Effect of multilayer CrN/CrAlN coating on the corrosion and contact resistance behavior of 316L SS bipolar plate for high temperature proton exchange membrane fuel cell

doi:10.1016/j.jmst.2021.04.043

Abstract

Abstract:

Stainless steels have received wide attention as a substitute material for bipolar plates in high temperature proton exchange membrane fuel cell (HT-PEMFC). In the present work, the CrN, CrAlN and multilayer CrN/CrAlN coatings were deposited on 316L SS to increase the corrosion resistance and decrease the interfacial contact resistance. The deposited coatings exhibited face centered cubic phase structure and it was verified from the X-ray diffraction pattern. X-ray photo electron spectroscopy results showed the formation of both CrN and CrAlN layers on 316L SS. CrN/CrAlN coating is more helpful in water management due to low surface roughness and high contact angle in the HT-PEMFC environment. The corrosion resistance behavior of all the samples were studied in 85% H₃PO₄ solution at 140 °C purged with H₂ (HT-PEMFC anode) and O₂ (HT-PEMFC cathode) gases. The results showed that all the coatings considerably improved the performance of 316L SS and superior corrosion resistance was observed for CrN/CrAlN multilayer coating, whose protective efficiency was 98.12% and 96.14% in the two simulated HT-PEMFC environments. The results of electrochemical impedance spectroscopic studies demonstrated higher impedance for CrN/CrAlN coating. Surface morphological studies performed after corrosion studies revealed that protection ability of CrN/CrAlN coating still remained acceptable. A very low interfacial contact resistance value of 6 mΩ cm² at 140 N/cm² was observed for CrN/CrAlN coating. Moreover, after corrosion studies, the interfacial contact resistance value of CrN/CrAlN coated 316L was much lower than that of CrN and CrAlN coatings due to the increased oxidation resistance. The maximum power density of about 0.93 W/cm² at 2 A/cm² and output voltage of 0.96 V was observed for CrN/CrAlN coating.

Key words: Bipolar plate, 316L SS, Corrosion, Contact resistance, Contact angle, Surface roughness

S. Pugal Mani, P. Agilan, M. Kalaiarasan, K. Ravichandran, N. Rajendran, Y. Meng. Effect of multilayer CrN/CrAlN coating on the corrosion and contact resistance behavior of 316L SS bipolar plate for high temperature proton exchange membrane fuel cell[J]. J. Mater. Sci. Technol., 2022, 97: 134-146.

Figures/Tables 15

Table 1 Chemical composition of 316L SS (Wt%) bipolar plate.

C	Mn	P	Si	Cr	Ni	Mo	Cu	Fe
0.02	1.48	0.03	0.43	16.20	10.03	2.06	0.43	Bal

Table 2 Corrosion parameters of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L SS at HT- PEMFC anode and cathode environments.

Environment	Material	E_{corr (V)}	β_a (V/dec)	β_c (V/dec)	R_p (_{Ω cm}²)	i_corr (_{µA/ cm}²)	PE (%)	CR (mil/year)	P(%)
HT-PEMFC Anode
	316L SS	-0.096	0.465	3.783	2172	46.15	-	9.81	-
	CrN	-0.206	1.996	5.040	21,192	2.91	51.12	0.66	0.031
	CrAlN	-0.147	0.484	4.419	32,021	2.76	76.3	0.5	0.009
	CrN/CrAlN	-0.010	4.190	5.981	248,103	0.17	98.12	0.03	0.001
HT-PEMFC Cathode
	316L SS	-0.087	0.082	2.999	1872	75.37	-	16.1	-
	CrN	-0.190	3.666	3.769	12,392	4.22	55.16	1.003	0.036
	CrAlN	-0.193	6.801	7.594	13,564	3.48	73.4	0.47	0.011
	CrN/CrAlN	-0.224	3.767	7.849	39,053	0.91	96.14	0.22	0.002

Fig. 1. XRD patterns of CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L SS.

Fig. 2. XPS spectra of (a) CrN-316L S (N1s, Cr2p) (b) CrAlN-316L SS (N1s, Cr2p, Al2p) and CrN/CrAlN-316L SS (N1s, Cr2p, Al2p).

Fig. 3. Contact angle images of 316L, SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L SS.

Fig. 4. Potentiodynamic polarization studies of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L in HT-PEMFC (a) anode and (b) cathode environments.

Fig. 5. EIS studies-(a) Nyquist, (b) Bode-impedance and (c) phase angle plots of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L in HT-PEMFC anode environment.

Fig. 6. EIS studies-(a) Nyquist, (b) Bode-impedance and (c) phase angle plots of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L in HT-PEMFC cathode environment, equivalent circuits for (e) 316L SS and (f) CrN-316L SS, CrAlN-316L SS, CrN/CrAlN-316L SS in HT-PEMFC anode and cathode environments.

Table 3 EIS parameters of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L SS at HT-PEMFC anode and cathode environments.

Environment	Material	R_s (_{Ω cm}²)	CPE₁		R_ct (_{Ω cm}²) × 10⁴	CPE₂		R_coat (_{Ω cm}²)	χ² × 10^-4
			Q_dl (_{µF cm}^-2)	n₁		Q_c (_{µF cm}^-2)	n₂
HT-PEMFC Anode	316L SS	1.6	31.30	0.83	3.184	-	-	-	4.18
	CrN	1.2	7.15	0.86	4.124	127.12	0.80	117.8	6.34
	CrAlN	2.4	1.74	0.90	7.321	71.84	0.83	437.5	4.34
	CrN/CrAlN	2.1	0.61	0.93	13.427	9.87	0.89	891.2	6.19
HT-PEMFC Cathode	316L SS	0.9	208.28	0.82	1.672	-	-	-	8.34
	CrN	1.8	112.95	0.82	2.927	413.7	0.81	71.3	4.17
	CrAlN	3.2	31.23	0.89	3.834	109.4	0.83	196.4	5.17
	CrN/CrAlN	2.6	8.76	0.93	9.423	21.7	0.89	635.2	3.57

Fig. 7. Potentiostatic polarization studies of CrN-316L SS, CrAlN-316L SS and CrN/CrAlN-316L SS in HT-PEMFC (a) anode and (b) cathode environments.

Fig. 8. Overall corrosion mechanism of CrN, CrAlN and CrN/CrAlN coatings.

Fig. 9. SEM-EDS images of (a) CrN-316L SS, (b) CrAlN-316L SS, (c) CrN-CrAlN-316L SS and (d) cross section image of CrN/CrAlN-316L SS.

Fig. 10. After polarization-SEM images of (a) & (b) CrN-316L SS and (c) & (d) pit profile for CrN-316L SS, SEM images of (e) & (f) CrAlN-316L SS, (g) & (h) CrN-CrAlN-316L SS and (i) surface roughness of CrN-316L SS, CrAlN-316L SS, CrN-CrAlN-316L SS.

Fig. 11. ICR values of 316L SS, CrN-316L SS, CrAlN-316L SS and CrN-CrAlN-316L SS in (a) 60 to 180 N/cm2 and (b) at 140 N/cm2 (before and polarization studies).

Fig. 12. Single fuel cell test for CrN-316L SS, CrAlN-316L SS and CrN-CrAlN-316L- SS.

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