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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Optimization of Extended-Surface PtNi Nanowire Oxygen Reduction Electrocatalysts Produced via Atomic Layer Deposition

Polymer electrolyte membrane fuel cells (PEMFCs) produce electricity with only heat and water as byproducts, but sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode and durability limitations restrict widespread commercialization, motivating the development of advanced catalysts. In this research, extended-surface platinum nickel (PtNi) nanowires (NWs) synthesized using the scalable atomic layer deposition (ALD) technique are investigated with the goal of exploring the durability benefits of high-aspect-ratio electrocatalysts and the tunability of beneficial kinetic properties. The surface and bulk composition and the structure of the PtNi NWs were investigated as a function of a series of postsynthesis modifications. The results from a combination of electron microscopy and X-ray spectroscopy characterization techniques were correlated to electrochemical performance to gain a comprehensive understanding of the structure-property-performance relationships. The robust structure of the ALD-derived NWs enabled additional postsynthesis optimization steps, which were not possible with previous-generation materials synthesized via spontaneous galvanic displacement, resulting in a catalyst with beneficial properties for catalyst kinetics as well as improved durability. Our study demonstrates potential pathways toward further improving the performance of this class of materials through optimization of bulk and surface properties of the catalyst.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Review—Development of Highly Active and Stable Catalyst Supports and Platinum–Free Catalysts for PEM Fuel Cell

Metal-free, metal-containing, and template-assisted metal-containing nitrogen-modified carbon-based catalysts carbon composite supports, and highly active and electrochemically stable hybrid cathode catalysts for oxygen reduction reaction are reviewed in this manuscript. Here, novel procedures are developed for the synthesis of (i) highly catalytically active PGM-free catalyst and stable carbon composite catalyst supports. The carbon composite catalyst supports are engineered with optimized BET surface area and pore size distribution and with a well-defined kinetic and mass transfer region during the reaction and their performance is dicussed in detail in this review. The surface activation results in increasing carbon graphitization and inclusion of non-metallic active sites on the support surface. The USC catalysts exhibit the initial performance of 0.91 V and a maximum power density of 177 mW cm –2 , with well-defined kinetic and mass-transfer regions and ~2.5% H 2 O 2 production. Activated carbon composite support (ACCS) is modified to optimize its kinetic activity and its electrochemical stability shows excellent thermal stability and support stability under simulated start-up/shut-down operating conditions. The stabilities of various supports developed in this study are compared with those of a commercial Pt/C catalyst. The active sites for the ORR identified with electrochemical and physicochemical methods are pyridinic-N and quaternary-N.

25 ENERGY STORAGE↗
DOE OSTI2023

The effect of ink ball milling time on interparticle interactions and ink microstructure and their influence on crack formation in rod-coated catalyst layers

This work investigates the influence of ballmilling (sometimes also referred to as jar roller milling) time on cathode catalyst layer (CL) inks and electrode properties using formulations and coating methods relevant for industrial manufacturing. Four CL inks with the same composition were milled for 24, 48, 72, or 96 h. Rheological investigation of these inks showed a reduction of elastic moduli and steady-shear viscosity with continuous ink milling, which is correlated to a decrease in particle-particle interactions as well as formation of smaller agglomerates. Optical microscopy (OM) analysis of the fabricated electrodes revealed a trend in surface crack formation; formulations milled for 24 h contained the lowest average surface crack area percentages of 0.370% at heavy-duty loadings of ~0.300 mg Pt cm -2 , compared to 2.418% for the ink milled for 96 h. Further characterization of the CL through transmission electron microscopy (TEM) imaging showed a decrease in the mean agglomerate and pore size with milling time. Furthermore, these smaller electrode features were consistent with reduced fracture resistance and, hence, development of larger stresses during drying. Our results highlight the need to consider ink processing as an important component in defect-free CL manufacturing.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Ni oxides and oxyhydroxides (NiO x ) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO x . Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO 2 layers. All the Ni 3+ cations in this structure exhibit an identical t g 6 e g 1 electronic configuration with an occupied 3d z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Modifying the organic/electrode interface in Organic Solar Cells (OSCs) and improving the efficiency of solution-processed phosphorescent Organic Light-Emitting Diodes (OLEDs)

