Breaking Free - Unlocking the Potential of Dynamic Hydrogen Bubble Templating Materials
Authors: Mularczyk Adrian A , Wijpkema Adam , Forner-Cuenca Antoni 
Published: February 2024

In recent years, porous electrodes for electrochemical conversion devices, such as low-temperature fuel cells or water electrolyzers, have been engineered to address issues related to mass transport to and within the catalyst. For example, the addition of a layer with reduced pore size facing the catalyst layer (i.e., microporous layer) results in an increased performance[1–3]. Furthermore, chemical[4], as well as mechanical[5,6]. methods of creating dedicated liquid and gas pathways in the porous electrodes, have been investigated with promising results, highlighting the need for further optimization of state-of-the-art materials with regards to multi-phase transport. The range of possible modifications is intrinsically limited by the microstructure of the material they are applied to and add cost and complexity to the already costly electrode production procedure, motivating the development of novel materials which contain these desired features, offer a large morphological design space, and are cost competitive.

To tackle these stringent targets, we investigate the dynamic hydrogen bubble templating (DHBT) method to generate hierarchical structures containing both a pore size gradient as well as dedicated water and gas pathways in the form of bimodal pore size distributions. It leverages simultaneous deposition of a metal and gas evolution on the same surface to form complex structures from solution using electricity. It results in a hierarchical structure of primary pores (~5-40 µm) separated by porous walls containing secondary pores (10-1000 nm) . This type of material has been used successfully to improve boiling heat transfer[7], another process limited by the counterflow of liquid and gas. They have also been investigated as high surface area material for microbial anodes[8] and have been postulated to be appealing in other electrochemical devices such as batteries or fuel cells[9]. A significant hurdle to unlock the full potential of DHBT foams is the attachment of the foam to the solid electrode surface it is generated on. The presence of the electrode blocks the transport of media in the through-plane direction of the foam and thereby prevents its use in many electrochemical applications. Due to its fragile nature, separation of the foam from this surface easily damages the structure, which is why previous research was done exclusively in the presence of the electrode. Overcoming this limitation would enable new applications for DHBT foams and has the potential to address a wide range of problems in electrochemical systems related to porous media.

In this talk, I will discuss our work towards creating free-standing, hierarchically structured metal electrodes through DHBT and the developments needed to adapt this material for the use in electrochemical systems. Owing to its well-studied synthetic parameters and facile electrodeposition, we chose copper foams to advance DHBT materials in terms of characterization and mechanical properties. As a key step of the synthesis route, we realized a method to manufacture free-standing sheets from this material from copper metal while preserving its delicate microstructure. This was supported by an optimization of synthesis parameters to improve and ensure adequate mechanical stability of the freestanding foams after isolation. This development enables the application of a wide range of characterization methods such as XTM, BET, SEM and interferometry and I will discuss how the synthesis parameters link to the resulting material microstructure. Building on this initial success, current work focuses on the transferring this knowledge to the synthesis of foams made from other metals which are more relevant to electrochemical applications such as nickel for the use in alkaline electrolyzers and paves the way to develop DHBT material into the next generation transport layer for electrochemical systems.

References:

[1] T. Schuler, J. M. Ciccone, B. Krentscher, F. Marone, C. Peter, T. J. Schmidt, F. N. Büchi, Advanced Energy Materials
2020, 10, 1903216.

[2] Z. Qi, A. Kaufman, Journal of Power Sources
2002, 109, 38.

[3] A. Iranzo, P. Boillat, P. Oberholzer, J. Guerra, Energy
2014, 68, 971.

[4] A. Forner-Cuenca, J. Biesdorf, L. Gubler, P. Magnus Kristiansen, T. Justus Schmidt, P. A. Boillat Forner-Cuenca, J. Biesdorf, L. Gubler, T. J. Schmidt, P. Boillat, P. M. Kristiansen, Advanced Materials
2015, 27, 6317.

[5] C. Csoklich, H. Xu, F. Marone, T. J. Schmidt, F. N. Büchi, ACS Applied Energy Materials
2021, 4, 12808.

[6] D. Gerteisen, T. Heilmann, C. Ziegler, Journal of Power Sources
2008, 177, 348.

[7] R. Furberg, B. Palm, Applied Thermal Engineering
2011, 31, 3595.

[8] P. Champigneux, C. Renault-Sentenac, D. Bourrier, C. Rossi, M.-L. Délia-Dupuy, A. Bergel, Bioelectrochemistry
2019, 128, 17.

[9] N. D. Nikolic, K. I. Popov, L. J. Pavlovic, M. G. Pavlovic, Sensors
2007, 7, 1.

Figure 1