Chapter 1 Introduction
6.3 Results and Discussion
6.3.3 Effect of oxidation on the specific capacitance
Figure 6.8. Galvanostatic charge discharge cycle of CNT arrays with different oxida- tion levels in KOH electrolyte.
Figure 6.9. Galvanostatic charge discharge cycle of CNT arrays with different oxida- tion levels in Et4NBF4/PC electrolyte.
EDLC for both KOH and Et4NBF4/PC electrolyte can be observed by plotting their specific capacitance against their O/C ratio. As mentioned above, presence of polar oxygenated groups on the surface of CNT arrays should improve their wettability in highly polar electrolytes. On the other hand, presence of such groups has also shown to negatively affect the ESR (Figure 6.5.b and Figure 6.7.b), the self-discharge, and cyclability characteristics, as well as the ion adsorption behavior of the CNT arrays.
Works by Hirsch (2002) and Lee et al. (2010) have shown that the specific capaci- tance of the CNT arrays can be increased dramatically by the presence of oxygenated groups which increase the number of contact sites with ions of the electrolytes (Lee et al., 2010; Hirsch, 2002; Aria and Gharib, 2011). It has also been known that highly oxidized CNT arrays have higher surface areas and better pore size distributions than the non-oxidized ones. The relation between surface areas and O/C ratio of CNT ar- rays can be read in Chapter 4. A combination of better wettability and better pore size distributions amplifies the total area of the electric double layer and ultimately enhances the specific capacitance of oxidized CNT arrays.
In this study, the specific capacitive of active electrode materials is measured
using galvanostatic charge/discharge analysis at a constant current density, where the response potential is recorded and plotted against the time. For an ideal capacitor, the shape of potential versus time curve is perfectly triangular, with constant slopes showing a perfect capacitative behavior. Since, in reality, the ESR is always nonzero, the charge/discharge curves of an EDLC are typically curved. An IR drop can be seen obviously from the charge/discharge curves when the ESR is significantly high.
It is possible for a CNT array EDLC to have a high ESR. As mentioned earlier, factors that influence ESR of an EDLC include internal resistance of active electrode materials, contact resistance between active electrode materials and current collectors, wettability of active electrode materials by the electrolytes, and conductivity of the electrolyte. Since the internal resistance of CNT arrays is typically very low, such a high ESR may be attributed to a poor wettability by the electrolyte and a poor contact to the current collector.
The shape of potential versus time curves of CNT arrays with low oxidation level in KOH electrolyte is almost perfectly triangular, with constant charging and dis- charging slopes (Figure 6.8). For CNT arrays with an average O/C ratio of about 5.5%, a full charge and discharge cycle at a current density of 5 A/g can be com- pleted in about three seconds. In addition to their near perfect triangular shape, their galvanostatic curves also exhibit non obvious IR drops, indicating the presence of a non zero but negligible ESR. In fact, their IR drop is measured to be just about tens of millivolts. Similar behavior is also observed from CNT arrays with an average O/C ratio of about 13.5%. Not only are their galvanostatic curves almost perfectly triangular, their IR drop is also measured to be about tens of millivolts. These CNT arrays complete a full charge and discharge cycle at a current density of 5 A/g in about 13 seconds. In contrast, the shape of potential versus time curves of CNT arrays with high oxidation levels in KOH electrolyte is no longer triangular and their charging and discharging slopes are no longer constant. This implies that Faradaic redox reactions are involved during the charging and discharging cycles. For CNT arrays with an average O/C ratio of about 21%, an obvious IR drop can be observed from their galvanostatic curves. In fact, the IR drop of these CNT arrays is measured
to be between 300-400 mV. Undoubtedly, such a large IR drop decreases the perfor- mance of these CNT arrays by limiting their effective operating potential to about 60-70% of their original operating potential.
Similar behavior can be observed from CNT arrays in Et4NBF4/PC electrolyte.