Organic semiconductors devices, such as, organic solar cells (OSCs), organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs) have drawn increasing interest in recent decades. As organic materials are flexible, light weight, and potentially low-cost, organic semiconductor devices are considered to be an alternative to their inorganic counterparts. This dissertation will focus mainly on OSCs and OLEDs. As a clean and renewable energy source, the development of OSCs is very promising. Cells with 9.2% power conversion efficiency (PCE) were reported this year, compared to < 8% two years ago. OSCs belong to the so-called third generation solar cells and are still under development. While OLEDs are a more mature and better studied field, with commercial products already launched in the market, there are still several key issues: (1) the cost of OSCs/OLEDs is still high, largely due to the costly manufacturing processes; (2) the efficiency of OSCs/OLEDs needs to be improved; (3) the lifetime of OSCs/OLEDs is not sufficient compared to their inorganic counterparts; (4) the physics models of the behavior of the devices are not satisfactory. All these limitations invoke the demand for new organic materials, improved device architectures, low-cost fabrication methods, and better understanding of device physics. For OSCs, we attempted to improve the PCE by modifying the interlayer between active layer/metal. We found that ethylene glycol (EG) treated poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) improves hole collection at the metal/polymer interface, furthermore it also affects the growth of the poly(3- hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) blends, making the phase segregation more favorable for charge collection. We then studied organic/inorganic tandem cells. We also investigated the effect of a thin LiF layer on the hole-collection of copper phthalocyanine (CuPc)/C70-based small molecular OSCs. A thin LiF layer serves typically as the electron injection layer in OLEDs and electron collection interlayer in the OSCs. However, several reports showed that it can also assist in holeinjection in OLEDs. Here we first demonstrate that it assists hole-collection in OSCs, which is more obvious after air-plasma treatment, and explore this intriguing dual role. For OLEDs, we focus on solution processing methods to fabricate highly efficient phosphorescent OLEDs. First, we investigated OLEDs with a polymer host matrix, and enhanced charge injection by adding hole- and electron-transport materials into the system. We also applied a hole-blocking and electron-transport material to prevent luminescence quenching by the cathode. Finally, we substituted the polymer host by a small molecule, to achieve more efficient solution processed small molecular OLEDs (SMOLEDs); this approach is cost-effective in comparison to the more common vacuum thermal evaporation. All these studies help us to better understand the underlying relationship between the organic semiconductor materials and the OSCs and OLEDs’ performance and will subsequently assist in further enhancing the efficiencies of OSCs and OLEDs. With better efficiency and longer lifetime, the OSCs and OLEDs will be competitive with their inorganic counterparts.

14 SOLAR ENERGY↗
DOE OSTI2019

Roll-to-Roll SOFC Manufacturing for Low Cost Energy Generation

Oak Ridge National Laboratory (ORNL) and Redox Power Systems, LLC. collaborated on this project to develop an integrated, continuous roll-to-toll (R2R) manufacturing processes to produce solid oxide fuel cells (SOFCs). SOFCs are ceramic-based electrochemical devices that efficiently produce electricity from hydrogen-containing fuels, including natural gas. Standard processes for manufacturing SOFCs include tape casting of the anode and electrolyte, followed by stacking of the layers, and lamination using a uniaxial press or isostatic press. After high temperature firing, the cathode and electrical contact are screen printed and fired once again to complete the cell. This effort aimed to further develop R2R tape fabrication processes for green cell fabrication with the DOE Battery Manufacturing Facility (BMF) at ORNL as next generation improvements to current methods, focusing on R2R calendering and slot die coating for lower cost, high volume approaches for multilayer green cell fabrication. Two paths were investigated in parallel in this project. The first path was to optimize R2R processing using traditional tape cast materials from the Redox production chain on the BMF’s heated calender for compressing and laminating multilayer materials. The second path was to use BMF’s pilot-scale slot-die coater for R2R manufacturing as an alternative to tape casting of some or all of the layers in the green cell. Processes have been developed and and process conditions have been identified. Additionally, basic process economics were estimated for comparison to Redox current manufacturing approaches for the applicable process modules. The SBV program results will enable Redox to advance lower cost R2R manufacturing processes to produce millions of green cells per year on a single production line. As a result of this work, one invention disclosure has been submitted. In addition, one paper is under preparation for submission to a peer-reviewed journal.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Anode Upcycling via Tailored Solvent Treatment

