Elucidation of Critical Catalyst Layer Phenomena toward High Production Rates for the Electrochemical Conversion of CO to Ethylene.

This work utilizes EIS to elucidate the impact of catalyst-ionomer interactions and cathode hydroxide ion transport resistance (RCL,OH-) on cell voltage and product selectivity for the electrochemical conversion of CO to ethylene. When using the same Cu catalyst and a Nafion ionomer, varying ink dispersion and electrode deposition methods results in a change of 2 orders of magnitude for RCL,OH- and ca. a 25% change in electrode porosity. Decreasing RCL,OH- results in improved ethylene Faradaic efficiency (FE), up to ∼57%, decrease in hydrogen FE, by ∼36%, and reduction in cell voltage by up to 1 V at 700 mA/cm2. Through the optimization of electrode fabrication conditions, we achieve a maximum of 48% ethylene with >90% FE for non-hydrogen products in a 25 cm2 membrane electrode assembly at 700 mA/cm2 and <3 V. Additionally, the implications of optimizing RCL,OH- is translated to other material requirements, such as anode porosity. We find that the best performing electrodes use ink dispersion and deposition techniques that project well into roll-to-roll processes, demonstrating the scalability of the optimized process.

A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid.

The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO2 utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H2 electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm2 in a 25 cm2 cell. More critically, a 55-hour stability test at 200 mA/cm2 shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods.

Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe-N-C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells.

We present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe-N-C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol (nPA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H2O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructure for catalyst concentrations as low as 2 wt %. The effect of H2O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H2O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H2O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H2O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between nPA-rich inks (H2O % ≤ 50%) and H2O-rich (82% H2O) inks. The nPA-rich inks remained predominantly stable-ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H2O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H2O % in the DM.

High-Performance Bipolar Membrane Development for Improved Water Dissociation.

Bipolar membranes (BPMs) are the enabling component of many promising electrochemical devices used for separation and energy conversion. Here, we describe the development of high-performance BPMs, including two-dimensional BPMs (2D BPMs) prepared by hot-pressing two preformed membranes and three-dimensional BPMs (3D BPMs) prepared by electrospinning ionomer solutions and polyethylene oxide. Graphene oxide (GOx) was introduced into the BPM junction as a water-dissociation catalyst. We assessed electrochemical performance of the prepared BPMs by voltage-current (V-I) curves and galvanostatic electrochemical impedance spectroscopy. We found the optimal GOx loading in 2D BPMs to be 100 µg cm-2, which led to complete coverage of GOx at the interface. The integration of GOx beyond this loading moderately improved electrochemical performance but significantly compromised mechanical strength. GOx-catalyzed 2D BPMs showed comparable performance with a commercially available Fumasep BPM at current densities up to 500 mA cm-2. The 3D BPMs exhibited even better performance: lower resistance and higher efficiency for water dissociation and substantially higher stability under repeated cycling up to high current densities. The improved electrochemical performance and mechanical stability of the 3D BPMs make them suitable for incorporation into CO2 electrolysis devices where high current densities are necessary.

Modifying the Electrocatalyst-Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells.

Polymer electrolyte membrane fuel cell (PEMFC) electrodes with a 0.07 mgPt cm-2 Pt/Vulcan electrocatalyst loading, containing only a sulfonated poly(ionic liquid) block copolymer (SPILBCP) ionomer, were fabricated and achieved a ca. 2× enhancement of kinetic performance through the suppression of Pt surface oxidation. However, SPILBCP electrodes lost over 70% of their electrochemical active area at 30% RH because of poor ionomer network connectivity. To combat these effects, electrodes made with a mix of Nafion/SPILBCP ionomers were developed. Mixed Nafion/SPILBCP electrodes resulted in a substantial improvement in MEA performance across the kinetic and mass transport-limited regions. Notably, this is the first time that specific activity values determined from an MEA were observed to be on par with prior half-cell results for Nafion-free Pt/Vulcan systems. These findings present a prospective strategy to improve the overall performance of MEAs fabricated with surface accessible electrocatalysts, providing a pathway to tailor the local electrocatalyst/ionomer interface.

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.

In situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena.

Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study.

To increase the commercialization of fuel cell electric vehicles, it is imperative to improve the activity and performance of electrocatalysts through combined efforts focused on material characterization and device-level integration. Obtaining fundamental insights into the ongoing structural and compositional changes of electrocatalysts is crucial for not only transitioning an electrode from its as-prepared to functional state, also known as "conditioning", but also for establishing intrinsic electrochemical performances. Here, we investigated several oxygen reduction reaction (ORR) electrocatalysts via in situ and ex situ characterization techniques to provide fundamental insights into the interfacial phenomena that enable peak ORR mass activity and high current density performance. A mechanistic understanding of a fuel cell conditioning procedure is described, which encompasses voltage cycling and subsequent voltage recovery (VR) steps at low potential. In particular, ex situ membrane electrode assembly characterization using transmission electron microscopy and ultra-small angle X-ray scattering were performed to determine changes in carbon and Pt particle size and morphology, while in situ electrochemical diagnostics were performed either during or after specific points in the testing protocol to determine the electrochemical and interfacial changes occurring on the catalyst surface responsible for oxygen transport resistances through ionomer films. The results demonstrate that the voltage cycling (break-in) step aids in the removal of sulfate and fluoride and concomitantly reduces non-Fickian oxygen transport resistances, especially for catalysts where Pt is located within the pores of the carbon support. Subsequent low voltage holds at low temperature and oversaturated conditions, i.e., VR cycles, serve to improve mass activities by a factor of two to three, through a combined removal of contaminants, surface-blocking species (e.g., oxides), and rearrangement of the catalyst atomic structure (e.g., Pt-Pt and Pt-Co coordination).

Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks.

We present a rheological investigation of fuel cell catalyst inks. The effects of ink parameters, which include carbon black-support structure, Pt presence on carbon support (Pt-carbon), and ionomer (Nafion) concentration, on the ink microstructure of catalyst inks were studied using rheometry in combination with ultrasmall-angle X-ray scattering (USAXS) and dynamic light scattering (DLS). Dispersions of a high-surface-area carbon (HSC), or Ketjen black type, demonstrated a higher viscosity than Vulcan XC-72 carbon due to both a higher internal porosity and a more agglomerated structure that increased the effective particle volume fraction of the inks. The presence of Pt catalyst on both the carbon supports reduced the viscosity through electrostatic stabilization. For carbon-only dispersions (without Pt), the addition of ionomer up to a critical concentration decreased the viscosity due to electrosteric stabilization of carbon agglomerates. However, with Pt-carbon dispersions, the addition of ionomer showed contrasting behavior between Vulcan and HSC supports. In the Pt-Vulcan dispersions, the effect of ionomer addition on the rheology was qualitatively similar to Vulcan dispersions without Pt. The Pt-HSC dispersions showed an increased viscosity with ionomer addition and a strong shear-thinning nature, indicating that Nafion likely flocculated the Pt-HSC aggregates. These results were verified using DLS and USAXS. Further, the observations of the effect of ionomer:carbon ratio and a comparison between carbons of different surface areas provided insights on the microstructure of the catalyst ink corresponding to the optimized I/ C ratio for fuel cell performance reported in the literature.