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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Roll-to-roll (R2R) coating is the most economical and highest throughput method for producing fuel cell electrodes. R2R coating encompasses many different methodologies to create uniform films on a moving web substrate. Here we explore two coating methods, gravure and slot die, to understand the impacts of each on film uniformity and performance.
As production of fuel cell vehicles and power systems increases there is a need to understand the process science of fuel cell manufacturing. Industrial production of polymer electrolyte membrane fuel cell (PEMFC) electrodes will rely on continuous roll-to-roll (R2R) coating methods to meet the rates needed for mass production. There are a variety of coating methods that could be used to coat catalyst layers. The different physics of each method may result in different morphologies and performance. Here we present the results of a study comparing fuel cell catalyst layers coated using two R2R coating methods: slot-die and gravure. These two methods were selected because the physics of applying the liquid to the substrate is very different between the two cases. Pt/C catalysts layers were coated directly onto carbon-fiber gas diffusion media to create gas diffusion electrodes (GDEs), without the use of a decal transfer process. These GDEs were assembled into membrane electrode assemblies (MEAs) by hot pressing to Nafion membranes. In situ performance and other electrochemical diagnostics were used to determine the influence of coating method on catalyst layer electrochemical properties. Electron microscopy was utilized to understand the influence of coating method on electrode morphology and its influence on electrochemical properties. We also explored the influence of solvent ratio to understand the potential coupling between ink formulation and coating methodology.
Further development of low temperature electrolysis (LTE) systems is of importance to ensure the renewable hydrogen production for hydrogen-based energy systems. The membrane electrode assembly (MEA) is a key component of the LTE system and typically contains a catalyst coated membrane (CCM). To enable the U.S. Department of Energy's hydrogen production cost goal of $2/kg, high volume manufacturing processes will be required to lower manufacturing costs of the CCM. A promising way for high-throughput manufacturing of CCM is using roll-to-roll (R2R) methods that allow the direct coating of electrodes on membrane films. However, there are many challenges with this methodology, both in the coating process as well as with web handling. In this talk, we discuss the membrane-ink interaction by evaluating the solvent uptake of a Nafion membrane system and verify the coatability of various inks through lab-scale coatings onto this system. Furthermore, rheology and surface tension data of the ink will be discussed together with the resulting morphology of the coated electrodes. The R2R-processed CCMs will finally be analyzed using electrochemical performance data and the results put in context with the challenges that the mass production of CCMs for LTE system faces to date.
To enable mass production of fuel cell membrane electrode assemblies (MEAs) catalyst layers production will require continuous roll-to-roll (R2R) coating processes. Gas diffusion electrodes (GDEs) are advantageous for mass production because the catalyst layer can be directely coated on the microporous layer of the gas diffusion media without the need for a decal-transfer process. It is known that the water-to-alcohol ratio in the catalyst ink influences the interactions of the ionomer with the catalyst leading to different distributions of ionomer in spray-coated catalyst layers. It is also known that during drying of colloidal mixtures, like fuel cell inks, factors such as drying rate, particle size, and agglomeration influence how the materials distribute themselves throughout the thickness of the dired film. Thus far there have only been limited studies to understand how process conditions such as ink formulation and drying temperature influence the distribution of ionomer and catalyst coated using scalable methods. This understanding is especially important for GDEs since it is known that having a sufficient amount of ionomer at the catalyst layer-membrane interface is critical for high performance. In this study we have focused on determining how the ratio of water to 1-propanol in the catalyst ink ink and drying temperature influence the distribution of ionomer throughout the thickness of the catalyst layer. Using a combination of Kelvin probe and x-ray photoelectron spectroscopy we show that an ionomer-rich surface is promoted by a higher drying rate and a water-rich catalyst ink. In contrast, a 1-propanol catalyst ink leads to a lower concentration of ionomer on the top surface. Using x-ray computed tomography, we are able to characterize the ionomer distribution throughout the thickness of the layer. We find that, in addition to promoting an ionomer-rich top surface, water-rich inks lead to a more homogenous distribution of ionomer, whereas a 1-propanol-rich ink leads to a more irregular distribution. It is found that MEA performance is improved by selecting conditions and ink formulations that promote ionomer enrichment at the top surface to facilitate a good interface with the membrane. MEAs prepared with a 75 wt% water catalyst ink with a 0.9 I/C have equivalent performance to spray-coated GDEs. Critically, these R2R-coated GDEs do not need an additional ionomer overlayer like the spray-coated GDEs do, reducing the number of processing steps in a manufacturing setting. This work shows that with the appropriate selection of materials, ink formulation, and processing conditions gas-diffusion electrodes are a viable pathway for fuel cell manufacturing.
