UCLM and CISTEM. CISTEM: Cogeneration with PEM fuel cells. Role of UCLM. Justo Lobato, Pablo Cañizares, Sara Mateo, Héctor Zamora, Manuel A.

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1 UCLM and CISTEM CISTEM: Cogeneration with PEM fuel cells. Role of UCLM. Justo Lobato, Pablo Cañizares, Sara Mateo, Héctor Zamora, Manuel A.Rodrigo Construction of Improved HT-PEM MEAs and Stacksfor Long Term Stable Modular CHP Units

2 Development a new fuel cell (FC) based on a combined heat power (CHP) technology.

3 List of Beneficiaries Nº Name Short Name Country 1 EWE-Forschungszentrum für Energietechnologie e. V. NEXT ENERGY 2 DANISH POWER SYSTEM APS Danish Power Systems 3 INHOUSE ENGINEERING GMBH inhouse 4 Eisenhuth GmbH & Co. KG Eisenhuth 5 UNIVERSIDAD DE CASTILLA LA MANCHA UCLM 6 VYSOKA SKOLA CHEMICKO-TECHNOLOGICKA V PRAZE ICTP 7 ICI CALDAIE SPA ICI 8 OWI oel-waerme Institu GmbH OWI

4 Distribution of the Work Packages WP Number WP title Lead beneficiary number Start month End month WP1 Management of the Consortium NEXT 1 36 ENERGY WP2 Materials beyond State of the UCLM 1 30 Art WP3 Degradation with SoA Materials Danish Power 1 36 Systems WP4 Balance of Plant Design OWI 1 24 WP5 CHP Design and Setup OWI 1 36 WP6 Degradation Modeling ICTP 1 36 WP7 Dissemination and Public Awareness NEXT ENERGY 1 36

5 Objectives of the project

6 Work Package Description WP 1: Management of the Consortium Objectives To ensure that the activities in the different work packages are in line with the respective tasks defined in such work packages with proper achievements as well as with respect to the budget and timing. To manage communication with the FCH Joint Undertaking / European Commission To ensure all requirements are met with respect to reporting and financial management as outlined in detail in the contract between the EU and the consortium. To pursue information, technological developments and demonstrations within the project to the outside world to foster industrial exploitation. WP 2: Materials beyond the State of Art Objectives Optimisation of fuel/oxidant strategy; Optimisation of electrodes and membranes; Optimised MEA design for the chosen fuel/oxidant strategy. The result of the activities will be at MEA designed for the proposed CHP application.

7 WP 3: Degradation with SoA Materials Objectives To achieve general agreement on various test and operating procedures as well as long-term and accelerated stress testing. To identify the optimal gas composition for oxygen enriched cathode air with respect to durability and degradation. To make some single cells with SoA components and test the MEAs for durability and degradation analysis. To make a few short stacks for lifetime testing. WP 4: Balance Of Plant Design Objectives The development of the main components of the plant (BoP) with respect to Maximum electrical efficiency of the system, lifetime of the components, minimum component costs and compliance to technical rules and legal aspects and limitations. Design and test of plant components under system equivalent conditions, optimization of components in single components tests and specification of components for system operation. Construction and delivery of BoP components for two modules of 5 kwel each for the evaluation unit.

8 WP 5: CHP Design and Setup Objectives Proof of concept for the modular CHP design Setup of 2 full stack modules in one modular CHP unit Investigation of controls options and operational strategies Detailed analysis of system potential and providing guidelines and rules for numbering up to larger units WP 6: Degradation Modelling Objectives to design, implement and validate mathematical model of the FC stack to provide parametric study of the stack behavior on the local scale with respect to the geometrical aspects and operational conditions. to implement catalyst degradation phenomenon into the FC model and to extract kinetic information to provide case studies for the different modes of operation and their impact on the catalyst degradation rate WP 7: Dissemination and public Awareness Objectives Development of external website and Set-up of internal website To prepared a set of dissemination material including presentations. To promote the utilization of the project results both within as well as outside the project consortium through a complete exploitation plan. Workshop for selected experts and companies for presenting results and discuss further input and needs

9 Graphical representation of the components showing their dependencies

10 CURRENT DISTRIBUTION, MASS FLOW CHANNELS, MODELISATION ELECTRODES FOR PBI BASED HT-PEMFC 50 cm 2 CELL i (A/cm²) Entrada oxígeno E 3 L UNIVERSITY OF CASTILLA-LA MANCHA Salida oxígeno PBI BASED HT-PEMFC FED WITH ORGANIC COMPOUNDS STACK, 50 cm 2 MEA PBI BASED MEMBRANES

