Scientific Highlights

Energy storage technologies with long storage duration are essential to stabilize electricity grids with a high share of intermittent renewable power. In a redox flow battery, the electrochemical conversion unit, where the charging and discharging reaction takes place, is spatially separated from the energy storage medium. In the all-vanadium redox flow battery (VRFB), a sulfuric acid aqueous electrolyte with dissolved vanadium ions is used as the storage medium. Vanadium is present in 4 different oxidation states, the redox couple vanadium(II) and (III) on the negative side of the cell, and vanadium(IV) and (V) on the positive side. This allows the battery to be repeatedly charged and discharged. A separator or membrane is used between the negative and positive electrode, which should selectively conduct the ions of the supporting electrolyte and minimize the passage of vanadium ions. Fluorinated membranes, such as Nafion™, are often used for this key component, but these ionomers were not originally developed for this application and therefore have functional shortcomings. Furthermore, the production and use of fluorinated materials is to be severely restricted or even banned in Europe. Therefore, the development of hydrocarbon-based membranes for the VRFB is of great importance. The study reported here focuses on polybenzimidazole polymers and membranes, which could be a promising materials class for next generation flow batteries. 

Employing a bipolar ion conducting membrane (BPM) in forward bias is a convenient solution for the biggest issues in the more common anion exchange membrane (AEM) CO2 co-electrolysis: the degradation of the performance caused by carbonate salt precipitation at the cathode and the decrease of net CO2 conversion caused by the crossover of this molecule from cathode to anode also requiring energy for downstream gas separation. However, the performance and stability of this device remain largely insufficient when using such a BPM configuration. To understand the reasons for this, we performed time-resolved X-ray tomographic microscopy of an operating BPM CO2 electrolyzer. The imaging method reveals partly unexpected degradation processes that result in design recommendations for improvement.

CeO₂ significantly enhances the oxygen evolution reaction (OER) activity of CoOx, although the mechanism behind this synergy is still unclear. Here, operando hard X-ray absorption spectroscopy (hXAS) is applied to monitor the Co-K edge and Ce L3 edge in CoOx/CeO2 to shed light on the evolution of Co and Ce oxidation states during OER. In addition, ex situ soft XAS (sXAS) characterizations provide information on the irreversible surface-specific transformations of the Co L3 edge as well as the O K edge.

The complex nature of liquid water saturation in polymer electrolyte fuel cell (PEFC) catalyst layers (CLs) greatly affects the device performance. To investigate this problem, a method to quantify the presence of liquid water in a PEFC CL using small-angle X-ray scattering (SAXS) was developed in a collaboration of researchers of the Federal Institute for Materials Research and Testing (BAM, Berlin, Germany), the Photon Science Division and the Electrochemistry Laboratory of PSI. The method leverages the differences in electron densities between the solid catalyst matrix and the CL-pores filled with liquid water under dry and wet conditions, respectively.

We report an in-depth investigation of the local atomic geometry, electronic and crystallographic structure evolution of nano-sized LiMn₂O₄ using operando XAS and XRD to shed light on (de-)lithiation mechanism when cycled in wide voltage range of 2.0 to 4.3 V vs Li⁺/Li. Leveraging on these findings, a novel electrochemical cycling protocol, with periodic deep discharge, yields superior electrochemical performance cycled in the range of 3.3 to 4.3 V exhibiting an excellent structure cyclability and an unprecedented increase in the specific capacity upon long cycling.

Electrochemical energy conversion devices, such as fuel cells and electrolyzers, using an anion exchange membrane (AEM) operating in the alkaline regime offer the prospect of the use of non-noble metal electrocatalysts and lower-cost cell construction materials. The wide-spread application of electrochemical cells with AEMs has been largely limited by the low chemical stability of the material. AEM degradation is triggered by i) nucleophilic attack by OH⁻, and ii) by reaction with free radicals formed during cell operation. Whereas the alkaline stability of AEMs has been greatly increased over the last 10 years, the understanding of mechanisms of radical induced degradation is limited. In this study, we have addressed this topic for the first time.

Our findings disclose that P-functionalization successfully enhances the oxygen evolution reaction (OER) activity of different cobalt-based catalysts (namely, La_0.2Sr_0.8CoO_3–δ, La_0.2Sr_0.8Co_0.8Fe_0.2O_3–δ, and CoO_x) at near-neutral pHs and that both phosphate ion assistance in the OER mechanism and catalyst Co oxidation state can play a role in the enhanced OER activity.