This presentation is a summary of work conducted by Roll-to-Roll Consortium.
AZ31 magnesium alloy was produced via variable-plane rolling (VPR) under different temperatures. The effects of rolling temperature on the microstructure, texture and mechanical properties were investigated. A double-peak basal texture was formed during VPR treatment. Dynamic recrystallization (DRX) was observed during the VPR treatment, and it can reduce the texture intensity owing to the coalescence of sub-grains. Four types of twins were observed in the VPR treatment: {10-12} extension twins, {10-13}, {10-11} contraction twins and {10-11}-{10-12} double twins. The suitable temperature of AZ31 magnesium alloy for VPR treatment is determined as 623 K through experiments with tensile yield strength of 240 MPa, compressive yield strength of 162 MPa and elongation of 13%. Owing to the important impact of temperature on mechanical properties, the alloy was further VPRed with a decrease in temperature pass-by-pass. The high temperature of 623 K at the initial passes randomized the texture, which led to notably high ductility.
In response to the growing demand for lithium-ion batteries (LIBs), we demonstrate a solvent-free manufacturing technology that can avoid toxic organic solvents and form unique electrode structures to overcome the bottlenecks in low costs and fast charging. The lower tortuosity achieved by the open pores in the dry-printed (DP) electrode allows for a shorter Li+ diffusion pathway, which leads to better rate performance. The DP pouch cells exhibit higher capacity retention of 78% and 69% at 3C and 4C, respectively, compared with 67% and 52% for the slurry cast (SL) cells at the same rates. Moreover, the coating layer on the surface of active materials prevents the excess side reaction between active materials and electrolytes, which prolongs the cycle life of the DP cells. This manufacturing process is a roll-to-roll system with immense potential to be scaled up, providing a more efficient and economical way for battery manufacturing.
Here this work reports the characterization of catalyst layer (CL) structure and composition for a set of gas-diffusion electrodes (GDEs) fabricated by different coating methods with the goal of developing a better understanding of CL processing-structure-property-performance relationships. The CL coating techniques used in this study were ultrasonic spray coating, and two roll-to-roll (R2R) methods - gravure and slot die. Scanning transmission electron microscopy (STEM) coupled with X-ray energy dispersive spectroscopy (EDS) analysis of GDE cross-sections provided bulk information, while scanning electron microscopy (SEM) with EDS and X-ray photoelectron spectroscopy (XPS) were used to investigate the near surface and surface composition of the CLs that will be in direct contact with the membrane once the membrane electrode assembly (MEA) is constructed. This study demonstrates that common quantification parameters, namely the F:Pt ratio extracted from cross-sectional STEM-EDS maps and top-down CL measurements with SEM and XPS, along with roughness parameters quantified from SEM micrographs are useful parameters in explaining and potentially predicting performance trends. Additionally, it highlights the importance of understanding key CL surface properties for advancing the manufacturability of high-performance components for polymer electrolyte membrane (PEM) technologies.
Inextensible cylindrical shell theory and lubrication theory combine into a model for the elastohydrodynamics of a rolling-imprint modality of nanoimprint lithography (NIL). Foil-bearing theory describes the formation of the lubrication gap due to relative motion between a tensioned substrate and a rigid, cylindrical surface. Reproduction of the results of foil-bearing theory for both stiff and perfectly-flexible substrates validates this coupled model and reveals a highly predictable region of uniformity that provides low shear stress conditions ideal for UV-cure. Here, these results show theoretical limitations that are used to construct an operating window for predicting rolling-mode NIL process feasibility.
