7 Results and discussion
6.4 Degradation tests
6.4.1 Degradation test performed at 60°C and 80°C, 0.5bar, closed cathode, 10% mass flow
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The effective temperature during the experiment oscillates around 61°C whereas the real gauge pressure at the anode and cathode was 0,89 bar and 0,44 bar respectively.
The study shows an increase of pressure at the heater (from 1 to 1.3 bar), instead cell temperature remains in a range of values between 61-61,39°C and fluid temperature at the heater between 61,35-63,32°C.
Figure 138
Figure 139
During the experiment there was a fault of the system on 3rd August afternoon that explains the anomaly on the cell voltage. Another remark should be done for the measurement done on 4th August. In the cell voltage graph a steep increase of the voltage is noticed, probably related to a decrease of the pressure at the heater, which also caused a decrease of cell temperature and fluid temperature.
Figures 140 and 141 show the overall EIS measurements performed under voltage and current control during the degradation test at 60°C.
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Figure 140 All EIS measurements with potentiostatic mode.
Figure 141 All EIS measurements with galvanostatic mode.
Data quality assessment
Validation through KK relations shows that impedance spectra obtained with both modes have similar residuals behaviour, i.e. low residuals of high frequency data and larger residuals as data are collected at lower frequencies. This is probably related to the drift of the system during the measurements at low frequency, which are more time consuming.
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Impedance spectra showing very high residuals in all frequency range are discarded. These are 2nd, 4th and 5th morning for the potentiostatic and 2nd evening, 3rd 4th and 5th morning for the galvanostatic. Another EIS test not considered due to tripping of the system is the one performed on the 3rd evening.
By visual inspection of the Nyquist and Bode plots it is possible to say that EIS measurements with galvanostatic and potentiostatic mode have produced impedance spectra characterized by at least two time constants. The low frequency impedance spectra in both modes- particularly in the potentiostatic mode- is affected by noise and/or time variance of the cell behaviour. Consequently, the impedance spectra obtained at lower frequencies is considered only from a qualitative point of view because its approximation to an ECM will probably produce a poor fit. Hence, the impedance spectra are fitted up to where data show a good trend, typically the first semicircle at HF and the initial part of the second semicircle appearing in the mid frequency range. Accordingly, the ECM used is LR(QR)(QR).
Modelling
Figure 142 shows Nyquist plots of EIS data measured at 0V, with invalid spectra removed. It is possible to notice the presence of an arc at high frequency, and an incomplete second arc in the mid frequency region. The low frequency data are affected by noise but it is possible to notice a third semicircle.
It is observed a general increase of HF arc, and a decrease of the second arc in favour of an increment of the LF arc even if it is affected by noise.
Figure 142 EIS measurements with potentiostatic mode- removed invalid impedance spectra.
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Figure 143 shows Nyquist plots of EIS data measured at 0 mA, corresponding to the open circuit voltage of the cell, with invalid spectra removed. It is observed the presence of an arc at high frequency, and a second arc in the mid-low frequency region affected by noise. The latter seems to be made of two merged semicircles.
It seems that the HF arc increases but the second arc shows a decreasing behaviour.
Figure 143 EIS measurements with galvanostatic mode- removed invalid impedance spectra.
DISCUSSION
The analysis considers both EIS results gained from potentiostatic and galvanostatic modes.
The trend of ohmic resistance, high frequency charge transfer resistance and capacitance is shown in Figures 144 and 145.
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Figure 144
Figure 145
For both EIS tests the ohmic resistance seems to have a very slight decrease- although an oscillating behaviour between 0.818-0.542 Ωcm2 and 0.0806- 0.593 Ωcm2 is noticed for potentiostatic and galvanostatic respectively- whereas the charge transfer resistance increment is much more evident from 1.51 to 3.92 Ωcm2 for potentiostatic and 1.55 to 3.35 Ωcm2 for galvanostatic. The capacitance of the high frequency arc is characterized by a decreasing trend, at least during the first part of the test. Anyway, possible oscillations of the value may be related to time-variance of the system during the whole test but if the start and the end are considered, a decrease can be observed. It is not possible to say much about the low frequency arc due to the presence of noise, particularly in the impedance spectra obtained with voltage control. Hence, it is not possible to gain a quantitative and reliable measurement of the overall polarization resistance. On the other hand, some qualitative considerations can be done for the LF results gained with galvanostatic tests. The low frequency intercept with the real axis seems to show increasing values, hence it is suggested an increase of the total
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polarization resistance. As it is shown in the figure below, the trend of the total polarization resistance is mainly due to that of the charge transfer resistance of the HF arc.
