Periodic Reporting for period 2 - WINNER (WORLD CLASS INNOVATIVE NOVEL NANOSCALE OPTIMIZED ELECTRODES AND ELECTROLYTES FOR ELECTROCHEMICAL REACTIONS)
Reporting period: 2022-07-01 to 2024-03-31
The WINNER project is contributing to the shift towards a more sustainable energy future by developing an efficient and durable technology platform based on electrochemical proton ceramic conducting (PCC) cells designed for unlocking a path towards commercially viable production, extraction, purification and compression of hydrogen at small to medium scale of three process chains: Cracking of ammonia to pressurized hydrogen or to power; Dehydrogenation of ethane to produce ethylene and pressurized hydrogen, Reversible steam electrolysis (RePCEC). The WINNER project builds on the pioneering multidisciplinary expertise of world leading partners in the fields of proton conducting ceramic (PCC) materials and technologies to combine materials science, multi-scale multi-physics modelling and advanced in-situ and operando characterisation methods to unveil unprecedent performance of tubular PCC cells assembled in a flexible multi-tube module operating at industrially relevant conditions. WINNER will develop innovative cell architectures with multifunctional electrodes and a novel pressure-less current collection system using eco-friendly and scalable manufacturing routes. These activities will be steered by a novel multiscale multi-physics modelling platform and enhanced experimentation methodologies. These tools combined with advanced operando and in situ methods will serve at establishing correlations between performance and degradation mechanisms associated with both materials properties and interface's evolution upon operation. Testing of cells and modules will also be conducted to define performance and durability in various operation modes. Techno-economic assessment of the novel PCC processes will be conducted as well as Life Cycle Assessment.
During the second period, the project has contributed to the following advancements:
- Novel materials were developed as redox-stable electrodes and reversible electrodes for the various applications. Both disk-shaped samples and complete tubular cells have been successfully produced with these novel electrode architectures and tested by EIS and IV measurements. The results on cell test for reversible electrolysis are showing significant improvement of the new architectures in terms of ASR and Faradaic efficiency, as compared to the state-of-the-art cell configuration established from former project. Regarding the development of redox stable electrodes, the best candidate materials were tested in planar configuration at ambient pressure. It was found that the candidate presents a suitable redox stability, maintaining its performance after several cycles of exposure in oxidizing and ethane-H2 atmosphere. Selectivity towards ethylene is currently limited by the low hydrogen flux from the electrolyte supported disk shaped cell. The results are encouraging and further work on complete tubular cell is needed to validate the potential of this route.
- Novel architectures of electrodes and cells have been produced, which encompass tubular half-cells with improved microstructure of the H2 electrode and stoichiometry of the electrolyte; novel current collection system for tubular cell integrating steel mesh; various BGLC-BZCY electrodes with variable BGLC stoichiometry and a bi-layered BGLC//BZCY-BGLC electrode.
- Regarding the development of a hybrid AI-Multiphysics tools, CSIC has developed a modelling platform, as described in WP3 and in D3.3. The platform software is called 3DM, is based on Python and comprises 4 main programmatic units, namely structures, geometries, generators and models.
- A multi-scale multi-physics modelling platform has been developed with partial integration of all disciplines (atomistic, electro-chemical, mechanical, fluid flow, reactor engineering, electric, heat). The partners have worked on establishing a communication platform to establish a link between the different models and competences. This has notably resulted in the development of an engineering model for each of the WINNER application. Furthermore, atomistic modelling has been used to define activation energies and pre-exponential values over a sequence of electrode reaction steps. These has been implemented as input parameters in the electrochemical model. A DC current-potential (I-V) relation was also developed. AA generic model for expressing electrode overpotential versus current based on measured polarisation resistance has been developed and exemplified for BLC and BGLC37.
- Tubular half-cells have been characterized via a four-point bending technique to assess their linear behaviour and mechanical properties. Different testing conditions have been investigated, varying parameters such as temperature, gas atmosphere composition and time of exposure to the latter conditions to determine the effect of relevant operating parameters on the mechanical reliability of the aforementioned components.The tubular half-cells showed satisfactory mechanical performance in all the conditions.
-Process diagram with BoP for each application has been defined by all industrial partners. This has been used as a basis for defining the engineering models, and furthermore to carry out techno-economic analysis, as well as life cycle asssessment of the technologies.
- Novel materials were developed as redox-stable electrodes and reversible electrodes for the various applications. Both disk-shaped samples and complete tubular cells have been successfully produced with these novel electrode architectures and tested by EIS and IV measurements. The results on cell test for reversible electrolysis are showing significant improvement of the new architectures in terms of ASR and Faradaic efficiency, as compared to the state-of-the-art cell configuration established from former project. Regarding the development of redox stable electrodes, the best candidate materials were tested in planar configuration at ambient pressure. It was found that the candidate presents a suitable redox stability, maintaining its performance after several cycles of exposure in oxidizing and ethane-H2 atmosphere. Selectivity towards ethylene is currently limited by the low hydrogen flux from the electrolyte supported disk shaped cell. The results are encouraging and further work on complete tubular cell is needed to validate the potential of this route.