To achieve a truly closed-loop direct recycling process for lithium-ion batteries, all component materials must be recovered. To date, direct recycling method development has primarily focused on the high-value transition-metal cathode materials, while the inherently lower-value graphite has been challenging to recover in a cost-effective manner. However, end-of-life graphite contains a unique engineered value due to the presence of the solid electrolyte interphase (SEI). Growth of the SEI during the cell's active lifetime stabilizes the electronically reactive graphite surface through an irreversible consumption of Li, and thus necessitates both excess lithiation of the cathode and a costly and time-intensive formation procedure during manufacturing. An optimized pre-formed SEI that capitalizes on existing SEI components from end-of-life batteries has the potential to significantly reduce cathode lithiation requirements and eliminate the critical bottleneck of formation cycling during cell remanufacturing. Further, retaining Li at the anode obviates the need for a separate Li leaching and recovery step, improving the overall efficiency of the direct recycling line. In this work, we present a novel approach to "upcycling" spent graphite through use of tailored chemical treatment to remove adverse (i.e., highly resistive and/or poorly passivating) SEI species while retaining beneficially passivating components. We have explored a rational set of solvents spanning a range of polarity, proticity, and molecular size to evaluate structure-property-performance relationships between applied solvent(s), removed and remaining SEI species, and electrochemical response of the resulting graphite product. Further, we have developed and optimized a robust and holistic analysis procedure that couples symmetric-cell electrochemical testing, multi-modal materials characterization, and advanced electrochemical modeling. These analysis results inform a set of correlative metrics for graphite performance relative to both solvent properties and upcycled SEI composition. We demonstrate effective tunability in the residual SEI composition by varying solvent identity and concentration, and report on several promising solvent systems that achieve comparable or performance to pristine graphite.

anode recycling↗
DOE OSTI2025

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

Galvanostatic Intermittent Titration and Performance Based Analysis of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode

Galvanostatic intermittent titration technique (GITT) - a popular method for characterizing kinetic and transport properties of battery electrodes - is predicated on the proper evaluation of electrode active area. LiNi 0.5044 Co 0.1986 Mn 0.2970 O 2 (NCM523) material exhibits a complex morphology in which sub-micron primary particles aggregate to form secondary particle agglomerates. Our work proposes a new active area formulation for primary/secondary particle agglomerate materials to better mimic the morphology of NCM532 electrodes. Furthermore, this formulation is then coupled with macro-homogeneous models to simulate GITT and half-cell performance of NCM523 electrodes. Subsequently, the model results are compared against the experimental results to refine the area formulation. A single parameter, the surface roughness factor, is proposed to mimic the change in interfacial area, diffusivity and exchange current density simultaneously and detailed modeling results are presented to provide valuable insights into the efficacy of the formulation.

