EUROPEAN INSTITUTE FOR ENERGY RESEARCH Elaboration of a non intrusive diagnosis tool for the detection of water management and CO poisoning defaults in PEMFC stacks Philippe MOÇOTÉGUY EUROPÄISCHES INSTITUT FÜR ENERGIEFORSCHUNG INSTITUT EUROPEEN DE RECHERCHE SUR L’ENERGIE Vincent RAIMBAULT EUROPEAN INSTITUTE FOR ENERGY RESEARCH Nadia STEINER Sébastien WASTERLAIN Daniel HISSEL Alain GIRAUD Denis CANDUSSO Fabrice AUZANNEAU Fabien HAREL Sébastien ROSINI Xavier FRANCOIS Pierre-Alexandre BLIMAN Mohamad SAFA Edition 2006 Michel SORINE
Outline Outline • Introduction • Developped measurements • Stacks characterization • Developped model • Conclusions and future work SINTEF Conference – Trondheim – 24/06/2009 –- 2/20
Scope of the study Scope of the study • Fuel cell insufficiently mature, partly due to limited Fuel cell insufficiently mature, partly due to limited lifet lifet ime ime Need for diagnosis tools to detect and classify failures ⇒ or faulty operation modes so as to prevent or limit degradation. • Important portant causes of causes of degradations / degradations / failures: failures: – Bad water management (flooding, drying): Bad water management (flooding, drying): usually reversible and usually reversible and quite easy uite easy to co to contro ntrol. l. – Poisoning: reversibility = f(pollut Poisoning: reversibility = f(pollutant ant natu ature, c e, concentratio ncentration), hardly n), hardly controllable for air pollution, more easily for fuel pollutant like CO. controllable for air pollution, more easily for fuel pollutant like CO. – Carbon corrosion, catalyst o Carbon corrosion, catalyst oxidation; idation; usually irreversible and impossible to usually irreversible and impossible to control, particularly at stack level. control, particularly at stack level. ⇒ focus on water management and CO poisoning issues . SINTEF Conference – Trondheim – 24/06/2009 –- 3/20
Basics on diagnostic Basics on diagnostic Fuel Cell Pre-treatment Raw Input variables Measurements Corrective actions Detection Model System regulation Estimated Output Experimental indicators Output indicators + - Corrective actions determination Residual Fault Decision identification Alarm OK SINTEF Conference – Trondheim – 24/06/2009 –- 4/20
Outline Outline • Introduction • Developpement of new measurement tools � New high New high power impedancemeter. power impedancemeter. � Integrated Integrated acquisition cardboard. acquisition cardboard. • Stacks characterization • Developped algorithm • Conclusions and future work SINTEF Conference – Trondheim – 24/06/2009 –- 5/20
EIS measurement for high power stack • Previous systems' limitations: Many Many impedan impedancemeters emeters of the pubic market are f the pubic market are limited to a limited to a few Volts with regard to few Volts with regard to the mea the measurement volta urement voltage. e. Development of a new EIS system: ⇒ � High resolution High resolution digital analogic digital analogic converte converter (26 bits). 26 bits). � 32 acquis 32 acquisition channels (1 fo ition channels (1 for I + 31 for U up to 300V). r I + 31 for U up to 300V). � Allows 2 simultaneous measurements (stack Allows 2 simultaneous measurements (stack + individual cells or groups of cells). + individual cells or groups of cells). � Large dispersion in cell � Stack impedance spectra impedance spectra due to are close and do not depend - cell position in the stack, on time - cell state of health. SINTEF Conference – Trondheim – 24/06/2009 –- 6/20
Developped Developped acquisition tool acquisition tool principle principle Imput signal generation: • Current steps. • EIS. Acquisition cardboard Cell n r Data treatment cardboard (AMR 7) • Data acquisition and treatment.software. (Labview) • Control and reading of data coming from test bench. U cell U stack PAC Stack SINTEF Conference – Trondheim – 24/06/2009 –- 7/20
Acquisition cardboard Acquisition cardboard • GMR Performances: GMR Performances: • Basic principle: 0.06 y = 0.0396x - 0.0066 Generation of a bias current: 0.04 U stack U GMR (V) 0.02 I bias R bias 0 or -0.02 U cell -0.04 r -0.06 Intrinsic galvanic -0.08 B insulation -2 -1.5 -1 -0.5 0 0.5 1 1.5 2 U cell (V) Error < 1% (can be reduced but with U supply sensitivity loss) GMR cell • Integration: U GMR 0V Measurement of U GMR similar with Wheatstone Amplifier & bridge principle multiplexer SINTEF Conference – Trondheim – 24/06/2009 –- 8/20