11 UCLM CISTEM WP WP Title Managment of the consortium Materials beyond SoA Degradation with SoA Materials Balance of Plant Design CHP Design and Setup Degradation Modeling Dissemination and Public Awareness LEADER NEXT UCLM DPS OWI OWI ICTP NEXT Person Months UCLM (% ) 2 (6.25 %) 62 (40 %) 62 (29 %) 3 (2.3 ) 0 (0 %) 2 (4 %) 1 (7 %)

12 UCLM CISTEM WP2. MATERIALS BEYOND THE SoA PARTICIPANT NEXT ENERGY DANISH POWER SYSTEM INHOUSE EISENHUTH UCLM ICTP Person Months From month 1 to month 30 Optimize the performance and durability of the MEAs towards the target of the project by: - Optimisation of fuel/oxidant strategy - Optimisation of electrodes and membranes - Optimised MEA design for the chosen fuel/oxidant strategy

13 UCLM CISTEM WP2. MATERIALS BEYOND THE SoA Task 2.1 Fuel and Air/O 2 optimization Pressure Hydrogen Reformate from N. G. Pressurized H 2 and Air/O 2 from electrolysis

14 UCLM CISTEM WP2. MATERIALS BEYOND THE SoA Task 2.1 Fuel and Air/O 2 optimization Pressure Hydrogen Reformate from N. G. * Reduction of Pt - P and O 2 - RDE and Single cells Pressurized H 2 and Air/O 2 from electrolysis Task 2.2 Electrode and Membrane optimization * Improvements of Catalyst -Pt Support C and non/c - Performance and Stability Single cells * BPP optimisation - Durability in PA media * Cell optimisation - Cells for durability test in WP3 * Membrane optimisation - Crosslinking, thermal curing,fillers - Durability in O 2

15 UCLM CISTEM WP2. MATERIALS BEYOND THE SoA Task 2.3 MEA Design Membrane Manufacture Electrode Manufacture BPP Manufacture MEA Manufacture NEXT UCLM EISENHUTH DPS SUCCESS FOR THE WP2

16 UCLM CISTEM WP2. MATERIALS BEYOND THE SoA DELIVERABLES AND RELEVANT MILESTONES 2.1 Optimized PBI based membranes. Membranes from DPS and UCLM with 1000 h of durability (DPS) month MEA performance data. Single cells with the best membrane and catalyst. Performance and durability Data (UCLM). month Short stack durability testing. 3 or 4 MEA short stack running with the best MEA and BPP. Target> 1,500 h (UCLM). month Definition of operation conditions. Must be defined for BoP and Model (WP 4 and WP 6) (NEXT). month 18 MS3 OPTIMIZED MEAs. month 24

17 PARTICIPANT NEXT ENERGY DANISH POWER SYSTEM INHOUSE EISENHUTH UCLM UCLM CISTEM WP3. DEGRADATION WITH SoA MATERIALS Person Months From month 4 to month 36 ICTP * Achieve general agreement on various test and operating procedures. * Identify the optimal composition for O 2 enriched cathode air to increase the durability. * Durability test under various conditions with SoA MEAs * Make few short stacks for lifetime testing and Identify relevant degradation mechanisms. * Do post mortem analysis and verify the targeted life time of the system.

18 UCLM CISTEM WP3. DEGRADATION WITH SoA MATERIALS Task 3.1 Definition and General agreement on test and operating procedure Test protocols for long-term testing of MEAs and stacks Test protocols for accelerate stress tests of MEAs and Stacks Test protocols for evaluating different fuel supplies and cathode air composition

19 UCLM CISTEM WP3. DEGRADATION WITH SoA MATERIALS Task 3.1 Definition and General agreement on test and operating procedure Test protocols for long-term testing of MEAs and stacks Test protocols for accelerate stress tests of MEAs and Stacks Test protocols for evaluating different fuel supplies and cathode air composition Task 3.2 Durability operating conditions for single cell testing After mapping the effect of pressure and enrichment the setup will be used for durability measurements for the Project. WP2

20 UCLM CISTEM WP3. DEGRADATION WITH SoA MATERIALS Task 3.3 Durability testing of individual materials * Membranes, electrodes, reinforcement materials, sealing, etc will be tested * Durability tests in PA media, oxidative ambient and elevated T. Task 3.4 MEA and Single cell degradation * Single and short-stacks tests according the results of task 3.2 Correlation between variables and degradation modes Inputs for the WP6.