25 ENERGY STORAGE↗
DOE OSTI2018

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2 -Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s ) due to higher initial Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology

25 ENERGY STORAGE↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly 4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Cost-effective Manufacturing and Morphological Stabilization of Nanostructured Cathodes for Commercial Solid Oxide Fuel Cells (SOFCs) [Slides]

The overall goals of the program were to develop methods for preparing and stabilizing SOFC electrodes by infiltration that can be manufactured on a practical scale, then transfer those methods to cells in stacks. Cathodes prepared by infiltration of nanoparticles into a porous scaffold of the electrolyte have demonstrated outstanding electrochemical performance and mechanical strength but are difficult to manufacture due to the large number of infiltration steps required to produce a conductive composite and show poor stability due to sintering of the nanoparticles. At Penn, the main goal was to develop a fabrication method that uses only a small number of infiltration steps. Infiltration with molten salts and electrodeposition were pursued but deemed impractical. A method in which an electronically conductive scaffold consisted of a composite of a mixed conductor, LSF (La 0.9 Sr 0.1 FeO 3 ), with yttria-stabilized zirconia (YSZ) was found to be promising. While some cation mixing between LSF and YSZ was observed during calcination, there was no evidence for new phases in XRD and incorporation of Zr into the perovskite could be minimized by reducing the Sr content of the LSF. To stabilize nanoparticles infiltrated into the LSF-YSZ composite scaffold, the USC team examined the effects of Atomic Layer Deposition with ZrO 2 and infiltrated nanoparticles. Significantly enhanced stability was observed with the infiltrated nanoparticles. The FuelCell Energy team prepared 4”x4” cells in which an LSF-YSZ composite scaffold was cofired with the YSZ electrolyte and infiltrated with LSCF nanoparticles. Apparently because the LSF-YSZ scaffold layer was very thin in this case, the cation mixing that occurred during calcination resulted in a poor scaffold-electrolyte interface which caused reduced performance.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

On-Demand Designing of Cathode Internal Surface Architecture for Dramatic Enhancement of SOFC Performance and Durability

This project is aimed to design and modify the internal surfaces of porous composite cathode from currently commercially viable Solid Oxide Fuel Cells (SOFCs), using additive manufacturing process of Atomic Layer Deposition (ALD). The material systems being investigated are commercial composite electrodes complex three-dimensional topographies. In term of the chemistry of the ALD layer applied on the internal surface of the porous cathode, this project has employed commercially relevant electrolyte, electrocatalyst and noble metal materials set. Such materials are fully compatible with the commercial fuel cells, and this project has developed special nanostructure on the surface of the commercial composite cathodes. The formation of the designed nanoarchitecture on the surface of SOFC cathode has been achieved through precise control of ALD parameters and their effect on overall cell performance and resultant electrochemical reaction mechanism of cathodes has been investigated through full cell electrochemical performance testing and nanostructure characterization by transmission electron microscopy (TEM). Under the support of this award, following has been achieved: (1). For cathode materials in solid oxide fuel cells (SOFCs), such as perovskite mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x (LSCF), cation surface segregation and consequently losing conductivity and active sites for the oxygen reduction reaction (ORR) are problematic. To mitigate the cation segregation and enhance SOFC durability, further decorating the internal backbone surface using the desired electrocatalysts could be a promoting approach. Commonly, the cation segregation such as Sr is very volatile, so the effective surface decoration is ideally conformal. Nevertheless, the conformal surface coating would inevitably alter the ORR pathways that initially take place on the surface of the backbone. To reveal the impact of the conformal coating on both the catalytic activity and the conductivity of the cathode, the unary electrocatalyst of Pt or CoO x , was applied to the LSCF/SDC composite electrode of inherently functional SOFCs, respectively. Both ALD coating layers evolve strong interaction with the LSCF composite cathode. Upon operations, the Pt coating layer remains conformal on LSCF grain surfaces but turns into discrete particles on SDC grain surfaces. Meanwhile, CoO x conformal coating grows to be the discrete nanograins on both the LSCF and SDC grains. ALD coating of the cathode alone reduces the ohmic resistance up to 28 % for the entire cells. The increased conductivity induced by the ALD coating of Pt or CoO x is ascribed to different mechanisms. For the inherent functional SOFCs, the present study presents a novel and feasible approach to apply a conformal, dense coating layer on the surface of a mixed conductor, simultaneously increasing the conductivity and durability of the SOFC cathode. (2). High resistance of the oxygen electrode still significantly hinders the state-of-the-art Solid Oxide Fuel Cells (SOFCs). In particular, for an oxygen electrode consisting of mixed electronic and ionic conductors, such as perovskite lanthanum strontium cobalt ferrite (LSCF), it deteriorates due to its low chemical stability of the grain surface. Such degradation is often associated with the segregation of cations. To prevent the cation surface segregation and its resultant perovskite phase decomposition, we demonstrate a conformal ultra-thin (7-10 nm) surface heterogeneous coating layer consisting of subjacent discrete Pt nanoparticles capped with a superjacent fully dense conformal CoO x layer. The performance studies indicate the ALD coating reduces the cell series resistance by up to 40 %. The conformal CoO x layer consists of randomly orientated but single-layered nanograins, with high-density intergranular and surface grain boundaries serving as the electrochemical reaction sites and facilitating mass transport. The conformal coating layer appears to have successfully suppressed the Sr outward diffusion and confined the Sr enriched layer to a ~ 2 nm interface perovskite phase between the coating layer and the LSCF grain surface. Moreover, this ultra-thin Sr enriched perovskite layer presumably possesses high oxygen vacancy and high ionic conductivity and further imposes tensile strain to the LSCF grain surfaces. With the combination of a conformal CoO x nanoionics, Sr enriched layer, and its strained interface, the ALD coating induced surface layer is estimated to have a conductivity of ~ 1.27x10 4 S/cm, which is over two orders magnitude of that from LSCF at 750 ºC.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2019

