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B10-0882R 1 B10-0882 2011-07-21 12:13:09 Days to Render Final Decision: 31 Manuscript Ready for Publication Stochastic Reconstruction at Two Scales and Experimental Validation to Determine the Effective Electrical Resistivity of a PEMFC Catalyst Layer Regular Paper 882 Polymer Electrolyte Fuel Cells 11 Romeli Barbosa (Universidad Nacional Autonma de Mxico) Beatriz Escobar , Ulises Cano , Rolando Pedicini , Rubn Ornelas , Enza Passalacqua In this paper we report on the application of statistical information obtained from 2D micrographs of catalyst layers (CL) of proton exchange membrane fuel cell (PEMFC), to derive stochastic replicas of their 3D pore networks at two scales. The main focus is on assessing the scaling strategy to determine effective transport coefficients and the analysis of the experimental results. The continuity equation for charge transport is solved directly on the 3D reconstructed CL to determine effective electrical conductivities at "internal-scale" and to simulate the electrical global performance at "macro-scale". The electrical performance is experimentally determined. The applied image processing method makes use of two immediate scales to improve the image resolution. Pore size distribution of the reconstructed scales is used to avoid the superposition of equal pore sizes. The relative porosities were determined by the statistical analysis of SEM micrographs and verified by mercury intrusion porosimetry. Hubert Gasteiger We agree to the ECS Transfer of Copyright Agreement and hereby transfer the copyright for this manuscript to The Electrochemical Society. Publish as is / 2011-08-01

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R. Barbosa, et al. The Electrochemical Society Proceedings Series (2011) 41: 2061-2072

Stochastic reconstruction at two scales and experimental validation to determine the effective electrical resistivity of a PEMFC catalyst layer R. Barbosaa, B. Escobarb, U. Canoc, R. Pedicinid, R. Ornelase and E. Passalacquad
a

Centro de Investigacin en Energa (CIE-UNAM), Temixco, Morelos 62580, Mxico. b Instituto Tecnolgico de Cancn, Cancn, Q. Roo 77515, Mxico. c Instituto de Investigaciones Elctricas, Cuernavaca, Morelos 62490, Mxico. d Institute for advanced energy technologies "Nicola Giordano" (CNR-ITAE), Messina 98126, Italy. e Tozzi Renewable Energy SpA, Mezzano, RA 48010, Italy.

In this paper we report on the application of statistical information (two-point and linear-path correlation function), obtained from 2D micrographs of catalyst layers (CL) of proton exchange membrane fuel cell (PEMFC), to derive stochastic replicas of their 3D pore networks at two scales. The main focus is on assessing the scaling strategy to determine effective transport coefficients and the analysis of the experimental results. The continuity equation for charge transport is solved directly on the 3D reconstructed CL, to determine effective electrical conductivities at internal-scale and to simulate the electrical global performance at macro-scale. The electrical performance is experimentally determined. The applied image processing method makes use of two immediate scales to improve the image resolution. Pore size distribution of the reconstructed scales is used to avoid the superposition of equal pore sizes. The relative porosities were determined by the statistical analysis of SEM micrographs and verified by the total experimental porosity obtained by mercury intrusion porosimetry.

Introduction It is well recognized that the catalyst layer (CL) has a great influence on the performance of a proton exchange membrane fuel cell (PEMFC). This is because this component is central to the operation of a fuel cell, as it not only provides reactive sites for electricity generation, but also its structure defines the efficiency of many of the processes involved during the operation of a PEMFC, in particular transport phenomena. On the other hand, the CLs structure strongly depends on several factors particularly ink composition and the deposition technique used for MEA manufacturing. Once a certain structure is attained properties such as electrical and ionic conduction, gas and liquid transport and catalytic properties are defined for a given operating condition. This in turn, defines the overall efficiency of the PEMFC (1-3). The structure and composition of a PEMFC CL define this component as a random heterogeneous material. This heterogeneity arises from the fact that it is constituted by different phases, a phase being an identifiable domain with its own particular properties that differentiate it from the rest of the other phases in the CL (i.e. voids, gases, liquids or
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representative structures). Proportionality coefficients for mass, energy and charge transport in a heterogeneous material are significantly affected by the properties of the phases from which this is composed, by the volume fraction composition, and by the structure of such phases. For this reason, an effective transport coefficient (ETC) is defined for a heterogeneous material as a proportionality coefficient, which characterizes the domain of the material. For a randomly formed heterogeneous material with M phases, a general ETC, Ke is: Ke = f (K1, K2,,KM; 1, 2,,M; ) [1]

