Chapter 3. Investigation of supercapacitor effect of SWBs
3.3 Conclusion
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4. Summary
Owing to various ecological problems (e.g. average temperature increasing and unexpected downpour) caused by fossil fuel resource (i.e. petroleum and gas), the eco-friendly energy sources such as wind and solar power are being studied by many researchers. Accordingly, the development of effective and highly efficient energy storage systems (ESSs) are being considered due to its unstable energy production and supplement. Because it can utilize the huge and reasonable ESSs, the seawater batteries (SWBs) which use the naturally abundant and eco-friendly material are promising ESS.
However, the sluggish kinetics of OER/ORR can deteriorate the energy efficiency due to induced overpotential.
To solve this problem, we proposed the slurry cathode which has a large surface area to improve the reaction kinetics using activated carbon powder (ACP) produced by ball-milling of activated carbon cloth (ACC) and platinum on carbon as ORR catalyst. The high surface area electrode can stabilize the voltage profiles and improve energy efficiency due to the capacitance effect related to EDL formation.
To fabricate the slurry cathode, the binder which can bond the materials must be used. However, the hydrophobic binder (i.e. PvdF) can cause the contact issue between seawater and cathode current collector. Therefore, all of the battery performances can be deteriorated due to poor wettability.
We developed the polymeric binder (DPA642) using 3,4-dihydroxyphenylalanine (DOPA), which has underwater wetting and adhesion properties, and poly(ethylene glycol) (PEG) through thermal copolymerization and produced the slurry cathode current collector using this polymer. Finally, we investigated the ACP-DPA642 performance compared to ACC and ACP-PvdF through the galvanostatic charge-discharge test at 0.2 mA (0.13 mA cm-2) for 1000 h (1 cycle = 10h).
The electrochemical results of ACP-DPA642 showed a lower voltage gap (0.51 V) and enhanced energy efficiency (94.9 %) compared to those of ACC (0.90 V, 86.8%) and ACP-PvdF (0.89 V, 88.1%, respectively). Also, ACP-DPA642 has the best cycle retention by the antioxidant effect of DOPA which prevents the oxidative degradation of carbon electrodes.
To investigate the secondary batteries performances, we used the metal-free SWBs using hard carbon anode at 0.2 mA (0.13 mA cm-2) with a capacity control of 200 mAh g-1 and discharge voltage limitation of 0.5 V. The metal-free ACP-DPA642 shows the higher average discharge voltage and energy efficiency (2.68 V, 74.1%) than ACC (2.52 V, 67.7%) and ACP-PvdF (2.46 V, 43.8%) at second cycle, respectively. We can confirm that the ACP-DPA642 has the best electrochemical properties.
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Also, we measured the specific capacitance of each carbon electrode through cyclic voltammetry and galvanostatic charge-discharge test. As a result, the specific capacitance of ACC-DPA642 (~ 822 F g-1) was larger than ACC (~ 728 F g-1) and ACP-PvdF (~ 516 F g-1) at cyclic voltammetry and galvanostatic charge-discharge test, respectively, despite the large specific surface area of ACC (~ 1787 m2 g-1) (ACP- DPA642 (~ 1697 m2 g-1) and ACP-PvdF (~ 627.27 m2 g-1), respectively). It seems that the redox-active property of DOPA can induce the pseudocapacitor effect which offers the charge through the fast-redox reactions.
We are convinced that this research can accelerate the progress of an eco-friendly green grid and long-life and high-performance ESS for green energy sources.
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