Dino Klotz

Solid oxide fuel cells have the potential to render the conversion from fuel to electrical energy more efficienct while lowering emissions. The technology, however, suffers from performance degradation due to cathode poisoning by chromia from metal interconnects. We confirm the deleterious impact of chromia on the performance of the model mixed conducting cathode material Pr_0.1Ce_0.9O_2−δ by examining the oxygen exchange coefficient (k_chem) via electrical conductivity relaxation measurements, and the area-specific resistance (ASR) by electrochemical impedance spectroscopy. Liquid Cr-infiltration decreases k_chem 20-fold and the oxygen exchange component of ASR increases 20-fold while maintaining the same activation energy. We then demonstrate the ability to not only recover initial k_chem and ASR values, but improve properties above those exhibited by the pristine specimen through subsequent Li-infiltration, leading to enhancement of k_chem by more than three orders of magnitude and reduction in oxygen exchange component of the ASR by over a factor 100. We attribute these dramatic changes to the depletion of electrons induced by the acidic Cr-infiltrant on the Pr_0.1Ce_0.9O_2−δ surface and the recovery to accumulation of electrons from the basic Li-infiltrant. These results point to acidity as a key descriptor in addressing the long-standing challenge of reactive surface poisoning in applications reliant on rapid oxygen exchange and recovery behavior. The ability to achieve remarkable levels of recovery of electrocatalytic surfaces by controlling the relative acidity of surface species is demonstrated for the first time.

Nanocellulose is a sustainable material which holds promise for many energy-related applications. Here, nanocrystalline cellulose is used to prepare proton exchange membranes (PEMs). Normally, this nanomaterial is highly dispersible in water, preventing its use as an ionomer in many electrochemical applications. To solve this, we utilized a sulfonic acid crosslinker to simultaneously improve the mechanical robustness, water-stability, and proton conductivity (by introducing -SO₃⁻H⁺ functional groups). The optimization of the proportion of crosslinker used and the crosslinking reaction time resulted in enhanced proton conductivity up to 15 mS/cm (in the fully hydrated state, at 120 °C). Considering the many advantages, we believe that nanocellulose can act as a sustainable and low-cost alternative to conventional, ecologically problematic, perfluorosulfonic acid ionomers for applications in, e. fuel cells and electrolyzers.

While Cr poisoning of the oxygen reduction reaction (ORR) at SOFC cathodes is widely agreed to involve deactivation of oxygen exchange sites, the degradation mechanism remains ambiguous. Here, we selected an alternative cathode material Pr_0.1Ce_0.9O₂₋ δ , free of Sr segregation, to systematically investigate the effect of Cr-induced degradation in ORR. We expand on our previous studies in which the acidity/basicity of binary additives was found to be a strong indicator of the rate of oxygen surface exchange, by electrochemically investigating the ORR activity of the PCO cathode by impedance spectroscopy. Serial infiltration with acidic Cr-based oxides was found to degrade ORR activity as reflected in a 20-fold increase in area specific resistance (ASR) without corresponding changes in activation energy, with the opposite trend obtained with Ca-based oxides. Detected changes in total capacitance, attributed to changes in surface capacitance, also suggest depressed/enhanced PCO surface redox behavior with Cr/Ca-based infiltrants. Taken together, these results point to a more universal source of ORR poisoning/activation, based on acidity/basicity, rather than physical blocking of active sites. With this improved understanding, one can expect progress to be made in the coming years in optimizing means for protecting catalytic surfaces from degradation and/or improving their performance.

Grain boundary conductivity limitations are ubiquitous in material science. We show that illumination with above-bandgap light can decrease the grain boundary resistance in solid ionic conductors. Specifically, we demonstrate the increase of the grain boundary conductance of a 3 mol% Gd-doped ceria thin film by a factor of approximately 3.5 at 250 °C and the reduction of its activation energy from 1.12 to 0.68 eV under illumination, while light-induced heating and electronic conductivity could be excluded as potential sources for the observed opto-ionic effect. The presented model predicts that photo-generated electrons decrease the potential barrier heights associated with space charge zones depleted in charge carriers between adjacent grains. The discovered opto-ionic effect could pave the way for the development of new electrochemical storage and conversion technologies operating at lower temperatures and/or higher efficiencies and could be further used for fast and contactless control or diagnosis of ionic conduction in polycrystalline solids.

Impedance spectroscopy (IS) has great potential to become a standard technique for the characterisation, analysis, and diagnosis of perovskite solar cells (PSC).

Organic–inorganic halide perovskites are promising for use in solar cells because of their efficient solar power conversion. Current–voltage hysteresis and degradation under illumination are still issues that need to be solved for their future commercialization. However, why hysteresis and degradation occur in typical perovskite solar cell structures, with an electron transport layer of metal oxide such as SnO₂, has not been well understood. Here we show that one reason for the hysteresis and degradation is because of the localization of positive ions caused by hydroxyl groups existing at the SnO₂ surface. We deactivate these hydroxyl groups by treating the SnO₂ surface with a self-assembled monolayer. With this surface treatment method, we demonstrate hysteresis-less and highly stable perovskite solar cells, with no degradation after 1000 h of continuous illumination.

The current status of electrochemical impedance spectroscopy (EIS) and related analysis on perovskite solar cells (PSC) is still unsatisfactory. The provided models are still vague and not really helpful for guiding the efforts to develop more efficient and stable devices. Due to the slow and complex dynamics of these devices, the obtained spectra need to be validated, which is hardly ever done. This study may be the first to provide fully validated impedance spectra and presents reproducible EIS time series at open circuit voltage (V_OC) for more than 20 hours, with a total of 140 analysed spectra. We conclude that the observed changes stem from a temporary reduction of the electronically active area of the devices, as can be deduced from the inverse behaviour of resistance and capacitance. The changes in these values are almost 100% reversible if the devices are kept in the dark for only one day, while the time constant of the high-frequency process remains unchanged throughout the whole characterization procedure. The tested devices are full PSC devices that have proven to be stable over more than 500 hours, and the non-steady impedance measurements shine a critical light on previously published EIS data. With the results of this study, it can be rationalized that the high-frequency semicircle can serve as a good indicator for ionic migration by monitoring its consequences. The results presented here are helpful to quantify ionic migration on the device level in order to derive new stability criteria and countermeasures against degradation.

H₂O₂ is a sacrificial reductant that is often used as a hole scavenger to gain insight into photoanode properties. Here we show a distinct mechanism of H₂O₂ photo-oxidation on haematite (α-Fe₂O₃) photoanodes. We found that the photocurrent voltammograms display non-monotonous behaviour upon varying the H₂O₂ concentration, which is not in accord with a linear surface reaction mechanism that involves a single reaction site as in Eley–Rideal reactions. We postulate a nonlinear kinetic mechanism that involves concerted interaction between adions induced by H₂O₂ deprotonation in the alkaline solution with adjacent intermediate species of the water photo-oxidation reaction, thereby involving two reaction sites as in Langmuir–Hinshelwood reactions. The devised kinetic model reproduces our main observations and predicts coexistence of two surface reaction paths (bi-stability) in a certain range of potentials and H₂O₂ concentrations. This prediction is confirmed experimentally by observing a hysteresis loop in the photocurrent voltammogram measured in the predicted coexistence range.

The charge transfer efficiency, η _t , is important to distinguish between bulk and surface recombination losses, but it is difficult to determine it accurately. We provide a comparison of methods and give recommendations, how to obtain reliable values for η _t .