where subscript of variables indicates a respective phase, K is the proportionality constant for that phase, is the phase volume fraction and is a microstructural information of the domain (4). In literature there are different mathematical relationships to determine ETCs (5-7). However, a more powerful technique to determine effective properties of random heterogeneous materials, is the so called stochastic reconstruction (8-10). Unfortunately, the large number of control volumes required to detail the main elements that form the CL, in a computing domain that covers the whole electrode, makes it an expensive computation-wise method. Barbosa et al. (11) recently proposed a scaling method to determine effective transport coefficients in a CL PEMFC. In this work, the scaling method was applied for two scales. Scales are defined based on different observable structures at different resolutions of scanning electron microscopy (SEM) and their statistical information. The annealing stochastic reconstruction, the direct simulation of the charge continuity equation and experimental resistivity of three manufactured CLs with different microstructures is presented.

Theory and calculation Most of the PEMFC CL can be defined as a randomly-distributed heterogeneous material. In these stochastic CLs, internal substructures can be defined at different scale levels. One way to explain these apparent structural changes at different scale levels is by picturing you infinitely faraway and getting closer and closer into the CL structure. In a hypothetical example, when the vision scale is ~50000 nm, one will observe a homogenous dispersion of mesoporous structure; for a scale of ~5000 nm and focusing areas where mesoporous are absent, the structure is defined by agglomerates and micropores; finally at a vision scale of ~500 nm and focusing at an agglomerate the observer will distinguish a structure formed by a random distribution of Pt/C particles, ionomer and probably nanometric pores. Although the scales are defined by an empirical observation, the relative porosities of each scale are related mathematically to the total porosity by equation 2, T=1-(1-i ) [2]

where T represents the total porosity of the complete CL and i the relative porosity of each i scale. On the other hand, the total porosity (T), the thickness () and the CL composition (design parameters) are related by the following equation:
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R. Barbosa, et al. The Electrochemical Society Proceedings Series (2011) 41: 2061-2072

= [1/Pt + 1/PtC + N(1+Pt)/Pt/(1-N)/N] Pt / (1-T)

[3]

where Pt, C, N are platinum, carbon and nafion densities respectively; pt is the platinum load, N the ionomer load and pt the platinum to carbon weight ratio. The design parameters (pt, N and pt), are controlled before CL manufacturing but can be assumed the same in the CL microstructures fabricated by physical techniques, in which chemical reactions do not occur. Other important structural information that can be assumed as the same before and after the CL manufacturing is the individual platinum and carbon particle sizes and the fact that platinum is supported on carbon. Structural reconstruction algorithm The simulated annealing method (4) was applied for the microstructural reconstruction. This method generates a system that has the same statistical correlation functions as a specified reference system. It involves finding a state of minimum energy by interchanging the phases of the pixels in the digitized system. The energy (E) is defined in terms of the squared difference of the reference (f(r)) and simulated (f(r)) correlation functions. E = f [f(r)-f(r)]2 [4]

Where f is an arbitrary weight that assigns the relative importance of each individual correlation function. The first moment of the algorithm generates a stochastic microstructure with the same volume fraction of the reference system as the initial structure. After this initialization, the states of two random pixels of different phases are interchanged. The energy change (E=E'-E) between the two successive states is computed. This phase interchange is accepted with probability P(E). P(E)=1, if (E 0); P(E)=exp(-E/T), if (E>0) [5]

where T is a fictitious temperature. This method causes fs(r) to converge gradually to fs(r). The algorithm ends when the energy E is less than a tolerance value. The concept of finding the lowest error state (lowest energy) by simulated annealing is based on a well known physical fact: If a system is heated to a high temperature T and then slowly cooled down to absolute zero, the system equilibrates to its ground state. Two correlation functions were used: (i) the two-point correlation function (S2F) which is obtained by randomly tossing a line segment of r length with a specific orientation and counting the number of times that the beginning (x) and the end (x+r) of the line fall in phase j. (ii) The lineal-path function (LPF) which is defined as the probability of finding a line segment with end points at x and x+r entirely in phase j. The S2F was applied at the two phases and the LPF only at the most relevant phase. In this way, the total energy was defined by equation 6, E = 0.33[S2s-S2s]2+0.33[S2v-S2v]2+0.33[LPFs-LPFs ]2 [6]

where S2s and S2v is the simulated S2F of the solid phase and the empty phase respectively; S2s and S2v is the reference S2F of the solid phase and the empty phase
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respectively; LPFs and LPFs is respectively the simulated and the reference LPF of the solid phase; and 0.33 is the assigned function weight. Theoretical effective electric resistivity The effective resistivity (eff) of a heterogeneous material, composed by a conductive phase and one or more insulating phases, of an element formed by subdomains of smaller scales is: eff = m Leff_i/Aeff_i Am_i/Lm_i [7]