- Novel architectures of electrodes and cells have been produced, which encompass tubular half-cells with improved microstructure of the H2 electrode and stoichiometry of the electrolyte; novel current collection system for tubular cell integrating steel mesh; various BGLC-BZCY electrodes with variable BGLC stoichiometry and a bi-layered BGLC//BZCY-BGLC electrode.
- Regarding the development of a hybrid AI-Multiphysics tools, CSIC has developed a modelling platform, as described in WP3 and in D3.3. The platform software is called 3DM, is based on Python and comprises 4 main programmatic units, namely structures, geometries, generators and models.
- A multi-scale multi-physics modelling platform has been developed with partial integration of all disciplines (atomistic, electro-chemical, mechanical, fluid flow, reactor engineering, electric, heat). The partners have worked on establishing a communication platform to establish a link between the different models and competences. This has notably resulted in the development of an engineering model for each of the WINNER application. Furthermore, atomistic modelling has been used to define activation energies and pre-exponential values over a sequence of electrode reaction steps. These has been implemented as input parameters in the electrochemical model. A DC current-potential (I-V) relation was also developed. AA generic model for expressing electrode overpotential versus current based on measured polarisation resistance has been developed and exemplified for BLC and BGLC37.
- Tubular half-cells have been characterized via a four-point bending technique to assess their linear behaviour and mechanical properties. Different testing conditions have been investigated, varying parameters such as temperature, gas atmosphere composition and time of exposure to the latter conditions to determine the effect of relevant operating parameters on the mechanical reliability of the aforementioned components.The tubular half-cells showed satisfactory mechanical performance in all the conditions.
-Process diagram with BoP for each application has been defined by all industrial partners. This has been used as a basis for defining the engineering models, and furthermore to carry out techno-economic analysis, as well as life cycle asssessment of the technologies.
The project has developed novel tubular cells based on Ni-BZCY72 electrode with BZCY81 dense electrolyte. Various electrode materials and architectures have been screened for the multiple applications of the project. As a summary, the following performance criteria were successfully met for the reversible electrolysis cells and ammonia to hydrogen cells: a cell ASR below 1 ohm.cm2 at 650C; a faradaic efficiency of 80-90%; a degradation rate below 1.2% khour under reversible operation. For the ammonia to hydrogen: the NH3 conversion is above 99% with H2 extraction > 98%.
The partners have established common nomenclature, parameters and models to establish a link between the different models and competences developed from the atomistic scale to the process scale. An engineering model has been defined for each of the WINNER applications, which is available in the excel format and converted in ASPEN file. The model is built based on the definition of the process flowsheet with necessary BoP and the operating conditions, the electrochemistry, kinetic and heat balance, etc. The tool is now functioning with multiple models integrated together (e.g. integrated atomistic + kinetics + electrochemistry models at cell levels; engineering tool + ASPEN models at cells, reactors and process levels; mechanical model). The outputs of the engineering tool are the energy demand per BoP and for the overall process for the selected input parameters (temperature, selectivity, conversion efficiency, cell voltage, Faradaic efficiency, etc.). The tool has been integrated in ASPEN for process flowsheeting and setting up the techno-economic assessment of WINNER applications. Several deliverables and one master thesis report on the findings from this assessment.
Life cycle assessment evaluation has been conducted showing the benefits of proton ceramic based technologies versus the benchmark cases, and will be disseminated in 2024.
The year 2023 has also been dedicated to the preparation of a multi-tube testing unit at CSIC. Extensive upgrades of the unit (software and hardware) to ensure high operational safety and functionality have been conducted.
The partners have established common nomenclature, parameters and models to establish a link between the different models and competences developed from the atomistic scale to the process scale. An engineering model has been defined for each of the WINNER applications, which is available in the excel format and converted in ASPEN file. The model is built based on the definition of the process flowsheet with necessary BoP and the operating conditions, the electrochemistry, kinetic and heat balance, etc. The tool is now functioning with multiple models integrated together (e.g. integrated atomistic + kinetics + electrochemistry models at cell levels; engineering tool + ASPEN models at cells, reactors and process levels; mechanical model). The outputs of the engineering tool are the energy demand per BoP and for the overall process for the selected input parameters (temperature, selectivity, conversion efficiency, cell voltage, Faradaic efficiency, etc.). The tool has been integrated in ASPEN for process flowsheeting and setting up the techno-economic assessment of WINNER applications. Several deliverables and one master thesis report on the findings from this assessment.
Life cycle assessment evaluation has been conducted showing the benefits of proton ceramic based technologies versus the benchmark cases, and will be disseminated in 2024.
The year 2023 has also been dedicated to the preparation of a multi-tube testing unit at CSIC. Extensive upgrades of the unit (software and hardware) to ensure high operational safety and functionality have been conducted.