Periodic Reporting for period 2 - LOTER.CO2M (CRM-free Low Temperature Electrochemical Reduction of CO2 to Methanol)
Período documentado: 2019-07-01 hasta 2022-03-31
The weaknesses of current proposed low temperature electrochemical utilization of CO2 are many. Proposed aqueous systems suffer from i) a competitive hydrogen evolution process ii) a small potential window, iii) low CO2 solubility, iv) formic acid as major product. Non-aqueous proposed systems on the other hand suffer from i) low electrolytic conductivity, ii) costs, iii) environmental impact, and iv) catalyst stability in these solutions. Gas phase electrocatalytic reduction of CO2 would overcome these problems and allow the formation of more valuable products; in this project the primary focus will be on carbonaceous products such as methanol. The LOTER.CO2M project will demonstrate the industrial potential of this concept.
LOTER.CO2M represents an excellent potential solution to decrease greenhouse gas emissions and to store electrical energy in the chemical bonds of carbonaceous products such as methanol. The development of a cheap and flexible prototype with modular characteristics will alleviate geographical constraints for efficient low carbon energy conversion at a reduced cost. Moreover, the foreseen LOTER.CO2M technology will promote the penetration rate of distributed and/or intermittent renewable energy sources by acting as storage medium through the conversion of CO2 in fuels. The use of a convenient storage technology will reduce the existing barrier for implementation of renewable power sources on a distributed scale. Thus, the conversion of CO2 will affect favorably the global carbon balance while providing a source of renewable fuels.
LOTER.CO2M aims to develop advanced, low-cost electro-catalysts and membranes for the direct electrochemical reduction of CO2 to methanol by low temperature CO2-H2O co-electrolysis. The materials, especially, the catalyst for the oxygen evolution reaction as well as the CO2 reduction reaction will be developed using sustainable, non-toxic and non-critical raw materials. They will be scaled-up and integrated into a gas fed electrochemical reactor, and the process validated for both technical and economic feasibility under industrially relevant conditions.
LOTER.CO2M represents an excellent potential solution to decrease greenhouse gas emissions and to store electrical energy in the chemical bonds of carbonaceous products such as methanol. The development of a cheap and flexible prototype with modular characteristics will alleviate geographical constraints for efficient low carbon energy conversion at a reduced cost. Moreover, the foreseen LOTER.CO2M technology will promote the penetration rate of distributed and/or intermittent renewable energy sources by acting as storage medium through the conversion of CO2 in fuels. The use of a convenient storage technology will reduce the existing barrier for implementation of renewable power sources on a distributed scale. Thus, the conversion of CO2 will affect favorably the global carbon balance while providing a source of renewable fuels.
LOTER.CO2M aims to develop advanced, low-cost electro-catalysts and membranes for the direct electrochemical reduction of CO2 to methanol by low temperature CO2-H2O co-electrolysis. The materials, especially, the catalyst for the oxygen evolution reaction as well as the CO2 reduction reaction will be developed using sustainable, non-toxic and non-critical raw materials. They will be scaled-up and integrated into a gas fed electrochemical reactor, and the process validated for both technical and economic feasibility under industrially relevant conditions.
Under each of the WPs the targets for the reporting period were achieved. While WP1 and WP8 are focused on management, dissemination and sustainable impact the scientific and engineering packages WP2-WP7 are concerned with the component and system development. here the following result were achieved.
WP2:In this reporting period the system requirements and specifications were assessed and according to these the overall design parameters, description of the process, as well as location for the final demonstrator to be operated at the site of RWE specified. These parameters and descriptions are crucial and vital for WP7. Furthermore it was decided within WP2 that the final system will be operating with an AEM which will allow the catalysts to be CRM free.
WP3: In this reporting period oxygen evolution catalyst based on non-critical raw materials e.g. Ni, Mn and Fe with spinel structure were synthetized and investigated for operation in the alkaline environment. Whereas, for the acidic environment silver–based catalysts were synthetized and investigated. Among many synthetized catalyst for the oxygen evolution reaction the most promising for alakaline and acidic environment were tested in single cells. NiFe-LDH catalysts considerably exceeded the targeted mass activity of 50 A g-1 at 1.5 V vs. RHE, their electrochemical stability falls far short of the project target.
WP4: In this WP a wide spectrum of approaches was covered to synthetize and investigate critical raw material free electrocatalysts for the CO2 reduction at the cathode side. The final down selected material for the demonstrator has been set to be for the alkaline system Cu2O nanoparticles which were synthesised at the DLR and which will now be upscaled for the final MEA production by JM.
WP5: Promising AEM and PEM commercial available membranes were purchased and characterized in terms of methanol vapour (and hydrogen as well) permeability, in- and through-plane conductivity, tensile strength, water uptake and swelling. Further characterizations were done under the conditions relevant to the project, i.e. at elevated temperatures and high partial pressures of water vapour. Based on the candidate materials, composite membranes are initially prepared and ready for further characterization. Based on the test results PEM and AEM membranes were chosen and supplied for the MEA benchmarking for WP6.
WP6: Various types of membrane electrode assemblies with different catalysts for the oxygen evolution from WP3 and CO2 reduction reaction from WP4 were prepared and investigated in WP6. Based on the investigation of the consortium partners in WP3, WP4, and WP6 the most promising materials were chosen for MEA manufacturing at IRD. Here PEM and AEM benchmark MEAs were designed and produced (up to now only PEM MEAs, while AEM MEAs will be shipped in September 2019 to the consortium).