A new method, “nonvolatile solvent vapor annealing” (NVASA), has been developed to anneal block copolymers during film deposition by controlling the solvent drying process. Precise amounts of high boiling point additive added to the polymer solution briefly remain in the polymer film after casting, leaving the film in a swollen state, increasing its chain mobility, and ultimately improving domain order. We demonstrated the effectiveness of NVASA on several block copolymer systems and used in situ grazing incidence small-angle X-ray scattering (GISAXS) to validate the ordering process during the self-assembly. The simplicity and reproducibility of the method is attractive for implementation in large-scale manufacturing processes such as roll-to-roll printing as swell ratio is easily controlled by the amount of additive used and separate annealing steps are not needed. This work potentially introduces a new way to quickly and cost effectively anneal block copolymers.
In this work, we describe a unique roll-to-roll plasma-enhanced chemical vapor deposition (R2R-PECVD) technique to grow high-quality single-crystalline-like Ge films on flexible metal foils, an important advancement towards scalable processing of epitaxial Ge films at low-cost. Ion-beam assisted deposition was used to create single-crystalline-like substrate templates to enable epitaxial growth of Ge films. The Ge films were highly (004) oriented, biaxially-textured and showed remarkable crystalline quality, equivalent to single-crystal Ge wafers. Subsequently, the Ge films on metal foils were used as substrates to fabricate flexible GaAs single-junction solar cell by metal-oxide chemical vapor deposition (MOCVD). The champion device showed efficiency of 11.5%, and the average efficiency of four devices was 8% at 1 sun, the highest reported on GaAs PV directly deposited on alternative flexible substrates. Devices made on CVD-Ge film exhibited significantly improved performance compared to the ones grown on sputtered Ge films. Scalable production of inexpensive and flexible epi-Ge films will not only be useful for developing low-cost and high-performance III–V solar cells, but also for emerging flexible electronic devices applications.
We demonstrate a self-rolled-up microtube-based vertical photonic coupler monolithically integrated on top of a ridge waveguide to achieve three-dimensional (3D) photonic integration. The fabrication process is fully compatible with standard planar silicon processing technology. Strong light coupling between the vertical coupler and the ridge waveguide was observed experimentally, which may provide an alternative route for 3D heterogeneous photonic integration. The highest extinction ratio observed in the transmission spectrum passing through the ridge waveguide was 23 dB.
The aim of this paper is to better understand the transition from Townsend to radio-frequency homogeneous dielectric barrier discharge (DBD) at atmospheric pressure. The study is done in an Ar/NH{sub 3} Penning mixture for an electrode configuration adapted to roll-to-roll plasma surface treatment. The study was led in a frequency range running from 50 kHz up to 8.3 MHz leading to different DBD modes with a 1 mm gas gap: Glow (GDBD), Townsend (TDBD), and Radio-frequency (RF-DBD). In the frequency range between TDBD and RF-DBD, from 250 kHz to 2.3 MHz, additional discharges are observed outside the inter-electrode gas gap. Because each high voltage electrode are inside a dielectric barrel, these additional discharges occur on the side of the barrel where the gap is larger. They disappear when the RF-DBD mode is attained in the 1 mm inter-electrode gas gap, i.e., for frequencies equal or higher than 3 MHz. Fast imaging and optical emission spectroscopy show that the additional discharges are radio-frequency DBDs while the inter-electrode discharge is a TDBD. The RF-DBD discharge mode is attained when electrons drift becomes low enough compared to the voltage oscillation frequency to limit electron loss at the anode. To check that the additional discharges are due to a larger gas gap and a lower voltage amplitude, the TDBD/RF-DBD transition is investigated as a function of the gas gap and the applied voltage frequency and amplitude. Results show that the increase in the frequency at constant gas gap or in the gas gap at constant frequency allows to obtain RF-DBD instead of TDBD. At low frequency and large gap, the increase in the applied voltage allows RF-DBD/TDBD transition. As a consequence, an electrode configuration allowing different gap values is a solution to successively have different discharge modes with the same applied voltage.
