Hydrogen and Oxygen Permeability through PEFC Membrane and Membrane Electrode Assembly
Authors: Kageyama Miho , Balci Beste , Danjo Shotaro , Nakamichi Kimiyo , Kawase Motoaki 
Published: February 2024

Introduction
The permeation of feed gas through a proton exchange membrane (PEM) affects a PEFC performance [1, 2]. The temperature and relative humidity (RH) dependences of the hydrogen and oxygen permeability through the perfluorinated sulfonic-acid (PFSA) membrane were investigated. A membrane is considered to consist of a bulk layer sandwiched between skin layers [3]. In this study, by measuring the hydrogen and oxygen permeation flux through a membrane and plotting the permeation resistance against the membrane thickness, the bulk layer effective diffusion coefficients and the skin layer mass transport coefficients of PEM and membrane electrode assembly (MEA) were examined.
Experimental
Nafion™ NR-211, NR-212, and N115 (Chemours) with different thickness (at RH of 50 %), 25.8, 51, and 127 μm, respectively, were used as PEM. Catalyst layers made of Pt-loaded carbon (Pt 50 wt%) and Nafion ionomer (I/C = 1.0) with a thickness of 8.5-10 μm on both sides of PEMs were prepared as MEA. They were installed separately in a Japan Automobile Research Institute (JARI) standard cell whose active area was 5.0 cm×5.0 cm. The cell was placed in the constant temperature and humidity oven (ESPEC, LHL-113) and the relative humidity of the supplied gas was controlled by the bubbler temperature. The hydrogen and oxygen fluxes through a membrane were measured at cell temperatures of 60-90 °C and RH of 0.2-1.0 (moisture content λ = 1.7-10.5) with different partial pressures of nitrogen diluent gas. Permeate gas was quantified by a gas chromatograph (Agilent 990 micro GC, column: MSieve5A, detector: TCD). The schematic drawing of the measurement system is shown in Fig. 1.
Results and discussion
The permeate gas flux through a membrane, Nj
(j = H, O), is expressed asNj = k
pj
Δpj
, where k
pj
is the gas permeance and Δpj
is the partial pressure difference between the supply side and the permeate side.
Fig. 2 shows the temperature and RH dependences of O2 permeance through PEM and Fig. 3 shows the permeation resistance against the membrane thickness. k
pO increases with increasing RH and 1/k
pj
becomes lower at higher temperature. The permeation resistance through MEA tends to be lower than PEM. By assuming that Nafion has a bulk layer and skin layers [3], the bulk layer and skin layer resistances were separated from a slope and an intercept of trend lines in Fig. 3. The permeation resistances through MEA do not have y-axis intercept. The fused layer can be created by hot press process in manufacturing MEA and an x-axis intercept might be a fused layer thickness. It is easier to permeate gas through the fused layer than the skin layer of PEM. The temperature dependences of the bulk layer effective diffusion coefficient, D
ej

(B), are shown in Fig. 4. D
eH
(B) and D
eO
(B) of PEM and MEA are on the same line, with activation energies, E
a, of 23.9 and 20.6 kJ/mol, respectively at λ = 6. D
ej

(B) can be formulated as follows:

D
eH
(B) = (4.26×10-11 + 6.50×10-11RH) exp(-E
aH/R (1/T-1/T
ref)) m2/s

D
eO
(B) = (8.16×10-12 + 3.39×10-11RH) exp(-E
aO/R (1/T-1/T
ref)) m2/s

T
ref = 353.15 K, E
aH = 0.65 λ + 20.0 kJ/mol, E
aO = 21.2 kJ/mol,
Reproduced D
eH
(B) and D
eO
(B) are shown in Fig. 5. The skin layer mass transport coefficient, k
pj

(S), can be obtained from the y-axis intercept of a trend line in Fig. 4 and it shows that only PEM has skin layers. It is necessary to consider the gas permeation through MEA not through PEM in designing PEFCs because using the transport properties through PEM may lead to overestimate the performance.
Conclusions
By measuring the hydrogen and oxygen permeation flux through PEM and MEA in PEFC, the bulk layer effective diffusion coefficients and the skin layer mass transport coefficients of hydrogen and oxygen were obtained. The bulk layer effective diffusion coefficients of PEM and MEA were found to be the same and the temperature and RH dependences of D
ej

(B) were formulated as a function of temperature and RH. The skin layer mass transport coefficient appears only in PEM.
Acknowledgement
This work was supported by the FC Platform Program: Development of design-for-purpose numerical simulators for attaining long life and high-performance project (FY 2020–FY 2023) conducted by the New Energy and Industrial Technology Development Organization (NEDO), Japan.
References
[1] K. D. Baik et al., Applied Energy, 101, 560-566 (2013).
[2] N. T. Truc et al., J. Heat Mass Transf., 127, 447–456 (2018).
[3] L. Dehabadi et al., J. Therm. Anal. Calorim, 126, 1851–1866 (2016).

Figure 1