Degradation and Protection Mechanisms of Platinum-Based Catalysts in Hydrogen-Bromine Flow Batteries
Authors: Hugo Yohanes , Yang Kailun , Kout Wiebrand 
Published: August 2024

Cost-effective and large-scale electrical energy storage is pivotal in facilitating the assimilation of renewable energy sources like wind and solar, as well as enhancing the resilience of the future electricity grid. Hydrogen-Bromine flow battery (HBFB) technology is a candidate for a low cost and flexible system. Bromine is abundantly available on Earth. In addition, the reaction between bromine and bromide is characterized by rapid kinetic properties, thus no platinum group metals (PGMs) are required on the bromine side of the cell as a catalyst to sustain a high current density of >500 mA/cm2. Moreover, hydrogen-based flow batteries can be coupled with hydrogen pipelines & electrolyzers to boost the integration of new energy systems.
However, the selection of bromine brings technical challenges that can limit the commercial deployment of such HBFB systems. We have proven a lifetime of more than 8,000 hours of continuous cycling at the lab scale. During this proof-of-concept validation, we found that bromine species (liquid) crosses through a dense proton exchange membrane to the hydrogen side of the cell. On this side, a Platinum-based catalyst layer is present to promote hydrogen oxidation-evolution reactions (HOR/HER). The crossover liquid interacts first with the catalyst layer before it crosses through the gas diffusion layer and exits the membrane electrode assembly (MEA). Chemical interactions between the crossover liquid and the catalyst can lead to catalyst migration, Ostwald ripening, or even permanent catalyst dissolution. This is a concern and must be addressed. The root of this concern is that the Platinum-based catalyst is highly reactive (high surface-active area respective to the loading, m2/g), and also the crossover bromine species are likely corrosive (highly acidic, pH <0, and contain polybromides). Therefore, chemical interaction cannot be fully avoided. Nevertheless, the cathodic protection reduces this interaction, which prolongs the lifetime of the electrochemical system. The cathodic protection consists of an applied positive potential and the presence of hydrogen gas on the catalyst nanoparticles. The catalyst degradation together with cathodic protection needs to be better understood and quantified to gain the confidence that the HBFB system fundamentally can last for more than 10 years of continuous operation. This confidence is essential to deliver a minimum viable product (MVP) of HBFB, e.g. on a 100 kW – 1 MW scale, to the market.
To address the aforementioned scientific challenges, this work studies the liquid crossover phenomena and the interaction between the crossover liquid and platinum-based catalyst in depth. Liquid crossover rate, concentration, and bromine speciation from working electrochemical cells are quantified at different states of charge (SoCs) and different modes (charge or discharge). This information is used to set up further ex-situ experiments to understand and determine the chemical interaction between crossover liquid and catalyst. Electrochemical ex-situ tests for Pt dissolution measurement such as determination of the electrochemically active surface area (ECSA), are performed before and after soaking hydrogen electrodes in different concentrations of hydrogen bromide solutions that mimic the crossover liquid. These results are then combined with in-situ tests, where the catalyst dissolution rate is quantified in actual crossover liquid and electrolyte by the inductively coupled plasma (ICP) method. Finally, post-mortem analyses on the catalyst layer based on scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. will give quantitative and qualitative insights into the impact of cycling and liquid crossover on the catalyst performance, morphology, crystal structure, and chemical state of the catalyst.
The goal of this work is to quantify the extrapolated lifetime of HBFB systems within a high confidence level. Then conclude if this technology is fundamentally sound and can be scaled up to an MVP to be deployed to the market. As a low cost energy storage solution, the HBFB’s lifetime should be at least 5 years and preferably more than 10 years to attract commercial attention. Moreover, the collective knowledge gained in this work about the catalyst degradation mechanisms will spark further ideas and guide the next generation of the system and its operating conditions to reduce the degradation rate. These presented ideas may also shine a light on catalyst degradation and protection mechanisms in other electrochemical applications that operate in corrosive conditions.
Figure 1 Membrane electrode assembly architecture, incl. electrochemical reactions and species transport phenomena in the charge and discharge modes.

Figure 1