Outline Outline • Introduction • Developpement of new measurement tools • Stacks characterization • Developped algorithm • Conclusions and future work SINTEF Conference – Trondheim – 24/06/2009 –- 9/20
Experimentals Experimentals • 3 stacks technologies: 3M • Design of experiment methodology: � 6 parameters: anodi 6 parameters: anodic and cathodi and cathodic overst overstoich oichiometric iometric ratios, fuel a ratios, fuel and oxident d oxident rela relative humidities, fuel CO tive humidities, fuel CO con conten tent, stack temperature. t, stack temperature. � 2 6- 6-2 2 (16 (16 experiments) design of experiments, experiments) design of experiments, with with aliases. iases. • Characterisations: � Current Current steps teps profile: profile: � Current + Individual and total stack voltages: 100 kHz during 5 to 10s. � Process regulation parameters + pressure drops: 1 Hz. � EIS. EIS. SINTEF Conference – Trondheim – 24/06/2009 –- 10/20
Transient Transient behavior ehavior of CEA 5 cells of CEA 5 cells stack during stack during a a current current step tep from rom 0.4 A/cm² .4 A/cm² to 0.2 A/cm² o 0.2 A/cm² 4.2 h a = h c = 35 %, s a = 2.5, s c = 3, T = 80°C h a =35 %, h c = 75 %, s a = 1.5, s c = 3, T = 80°C 4.1 h a = 75 %, h c = 35 %, s a = 2.5, s c = 3, T = 50°C h a = h c = 75 %, s a = 1.5, s c = 3, T = 50°C 4 h a = h c = 75 %, s a = 2.5, s c = 1.5, T = 80°C h a = h c = 50 %, s a = 2, s c = 2.25, T = 65°C h a = h c = 50 %, s a = s c = 2, T = 80°C 3.9 4.2 3.8 U stack [V] 4.1 4 3.7 3.9 3.9 3.8 U stack [V] 3.8 3.6 3.7 U stack [V] 3.7 3.6 3.5 3.5 3.6 3.4 3.5 3.4 3.3 3.4 0 1 2 3 4 time [ms] 3.3 3.3 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0 1 2 3 4 5 6 7 8 9 time [s] time [s] SINTEF Conference – Trondheim – 24/06/2009 –- 11/20
5 cells 5 cells stack resistivity and individual stack resistivity and individual cell cell resistivity scatterin resistivity scattering 40% 1 0.9 35% 0.8 30% 0.7 5* σ ( ρ )/ ρ stack 25% ρ stack ( Ω .cm²) 0.6 20% 0.5 15% 0.4 10% 0.3 5% 0.2 0.1 0% 2 4 5 ) ) 4 6 7 0 f i 1 1 1 u l l p p p p i e e 0 p p p i i i i n n n n n i v i i i n n n a a a a ( ( a a a M M M M A A M M M 2 4 5 ) ) E 4 6 7 0 E f i l 1 1 1 u C l C p p p p i e e p p p i i i i n f n n n n i f v e i i i n n n e a a a a ( ( R R a a a M M M M A A M M M E E C C Manip 4 h a = h c = 35%, s a = 2.5, s c = 3, T = 80°C f f e e R R de 0.5 A/cm² à 0.9 A/cm² Manip 6 h a = 35%, h c = 75%, s a = 1.5, s c = 3, T = 80°C de 0.9 A/cm² à 0.7 A/cm² Manip 7 h a = 75%, h c = 35%, s a = s c = 1.8, T = 80°C de 0.7 A/cm² à 0.6 A/cm² Manip 12 h a = 75%, h c = 35%, s a = 2.5, s c = 3, T = 50°C de 0.6 A/cm² à 0.4 A/cm² de 0.4 A/cm² à 0.2 A/cm² Manip 14 h a = h c = 75%, s a = 1.5, s c = 3, T = 50°C de 0.2 A/cm² à 0.1 A/cm² Manip 15 h a = h c = 75%, s a = 2.5, s c = 1.5, T = 80°C de 0 à 0.5 A/cm² Manip 0 h a = h c = 50%, s a = 2, s c = 2.25, T = 65°C Ref CEA h a = h c = 50%, s a = s c = 2, T = 80°C SINTEF Conference – Trondheim – 24/06/2009 –- 12/20
Transient Transient behavior ehavior of 3M 20 cells of 3M 20 cells stack during stack during a current a current step tep from rom 0.5 A/cm² .5 A/cm² to 0.7 A/cm² o 0.7 A/cm² 0.7 h a = 50% ; h c = 50% ; s a = 2.4 ; s c = 2.5 ; T = 70°C 0.7 current step: 0,5 to 0,7 A.cm -2 0.68 Vcell 1 0.7 0.66 voltage [V] Vcell 2 0.68 0.64 Vcell 3 0.68 Vcell 4 0.62 0.66 Vcell 5 0.66 0.6 Vcell 6 0.64 0.58 Vcell 7 0 0,5 1 1,5 2 2,5 3 3,5 4 0.64 Vcell 8 time [ms] 0.62 Vcell 9 voltage [V] 0.62 Vcell 10 voltage [V] Vcell 11 0.6 0.6 Vcell 12 Vcell 13 0.58 0.58 Vcell 14 Vcell 15 0.56 0.56 Vcell 16 Vcell 17 0.54 0.54 Vcell 18 Vcell 19 0.52 Vcell 20 0.52 0 2 4 6 8 0 0,1 0,2 0,3 0,4 time [s] SINTEF Conference – Trondheim – 24/06/2009 –- 13/20 time [s]
Outline Outline • Introduction • Development of new measurement tools • Stacks characterization • Developped algorithms: � Physical Physical model based. model based. � Black box model based. Black box model based. • Conclusions and future work SINTEF Conference – Trondheim – 24/06/2009 –- 14/20
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