The mass loading of Si-graphite electrodes is often considered as a parameter of secondary importance when testing their performance. However, if a sacrificial additive is present in the electrolyte, the electrode loading becomes the battery cycle-life-determining factor. A lower loading was obtained by keeping slurry preparation steps unchanged from binder to binder and resulted in a longer lifetime for some of the binders. When the final loading was kept constant instead, the performance became independent of the binder used.

Reducing precious metal loading in the anodic catalyst layer (CL) is indispensable for lowering capital costs and enabling the widespread adoption of polymer electrolyte water electrolysis (PEWE). This work presents the first three-dimensional reconstruction of a TiO2-supported IrO2 based core shell catalyst layer, using high-resolution X-ray ptychographic tomography at cryogenic temperature of 90 K. The high data quality and phase sensitivity of the technique have allowed the reconstruction of all four phases namely pore space, IrO2, TiO2 support matrix and the ionomer network, the latter of which has proven to be a challenge in the past.

The evolution of O₂ occurring in polymer electrolyte water electrolyzer anodes is a very slow reaction that must be catalyzed using iridium (Ir-) based materials. However, Ir is an extremely scarce metal, and thus the extended commercialization of these electrolyzers will only be possible if the amount of Ir implemented in their anodes is drastically reduced. This requires an improved understanding of the individual steps through which these Ir-based materials catalyze the evolution of O₂. To shed light on this matter, in this work we studied four different Ir-based catalysts under operative conditions using time resolved X-ray absorption spectroscopy. Our results show for the first time that, despite the differences between these materials, their surfaces must systematically be completely oxidized to a +5 state in order for the evolution of O₂ to proceed on them.

The conversion efficiency for green hydrogen production in a polymer electrolyte water electrolyzer (PEWE) is strongly influenced by the ohmic cell resistance and therefore the thickness of the membrane. The use of thin membranes (~50 micron or below) is limited by gas crossover of H₂ and O₂, which can lead to the formation of an explosive gas mixture. The incorporation of a Pt recombination catalyst provides remedy and allows a more dynamic operating mode (cf. Highlight 03/2022). However, the presence of Pt nanoparticles leads to an increase in the rate of membrane degradation. Therefore, we have additionally doped the membrane with cerium-zirconium-oxide (CZO) nanoparticles, which act as radical scavenger. The rate of membrane degradation can thus be reduced.

The growth of crystalline Li-based oxide thin films on silicon substrates is essential for the integration of next-generation solid-state lithionic and electronic devices. In this work, we employ a 2 nm γ-Al₂O₃ buffer layer on Si substrates in order to grow high quality crystalline thin films Li₄Ti₅O₁₂ (LTO). Long-term galvanostatic cycling of 50 nm LTO demonstrates exceptional electrochemical performance, specific capacity of 175 mAh g^-1 and 56 mAh g^-1 at 100C and 5000C respectively, with a capacity retention of 91% after 5000 cycles.

Lithium metal negative electrodes are often used as counter electrodes while testing other electrochemically active materials, and are considered to be equivalent, independently of their thickness, supplier and production processes used. Here, we clearly demonstrate, using Electrochemical Impedance spectroscopy (EIS) that it is not the case, as well as the often-used symmetric cells are actually not so symmetric, when EIS spectra are disentangled using Thee-electrode cells.

The ability to start-up in extreme environmental conditions, including sub-freezing temperatures, is essential to the deployment of the fuel cell technology. Water produced in fuel cells at these temperatures can be in the super-cooled state, and freezing can lead to a rapid shutdown, as water cannot be removed anymore as a liquid. By segmenting a fuel cell, it is possible to prevent the propagation of freezing, which enables the cell operation even after the first freezing event occurred.

Evaluating potential electrolyte candidates is typically a lengthy procedure requiring long-term cycling experiments. To speed this process up, we have investigated potentiostatic lithium plating as a potential method for fast electrolyte suitability investigation. The applications of this methodology is not limited to liquid electrolytes, - effects of solid-state electrolytes, coatings, and other modifications can be readily assessed.

