Final Report Summary - SMARTCAT (Systematic, Material-oriented Approach using Rational design to develop break-Through Catalysts for commercial automotive PEMFC stacks)
Executive Summary:
The SMARTCat project is intended to provide new trimetallic catalysts (WP2) deposited on new support materials (WP3) expected to operate at high temperatures suitable for car applications. This involves a relevant high temperature membrane, which is developed especially for the project (WP4). Emphasis is also given to automated membrane electrodes assembly with these new materials (WP4). Special care is further devoted to fuel cell tests in automotive conditions with selected MEAs (WP5) in agreement with harmonization protocol discussed with the JRC-IET. A technico-economic assessment has been achieved (WP5)
a) New trimetallic catalysts
The modelling of trimetallic structures has shown 0.05 eV reduction of OH binding energy on PtAuCo and PtAuNi rendering them highly active for ORR. Addition of small amount of Au is found to increase the stability of the catalysts.
On the experimental side, the targeted exchange current was reached for Pt3NiAu, Pt3CuAu and Pt3AuCo ternary catalysts. The higher stability is obtained with the Pt6Cu2Au2/C catalyst with an activity loss of only 45% after 1000 cycles.
Plasma sputtering deposition was designed to prepare low Pt content nanocatalysts of 220 cm-2 large area cathodes with Pt6Ni2Au2 and Pt6Ni1Cu1 loading.
Molecular dynamics simulations of PtxPdyAuz, PtxNiyAuz PtxCuyAuz growth on model porous carbon have been carried out and leads to successful comparison with DFT and experiments.
b) New supports for high temperature operation.
Computational DFT techniques have been carried out for studying interactions between oxygen vacancy (Ov), doping Sb atom in SnO2, effect of Sb doping on the interaction between small Pt clusters and Ov-SnO2(110) surface. Segregation and transport properties at antimony-doped tin oxide (ATO)/Pt interfaces and at niobium-doped tin oxide (NTO)/Pt interfaces have been examined as well as transport properties. Stability and ORR of ternary catalysts Pt3NiAu and Pt3CuAu has been studied.
On the experimental side, addition of Nb into the SnO2 support stabilizes the support and suppress the agglomeration of deposited catalyst particles. For the tri-metallic catalyst with Ni a significant diffusion of Ni out of the particles and onto the support is observed. This effect is suppressed when replacing Ni by Cu. Primarily work was put into synthesizing supported catalyst nanoparticles in a one-step flame synthesis.
c) Optimization and demonstration of MEA
Despite a huge amount of optimisation work during the project on the HT PYPO membrane, unfortunately no plausible route to prepare satisfactory fuel cells was found. On the other hand, the new polymer may find other applications in a hydrogen/bromine flow battery
For optimizing MEA fabrication using SMARTCat electrodes, new ink was defined and optimized for carbon supported Pt60Ni20Au20 trimetallic powder, and defining a pressing protocol for the MEAs manufacturing using the automated equipment. Constant improvement of the automated MEA Fabrication equipment led to highly reproducible features: achieve membrane size = electrode size + 5%; implementation of quality control procedure: 60 measurements per MEA, Optical measurement precision: 20µm Process reproducibility: 100 µm (based on more than 100 MEA). A rate of 70 of highly reproducible MEA/day is reached instead of the planned 60 MEA/day.
d) Fuel cell testing
The SMARTCat MEAs manufactured with classical screen printing method and with a classical loading exhibits a stack performance equivalent to reference MEAs: 0.8 W/cm2. On contrary the low loaded PVD MEAs exhibit lower performances. In parallel to test, a technical economic study has been made in order to assess the capacity to use PVD catalyst. Despite a process cost estimated to 2.6 times more expensive than the conventional ink deposition, the cost assessment shows that it could became negligible at high production rate. If the SMARTCat PVD MEA would have reached the performance target of 1 W/cm2, it would have reduced the MEA cost by 30% and dropped below 20 €/kWgross. Nevertheless, the techno-economic analysis demonstrates the high potential of this coating technology.
e) Dissemination
SMARTCat has led to 13 publications in international peer reviewed journals, 7 invited lectures and 21 communications in international conferences. 2 patents have been delivered (2015, WP4), 8 patents applications have been submitted in 2017 (WP4).
A successful dissemination activity was the European Fuel Cell Car Workshop held on March 1-3, 2017 in Orléans France. 80 participants (academics and industrials) joined the workshop coming from all Europe.