Impact of Catalyst Ink Dispersing Methodology on Fuel Cell Performance Using in-Situ X-ray Scattering

This work presents a study of the effects of ultrasonic dispersing methodology and time on catalyst agglomerate size in polymer electrolyte membrane fuel cell catalyst ink dispersions. Cathode catalyst inks were prepared and characterized to elucidate the influences of ultrasonic dispersing method and time on catalyst ink particle size and CCL electrochemical properties. In situ ultra-small-, small-, and wide-angle X-ray scattering analyses were used to study the impact of ultrasonication time and methodology on changes in the agglomerate, aggregate, and particle size and distribution during the dispersing process. Ex-situ transmission electron microscopy was also used to investigate the particle size of these inks. Fuel cell membrane electrode assemblies (MEAs) were prepared and tested to determine the influence of ink properties on CCL electrochemical properties, including the electrochemical active surface area, mass activity, H2/air polarization curves, and oxygen mass-transport resistances. It was found that a combination of brief tip sonication followed by bath sonication was most effective at breaking up agglomerates, leading to maximum catalyst activity and MEA performance. Extended tip sonication was found to be too aggressive and resulted in detachment of the platinum nanoparticles from the carbon black support, which decreased electrochemical surface area and MEA performance. Quantification of oxygen mass transport resistance showed that electrodes with large catalyst agglomerates due to insufficient sonication had a higher non-Fickian (pressure independent) than properly dispersed catalyst. Through correlation of the performance with catalyst particle size, the desired CCL structure was proposed, which will provide insight into dispersion strategies for lab-scale spray coating and other processing techniques, as well as for large-scale manufacturing.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS2015