where eff is the effective resistivity of the global domain formed by various smaller scale subdomains i, m is the materials resistivity, Leff_i is the effective length and Aeff_i is the effective area of the phase under study in every subdomain and Lm_i is the length and Am_i is the area of the scale of every subdomain. To normalize and generalize results, in this work calculated resistivities are used to estimate conduction efficiency (k). As conductivity is the inverse of resistivity, the CLs effective conductivity is the inverse of the effective resistivity value keff=eff-1. k is calculated by comparing the effective conductivity with a reference or nominal conductivity, as described by equation 8. By substituting equation 7 in equation 8, we can obtain a relation that provides the conduction efficiency of the global domain which is formed by several subdomains (equation 9), k = keff / km k=Aeff_i/Leff_i Lm_i/Am_i [8] [9]

Experimental procedure Three electrodes, with different pore promoter load, were manufactured in this study. Its microstructure at two different scales and the electric resistivity were characterized. In this section we describe the experimental methodology used. Electrode manufacture The decal process was used to prepare all CLs used in this study. The ink mixture, made of the catalyst carbon (50 wt % Pt/C), 5% Nafion solution, and water solution of ammonium carbonate, was mixed using ultrasound for 30min. Then it was spraydeposited on an inert decal substrate (PTFE). The decal was heated in an oven at 70C for ~5 min. The process of spray and heating was repeated until the desired catalyst loading was reached, which in this study was equivalent to ~0.5 mg Pt/cm2 (nominal). When the desired loading is reached a drying step at 70C and 125C for 30 min each was carried out. Three loads of pore former (ammonium carbonate) were studied: 40, 20 and 0 %wt. To characterize the CL without the proton exchange membrane (PEM), the single CL (without membrane) was hot-pressed at 100 kg/cm2 and 125C for 5 minutes between two graphite plates. This technique emulates the microstructural condition of a
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membrane-electrode assembly (MEA) but without separating the CL of the decal substrate (PTFE). A 40 x 100 mm sample of electrode was used for the mercury intrusion porosimetry measurements, a 10 x 10 mm sample was cut for scanning electron microscopy (SEM) examination and a 25 x 25 mm sample was also cut for electronic resistivity characterization. Experimental electronic resistivity The electronic resistivity was measured exclusively for the CL by a four-point probe method using the combined system of a current supplier and a voltmeter. Four in-line, equally spaced probes are placed in contact with the CL surface. A current (I) is passed through the outside two points of the probe and measuring the voltage (E) across the inside two points. Electrostatic analysis of the electric potential and field distributions in this configuration yields: = E/I [10]

where is a constant dependent on the configuration and spacing of the contacts and is the thickness of the film. This method is a long established technique to measure the average resistivity () of a thin layer (12, 13). In this work, the device was specified to have in-line fixed four probes made of platinum wire (diameter of 0.52 mm), equal probe spacing was 2.2 mm and downward force was approximately of 12.25 kPa per probe. Two currents were imposed (1 and 3 mA). CL microstructural characterization Relative porosities (i) were determined by the statistical analysis of SEM micrographs and verified by the total experimental porosity obtained by mercury intrusion porosimetry. CL thickness () was also determined by SEM. CLs were studied by SEM at different resolutions. Nevertheless, for the simulation study, two micrometric scales were empirically selected: (i) superficial scale at 500 X resolution, where we can obtain samples of ~120 m and (ii) micropores scale at 5000 X resolution, where we can obtain samples of ~12 m. It is important to point out that the nanometric scale (inside an agglomerate scale) was not experimentally studied. CL internal microstructure is characterized at 5000 X resolution. In this scale we can define stochastic micropores but is not possible to define CL primary components (Pt, C and ionomer). On the other hand, because the DECAL technique generates very thin CLs (10-20 m), the 500 X resolution characterizes a macro-superficial and isotropic structure. Image processing method Empty phase was selected by the pixel intensity in two stages: (i) the superficial fraction at double resolution of the studied scale was empirically determined by the intensity, (ii) the intensity at the studied resolution was automatically selected by the superficial fraction of the first stage. In this work, intensity at 1000X resolution fixes the superficial fraction of 500X resolution and 10000X resolution fixes the superficial
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fraction of 5000X resolution. This permits the study of a predetermined area with more resolution. Figure 1 shows schematically this micrograph initial process (P1).

