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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Comparison of chromium poisoning between lanthanum strontium manganite and lanthanum strontium ferrite composite cathodes in solid oxide fuel cells

Degradation mechanisms of chromium poisoning have been extensively investigated for last two decades on various cathode materials for solid oxide fuel cells. While most researchers used half-cell experiments to investigate the effects of chromium impurities, this paper compares the degradation phenomena of LSM-YSZ and LSF-GDC cathodes in full cells under different operating conditions, namely polarized current density and humidity over the cathode. Under cathodic load, performance degradation of LSF-GDC cathode is significantly less than that of LSM-YSZ cathode. Most interestingly, under humidified air condition, LSF-based cell hardly experiences performance degradation while LSM-based cell shows a catastrophic degradation. Cr deposition in LSM-based cells occurs mainly near the electrolyte under both dry and humidified air conditions. In contrast, Cr deposition in LSF-based cell concentrates at the cathode surface under dry air condition, but concentrates both at cathode surface and near electrolyte under humidified air condition. Microstructure analysis reveals Mn-associated Cr deposits in LSM-based cathode, and Sr- and Fe-associated Cr deposits in LSF-based cathode. With the help of distribution of relaxation time analysis, the different electrochemical behaviors of LSM- and LSF-based cells are carefully interpreted. The effects of electrochemical deposition, Sr surface segregation, and humidity on LSM- and LSF-based cathodes are discussed.

25 ENERGY STORAGE↗
DOE OSTI2026

Understanding the Performance Gap between Polycrystalline and Single-Crystal Nickel-Rich Layered Oxide Cathodes

Singe-crystal (SC) nickel-rich layered oxide cathodes, composed of boundary-free particles with high tap density, offer significant advantages in volumetric energy density and mechanical strength compared with polycrystalline (PC) cathode materials. However, as the nickel content increases (≥80%), SC Ni-rich cathodes often suffer from faster performance degradation than PC cathodes of the same composition, and the underlying causes of this discrepancy remain poorly understood. Herein, we reveal the distinct Ni redox behaviors that govern the electrochemical performance of SC and PC Ni-rich cathodes using multiscale and operando characterization techniques. Our results indicate that the increasingly heterogeneous Ni oxidation process in SC cathodes leads to the additional irreversible oxygen redox activity that deteriorates both the mechanical and chemical structures. In contrast, PC cathodes, despite with more pronounced surface reconstruction, exhibit greater chemomechanical stability due to homogeneous redox reactions during charging. Consequently, we find that bulk degradation, more than surface reactions, ultimately leads to fast capacity decay of SC Ni-rich cathodes during cycling. In conclusion, this work offers a comprehensive view on the impact of Ni redox evolutions on the chemomechanical stability in Ni-rich layered oxide cathodes, providing new insights into the longstanding performance gap between SC and PC cathodes, and guiding the rational design of Ni-rich cathode architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rarefied xenon flow in orificed hollow cathodes

A parametric study is conducted to quantify the effect of the keeper electrode geometry on the xenon neutral flow quantities within orificed hollow cathodes, prior to ignition. The keeper impinges directly on the flow out of the cathode orifice and its geometry influences the product between the pressure in the orifice–keeper region and the cathode-to-keeper distance. A representative cathode is simulated using the Direct Simulation Monte Carlo method. The numerical model is first validated with computational results from the literature. A parametric study is then conducted. Parameters include the cathode pressure–diameter in the range of 1–5 Torr cm and the following geometric ratios (and ranges): cathode orifice-to-inner radii (0.1–0.7), keeper orifice-to-cathode orifice radii (1–5), and keeper distance-to-cathode-orifice diameter (0.5–10). It is found that, if both keeper and cathode have identical orifice radii, the flow remains subsonic in the orifice-to-keeper region. In most cases, however, the flow becomes underexpanded and supersonic, and the static pressure within the orifice-to-keeper region is, on average, 4% that of the upstream pressure value. The orifice–keeper region pressure increases with either a decrease in the keeper orifice diameter or an increase in the distance between cathode and keeper, in agreement with literature data. Both trends are explained through conservation laws. A statistical study of numerical results reveals that the ratio of ignition-to-nominal mass flow rates has a most probable value of 50, which suggests that heaterless cathode ignition at a minimum DC voltage may be achieved by increasing the input mass flow rate by a factor of 50.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1979

