytic cell without formation of perfluorinated carbon gases (PFCs), the method comprising the steps of providing an electrolyte in the electrolytic cell and providing an anode in an anode region of the electrolyte and providing a cathode in a cathode region of the electrolytic cell. Dissolving an oxygen-containing neodymium compound in the electrolyte in the anode region and maintaining a more intense electrolyte circulation in the anode region than in the cathode region. Passing an electrolytic current between said anode and said cathode and depositing neodymium metal at the cathode, preventing the formation of perfluorinated carbon gases by limiting anode over voltage.

12Cao-7Al2o3 Electride Hollow Cathode

NASA Technical Reports Server (NTRS)

Martinez, Rafael A. (Inventor); Williams, John D. (Inventor); Rand, Lauren P. (Inventor)

2016-01-01

The use of the electride form of 12CaO-7Al.sub.2O.sub.3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

12CaO-7Al2O3 Electride Hollow Cathode

NASA Technical Reports Server (NTRS)

Williams, John D. (Inventor); Rand, Lauren P. (Inventor); Martinez, Rafael A. (Inventor)

2017-01-01

The use of the electride form of 12CaO-7Al2O3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

Novel carbon fiber cathode membrane with Fe/Mn/C/F/O elements in bio-electrochemical system (BES) to enhance wastewater treatment

NASA Astrophysics Data System (ADS)

Gao, Changfei; Liu, Lifen; Yang, Fenglin

2018-03-01

A novel conductive membrane with Fe/Mn/C/F/O elements is developed, it functions as the catalytic cathode of MFC and the antifouling filter of MBR simultaneously, in a newly designed integrated wastewater treatment system, without proton exchange membrane (PEM). The optimal conductive membrane is characterized using SEM-EDX, XRD and XPS. BET and porous structure analysis of the grounded membrane material indicate a narrow and small pore size (2-7 nm). The membrane surface is rich in Fe species (Fe - Fe2O3- Fe3O4) and manganese oxide (MnO2). Its characteristics such as excellent electro-chemical oxygen reduction reaction (ORR) activity, high clear water flux (>240 L/(m2·h)) and better antifouling filtration performance are further confirmed. The new system features bio-electrochemical system (BES) and integrates bio-filtration (trickling filter and air contact oxidation bed) and proton transfer through quartz sand chamber (QSC) which eliminates the use of expensive proton exchange membrane. The system removes chemical oxygen demand (>97.4%), ammonia nitrogen (>96.7%), total phosphorus (>98.0%) effectively, and it simultaneously generates electricity (446 mW/m3). The low cost and high performances, economic and advantageous system has good compatibility with existing wastewater treatment facilities and a wide application prospect.

Cable Bacteria in Freshwater Sediments

PubMed Central

Kristiansen, Michael; Frederiksen, Rasmus B.; Dittmer, Anders Lindequist; Bjerg, Jesper Tataru; Trojan, Daniela; Schreiber, Lars; Damgaard, Lars Riis; Schramm, Andreas; Nielsen, Lars Peter

2015-01-01

In marine sediments cathodic oxygen reduction at the sediment surface can be coupled to anodic sulfide oxidation in deeper anoxic layers through electrical currents mediated by filamentous, multicellular bacteria of the Desulfobulbaceae family, the so-called cable bacteria. Until now, cable bacteria have only been reported from marine environments. In this study, we demonstrate that cable bacteria also occur in freshwater sediments. In a first step, homogenized sediment collected from the freshwater stream Giber Å, Denmark, was incubated in the laboratory. After 2 weeks, pH signatures and electric fields indicated electron transfer between vertically separated anodic and cathodic half-reactions. Fluorescence in situ hybridization revealed the presence of Desulfobulbaceae filaments. In addition, in situ measurements of oxygen, pH, and electric potential distributions in the waterlogged banks of Giber Å demonstrated the presence of distant electric redox coupling in naturally occurring freshwater sediment. At the same site, filamentous Desulfobulbaceae with cable bacterium morphology were found to be present. Their 16S rRNA gene sequence placed them as a distinct sister group to the known marine cable bacteria, with the genus Desulfobulbus as the closest cultured lineage. The results of the present study indicate that electric currents mediated by cable bacteria could be important for the biogeochemistry in many more environments than anticipated thus far and suggest a common evolutionary origin of the cable phenotype within Desulfobulbaceae with subsequent diversification into a freshwater and a marine lineage. PMID:26116678

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

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

Li, Hui; Li, Qi; Wen, Peng

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

DOE PAGES

Li, Hui; Li, Qi; Wen, Peng; ...

2018-01-15

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

A hybrid DNA-templated gold nanocluster for enhanced enzymatic reduction of oxygen

DOE PAGES

Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; ...

