National Research And Development Institute For Cryogenic And Isotopic Technologies

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LASE-FC

Financing contract no.: 460PED/2020

Project No.: PN-III-P2-2.1-PED-2019-1894

Project implementation period: 12.11.2020-11.11.2022


All-laser-manufactured, graphene-based electrodes for PEM fuel cells produced via laser pyrolysis of a polymeric matrix embedded with catalytic organometallic complexes –  LASE-FC


Summary

The LASE-FC project brings together the complimentary expertise of the National R&D Institute for Cryogenics and Isotopic Technologies (ICSI, Energy department) and the National Institute for Laser, Plasma and Radiation Physics (INFLPR, Lasers department) to accelerate the R&D efforts of Romania in hydrogen economy, identified by the Strategic Energy Technology Plan of the EU as a key strategic issue regarding energy use and security, as well as the reduction of greenhouse gas emissions.

Targeting proton exchange membrane fuel cells (PEM FCs), the main technological vector of hydrogen energy presenting an alternative for decentralized energy production and long-distance transport, the project seeks to develop, demonstrate, and validate fully integrated electrodes for PEM FCs, realized primarily by laser methods and incorporating revolutionary 2D carbonic materials and catalytic nanoparticles. Though this approach, the project aims to significantly reduce FC fabrication costs and to increase their durability, at the same time achieving state-of-the-art power performances.

Electrode manufacturing will be realized by the controlled laser pyrolysis of solid polymeric substrates to produce laser-induced graphene (LIG), a porous graphene-based foam with tunable physical and chemical properties. Having already demonstrated the employment of LIG as the gas diffusion layer in PEM FCs, we will proceed by introducing organometallic complexes within the precursor polymeric matrix, to produce LIG embedded with catalytic and co-catalytic nanoparticles.

The LIG-based electrode will double as an integrated gas diffusion and catalytic layer to eliminate inter-layer ohmic losses and to incorporate the demonstrated mechanical stability and water management benefits. The novel electrodes will be transferred on proton exchange membranes according to an established decal transfer procedure, and will be validated according to standardized testing protocols.

Project Team

Coordinator (CO) : National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm. Valcea; ICSI ENERGY

Project leader: PhD. Chem. Adriana MARINOIU, https://orcid.org/0000-0001-5745-8029

Partner : National Institute for Laser, Plasma and Radiation Physics (INFLPR)

Responsible leader: Dr. Athanasios TILIAKOS, https://orcid.org/0000-0002-1803-5565

Project Scope and Objectives

The LASE-FC project brings together the complimentary expertise of the project’s Coordinator (CO), the National R&D Institute for Cryogenics and Isotopic Technologies (ICSI, Energy department) in Râmnicu Vâlcea, and the National Institute for Laser, Plasma and Radiation Physics (INFLPR, Lasers department) in Măgurele as partner (P1), to address exactly the above-mentioned concerns: we seek to develop a self-standing monolithic MEA, realized primarily by laser processing methods and incorporating revolutionary 2D carbonic materials and catalytic nanoparticles. Though this approach, the project aims to significantly reduce PEM FC fabrication costs and to increase its MEA durability, at the same time achieving competitive power performance comparable to the state-of-the-art in the FC industry.

The scope of the project is to demonstrate and validate fully integrated graphene-based electrodes for PEM FCs, that incorporate both gas-diffusion and catalytic layers in a single monolithic assembly, and are realized primarily by laser processing methods. On a second level, the project aims to introduce and demonstrate all-laser methods for streamlining the manufacturing of FC components. These can potentially replace the time-consuming and costly pyrolytic and chemical methods that currently dominate the industrial manufacturing of nanocarbonic materials for FC components, offering a competitive advantage to the national initiative in hydrogen economy.

In this project, we specifically target the gas diffusion layers (GDLs) of PEM FCs, aiming to produce monolithic graphene-based electrodes, encompassing both microporous and macroporous layers and doubling as catalyst supports bearing integrated catalytic layers, for both anodes and cathodes. Manufacturing the graphene-based electrodes will be realized by the laser pyrolysis of solid polymeric precursors, specifically the commercially available polyimide (PI), poly 4-4′ oxydiphenylene pyromellitimide (PMDA-ODA) using inexpensive CO2 laser engravers operating in pulsed mode (14 μs pulse duration) at the 10.6 μm IR wavelength. The method has been extensively researched, proven to result in the production of a highly porous and conductive graphene-based 3D foam of controllable physical and chemical properties, originally termed as Laser-Induced Graphene (LIG).

The integration of LIG-embedded nanoparticles of either pure platinum catalysts, alternative non-platinic metal catalysts, non-metal co-catalysts, or any viable combinations of the above will be realized by starting from the solid precursor of the PI: polyamic acid (PAA), also known as poly(pyromellitic dianhydride-co-4,4′-oxydianiline), in a solution of polar organic solvents (e.g. N-methylpyrrolidinone or dimethylformamide); this will allow the incorporation of organometallic complexes (MCs) in the polymeric matrix, specifically acetylacetonates bearing a wide selection of transition metals as coordination groups, including Pt, Pd, Fe, Ni, Co, Cu, Mo, Mn, V, and Cr (all employed as catalysts or co-catalysts in ORR/HOR reactions).

The project objectives are listed below according to their degree of correlation to the outcome of the project:

O1. To manufacture monolithic graphene-based electrodes incorporating both gas diffusion (GDL) and catalytic layers, obtained by the laser pyrolysis of polymeric precursors to produce laser-induced graphene of tunable physical and chemical properties: dimensions, porosity, conductivity, surface hydrophobicity, co-catalytic nitrogen content, and catalytic and co-catalytic nanoparticle content.

O2. To control the catalytic nanoparticle content in the precursor polymeric matrix and the porosity distribution of the resulting LIG network, in order to establish a hierarchical porous structure corresponding to the macroporous and microporous segments of the GDL, and to selectively optimize the catalytic activity according to ORR and HOR requirements for cathodic and anodic electrodes respectively.

O3. To adjust the demonstrated low-temperature decal transfer method (LTD-LIG) to the specifications of the manufactured electrodes, and to employ it for assembling a functional MEA consisting of LIG-based GDLs and a Nafion proton-exchange membrane, as the core of a prototype LIG-based PEM FC.

O4. To demonstrate and validate the prototype LIG-based PEM FC by running extensive testing according to international standards and protocols espoused by the FC industry.

O5. To introduce efficient and inexpensive laser manufacturing procedures for high-quality nanocarbonic FC components as an alternative to the current high-cost and low-yield methods, with the ulterior motive of reinforcing the ongoing hydrogen economy initiative of Romania.

Expected results

  • LIG monoliths optimized and differentiated for noble (Pt, Pd) and non-noble metal catalytic content;
  • LIG monoliths optimized and differentiated for cathodic or anodic applications (ORR or HOR catalysis)
  • Fully integrated PEM FC prototypes, comprised of specialized cathodic and anodic LIG-based electrodes
  • Fully integrated PEM FC prototypes differentiated according to employed catalysts (noble vs non-noble)
  • Full demonstration of all prototype models across a wide range of operating conditions

Budget

Total budget: 600 000 RON

Budget allocation by stages (in RON):

  • Stage 1: Development of protocols and functional and performance requirements for dedicated laser equipment

 Total budget: 92.076

  • Stage 2: Evaluation of fully integrated electrode manufacturing methods for PEM FCs, made exclusively by laser method, incorporating 2D carbon materials and catalytic nanoparticles

 Total budget: 296.350

  •  Stage 3: PEMFC testing: demonstration and validation of fuel cells with innovative electrodes

 Total budget: 211.574

 

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