(This summary is the section 1. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
Project Context and Objectives:
This summary description of context and objectives is the section 2. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf"
Project Results:
The description of the main S & T results/foregrounds is detailed in section 3. of the attachment SMARTCat FINAL REPORT PublishableVersonOnline.pdf
Potential Impact:
(This description of the project potential impact, the main dissemination activities and the exploitation of results is the section 4. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
List of Websites:
SMARTCat website was victim of an SQL injection attack and was down for a few month. It has been recovered but using WordPress web free management tool. Current address is https://smartcatfchju.wordpress.com. This website will be maintained beyond end of the SMARTCat project by the scientific coordinator (mailto:pascal.brault@univ-orleans.fr)
(This description of the project website is the section 5. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
The SMARTCat project is intended to provide new trimetallic catalysts (WP2) deposited on new support materials (WP3) expected to operate at high temperatures suitable for car applications. This involves a relevant high temperature membrane, which is developed especially for the project (WP4). Emphasis is also given to automated membrane electrodes assembly with these new materials (WP4). Special care is further devoted to fuel cell tests in automotive conditions with selected MEAs (WP5) in agreement with harmonization protocol discussed with the JRC-IET. A technico-economic assessment has been achieved (WP5)
a) New trimetallic catalysts
The modelling of trimetallic structures has shown 0.05 eV reduction of OH binding energy on PtAuCo and PtAuNi rendering them highly active for ORR. Addition of small amount of Au is found to increase the stability of the catalysts.
On the experimental side, the targeted exchange current was reached for Pt3NiAu, Pt3CuAu and Pt3AuCo ternary catalysts. The higher stability is obtained with the Pt6Cu2Au2/C catalyst with an activity loss of only 45% after 1000 cycles.
Plasma sputtering deposition was designed to prepare low Pt content nanocatalysts of 220 cm-2 large area cathodes with Pt6Ni2Au2 and Pt6Ni1Cu1 loading.
Molecular dynamics simulations of PtxPdyAuz, PtxNiyAuz PtxCuyAuz growth on model porous carbon have been carried out and leads to successful comparison with DFT and experiments.
b) New supports for high temperature operation.
Computational DFT techniques have been carried out for studying interactions between oxygen vacancy (Ov), doping Sb atom in SnO2, effect of Sb doping on the interaction between small Pt clusters and Ov-SnO2(110) surface. Segregation and transport properties at antimony-doped tin oxide (ATO)/Pt interfaces and at niobium-doped tin oxide (NTO)/Pt interfaces have been examined as well as transport properties. Stability and ORR of ternary catalysts Pt3NiAu and Pt3CuAu has been studied.
On the experimental side, addition of Nb into the SnO2 support stabilizes the support and suppress the agglomeration of deposited catalyst particles. For the tri-metallic catalyst with Ni a significant diffusion of Ni out of the particles and onto the support is observed. This effect is suppressed when replacing Ni by Cu. Primarily work was put into synthesizing supported catalyst nanoparticles in a one-step flame synthesis.
c) Optimization and demonstration of MEA
Despite a huge amount of optimisation work during the project on the HT PYPO membrane, unfortunately no plausible route to prepare satisfactory fuel cells was found. On the other hand, the new polymer may find other applications in a hydrogen/bromine flow battery
For optimizing MEA fabrication using SMARTCat electrodes, new ink was defined and optimized for carbon supported Pt60Ni20Au20 trimetallic powder, and defining a pressing protocol for the MEAs manufacturing using the automated equipment. Constant improvement of the automated MEA Fabrication equipment led to highly reproducible features: achieve membrane size = electrode size + 5%; implementation of quality control procedure: 60 measurements per MEA, Optical measurement precision: 20µm Process reproducibility: 100 µm (based on more than 100 MEA). A rate of 70 of highly reproducible MEA/day is reached instead of the planned 60 MEA/day.
d) Fuel cell testing
The SMARTCat MEAs manufactured with classical screen printing method and with a classical loading exhibits a stack performance equivalent to reference MEAs: 0.8 W/cm2. On contrary the low loaded PVD MEAs exhibit lower performances. In parallel to test, a technical economic study has been made in order to assess the capacity to use PVD catalyst. Despite a process cost estimated to 2.6 times more expensive than the conventional ink deposition, the cost assessment shows that it could became negligible at high production rate. If the SMARTCat PVD MEA would have reached the performance target of 1 W/cm2, it would have reduced the MEA cost by 30% and dropped below 20 €/kWgross. Nevertheless, the techno-economic analysis demonstrates the high potential of this coating technology.
e) Dissemination
SMARTCat has led to 13 publications in international peer reviewed journals, 7 invited lectures and 21 communications in international conferences. 2 patents have been delivered (2015, WP4), 8 patents applications have been submitted in 2017 (WP4).
A successful dissemination activity was the European Fuel Cell Car Workshop held on March 1-3, 2017 in Orléans France. 80 participants (academics and industrials) joined the workshop coming from all Europe.
(This summary is the section 1. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
Project Context and Objectives:
This summary description of context and objectives is the section 2. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf"
Project Results:
The description of the main S & T results/foregrounds is detailed in section 3. of the attachment SMARTCat FINAL REPORT PublishableVersonOnline.pdf
Potential Impact:
(This description of the project potential impact, the main dissemination activities and the exploitation of results is the section 4. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
List of Websites:
SMARTCat website was victim of an SQL injection attack and was down for a few month. It has been recovered but using WordPress web free management tool. Current address is https://smartcatfchju.wordpress.com. This website will be maintained beyond end of the SMARTCat project by the scientific coordinator (mailto:pascal.brault@univ-orleans.fr)
(This description of the project website is the section 5. of the attachment "SMARTCat FINAL REPORT PublishableVersonOnline.pdf")