2015-08-19

We report the synthesis and characterization of a new DNA-templated gold nanocluster (AuNC) of ~1 nm in diameter and possessing ~7 Au atoms. When integrated with bilirubin oxidase (BOD) and single walled carbon nanotubes (SWNTs), the AuNC acts as an enhancer of electron transfer (ET) and lowers the overpotential of electrocatalytic oxygen reduction reaction (ORR) by ~15 mV as compared to the enzyme alone. In addition, the presence of AuNC causes significant enhancements in the electrocatalytic current densities at the electrode. Control experiments show that such enhancement of ORR by the AuNC is specific to nanoclusters and not to plasmonicmore » gold particles. Rotating ring disk electrode (RRDE) measurements confirm 4e– reduction of O 2 to H 2O with minimal production of H 2O 2, suggesting that the presence of AuNC does not perturb the mechanism of ORR catalyzed by the enzyme. This unique role of the AuNC as enhancer of ET at the enzyme-electrode interface makes it a potential candidate for the development of cathodes in enzymatic fuel cells, which often suffer from poor electronic communication between the electrode surface and the enzyme active site. In conclusion, the AuNC displays phosphorescence with large Stokes shift and microsecond lifetime.« less

Bath for electrolytic reduction of alumina and method therefor

DOEpatents

Brown, Craig W.; Brooks, Richard J.; Frizzle, Patrick B.; Juric, Drago D.

2002-11-26

An electrolytic bath for use during the electrolytic reduction of alumina to aluminum. The bath comprises a molten electrolyte having the following ingredients: (a) AlF.sub.3 and at least one salt selected from the group consisting of NaF, KF, and LiF; and (b) about 0.004 wt. % to about 0.2 wt. %, based on total weight of the molten electrolyte, of at least one transition metal or at least one compound of the metal or both. The compound may be, for example, a fluoride, oxide, or carbonate. The metal can be nickel, iron, copper, cobalt, or molybdenum. The bath can be employed in a combination that includes a vessel for containing the bath and at least one non-consumable anode and at least one dimensionally stable cathode in the bath. Employing the bath of the present invention during electrolytic reduction of alumina to aluminum can improve the wetting of aluminum on a cathode by reducing or eliminating the formation of non-metallic deposits on the cathode. Removing sulfur from the bath can also minimize cathode deposits. Aluminum formed on the cathode can be removed directly from the cathode.

Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

NASA Astrophysics Data System (ADS)

Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2015-09-01

Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

A New Electron Source for Laboratory Simulation of the Space Environment

NASA Technical Reports Server (NTRS)

Krause, Linda Habash; Everding, Daniel; Bonner, Mathew; Swan, Brian

2012-01-01

We have developed a new collimated electron source called the Photoelectron Beam Generator (PEBG) for laboratory and spaceflight applications. This technology is needed to replace traditional cathodes because of serious fundamental weaknesses with the present state of the art. Filament cathodes suffer from numerous practical problems, even if expertly designed, including the dependence of electron emission on filament temperature, short lifetimes (approx 100 hours), and relatively high power (approx 10s of W). Other types of cathodes have solved some of these problems, but they are plagued with other difficult problems, such as the Spindt cathode's extreme sensitivity to molecular oxygen. None to date have been able to meet the demand of long lifetime, robust packaging, and precision energy and flux control. This new cathode design avoids many common pitfalls of traditional cathodes. Specifically, there are no fragile parts, no sensitivity to oxygen, no intrinsic emission dependencies on device temperature, and no vacuum requirements for protecting the source from contamination or damage. Recent advances in high-brightness Light Emitting Diodes (LEDs) have provided the key enabling technology for this new electron source. The LEDs are used to photoeject electrons off a target material of a low work-function, and these photoelectrons are subsequently focused into a laminar beam using electrostatic lenses. The PEBG works by illuminating a target material and steering photoelectrons into a laminar beam using electrostatic lenses

Study on structural refinement and electrochemical behaviour of Ba0.5Sr0.5Co0.8Fe0.2O3-δ as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC)

NASA Astrophysics Data System (ADS)

Kautkar, Pranay R.; Shirbhate, Shraddha C.; Acharya, Smita A.