WP7: Single cell and stack working parameters were set (see mid term report). The design of the single cells as well as the bipolar plates were also finanilized and integrated in the stack design planing. Additionally a preliminary P&ID of the LOTER.Co2M demonstrator was developed. The demonstrator design was also directed by the insights the partners DLR, CNR and IRD gained through the design and operation of their single cell systems. HyE started demonstrator development based on an alkaline system.
WP2:In this reporting period the system requirements and specifications were assessed and according to these the overall design parameters, description of the process, as well as location for the final demonstrator to be operated at the site of RWE specified. These parameters and descriptions are crucial and vital for WP7. Furthermore it was decided within WP2 that the final system will be operating with an AEM which will allow the catalysts to be CRM free.
WP3: In this reporting period oxygen evolution catalyst based on non-critical raw materials e.g. Ni, Mn and Fe with spinel structure were synthetized and investigated for operation in the alkaline environment. Whereas, for the acidic environment silver–based catalysts were synthetized and investigated. Among many synthetized catalyst for the oxygen evolution reaction the most promising for alakaline and acidic environment were tested in single cells. NiFe-LDH catalysts considerably exceeded the targeted mass activity of 50 A g-1 at 1.5 V vs. RHE, their electrochemical stability falls far short of the project target.
WP4: In this WP a wide spectrum of approaches was covered to synthetize and investigate critical raw material free electrocatalysts for the CO2 reduction at the cathode side. The final down selected material for the demonstrator has been set to be for the alkaline system Cu2O nanoparticles which were synthesised at the DLR and which will now be upscaled for the final MEA production by JM.
WP5: Promising AEM and PEM commercial available membranes were purchased and characterized in terms of methanol vapour (and hydrogen as well) permeability, in- and through-plane conductivity, tensile strength, water uptake and swelling. Further characterizations were done under the conditions relevant to the project, i.e. at elevated temperatures and high partial pressures of water vapour. Based on the candidate materials, composite membranes are initially prepared and ready for further characterization. Based on the test results PEM and AEM membranes were chosen and supplied for the MEA benchmarking for WP6.
WP6: Various types of membrane electrode assemblies with different catalysts for the oxygen evolution from WP3 and CO2 reduction reaction from WP4 were prepared and investigated in WP6. Based on the investigation of the consortium partners in WP3, WP4, and WP6 the most promising materials were chosen for MEA manufacturing at IRD. Here PEM and AEM benchmark MEAs were designed and produced (up to now only PEM MEAs, while AEM MEAs will be shipped in September 2019 to the consortium).
WP7: Single cell and stack working parameters were set (see mid term report). The design of the single cells as well as the bipolar plates were also finanilized and integrated in the stack design planing. Additionally a preliminary P&ID of the LOTER.Co2M demonstrator was developed. The demonstrator design was also directed by the insights the partners DLR, CNR and IRD gained through the design and operation of their single cell systems. HyE started demonstrator development based on an alkaline system.
The LOTER.CO2M project has already achieved targets that are beyond the state of the art. These being:
- The development of highly active and stable CRM free OER electrocatalysts with activates and stabilities beyond the state of the art alkaline OER catalysts can be operated at low alkalinity and be applied at ambient conditions without the need of any activations steps on AEMs. The operation at low alkalinities is not only important for the LOTER.CO2M project but also for various other electrochemical membrane reactors which are employing AEMs first and for most the anion exchange membrane water electrolysis (AEMWE) technology for green hydrogen production. The alkaline OER catalyst developed in the LOTER.CO2M project will help to overcome the issue of membrane degradation in the AEMWE through hydrolysis which is caused primarily through high alkalinity of the electrolyte needed until now due to low activity of the state of the art OER catalyst at low alkalinities.
- The results form the LOTER.CO2M project on the electrochemical CO2 reduction to carbonaceous fuels are therefore highly valuable for the development of efficient real world electrochemical CO2 reduction applications. Only through such a independent investigation step under real work conditions new CCU technologies can have a lasting positive impact on the CO2 reduction of the EU as only these will be effective enough to allow the EU to meet their CO2 reduction targets.
-The final demonstrator to be developed in the LOTER.CO2M project for which already the design and operation condition were set is a unique system which never has been reported before engaging the water electrolysis and the CO2 reduction in one system on a TRL5 operating under real world conditions. Such system is not existing so far and will have on many levels a valuable impact on the combativeness, economy, job market, and scientific progress of the EU.
- The development of highly active and stable CRM free OER electrocatalysts with activates and stabilities beyond the state of the art alkaline OER catalysts can be operated at low alkalinity and be applied at ambient conditions without the need of any activations steps on AEMs. The operation at low alkalinities is not only important for the LOTER.CO2M project but also for various other electrochemical membrane reactors which are employing AEMs first and for most the anion exchange membrane water electrolysis (AEMWE) technology for green hydrogen production. The alkaline OER catalyst developed in the LOTER.CO2M project will help to overcome the issue of membrane degradation in the AEMWE through hydrolysis which is caused primarily through high alkalinity of the electrolyte needed until now due to low activity of the state of the art OER catalyst at low alkalinities.
- The results form the LOTER.CO2M project on the electrochemical CO2 reduction to carbonaceous fuels are therefore highly valuable for the development of efficient real world electrochemical CO2 reduction applications. Only through such a independent investigation step under real work conditions new CCU technologies can have a lasting positive impact on the CO2 reduction of the EU as only these will be effective enough to allow the EU to meet their CO2 reduction targets.
-The final demonstrator to be developed in the LOTER.CO2M project for which already the design and operation condition were set is a unique system which never has been reported before engaging the water electrolysis and the CO2 reduction in one system on a TRL5 operating under real world conditions. Such system is not existing so far and will have on many levels a valuable impact on the combativeness, economy, job market, and scientific progress of the EU.