Thermionic cathode life-test studies

A NASA-Lewis Research Center program for life testing commercial, high-current-density thermionic cathodes has been in progress since 1971. The purpose of the program is to develop long-life power microwave tubes for space communications. Four commercial-type cathodes are being evaluated in this investigation. They are the 'Tungstate', 'S' type, 'B' type, and 'M' type cathodes, all of which are capable of delivering 1 A/ sq cm or more of emission current at an operating temperature in the range of 1000-1100 C. The life test vehicles used in these studies are similar in construction to that of a high-power microwave tube and employ a high-convergence electron-gun structure; in contrast to earlier studies that used close-space diodes. These guns were designed for operation at 2 A/sq cm of cathode loading. The 'Tungstate' cathodes failed at 700 h or less and the 'S' cathode exhibited a lifetime of about 20,000 h. One 'B' cathode has failed after 27,000 h, the remaining units continuing to operate after up to 30,000 h. Only limited data are now available for the 'M' cathode, because only one has been operated for as long as 19,000 h. However, the preliminary results indicate the emission current from the 'M' cathode is more stable than the 'B' cathode and that it can be operated at a true temperature approximately 100 C lower than for the 'B' cathode.

Forman, R.↗
NASA NTRS1991

Microanalyses of extended-test xenon hollow cathodes

Four hollow cathodes have been examined using boroscopy, scanning electron microscopy, energy dispersive X-ray analysis, and X-ray diffraction analysis to characterize the life-limiting phenomena that resulted from their extended operation. The first pair of cathodes was operated for approximately 500 h in an ion thruster simulator at a 5.0 kW-equivalent power level using different cathode activation and propellant feed-system procedures. The second pair of cathodes was the main discharge cathode and neutralizer cathode from an ion thruster which have completed an 89-hour life-test at a 5.5 kW power level. The greatest change to the cathode condition was found to be removal of refractory metals, primarily tungsten, and their subsequent deposition on other cathode surfaces. Barium tungstate and barium molybdate were also found in all four cathodes. Criteria for improved cathode longevity and discharge operation are proposed for use in hollow cathode and full thruster testing facilities.

Verhey, Timothy R.↗
NASA NTRS2000

Scenario for Hollow Cathode End-Of-Life

Recent successful hollow cathode life tests have demonstrated that lifetimes can meet the requirements of several space applications. However, there are no methods for assessing cathode lifetime short of demonstrating the requirement. Previous attempts to estimate or predict cathode lifetime were based on relatively simple chemical depletion models derived from the dispenser cathode community. To address this lack of predicative capability, a scenario for hollow cathode lifetime under steady-state operating conditions is proposed. This scenario has been derived primarily from the operating behavior and post-test condition of a hollow cathode that was operated for 28,000 hours. In this scenario, the insert chemistry evolves through three relatively distinct phases over the course of the cathode lifetime. These phases are believed to correspond to demonstrable changes in cathode operation. The implications for cathode lifetime limits resulting from this scenario are examined, including methods to assess cathode lifetime without operating to End-of- Life and methods to extend the cathode lifetime.

Sarver-Verhey, Timothy R.↗
NASA NTRS1988

Emission current control system for multiple hollow cathode devices

An emission current control system for balancing the individual emission currents from an array of hollow cathodes has current sensors for determining the current drawn by each cathode from a power supply. Each current sensor has an output signal which has a magnitude proportional to the current. The current sensor output signals are averaged, the average value so obtained being applied to a respective controller for controlling the flow of an ion source material through each cathode. Also applied to each controller are the respective sensor output signals for each cathode and a common reference signal. The flow of source material through each hollow cathode is thereby made proportional to the current drawn by that cathode, the average current drawn by all of the cathodes, and the reference signal. Thus, the emission current of each cathode is controlled such that each is made substantially equal to the emission current of each of the other cathodes. When utilized as a component of a multiple hollow cathode ion propulsion motor, the emission current control system of the invention provides for balancing the thrust of the motor about the thrust axis and also for preventing premature failure of a hollow cathode source due to operation above a maximum rated emission current.