2018-05-01

Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) was prepared by ethylene glycol-citrate combined sol-gel combustion route and calcined at optimized temperature 1050°C. The X-ray Diffraction (XRD) data revealing the crystal purity of BSCF cathode was refined by the Cubic-type structure having the space group Pm-3m by Rietveld analysis. Refined lattice parameter of BSCF cathode is a = 3.9759 Å and unit cell volume is 62.85 (4) Å3, Co/Fe-O bond length from VESTA program figured out to be 1.987 (3) Å. Electron density distribution (EDD) of the unit cell of BSCF cathode shows the bonding feature with oxygen ions, this could represent oxygen vacancies are present in the lattice. These results reflected in electrochemical impedance spectra measurement of symmetric cell. Area of specific resistance (ASR) of the BSCF cathode was found to be 0.17 Ω.cm2 at 700°C and respective activation energy (Ea) 1.15 eV. It shows surface exchange at cathode interface, surface diffusion and self-diffusion happened through Ce0.85Sd0.15O1.95 (SDC15) electrolyte.

Oxygen evolution from olivine M n1 -xMxP O4 (M =Fe ,Ni,Al,Mg) delithiated cathode materials

NASA Astrophysics Data System (ADS)

Snydacker, David H.; Wolverton, C.

2017-01-01

Olivine LiMnP O4 is a promising cathode material for Li-ion batteries. One drawback of this material is the propensity of its delithiated phase, MnP O4 , to evolve oxygen gas above approximately 200 °C. During thermal runaway of cells, this oxygen gas can burn the electrolyte and other cell components and thereby jeopardize safety. Partial substitution of Mn with M =Fe , Ni, Al, or Mg has been used to improve the lithium intercalation kinetics of L ixMnP O4 ; however, the effect of these substitutions on oxygen evolution is not fully documented. In this paper, we calculate phase diagrams and oxygen evolution diagrams for these M n1 -xMxP O4 delithiated cathode materials. To generate the phase diagrams, we use subregular solid-solution models and fit the energetic parameters of these models to density functional theory calculations of special quasirandom structures. The resulting thermodynamic models describe the effect of mixing on the initial temperature of oxygen evolution and on the cumulative amount of oxygen evolution at elevated temperatures. We find that addition of Fe increases the initial temperature and decreases the cumulative amount of oxygen evolution. M n0.5F e0.5P O4 exhibits an initial temperature 50 °C higher than MnP O4 and releases 70% less oxygen gas at 300 °C. Al is insoluble in MnP O4 , so addition of Al has no affect on the initial temperature. However, Al addition does slightly decrease the amount of oxygen evolution due to an inactive AlP O4 component. Mg and Ni both decrease the initial temperature of oxygen evolution, and therefore may worsen the safety of MnP O4 .

RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

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

Xu, Yue-Feng; Chen, Yuan; Xu, Gui-Liang

RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presentedmore » much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge process of Li-O-2 battery.« less

Flexible lithium–oxygen battery based on a recoverable cathode

PubMed Central

Liu, Qing-Chao; Xu, Ji-Jing; Xu, Dan; Zhang, Xin-Bo

2015-01-01

Although flexible power sources are crucial for the realization next-generation flexible electronics, their application in such devices is hindered by their low theoretical energy density. Rechargeable lithium–oxygen (Li–O2) batteries can provide extremely high specific energies, while the conventional Li–O2 battery is bulky, inflexible and limited by the absence of effective components and an adjustable cell configuration. Here we show that a flexible Li–O2 battery can be fabricated using unique TiO2 nanowire arrays grown onto carbon textiles (NAs/CT) as a free-standing cathode and that superior electrochemical performances can be obtained even under stringent bending and twisting conditions. Furthermore, the TiO2 NAs/CT cathode features excellent recoverability, which significantly extends the cycle life of the Li–O2 battery and lowers its life cycle cost. PMID:26235205

Cathodic Potential Dependence of Electrochemical Reduction of SiO2 Granules in Molten CaCl2

NASA Astrophysics Data System (ADS)

Yang, Xiao; Yasuda, Kouji; Nohira, Toshiyuki; Hagiwara, Rika; Homma, Takayuki

2016-09-01

As part of an ongoing fundamental study to develop a new process for producing solar-grade silicon, this paper examines the effects of cathodic potential on reduction kinetics, current efficiency, morphology, and purity of Si product during electrolysis of SiO2 granules in molten CaCl2 at 1123 K (850 °C). SiO2 granules were electrolyzed potentiostatically at different cathodic potentials (0.6, 0.8, 1.0, and 1.2 V vs Ca2+/Ca). The reduction kinetics was evaluated based on the growth of the reduced Si layer and the current behavior during electrolysis. The results suggest that a more negative cathodic potential is favorable for faster reduction. Current efficiencies in 60 minutes are greater than 65 pct at all the potentials examined. Si wires with sub-micron diameters are formed, and their morphologies show little dependence on the cathodic potential. The impurities in the Si product can be controlled at low level. The rate-determining step for the electrochemical reduction of SiO2 granules in molten CaCl2 changes with time. At the initial stage of electrolysis, the electron transfer is the rate-determining step. At the later stage, the diffusion of O2- ions is the rate-determining step. The major cause of the decrease in reduction rate with increasing electrolysis time is the potential drop from the current collector to the reaction front due to the increased contact resistance among the reduced Si particles.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

Freestanding and flexible graphene papers as bioelectrochemical cathode for selective and efficient CO2 conversion.