Figure 146
Considering the trends of Figures 144 and 145, it is assumed that the HF feature is related to current constrictions, whereas the second incomplete semicircle and third one are respectively associated to charge transfer kinetics in the anode and mass transport limitations.
Concluding, the EIS results are in accordance with the increase of voltage during the degradation test. A probable reason of the ohmic resistance decrease (from 0.8 to 0.6 Ωcm2) is the thinning of the membrane. It is suggested a loss of material from the aged membrane, which can also explain the decrease of the capacitance at high frequency. A loss of materials or agglomeration of catalyst particles can cause an increase of the distributed contact resistances at the electrolyte/anode interface. This determines current constrictions and thus a lower performance of the cell. About the low frequency region, qualitatively it is possible to say that the larger arc in the galvanostatic tests or the increment of the third arc in the potentiostatic tests may be insights of the anode degradation. Large arcs are characterized by lower value of the capacitance, which in turn is linked to the number of active sites in the electrode surface. A low value of the capacitance demonstrates the occurrence of degradation processes in the catalyst layer. Instead, the presence of a third arc at low frequencies suggests important mass transport limitations, another sign of degradation.
RESULTS SECOND SERIES
After around 135 h of operation at 0.5 𝐴/𝑐𝑚2 the cell has shown a degradation rate of about 720 𝜇𝑉/ℎ.
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Figure 147 Voltage trend during the degradation test at 80°C.
The effective temperature during the experiment oscillates around 79°C whereas real gauge pressure at the anode and cathode was 0,91 bar and 0,44 bar respectively.
The study shows an increase of the cell potential, instead pressure at the heater remains in a range between 1,14 bar-1,29bar, temperature at the heater between 79,3°C -79,8°C and cell temperature remain 79,5°C -79,7°C.
Figure 148
Figure 149
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Figures 150 and 151 show the overall EIS measurements performed under voltage and current control during the degradation test.
Figure 150 EIS measurements with potentiostatic mode.
Figure 151 All EIS measurements with galvanostatic mode.
166 Data quality assessment
Validation through KK relations shows that impedance spectra obtained with both modes have similar residuals behaviour, i.e. low residuals of high frequency data and larger residuals as data are collected at lower frequencies. Data quality is mostly affected by time variance rather than noise.
By visual inspection of both Nyquist and Bode plots, at least two time constants are individuated, so two distinguishable features are observed: high frequency arc and a mid-frequency arc, mainly affected by noise. As previously said, due to high level of noise the LF data are considered only in a qualitative way. Therefore, the ECM used to fit the experimental data is LR(QR)(QR).
DISCUSSION
The analysis is carried out with both EIS results gained from potentiostatic and galvanostatic modes. The trend of ohmic resistance, high frequency charge transfer resistance and
capacitance is shown in the figures below.
Figure 152
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Figure 153
For both EIS tests the high frequency arc shows a moderate increase: the ohmic resistance seems to oscillate in the between 0.8-1.1 Ωcm2 whereas there is an evident increment of the charge transfer resistance. Instead, the HF capacitance shows a small decrease, higher in the potentiostatic test (from 0.0209 to 0.0176 F) rather than in the galvanostatic (from 0.0160 to 0.0155). As before, it is possible to get a qualitative trend of the LF feature from the galvanostatic measurements. It is observed an increase of the diameter of the mid-low frequency arc; hence, it can be assumed an increase of the total polarization resistance.
Figure 154
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These results are consistent with the voltage increase during the experiment at 80°C.
Therefore, the cell is experiencing degradation mainly of the anode even if some loss of performance are individuated also in the membrane.
6.4.2 Degradation test performed at 80°C, 0.5bar, closed cathode, 10% mass flow rate,