The shape of potential versus time curves of CNT arrays with an average O/C ratio of 5.5% is almost perfectly triangular, with constant charging and discharging slopes (Figure 6.9). However the galvanostatic curves of CNT arrays exhibit noticeable IR drops of 100-200 mV, which are about an order of magnitude higher than that in KOH electrolyte. Such high IR drops may be caused to the higher electrolyte resistance of the Et4NBF4/PC electrolyte. These CNT arrays complete a full charge and discharge cycle at a current density of 5 A/g in about 50 seconds. Surprisingly, the shape of potential versus time curves of CNT arrays with an average O/C ratio of 13% is no longer triangular and their charging and discharging slopes are no longer constant. This implies that Faradaic redox reactions are involved during the charging and discharging cycles even when their oxygen content is still quite low. However, their average IR drop is still considered reasonable. In fact, their average IR drop is measured to be about 250 mV, which is comparable to that of CNT arrays with lower O/C ratio. This IR drop is considered reasonable, although slightly higher than that reported by previous studies (Kumar et al., 2006; Niu et al., 1997; Futaba et al., 2006). Since it takes about 80 seconds for these CNT arrays to complere a full charge and discharge cycle, their capacitance is expected to be higher than that of CNT arrays with lower O/C ratio. Similar non-triangular galvanostatic curves can also be observed from CNT arrays with an average O/C ratio of 22%. Although the shape of potential versus time curves of these CNT arrays are similar to that of CNT arrays with lower O/C ratio, their IR drop is significantly higher. Indeed, the IR drop of these CNT arrays is measured to be between 800-900 mV, which is about 30% of their original operating potential.
Gravimetric specific capacitance can be calculated directly from the galvanostatic
Figure 6.10. Specific capacitance vs oxygen/carbon ratio in KOH.
charge/discharge curves using the following equation:
CG = I
(dV /dt)m (6.2)
where the scan rate (dV /dt), is measured from the slope of the discharge curves.
Electrodes with a steeper slope exhibit a lower specific capacitance, while ones with mild slope exhibit a higher gravimetric capacitance. Since the discharge slope of CNT arrays in KOH electrolyte is much steeper than that in Et4NBF4/PC electrolyte (Figure 6.8 and Figure 6.9), it is expected that the specific capacitance of CNT arrays in KOH electrolyte is lower than that in Et4NBF4/PC electrolyte. Such a difference in discharge slope is apparent even though the potential range for both electrolytes is different. As mentioned earlier, the potential for CNT arrays in KOH electrolyte is swept between 0-1 V, while the potential for CNT arrays in Et4NBF4/PC electrolyte is swept between 0-2.5 V.
In KOH electrolyte, the gravimetric specific capacitance of CNT arrays with an average O/C ratio of 3% is measured to be about 0.003 F/g at a current density of 5 A/g. As expected, the specific capacitance of CNT arrays increases along with the
increase of the O/C ratio of the CNT arrays. In fact, the specific capacitance of CNT arrays increases very quickly at an O/C ratio below 10% (Figure 6.10). Their specific capacitance increases by three orders of magnitude to about 7 F/g, just by doubling the O/C ratio to 6%. As the O/C ratio of the CNT arrays reaches 8.5%, their specific capacitance has improved to almost 30 F/g. However, such a rapid increase of specific capacitance seems to hit a ceiling and start to plateau at an O/C ratio of about 10%.
At an O/C ratio of 14%, their specific capacitance reaches its maximum at about 32 F/g.
Interestingly, the specific capacitance of CNT arrays in KOH drops significantly as the O/C ratio goes higher than 15%. At an O/C ratio of about 21%, their specific capacitance is measured to be about 12 F/g. Such a drastic decrease in specific capacitance is very counter intuitive since the wettability of CNT arrays by aqueous solvent with an O/C ratio of 21% is as good as that of CNT arrays with an O/C ratio of 14% (Figure 6.10), as described in Chapter 3.3.3. Further, surface area measurement using BET and Langmuir analysis also indicates an increase of surface area with the increase of O/C ratio. In fact, the surface area of CNT arrays with an O/C ratio of 21% is about 50% higher than that of CNT arrays with an O/C ratio of 15%. Details on the relation between O/C ratio and BET and Langmuir surface area measurement can be read in Chapter 4.3.4.