We demonstrate continuous roll-to-roll (R2R) fabrication of single junction and tandem organic photovoltaic (OPV) cells on flexible plastic substrates employing a system that integrates organic deposition by high vacuum thermal evaporation (VTE) and low pressure organic vapor phase deposition (OVPD). By moving the substrate from chamber to chamber and then depositing films on stationary substrates, we achieve power conversion efficiencies of PCE = 8.6 ± 0.3% and 8.9 ± 0.2% for the single junction and tandem cells, respectively. Single junction OPVs are also fabricated on a continuously translating substrate at 0.3 cm/s, to achieve PCE = 8.5 ± 0.2%. Thin films grown on translating substrates by OVPD show <3% thickness non-uniformity and 0.66 nm root mean square surface roughness, similar to that obtained by VTE. Our results suggest that R2R film deposition comprising multiple vapor deposition technologies is a promising method for rapid speed and continuous manufacturing of high quality, small molecular weight organic electronic materials.
We investigate radiative corrections to the inflaton potential from heavy fields undergoing a fast-roll phase transition. We find that a logarithmic one-loop correction to the inflaton potential involving this field can induce a temporary running of the spectral index. The induced running can be a short burst of strong running, which may be related to the observed anomalies on large scales in the cosmic microwave spectrum, or extend over many e-folds, sustaining an effectively constant running to be searched for in the future. We implement this in a general class of models, where effects are mediated through a heavy messenger field sitting in its minimum. Interestingly, within the present framework it is a generic outcome that a large running implies a small field model with a vanishing tensor-to-scalar ratio, circumventing the normal expectation that small field models typically lead to an unobservably small running of the spectral index. An observable level of tensor modes can also be accommodated, but, surprisingly, this requires running to be induced by a curvaton. If upcoming observations are consistent with a small tensor-to-scalar ratio as predicted by small field models of inflation, then the present study serves as an explicit example contrary to the general expectation that the running will be unobservable.
In this paper, we provide a compact and unified treatment of power spectrum observables for the effective field theory (EFT) of inflation with the complete set of operators that lead to second-order equations of motion in metric perturbations in both space and time derivatives, including Horndeski and GLPV theories. We relate the EFT operators in ADM form to the four additional free functions of time in the scalar and tensor equations. Using the generalized slow roll formalism, we show that each power spectrum can be described by an integral over a single source that is a function of its respective sound horizon. With this correspondence, existing model independent constraints on the source function can be simply reinterpreted in the more general inflationary context. By expanding these sources around an optimized freeze-out epoch, we also provide characterizations of these spectra in terms of five slow-roll hierarchies whose leading order forms are compact and accurate as long as EFT coefficients vary only on timescales greater than an e-fold. Finally, we also clarify the relationship between the unitary gauge observables employed in the EFT and the comoving gauge observables of the post-inflationary universe.
At present flexible electronic devices are under extensive development and, among them, flexible organic light-emitting diode displays are the closest to a large market deployment. One of the remaining unsolved challenges is high throughput production of impermeable flexible transparent barrier layers that protect sensitive light-emitting materials against ambient moisture. The present studies deal with the adaptation of the atomic layer deposition (ALD) process to high-throughput roll-to-roll production using the spatial ALD concept. We report the development of such a process for the deposition of 20 nm thickness Al{sub 2}O{sub 3} diffusion barrier layers on 500 mm wide polymer webs. The process uses trimethylaluminum and water as precursors at a substrate temperature of 105 °C. The observation of self-limiting film growth behavior and uniformity of thickness confirms the ALD growth mechanism. Water vapor transmission rates for 20 nm Al{sub 2}O{sub 3} films deposited on polyethylene naphthalate (PEN) substrates were measured as a function of substrate residence time, that is, time of exposure of the substrate to one precursor zone. Moisture permeation levels measured at 38 °C/90% relative humidity by coulometric isostatic–isobaric method were below the detection limit of the instrument (<5 × 10{sup −4} g/m{sup 2} day) for films coated at web moving speed of 0.25 m/min. Measurements using the Ca test indicated water vapor transmission rates ∼5 × 10{sup −6} g/m{sup 2} day. Optical measurements on the coated web showed minimum transmission of 80% in the visible range that is the same as the original PEN substrate.