21 UCLM CISTEM WP3. DEGRADATION WITH SoA MATERIALS DELIVERABLES AND RELEVANT MILESTONES 3.1 MEA test protocols. Intensive degradation testing requires detailed and agreed testing protocols for comparison purposes between data of participants. (NEXT) 3.2 Optimized MEA delivery. For CHP unit 750 mv at 0.2 A/cm 2 and 670 mv at 0.5 A/cm 2. Accelerate stress test will be performed (DPS). 3.3 Optimized stack delivery. It will include new MEAs, BPP, sealing materials (DPS). 3.4 Degradation results. Report of the degradation of the different materials tested under different operation conditions (NEXT). MS4 OPTIMIZED MEAs. month 30 month 6 month 24 month 30 month 36

22 Renaining acid (g acid g membrane -1 ) UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Synthesis of Composite PBI membranes a) b) c) Pictures from membranes after casting. (a) Standard PBI membrane; (b) 16 wt. % TiO 2 Composite PBI membrane; (c) 16 wt. % TiOSO 4 Composite PBI membrane TiO 2 content (%) Phosphoric acid retained by the composite membranes containing TiO 2 after leaching test. Lines: membranes immersed into 75 wt. % H 3 PO 4 bath concentration. Columns: membranes immersed into 85 wt. % H 3 PO 4 bath concentration High Retention capability of PA

23 Cell Voltage (V) Power Density (W cm -2 ) Cell voltage (V) UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Single Cells (5 cm 2 ) tests with Composite PBI membranes PBI PBI (Direct Cast) spbi PBI-2% TiO 2 PBI-2% TiOSO Current Density (A cm -2 ) PBI spbi 2% TiO 2 -PBI 2% TiOSO 4 -PBI Time (h) 2% TiO 2 -PBI and spbi FCs HIGHEST VOLTAGE STABILITY: Acid Retention capability 2% TiOSO 4 -PBI FC High voltage degradation followed by a voltage stabilization EIS vs. time: Electrodes degradation > Membrane degradation

24 Stack voltage (V) Stack voltage (V) UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Short stacks (3 MEAs of 50 cm 2 ) tests with Composite PBI membranes FC Stack with standard membranes Lack of robustness FC Stack with TiO 2 -PBI Membranes < 2 % after 1,100 h of operation (1,700 h of study) T = 150 ºC, H 2 + Air, j = 0.2 Acm -2 Catalyst loading: 0.4 mgpt/cm 2 in each electrode mgpt/cm 2 in A; 0.35 mgpt/cm 2 in C Conditioning Stage: T= 125 ºC; Oxygen = PBI 2 % TiO 2 -PBI Time (h) Time (h)

25 UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Study of deposition of catalyst ink. Degradation studies with low Pt content. Electrospray (Madrid) Load of Pt Cathode Ánode Assembly mg/cm mg/cm 2 Assembly mg/cm mg/cm 2 I Activation stage. Performance II Degradation stage. Performance

26 I (A) UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Study of deposition of catalyst ink. Degradation studies with low Pt content Load Pt Assembly1 Assembly 2 Cathode Ánode 0.25 mg/cm mg/cm mg/cm mg/cm t (h) I Activation stage. Performance II Degradation stage. Performance 50 cm 2 single cell E = 0.6 V T = 150 ºC H 2 /O 2

27 UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Study of deposition of catalyst ink. Degradation studies with low Pt content Relative difference of the current density at =0.60 V with respect to the average value. (a) (b) (c) (d) (a) t=0 h; (b) t=37 h; (c) t=121 h; (d) t=227 h. (a) (b) (c) (d) 55 % 45 % 35 % 25 % 15 % 5.0 % -5.0 % -15 % -25 % -35 % -45 % -55 % 55 % 45 % 35 % 25 % 15 % 5.0 % -5.0 % -15 % -25 % -35 % -45 % -55 % 50 cm 2 single cell E = 0.6 V T = 150 ºC H 2 /O mg Pt /cm 2 total

28 UCLM CISTEM RECENT RESULTS FROM UCLM USEFUL FOR CISTEM Advanced carbon materials for electrodes in PBI based HT-PEMFC Initial Part. size (nm) Initial Grafitization Part. size (nm) after Thermal treatment (8 h at 185 ºC and in PA, 13 mg/cm 2 ) Grafitization after Thermal treatment Part. size (nm) after Corrosion test (VC in PA media) CNFA CNFR CNS Vulcan XC/

29 UCLM and CISTEM CISTEM: Cogeneration with PEM fuel cells. Role of UCLM. Justo Lobato, Pablo Cañizares, Sara Mateo, Héctor Zamora, Manuel A.Rodrigo

30 In summary the project thus comprises the following key points: Concept and testing of large area pressurized HT-PEM FC for large scale systems Improvement of the HT-PEM FC technology for performance and lifetime; Optimization of the effect of cathode air enrichment by pure oxygen for efficiency Development and integration of a modular designed natural Improved stack design for modular concept approach Modular CHP system design for a 100 kwel CHP unit based on 5 kwel units Proof of concept for the modular CHP system design for a 100 kwel CHP unit based on 5 kwel units using a hardware in the loop test bench System modeling provides detailed specifications for the CHP system numbering - up from 10 kwel up to 100 kwel General design rules for efficient operation of a modular HT-PEM based CHP system using fuel flexible conditions with respect to smart grid applications.gas reformer

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