skip to main content

Title: Promotion of oxygen reduction reaction on a double perovskite electrode by a water-induced surface modification
Highly efficient air electrodes are a key component of reversible fuel cells for energy storage and conversion; however, the development of efficient electrodes that are stable against water vapor remains a grand challenge. Here we report an air–electrode, composed of double perovskite material PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) backbone coated with nanoparticles (NPs) of BaCoO 3−δ (BCO), that exhibits remarkable electrocatalytic activity for oxygen reduction reaction (ORR) while maintaining excellent tolerance to water vapor. When tested in a symmetrical cell exposed to wet air with 3 vol% H 2 O at 750 °C, the electrode shows an area specific resistance of ∼0.03 Ω cm 2 in an extended period of time. The performance enhancement is attributed mainly to the electrocatalytic activity of the BCO NPs dispersed on the surface of the porous PBCC electrode. Moreover, in situ Raman spectroscopy is used to probe reaction intermediates ( e.g. , oxygen species) on electrode surfaces, as the electrochemical properties of the electrodes are characterized under the same conditions. The direct correlation between surface chemistry and electrochemical behavior of an electrode is vital to gaining insight into the mechanisms of the electrocatalytic processes in fuel cells and electrolysers.
Authors:
; ; ; ; ; ; ; ; ;
Award ID(s):
1742828
Publication Date:
NSF-PAR ID:
10226583
Journal Name:
Energy & Environmental Science
Volume:
14
Issue:
3
Page Range or eLocation-ID:
1506 to 1516
ISSN:
1754-5692
Sponsoring Org:
National Science Foundation
More Like this
  1. Sr(Ti 0.3 Fe 0.7 )O 3−δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3−δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3−δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3−δ –Zr 0.92 Y 0.16 O 2−δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3−δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm −2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than themore »same cell made with a Ni-YSZ electrode. Electrolysis current density as high as −1.72 A cm −2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. The STF fuel electrodes also provide good stability during redox cycling.« less
  2. This paper addresses the use of Ce 0.8 Gd 0.2 O 2−δ (GDC) infiltration into the Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 (YSZ) fuel electrode of solid oxide cells (SOCs) for improving their electrochemical performance in fuel cell and electrolysis operation. Although doped ceria infiltration into Ni–YSZ has recently been shown to improve the electrode performance and stability, the mechanisms defining how GDC impacts electrochemical characteristics are not fully delineated. Furthermore, the electrochemical characteristics have not yet been determined over the full range of conditions normally encountered in fuel cell and electrolysis operation. Here we present a study of both symmetric and full cells aimed at understanding the electrochemical mechanisms of GDC-modified Ni–YSZ over a wide range of fuel compositions and temperatures. Single-step GDC infiltration at an appropriate loading substantially reduced the polarization resistance of Ni–YSZ electrodes in electrolyte-supported cells, as measured using electrochemical impedance spectroscopy (EIS) at various temperatures (600–800 °C) in a range of H 2 O–H 2 mixtures (3–90 vol% H 2 O). Fuel-electrode-supported cells had significant concentration polarization due to the thick Ni–YSZ supports. A distribution of relaxation times approach is used to develop a physically-based electrochemical model; the results show thatmore »GDC reduces the reaction resistance associated with three-phase boundaries, but also appears to improve oxygen transport in the electrode. Increasing the H 2 O fraction in the H 2 –H 2 O fuel mixture reduced both the three-phase boundary resistance and the gas diffusion resistance for Ni–YSZ; with GDC infiltration, the electrode resistance showed less variation with fuel composition. GDC infiltration improved the performance of fuel-electrode-supported full cells, which yielded a maximum power density of 2.28 W cm −2 in fuel cell mode and an electrolysis current density at 1.3 V of 2.22 A cm −2 , both at 800 °C.« less
  3. Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell modemore »and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination.« less
  4. Here we report measurements of the oxygen reduction reaction (ORR) at single Pt nanoparticles (NPs) through their collision with a Au microdisk electrode of lower electrocatalytic activity. Performing measurements at an elevated pressure (10-atm, pure O2) raises the O2concentration ∼50-fold over air-saturated measurements, allowing the ORR activity of smaller Pt NPs to be resolved and quantified, compared to measurements taken at atmospheric pressure. Single-NP ORR current vs potential measurements for 2.6, 16, and 24 nm radius citrate-capped Pt NPs, show the catalytic activity of the smallest Pt NPs to be roughly one order of magnitude greater than the activity of the larger NPs. The particle-by-particle nature of our measurement quantifies the distribution of electrocatalytic activities of individual particles, which we determine to be larger than can be explained by the distribution of particle sizes. Additionally, we report that some of the observed ORR current transients contain multiple sharp peaks per single-NP measurement, indicating multiple collisions of a single Pt NP at the electrode surface.

  5. Electrocatalytic upgrading of biomass-derived feedstocks driven by renewable electricity offers a greener way to reduce the global carbon footprint associated with the production of value-added chemicals. Paired electrolysis is an emerging platform for cogenerating high-valued chemicals from both the cathode and anode, potentially powered by renewable electricity from wind or solar sources. By pairing with an anodic biomass oxidation upgrading reaction, the elimination of the sluggish and less valuable water oxidation increases flow cell productivity and efficiency. In this presentation, we report our research progress on paired electrolsysis of HMF to production of higher valued chemicals in electrochemical flow cells. We first prepared an oxide-derived Ag (OD-Ag) electrode with high activity and up to 98.2% selectivity for the ECH of 5-(hydroxymethyl)furfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF), and such efficient conversion was achieved in a three-electrode flow cell. The excellent BHMF selectivity was maintained over a broad potential range with long-term operational stability. In HMF-to-BHMF paired with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-mediated HMF-to-FDCA conversion, a markedly reduced cell voltage from ~7.5 V to ~2.0 V was observed by transferring the electrolysis from the H-type cell to the flow cell, corresponding to more than four-fold increase in energy efficiency in operation at 10 mA. Amore »combined faradaic efficiency of 163% was obtained to BHMF and FDCA. Alternatively, the anodic hydrogen oxidation reaction on platinum further reduced the cell voltage to only ~0.85 V at 10 mA. Next, we have demonstrated membrane electrode assembly (MEA)-based flow cells for the paired electrolysis of 5-(hydroxymethyl)furfural (HMF) paired electrolysis to bis(hydroxymethyl)furan (BHMF) and 2,5-furandicarboxylic acid (FDCA). In this work, the oxygen evolution reaction (OER) was substituted by TEMPO-mediated HMF oxidation, dropping the cell voltage was from 1.4 V to 0.7 V at a current density of 1.0 mA cm−2. A minimized cell voltage of ~1.5 V for a continuous 24 h co-electrolysis of HMF was then achieved at the current density of 2 mA cm−2(constant current of 10 mA), leading to the highest combined faradaic efficiency (FE) of 139% for HMF-to-BHMF and HMF-to-FDCA. A NiFe oxide catalyst on carbon cloth further replaced the anodic TEMPO mediator for HMF paired electrolysis in a pH-asymmetric flow cell. We envision renewable electrical energy can potentially drive the whole process, thus providing a sustainable avenue towards distributed, scalable, and energy-efficient electrosynthesis.« less