Beattie, John R.↗
NASA NTRSDate not supplied

Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries

Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2)are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged.The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3 for Li-CO2 batteries, are insoluble in the electrolyte.Therefore, in order for such batteries to function properly, an “air cathode”,which is a conductive scaffold within the battery cell,is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process. Here we present an ultrathick,holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness.The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials.The dry-pressed holey graphene air cathode platform is not only compatible with catalyst incorporation to improve battery reaction kinetics, but also allows for novel engineering of electrode architectures that is not achievable using conventional electrode fabrication approaches.The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.

Li-O2 batteries, Li-CO2 batteries, holey graphene,↗
DOE OSTI2024

Acid Etching‐Driven Self‐Assembly of Mn‐Shell Inducing Rock‐Salt Phase for Enhanced Single‐Crystal Ni‐Rich Cathodes

With the wide adoption of Li‐ion batteries, Ni‐rich cathode is considered as one of the most promising candidates of cathodes due to its high energy density and low cost. However, stability decreased with increasing Ni content in the Ni‐rich cathode. To solve this bottleneck, many strategies, such as coating, doping, surface modification, and special morphologies, have been developed. Herein, we introduce a groundbreaking approach for enhancing Ni‐rich cathode through an innovative acid etching process that promotes Mn shell self‐assembly, inducing a rock‐salt phase on the surface. This method not only simplifies the Ni‐rich cathode modification process, but also significantly improves the structural stability and electrochemical performance of Ni‐rich cathode. Our findings demonstrate that developed single‐crystal Ni‐rich cathode shows 3–34 % better stability compared to both commercial modified Ni‐rich cathode and unmodified counterparts. The unique Mn shell effectively mitigates reversible phase shifts during cycling, contributing to a remarkable enhancement in cycling stability. Additionally, this novel fabrication technique paves the way for cost‐effective production of high‐performance cathode materials, offering substantial benefits for lithium‐ion battery technology. And this study proves the potential of this method in advancing the design and development of durable, high‐capacity cathode materials for next‐generation batteries.

Ni-rich cathode↗
DOE OSTI2026

Effect of a transparent water-cooled cathode on the neutron production rate in the glow discharge-type fusion neutron source

In glow discharge-type deuterium–deuterium fusion neutron sources, fusion reactions occurring on the cathode surface contribute significantly to the neutron production rate (NPR); therefore, cathode design plays a crucial role in enhancing NPR. Although the NPR generally increases with discharge current, deuterium desorption caused by cathode heating tends to stagnate it in the high-current regime. Water cooling has been shown to mitigate this stagnation for nontransparent cathodes, but its effectiveness for transparent cathodes has not been experimentally clarified. Here, in this study, a transparent cathode with active water cooling and a spherical geometry was designed and fabricated using stainless steel tubing. Neutron production experiments were conducted with and without water cooling: with water cooling, applied voltages of 20–40 kV were investigated, while without water cooling, the applied voltage was limited to 25 kV. The results showed that the NPR increased continuously with discharge current without stagnation when water cooling was applied. A maximum NPR of (1.8 ± 0.02) × 10 6 n/s was achieved at 40 kV and 50 mA. Compared with our previously reported disk cathode and nontransparent water-cooled cathode of the same diameter, the transparent water-cooled cathode exhibited a significantly enhanced NPR. These findings indicate that combining cathode transparency with active cooling is an effective strategy for improving neutron production in glow discharge-type fusion neutron sources.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li 2 CO 3

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energy-density lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li 2 CO 3 impurity content on LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathodes using air, tank-air, and O 2 synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li 2 CO 3 impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li 2 CO 3 content and severe performance deterioration of Ni83 cathodes. The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Here, our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Ni-rich cathodes and prepares us for searching for rational strategies.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High-Nickel Cathode Materials for High-Energy, Long-Life, Low-Cost Lithium-Ion Batteries (Final Report)