Figure 1. Initial process (P1) of the micrographs. The Internal box is twice resolution than dotted box. The Internal box fixes the superficial fraction of dotted box. After intensity selection process o micrograph initial process (P1) the pore size distribution at the two studied scales are adjusted for avoid the superposition of the same pore size by pore elimination. Figure 2 shows a representative example of the total image process: from (a) to (b) the P1 process is applied; from (b) to (c) the pore size distribution is analyzed and the proper size pores are deleted; from (c) to (d) the correlation functions (S2F and LPF) are obtained.

Figure 2. Total image process. a)b) pixel intensity selection; b)c) proper pore deleted; c)(d) statistical characterization.
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Results and discussion

Three CLs with different pore former load (PFL) were manufactured and characterized: (i) PCL40 with PFL 40.0 %wt, (ii) PCL20 with PFL 20.0 %wt and (iii) PCL00 with PFL 0.0%wt. The electronic resistivity and SEM analysis of each CL were characterized at three different locations on each CL specimen. In Table 1 the experimental results are presented: Pt load (pt), total porosity (T), CL thickness (), electronic conductivity (keff) and electric conduction efficiency (k). k was estimated by considering the electric conductivity of Vulcan carbon (~400 S/m) (14).

Table I. Experimental results.

Electrode name PCL40 PCL20 PCL00

PFL (%) 40.0 20.0 00.0

pt (mg/cm2) 0.47 0.57 0.47

T (%) 13.42 19.93 14.59

(m) 9.59 0.27 14.83 0.36 9.64 0.52

keff (S/m) 40 58 140

k 0.10 0.14 0.35

In this work, the electrical performance of the nanometric structure was fixed to adjust the experimental data with the simulated results. Table 2 briefs the dimension of the computing domain (Nx, Ny and Nz) and the finite control volumes (dx, dy and dz) used for the reconstruction and simulation procedure.
Table II. Dimensions of the domain and control volume for the studied samples

Sample 500 X 5000 X

Nx; Ny; Nz (m) 161; 161; 10 10; 10; 10

dx; dy; dz (m) 0.5; 0.5; 0.5 0.1; 0.1; 0.1

Original and processed images of some studied CLs are showing in Figure 3. Figures 3(a) and 3(b) correspond to PCL40, 3(c) and 3(d) correspond to PCL20 and 3(e) and 3(f) correspond to PCL00. The left side of figure is for 500 X resolution and the right is for 5000 X resolution. 5000 X resolution characterizes a micropores scale. Statistical information of these samples was used for a 3D isotropic reconstruction. However, the microstructure at 500 X resolution has elements with a longer dimension than CL thickness. These samples were reconstructed in two stages: i) representative elements with a dimension greater than 1/3 of the CL thickness were considered as anisotropic gaps, therefore they were first reconstructed by 2D isotropic way and then extruded to the CL thickness. ii) Representative elements with a dimension less than 1/3 of the CL thickness were reconstructed by a 3D isotropic way.

R. Barbosa, et al. The Electrochemical Society Proceedings Series (2011) 41: 2061-2072

Figure 3. Original and processed images of some studied CLs.

Figure 4 shows the two-point correlation (S2F) and lineal-path (LPF) functions for the CLs studied. These mean values are plotted versus a non-dimensional distance r/N, where r is the distance between two points and N the domain lattice. Each curve corresponds to a different pore promoter load (PCL) and is calculated for the pseudosolid phase. Figures 4(a) and 4(b) correspond to 500 X resolution with elements dimension less than 1/3 of the CL thickness. Figures 4(c) and 4(d) correspond to 500 X resolution with elements dimension greater than 1/3 of the CL thickness. Figures 4(e) and 4(f) correspond to 5000 X resolution. The left side of figure is for S2F and the right is for LPF.

R. Barbosa, et al. The Electrochemical Society Proceedings Series (2011) 41: 2061-2072

Figure 4. Two-point correlation (S2) and lineal-path (LP) function for the CLs. These statistical correlation functions were used as the reference systems in the annealing microstructural reconstruction. Each sample was reconstructed and simulated five times with different random series. Figure 5 shows representative images of reconstructed samples. Figures 5(a) and 5(d) correspond to PCL40, 5(b) and 5(e) correspond to PCL20 and 5(c) and 5(f) correspond to PCL00. The white color represents the pseudo-solid phase and black color the empty phase. In 5000X resolution (top side of figure), the reconstructed structures look alike in the three planes for each samples. In 500X resolution (bottom side of figure) there are two representative structures: i) elements with dimension greater than 1/3 of the CL thickness (anisotropic gabs) and ii) elements with dimension less than 1/3 of the CL thickness (isotropic structure).