PubMed

Aryal, Nabin; Halder, Arnab; Zhang, Minwei; Whelan, Patrick R; Tremblay, Pier-Luc; Chi, Qijin; Zhang, Tian

2017-08-22

During microbial electrosynthesis (MES) driven CO 2 reduction, cathode plays a vital role by donating electrons to microbe. Here, we exploited the advantage of reduced graphene oxide (RGO) paper as novel cathode material to enhance electron transfer between the cathode and microbe, which in turn facilitated CO 2 reduction. The acetate production rate of Sporomusa ovata-driven MES reactors was 168.5 ± 22.4 mmol m -2 d -1 with RGO paper cathodes poised at -690 mV versus standard hydrogen electrode. This rate was approximately 8 fold faster than for carbon paper electrodes of the same dimension. The current density with RGO paper cathodes of 2580 ± 540 mA m -2 was increased 7 fold compared to carbon paper cathodes. This also corresponded to a better cathodic current response on their cyclic voltammetric curves. The coulombic efficiency for the electrons conversion into acetate was 90.7 ± 9.3% with RGO paper cathodes and 83.8 ± 4.2% with carbon paper cathodes, respectively. Furthermore, more intensive cell attachment was observed on RGO paper electrodes than on carbon paper electrodes with confocal laser scanning microscopy and scanning electron microscopy. These results highlight the potential of RGO paper as a promising cathode for MES from CO 2 .

New Electrode and Electrolyte Configurations for Lithium-Oxygen Battery.

PubMed

Ulissi, Ulderico; Elia, Giuseppe Antonio; Jeong, Sangsik; Reiter, Jakub; Tsiouvaras, Nikolaos; Passerini, Stefano; Hassoun, Jusef

2018-03-02

Cathode configurations reported herein are alternative to the most diffused ones for application in lithium-oxygen batteries, using an ionic liquid-based electrolyte. The electrodes employ high surface area conductive carbon as the reaction host, and polytetrafluoroethylene as the binding agent to enhance the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) reversibility. Roll-pressed, self-standing electrodes (SSEs) and thinner, spray deposited electrodes (SDEs) are characterized in lithium-oxygen cells using an ionic liquid (IL) based electrolyte formed by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI). The electrochemical results reveal reversible reactions for both electrode configurations, but improved electrochemical performance for the self-standing electrodes in lithium-oxygen cells. These electrodes show charge/discharge polarizations at 60 °C limited to 0.4 V, with capacity up to 1 mAh cm -2 and energy efficiency of about 88 %, while the spray deposited electrodes reveal, under the same conditions, a polarization of 0.6 V and energy efficiency of 80 %. The roll pressed electrode combined with the DEMETFSI-LiTFSI electrolyte and a composite Li x Sn-C alloy anode forms a full Li-ion oxygen cell showing extremely limited polarization, and remarkable energy efficiency. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

PubMed Central

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-01-01

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g−1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g−1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes. PMID:27088834

Method for manufacturing high quality carbon nanotubes

NASA Technical Reports Server (NTRS)

Benavides, Jeanette M. (Inventor)

2006-01-01

A non-catalytic process for the production of carbon nanotubes includes supplying an electric current to a carbon anode and a carbon cathode which have been securely positioned in the open atmosphere with a gap between them. The electric current creates an electric arc between the carbon anode and the carbon cathode, which causes carbon to be vaporized from the carbon anode and a carbonaceous residue to be deposited on the carbon cathode. Inert gas is pumped into the gap to flush out oxygen, thereby preventing interference with the vaporization of carbon from the anode and preventing oxidation of the carbonaceous residue being deposited on the cathode. The anode and cathode are cooled while electric current is being supplied thereto. When the supply of electric current is terminated, the carbonaceous residue is removed from the cathode and is purified to yield carbon nanotubes.

Toward highly efficient electrocatalyst for Li–O 2 batteries using biphasic N-doping cobalt@graphene multiple-capsule heterostructures

DOE PAGES

Tan, Guoqiang; Chong, Lina; Amine, Rachid; ...

2017-04-12

To promote lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport, and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electro-active zones possible; furthermore, the colander-like porous electrode facilitates themore » oxygen diffusion, catalytic reaction, and stable deposition of discharge products. Finally, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.« less