The overall goal of this project is to produce Li-ion cells, which deliver at least 600 Wh kg -1 at the cathode level with usable lifetimes of at least 1,000 cycles or 15 years of storage (calendar life). A secondary goal of this project is to minimize the use of cobalt in the cathode, with the ultimate goal of eliminating cobalt entirely. To develop such a cathode, the University of Texas at Austin (UT Austin) team extensively investigated the structural, physical, and chemical properties of layered oxide materials. A panel of dopant elements were surveyed with an emphasis on identifying those, which impart electrochemical and thermal stability. Of those tested, Al and Mg showed the greatest performance improvements while still being easily incorporated into the cathode through simple alterations of the precursor coprecipitation method. Other dopants, such as Ta, Nb, B, and F significantly improved cathode performance, yet their mode of incorporation required additional processing which negated their use under scaled-up conditions. From this work, a first-generation cathode LiNi 0.85 Mn 0.075 Co 0.05 Al 0.02 Mg 0.005 O 2 (NMCAM-85) was produced and an initial set of 2 Ah cells was fabricated by Tesla Inc. These cells delivered 650 Wh kg -1 and a cycle life of just over 700 cycles. Further improvements were garnered through careful study of electrolyte additives. A tailored, ethylene carbonate (EC)-free electrolyte was developed, which improved capacity retention from 60% to 82% after 500 cycles in model LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA-90) full cells. This study identified the additives fluoroethylene carbonate (FEC) and lithium difluorophosphate (LiPO 2 F 2 ) as beneficial additives, which were included in the electrolyte for the end-of-project cells. The UT Austin team developed a high-Ni layered oxide cathode LiNi 0.85 Mn 0.1 Al 0.05 Mg 0.005 O 2 (NMAM-85) capable of meeting the project goals. This cathode was synthesized in kilogram quantities and delivered to Tesla for fabrication into 2 Ah pouch cells for DOE testing. These large-format cells achieved 630 Wh kg -1 at the cathode level under the designated testing parameters, meeting the project goal with a completely cobalt-free cathode. The large-format cells are currently undergoing cycle life and calendar life evaluation at Idaho National Lab.

25 ENERGY STORAGE↗
DOE OSTI2019

LaCoO 3-δ coated Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ cathode for intermediate temperature solid oxide fuel cells

Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) is a promising cathode for intermediate temperature solid oxide fuel cells. Yet, BSCF cathode performance stability has been a challenge and its electrochemical performance deteriorates severely in the presence of Cr2O3-forming metallic interconnect. We demonstrate that LaCoO 3-δ (LC) coating on BSCF cathode can not only enhance BSCF electrochemical performance, but also effectively improve the BSCF performance stability. Here, LC-coated BSCF-Gd 0.1 Ce 0.9 O 1.9 (LC@BSCF-GDC) cathode is prepared through a solution impregnation method and systematically characterized. EIS, XRD, Raman, SEM and EDS tests with and without SUS430 interconnect are conducted to characterize the Cr-tolerance. The results reflect that BSCF-GDC cathode is susceptible to Cr poisoning while LC@BSCF-GDC cathode has significantly enhanced tolerance to Cr poisoning. Single cells with LC@BSCF-GDC cathode achieve higher peak power density and smaller polarization resistance values than that of single cells with BSCF-GDC cathode. Furthermore, significant improvement of performance stability under a constant current load has been achieved for single cells with LC@BSCF-GDC cathode. This work provides a new solution for solving BSCF cathode performance stability.

25 ENERGY STORAGE↗
DOE OSTI2012

Particle size effect of Ni-rich cathode materials on lithium ion battery performance

