Improvement of Current Efficiency of PEM Electrolyzer for Organic Chemical Hydride Energy Carrier Production with Water Electrolysis by Humidified Air Supply to Anode
Authors: Mitsushima Shigenori , Kuroda Yoshiyuki , Nagasawa Kensaku 
Published: February 2024

Introduciton

To improve hydrogen energy carrier synthesis, we have studied toluene electrohydrogenation and water decomposition using proton exchange membrane (PEM) electrolysis. The cathode reaction is electrohydrogenation of toluene to synthesis methylcyclohexane instead of hydrogen evolution reaction of water electrolysis. Only side reaction of the cathode is hydrogen evolution reaction, which was affected by electroosmotic water from the anode to cathode. Sulfuric acid solution feeds as anolyte that is not only reactant reduces water transportation and increases current efficiency [1, 2]. As practical system, water transportation from anode to cathode should be suppressed without sulfuric acid utilization
In this study, to improve current efficiency by water management, we have investigated humidified air feed to reduce water transfer to cathode compare with liquid water feed.

Experimental

A single cell electrolyzer made of titanium with 16 cm2 of projected electrode area was used. Figure 1 shows the schematic drawing of toluene direct hydrogenation electrolyzers with humidified air feed. Membrane-electrodes assembly was consisted of Nafion® 117 (DuPont), 0.6 mg cm-2 of PtRu/C (TEC61E54, TKK, I/C = 0.8) cathode catalyst layer and 2.0 mg cm-2 of IrOx (TEC77100, TKK, I/IrOx = 0.28). Cathode backing was a carbon paper (10BC, SGL) of 0.02 mg cm-2 of Pt loading, which works flow filed of toluene-methylcyclohexane, too. Anode baking as a Pt plated sintered Ti web (Bekaert), and anode flow filed was serpentine type. 10 mL min-1 of toluene or 10% toluene – methylcyclohexane was fed to cathode. 5.0 L min-1 (313 mL min-1 cm-2) of fully humidified air or liquid water was fed to cathode. Operation temperature was 80oC. Internal resistance was determined by high frequency intercept of real axis of the electrochemical impedance spectroscopy in the current density region between 0.1 to 0.6 A cm-2. The water transportation through the membrane was determined by separated water in outlet liquid from cathode during constant current electrolysis, and the Faraday efficiency was determined by generated gas volume from the cathode, simultaneously.

Results and discussion

Figure 2 shows the cell voltage and current efficiency as a function of the current density for 10% toluene-methylcyclohexane or 100% toluene to cathode and 5.0 L min-1 of fully humidified air or liquid water to anode feed. Cell voltages were almost same for all experiments in less than 0.3 Acm-2 of current density region, while cell voltages of humidified air feed were higher than that of liquid water feed in higher current density region. Here, internal resistance of humidified air and liquid water feed were 0.29 and 0.21 Ω cm2. Therefore, membrane condition of the humidified air feed was drier than that of the liquid water feed. Water transportation through the membrane around 0.2 mg min-1 cm-2, which was less than 1/10 of the liquid water or 1 M H2SO4 feed electrolysis. The current efficiency for 100% toluene feed was more than 95% at 1 A cm-2, and slightly decreased with current density. In this case, the current efficiency of the liquid water feed was a little higher than that of the humidified air feed. The current efficiency of the humidified air feed was more than 95% up to 0.5 Acm-2, while the current efficiency of the liquid water feed decreased 95% around 0.2 Acm-2. In addition, the current efficiency of 10% toluene-methylcyclohexane significantly decrease with current density.
The current efficiency would be affected by the cathode potential and toluene transportation in the catalyst layer. For the 100% toluene feed, toluene transportation would less affect and cathode potential would much affect to the current efficiency. Larger internal resistance of the humidified air feed would correspond to dry condition of cathode ionomer, and it would decrease the cathode potential. Therefore, the current efficiency of humidified air was slightly lower than liquid water feed. On the other hand, the current efficiency of 10% toluene feed would be controlled by toluene transportation in the cathode catalyst layer and is significantly affected by the water transportation through the membrane. Therefore, the current efficiency of the humidified air feed significantly higher than that of the liquid water feed.

Acknowledgement

This study was based on results obtained from the Development of Fundamental Technology for Advancement of Water Electrolysis Hydrogen Production in Advancement of Hydrogen Technologies and Utilization Project (P14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

References

Nagasawa, K. Tanimoto, J. Koike, K. Ikegami, S. Mitsushima, J Power Sources, 439, 227070 (2019).

Oi, K. Nagasawa, T. Takamura, Y. Misu, K. Matsuoka, S. Mitsushima, ECS Meeting Abstracts, MA2021-02, 1737 (2021).

Figure 1