Testing of an Arcjet Thruster with Capability of Direct-Drive Operation

Electric thrusters typically require a power processing unit (PPU) to convert the spacecraft provided power to the voltage-current that a thruster needs for operation. Testing has been initiated to study whether an arcjet thruster can be operated directly with the power produced by solar arrays without any additional conversion. Elimination of the PPU significantly reduces system-level complexity of the propulsion system, and lowers developmental cost and risk. The work aims to identify and address technical questions related to power conditioning and noise suppression in the system and heating of the thruster in long-duration operation. The apparatus under investigation has a target power level from 400-1,000 W. However, the proposed direct-drive arcjet is potentially a highly scalable concept, applicable to solar-electric spacecraft with up to 100's of kW and beyond. A direct-drive electric propulsion system would be comprised of a thruster that operates with the power supplied directly from the power source (typically solar arrays) with no further power conditioning needed between those two components. Arcjet thrusters are electric propulsion devices, with the power supplied as a high current at low voltage; of all the different types of electric thruster, they are best suited for direct drive from solar arrays. One advantage of an arcjet over Hall or gridded ion thrusters is that for comparable power the arcjet is a much smaller device and can provide more thrust and orders of magnitude higher thrust density (approximately 1-10 N/sq m), albeit at lower I(sub sp) (approximately 800-1000 s). In addition, arcjets are capable of operating on a wide range of propellant options, having been demonstrated on H2, ammonia, N2, Ar, Kr, Xe, while present SOA Hall and ion thrusters are primarily limited to Xe propellant. Direct-drive is often discussed in terms of Hall thrusters, but they require 250-300 V for operation, which is difficult even with high-voltage solar arrays. The arcjet requires under 100 V, which is more in-line with what is easily possible with a solar array. Direct-drive of an electric propulsion system confers the advantage of reducing or eliminating the power processing unit (PPU) that is typically needed to convert the spacecraft-provided power to the voltage and current needed for thruster operation. Since the PPU is typically the most expensive piece of an electric thruster system, from both a fabrication and qualification standpoint, its elimination offers the potential for major reductions in system cost and risk. The design of the arcjet built for this effort was based on previous low power (1 kW class) arcjets. It has a precision machined 99.95% pure tungsten anode which also serves as the nozzle. The anode constrictor region is 1 mm (0.040-in) diameter and 1 mm (0.040-in) long. The cathode is a tungsten welding electrode doped with LaO2; its tip was precision ground to a 30◦ angle ending in a blunt end. The two electrodes are separated by a boron-nitride insulator which also serves as the propellant injection manifold; it ends in six small holes which introduce the propellant gas in the diverging section of the nozzle, directly adjacent to the cathode. The electrodes and insulator are housed in a stainless-steel outer-body, with a Macor insulator at the mid-plane to provide thermal isolation between the front and back halves of the device. The gas seals were made using Grafoil gaskets. Figure 1A shows the assembled thruster in the vacuum chamber; figure 1B shows the thruster in operation on argon at a flow rate of 676 sccm (20 mg/s). Initial testing was conducted in a 3.5-ft diameter vacuum chamber; the ultimate pressure reached during quasi-steady operation of the thruster was about 330 millitorr. The thruster was powered with a high-current, 0-100A, 15 kW power supply. The discharge was initiated with a high-voltage (approximately 10 kV) spark initiator that was isolated from the supply by a stack of diodes. The testing indicated that an operating point exists within the I-V characteristics that is compatible with direct-drive solar-electric operation; for a flow rate of 20 mg/s (argon) the arc could be sustained at a voltage of about 20 V and a current of 25 A (500W).

Martin, Adam K.↗
DOE OSTI2019

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration - FY2018 Final Report