Graphical abstract: The preparation condition of Ni-rich cathode materials was investigated. When the retention time was short, a poor cathode performance was observed. For long retention time condition, cathode performance displayed a best result at pH 12. Highlights: Black-Right-Pointing-Pointer Ni-rich cathode materials (LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}) were prepared by co-precipitation method using separate addition of Al salt. Black-Right-Pointing-Pointer Particle size of Ni-rich cathode materials became larger with increase of retention time and solution pH. Black-Right-Pointing-Pointer Cathode performance was poor for low retention time. Black-Right-Pointing-Pointer Optimal pH for co-precipitation was 12. -- Abstract: Herein, Ni-rich cathode materials (LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}) in lithium ion batteries are prepared by a separate addition of Ni/Co salt and Al sol solution using a continuously stirred tank reactor. Retention time and solution pH were controlled in order to obtain high performance cathode material. Particle size increase was observed with a higher retention time of the reactants. Also, primary and secondary particles became smaller according to an increase of solution pH, which was probably due to a decrease of growth rate. From the cathode application, a high discharge capacity (175 mAh g{sup -1}), a high initial efficiency (90%) and a good cycleability were observed in the cathode material prepared under pH 12 condition, which was attributed to its well-developed layered property and the optimal particle size. However, rate capability was inversely proportional to the particle size, which was clarified by a decrease of charge-transfer resistance measured in the electrochemical impedance spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Elucidating the Redox Behavior during Atomic Layer Deposition on Lithium-Ion Battery Cathode Materials

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials upon ALD coating are not fully studied. This paper describes a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al 2 O 3 ) using trimethyl aluminum (TMA) and H 2 O, and aluminum fluoride (AlF 3 ) using TMA and hydrogen fluoride pyridine (HFPy). Here, the surface composition of these cathode materials, which range from simple transition metal oxides (e.g. NiO and MnO) to complex multi-element cathode materials (e.g. LiNi x Mn 1-x-y Co y O 2 , NMC), was studied via X-ray photoelectron spectroscopy (XPS). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. The ability to chemically modify the surface of cathode materials via vapor-phase precursor adsorption will open new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.

25 ENERGY STORAGE↗
DOE OSTI2020

Magnetite nanoparticle anchored graphene cathode enhances microbial electrosynthesis of polyhydroxybutyrate by Rhodopseudomonas palustris TIE-1

Microbial electrosynthesis (MES) is an emerging technology that can convert carbon dioxide (CO 2 ) into value-added organic carbon compounds using electrons supplied from a cathode. However, MES is affected by low product formation due to limited extracellular electron uptake by microbes. Herein, a novel cathode was developed from chemically synthesized magnetite nanoparticles and reduced graphene oxide nanocomposite (rGO-MNPs). This nanocomposite was electrochemically deposited on carbon felt (CF/rGO-MNPs), and the modified material was used as a cathode for MES production. The bioplastic, polyhydroxybutyrate (PHB) produced by Rhodopseudomonas palustris TIE-1 (TIE-1), was measured from reactors with modified and unmodified cathodes. Results demonstrate that the magnetite nanoparticle anchored graphene cathode (CF/rGO-MNPs) exhibited higher PHB production (91.31 ± 0.9 mg l -1 ). This is ~4.2 times higher than unmodified carbon felt (CF), and 20 times higher than previously reported using graphite. This modified cathode enhanced electron uptake to -11.7 ± 0.1 μ A cm -2 , ~5 times higher than CF cathode (-2.3 ± 0.08 μ A cm -2 ). The faradaic efficiency of the modified cathode was ~2 times higher than the unmodified cathode. Electrochemical analysis and scanning electron microscopy suggest that rGO-MNPs facilitated electron uptake and improved PHB production by TIE-1. Overall, the nanocomposite (rGO-MNPs) cathode modification enhances MES efficiency.

Materials Science↗
DOE OSTI2018

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

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/FMNH 2 ) 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/FMNH 2 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. The majority of our knowledge of the physiology of extracellular electron transfer derives from studies of electrons moving to the exterior of the cell. The physiological mechanisms and/or consequences of the reverse processes are largely uncharacterized. This report demonstrates that when coupled to oxygen reduction, electrode oxidation can result in cellular energy acquisition. This respiratory process has potentially important implications for how microorganisms persist in energy-limited environments, such as reduced sediments under changing redox conditions. From an applied perspective, this work has important implications for microbially catalyzed processes on electrodes, particularly with regard to understanding models of cellular conversion of electrons from cathodes to microbially synthesized products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

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

New unique hetero-structured cathode has been developed in this project. La 2 NiO 4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 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 the enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO 2 & La 2-x NiO 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