R. Barbosa, et al. The Electrochemical Society Proceedings Series (2011) 41: 2061-2072

Figure 5. Images of some reconstructed samples. Figures 6(a) and 6(d) correspond to PCL40, 6(b) and 6(e) correspond to PCL20 and 6(c) and 6(f) correspond to PCL00. The white color represents the pseudo-solid phase and black color the empty phase. The electric conduction efficiency (k) obtained by direct simulation of the charge continuity equation in 500X (k,500) and 5000X (k,5000) resolution, can be generalized by its product in a single micrometric efficiency parameter (micro= k,500 k,5000). In this way, the electric conduction efficiency of the nanometric structure can be estimated by equation 11. nano=keff / km / micro [11]

where keff is the effective electric conductivity of the material, in this work it is experimentally obtained by the four-point probe; km is the electric conductivity of the pseudo-solid phase, in this work is the Vulcan carbon conductivity (km400 S/m). Table 3 resumes the electric conduction efficiencies in the studied scales (k,500 and k,5000), the generalized micrometric efficiency (micro) and the estimated nanometric efficiency (nano).
Table III. Electric conduction efficiency.

Sample PCL40 PCL20 PCL00

k,500 0.90 0.97 0.88

k,5000 0.93 0.92 0.87

micro 0.84 0.89 0.77

nano 0.12 0.16 0.45

In micrometric scale, PCL20 shows higher micro value than the other two manufactured CLs. However experimental results (see table I) shows that PCL00 has the highest global conduction efficiency (k). This suggests that the nanometric scale has a
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significant influence in the electric global performance. In this work, the conduction efficiency increases while the pore promoter load diminishes. On the other hand, the sample without pore promoter (PCL00) is particularly different than the other CLs. Conclusions In this article, theoretical and experimental techniques were applied for the study of electric charge transport of PEMFC CLs. Experimental study includes: electrode manufacture, effective electrical conduction and microstructural physic characterization. Theoretical study includes: processing and statistical characterization of micrographs, stochastic reconstruction of CLs structure and charge continuity direct simulation. The simulated annealing method and three correlation functions were applied for the reconstruction. SEM micrographs were processed to obtain the reference statistical functions at two micrometric scales. These micrometric-structures were generalized to obtain conduction efficiency at local micrometric scale (micro). The nanometric scale performance (nano) was estimated from the experimental total effective electric conductivity, a reference electric conductivity of the pseudo-solid phase and micro. It is interesting to observe that nano is more significant than micro. However, more work, including the nanometric structural study and local experimental resistivity (at representative scale) are required in order to draw a clear perspective directed toward the phenomenology. Finally, the techniques presented in this work can be applied to study already existent CL microstructures as well as to propose new and more efficient CLs. Acknowledgments B. Escobar recognizes the support to REDFE CONACYT and CONACYT FORDECYT under grant No. 116157. References
1. E. Passalacqua, F. Lufrano, G. Squadrito, A. Patti, L. Giorgi, Electrochim. Acta, 46, 799 (2001) . 2. B. Escobar, S.A. Gamboa, U. Pal, R. Guardin, D. Acosta, C. Magaa, X. Mathew, Int. J. Hydrogen Energy, 35, 4215 (2010). 3. J. Ledesma-Garca, R. Barbosa, T.W. Chapman, L.G. Arriaga, L. A. Godnez, Int. J. Hydrogen Energy, 34, 2008 (2009). 4. S. Torquato, Random Heterogeneous Materials: Microstructure and Macroscopic Properties, p. 12, Springer-Verlag, New York (2002). 5. P.K. Das, X. Li, Z.-S. Liu, Appl. Energy, 87, 2785 (2010). 6. Maxwell-Garnett, Philos. Trans. R. Soc. London Ser. A, 203, 385 (1904). 7. D. Bruggeman, Ann. Phys., 24, 636 (1935). 8. Quiblier, J.A., J. Colloid Interf. Sci., 98, 84 (1984). 9. S. H. Kim and H. Pitsch, J. Electrochem. Soc., 156, B673 (2009). 10. G. Wang, P. P. Mukherjee and C.-Y. Wang, Electrochim. Acta, 51, 3151 (2006). 11. R. Barbosa, J. Andaverde, B. Escobar and U. Cano, J. Power Sources, 196, 1248 (2011). 12. A. E. Yarimbiyik, H. A. Schafft, R. A. Allen, M. D. Vaudin, M. E. Zaghloul, Microelectronics Reliability, 49, 127 (2009). 13. F. M. Smits, Bell Syst Tech. J., 37, 711 (1958). 14.D. Pantea, H. Darmstadt, S. Kaliaguine, L. Summchen, C. Roy, Carbon, 39, 1147 (2001). 11