In Et4NBF4/PC electrolyte, the gravimetric specific capacitance of CNT arrays with an average O/C ratio of 3% is measured to be about 29 F/g at a current density of 5 A/g. This specific capacitance is significantly higher than that measured in KOH using CNT arrays with the same O/C ratio. Similar to the behavior observed in KOH electrolyte, the specific capacitance of CNT arrays in Et4NBF4/PC electrolyte increases with the increase of the O/C ratio of the CNT arrays, although the increase rate seems to be linear (Figure 6.10). Their specific capacitance increases to about 48 F/g when the O/C ratio is doubled to 6%. As the O/C ratio of the CNT arrays reaches 8.5%, their specific capacitance improves to almost 62 F/g. And when the O/C ratio of the CNT arrays reaches 12.5%, their specific capacitance reaches its maximum at 83 F/g.
Figure 6.11. Specific capacitance vs oxygen/carbon ratio in Et4NBF4.
Similar to the behavior observed in KOH electrolyte, the specific capacitance of CNT arrays in Et4NBF4/PC drops significantly as the O/C ratio goes higher than 15%. At an O/C ratio of about 17%, their specific capacitance is measured to be as low as 25 F/g. Such a decrease in specific capacitance continues at an even higher O/C ratio, such that when the O/C ratio of the CNT arrays reaches 22% their specific capacitance reaches an even lower value of 12 F/g. This finding is indeed surprising since these values are much lower than that of lowly oxidized CNT arrays.
Interestingly, this sudden drop in specific capacitance occurs near the threshold of reversible-irreversible oxidation. Detailed discussion on this threshold can be read in Chapter 3 and Chapter 4.
For CNT arrays with a very low O/C ratio, their capacitive behavior is dominated by the non-Faradaic electric double layer behavior. However, a nonzero O/C ratio of these CNT arrays also means that Faradaic redox reactions are also involved during the charging and discharging cycles, although their contribution is limited. As the O/C ratio of the CNT arrays increases due to a prolonged oxidation process, the contribution of Faradaic redox reactions relative to the non-Fardaic electric double
layer to the overall capacitance also increases. Oxygenated groups, whether acidic, basic, neutral, or amphoteric oxides, may act as pseudocapacitive materials attached to the surface of CNT. Oxygenated groups, such as hydroxyl (C-OH) and carbonyl (C=O), are known to be electroactive and may involve in redox reactions of oxygen as follows (Lee et al., 2010; Hsieh and Teng, 2002; Pan et al., 2010; Lee et al., 2012):
C-OH⇔C=O + H++ e− (6.3)
C=O + e− ⇔C-O− (6.4)
CNT arrays with an excessive surface concentration of oxygenated groups due to overoxidation are most likely to exhibit high rates of self-discharge (Pandolfo and Hollenkamp, 2006). During the charging process, dissociation of -OH groups may occur, leading to the formation of -H or -O free radicals. These free radicals may generate molecular H2, O2, or H2O2, which are typically involved in self-discharge processes. Moreover, these oxygenated groups are also known to be active catalysts for electrochemical decomposition of electrolytes (Hsieh and Teng, 2002; Pandolfo and Hollenkamp, 2006), resulting in a high leakage current and a high charge transfer resistance. Furthermore, overoxidized CNT arrays are expected to have a lower elec- trical conductivity than the pristine ones, due to the disappearance of their π-bond network. Detailed discussion about π-bond network of oxidized CNT arrays can be read in Chapter 4.3.1. A combination of low electrical conductivity of overoxidized CNT arrays and a high charge transfer resistance of the electrode-electrolyte interface results in a dramatic increase of ESR. The effect of a high ESR on the capacitive be- havior of CNT arrays can be seen obviously from their skewed cyclic voltammogram, where their resistive behavior becomes more dominant than their capacitive behavior (Figure 6.5.b and Figure 6.7.b). All the above mentioned factors contribute to a sig- nificant deterioration in capacitance for overoxidized CNT arrays, which is proven by a decrease of specific capacitance of CNT array EDLC by about 20 F/g and 70F/g as the O/C ratio increases by about 10% in KOH and Et4NBF4/PC electrolytes respectively.
Figure 6.12. Capacitance retention vs number of cycles of CNT arrays with different O/C ratios in both KOH and Et4NBF4/PC electrolytes.