We demonstrate the capability of conventional laboratory XPS to determine the anions solvation shell of Li⁺ cation within 1M of LiTFSI and 1M of LiFSI salts dissolved in (EMIM⁺-FSI^-) and (EMIM⁺-TFSI^-) ionic liquids. The binding energy difference between the N1s components originating from the EMIM⁺ cation and from TFSI^- or FSI^- anions, solvating the Li⁺, confirms that both TFSI^- and FSI^- contribute simultaneously to the Li⁺ solvation. Additionally, the degradation of the TFSI and FSI -based electrolytes under X-ray exposure is proved.   

The development of next generation fuel cell membranes based on aromatic hydrocarbon chemistry calls for a new antioxidant strategy to tackle radical induced membrane degradation. Although damage by radicals cannot be prevented, the formed aromatic intermediates can be repaired by a suitable additive. Fuel cell experiments demonstrate that the approach is viable on the device level and that repair is a catalytic mechanism.

Water management is crucial to the successful cold-start in polymer electrolyte fuel cells (PEFCs). The sudden freeze of supercooled water blocks the reactant gas in the cathode and causes rapid voltage failure. In this work, we statistically evaluated the effects of the gas diffusion layer (GDL) substrate, size, saturation, and the coating loads and methods of hydrophobic polymer on the freezing probability of supercooled water by differential scanning calorimetry (DSC).

Hydrogen will play an important role in a future energy system based on renewable sources, providing energy storage, being a base material for industry and an energy carrier in transport applications. For the efficient electrification of hydrogen, polymer electrolyte fuel cell technology is developed and applied today in trucks, passenger cars and stationary applications. It is envisaged that even more demanding applications such as airplanes may follow. For road transport applications an increase in power density is required to further reduce cost and future applications may need these advances to be technically competitive. In this work we describe a novel concept for gas diffusion layers, highly important for achieving high fuel cell power densities.

Li-rich nanoparticles of Li_1+xMn_2-xO₄ doped with Al, Co or Ni are successfully synthesized using a facile, fast and efficient microwave-assisted hydrothermal route. In this study, we demonstrate that nanocrystallinity and cationic doping play an important role in improving the electrochemical performance with respect to LiMn₂O₄ microparticles. They significantly reduce the charge-transfer resistance, lower the 1^st cycle irreversible capacity to 6%, and achieve a capacity retention between 85 and 90% after 380 cycles, with excellent columbic efficiency close to 99%.

Lithium-rich layered oxides, containing cobalt, despite being promising high-capacity cathode materials, need alternatives to eliminate toxic and geopolitically restricted cobalt. An ongoing search for low-cost, Co-free Li-rich cathode materials with a better structural stability lead to investigation of Li_1.16Ni_0.19Fe_0.18Mn_0.46O₂ (LNFM), where cobalt is replaced by abundant iron. Our LNFM not only delivered a high capacity of 229 mAh/g but also has a stable average discharge voltage when cycled to upper cutoff potential of 4.8 V in additive-free electrolyte.

To improve the performance of single atom catalysts (SACs),  the structure of their active sites under operative conditions needs to be better understood. For this, we have performed in situ X-ray absorption spectroscopy measurements using a modulation excitation approach selectively sensitive to the species involved in the electrochemical reactions. This has allowed us to study the structural changes undergone by two types of SACs, and to tie the observed differences to their catalytic activities.

The conversion efficiency for green hydrogen production in a polymer electrolyte water electrolyzer (PEWE) is strongly influenced by the ohmic cell resistance and therefore the thickness of the membrane used. The use of thin membranes (~50 micron or below) is limited by gas crossover of H₂ and O₂, which can lead to the formation of explosive gas mixtures. The incorporation of a recombination catalyst provides remedy and allows a more dynamic operating mode.

Understanding the water management in polymer electrolyte fuel cells (PEFCs) during sub-zero operation is crucial for designing effective freeze start strategies. In collaboration with Toyota Motor Europe sub-second X-ray tomographic microscopy was used to study the water distributions in the gas diffusion layer (GDL) of PEFCs during dynamic freeze starts from −30 °C that mimic automotive freeze start conditions at different pre-drying levels and  varying the feed gas humidity.

We carried out in situ and ex situ ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments on a La0.2Sr0.8CoO3-δ perovskite oxygen evolution reaction (OER) catalyst. The study shows that Sr is leached into the electrolyte after immersion, leading to surface Co active site enrichment. Such a Co-enriched surface evolves into a new phase during operation. With the help of theoretical simulations, such a species is assigned to Co-oxyhydroxide, providing direct evidence of its formation during the OER.