High-value R2R processing is used to support a wide range of products in applications which span many industrial business sectors. The overall R2R process technology can be considered as “mature” as the process methodology and has been in use for decades. This continuous processing technique traditionally involves deposition of material(s) onto moving webs or carriers or other continuous R2R, belt-fed, or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Current process technologies, which typify “roll to roll”, include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multi-layer technologies can be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, a means must be available to enable manufacture of these products in a cost-competitive manner that is affordable by the general consumer. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches.Within the DOE EERE AMO, it was recognized that establishment of a program supported at the DOE National Laboratories, along with their immense design of materials and equipment modelling capabilities enabled with use of high-performance computing, could take advantage of available R2R infrastructure to manufacture new technologies. In FY 2016, a R2R Consortium was established and provided with initial “seed” funding to take an approach that was envisioned to be supportable by advanced manufacturing R2R processes. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy product development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this collaborative project would leverage the capabilities and expertise at each of four laboratories to further the development of an enabling high-volume cost-competitive platform technology. The collaboration team that is comprised of ORNL, ANL, NREL and LBNL, coordinating with EPB and other selected industry partners, was formed in April 2016 to initially address enhancing battery electrode performance and R2R manufacturing challenges. The research efforts were to predict and measure changes and results in electrode morphology and performance based on process condition changes; to evaluate mixed, active, particle size deposition and drying for novel electrode materials; to model various process condition changes and the resulting morphology and electrode performance; and to develop and validate NDE techniques for in-line measurement of battery electrode material properties. These efforts carried through FY 2017 and completed at the end of FY 2018.The approach was to look at compositions of materials with different particle sizes to make electrode samples using a R2R manufacturing process. The shape, size, and morphology of the materials, the chemistry of the formulation, the nature of slurries, their coating rate, the rate of drying all play a role in determining the final coating architecture, quality, and performance. A commercial cathode material was selected to make a series of cathodes and anodes by single pass, dual pass and slot die methods. Analysis of all the compiled results for this battery electrode development were that the best performing cathodes included: dual-pass electrode with large particles near the foil, mixed small and large particles, and small particles only. Whereas, the best performing anodes were with a mix of small and large graphite particles. An additional core project was added in FY 2017 to conduct studies of fuel cell materials that can be produced using R2R processes. The goal of this project is to explore, understand and optimize material and process parameters to support increased throughput, increased quality, and reduced cost for high volume production of gas-diffusion electrodes (GDEs) for PEMFCs. Project work in FY 2018 were to use a R2R process to fabricate electrodes without ionomer overlayer that can produce the equivalent mass activity as spray-coated electrodes with an ionomer overlayer. Oxygen-limiting current measurements were utilized to optimize oxygen mass transport. Alcohol-rich solvents were investigated, and results were that the alcohol and water ratio can be tuned to control ionomer distribution. Water-rich solvents produce a more dispersed ink which results in better high-current density performance.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Techno-Economic Analysis of Scalable Coal-Based Fuel Cells

Researchers at The University of Akron (UA) have demonstrated the technical feasibility of a laboratory coal fuel cell that can economically convert high sulfur coal into electricity with near zero negative environmental impact. Scaling up this coal fuel cell technology to the megawatt scale for the nation’s electric power supply requires two key elements: (i) developing the manufacturing technology for the components of the coal-based fuel cell, and (ii) long term testing of a kW scale fuel cell pilot plant. This project was expected to develop a scalable coal fuel cell manufacturing process through testing, demonstrating the feasibility of building a large-scale coal fuel cell power plant. We have developed a reproducible tape casting technique for the mass production of the planner fuel cells. Low cost interconnect and cathode current collector material was identified and current collection was improved. In addition, this study has demonstrated that electrochemical oxidation of carbon can take place on the Ni anode surface and the CO and CO 2 product produced can further react with carbon to initiate the secondary reactions. One important secondary reaction is the reaction of carbon with CO 2 to produce CO. We found CO and carbon can be electrochemically oxidized simultaneously inside of the anode porous structure and on the surface of anode for producing electricity. Since CH 4 produced from coal during high temperature injection of coal into the anode chamber can cause severe deactivation of Ni-anode, we have studied how CH 4 can interact with CO 2 to produce in the anode chamber. CO produced was found able to inhibit coking and allow the rate of anode deactivation to be decreased. An injection system was developed to inject the solid carbon and coal fuels without bringing air into the anode chamber. Five planner fuel cells connected in a series configuration and tested. Extensive studies on the planner fuels and stack revealed that the planner fuel cell stack is not suitable for operation with carbon and coal fuels due to lack of mechanical strength and difficulty in sealing. We have developed scalable processes for manufacturing of process for planner and tubular cells. Our studies suggested that tubular cell stack could be the only option for scaling up the coal-based fuel cell. Although the direct feeding of coal into fuel cell can significantly simplify the fuel cell system, the durability of the fuel cell needs to be further improved before scaling up. We are developing a tubular fuel cell stack with a coal injection and a CO 2 recycling unit.

01 COAL, LIGNITE, AND PEAT↗