Detachment Suppression of NiCo Oxide Catalyst Layer for Oxygen Evolution Anode in Alkaline Medium Using Start and Stop Simulated Accelerated Degradation Test Protocol

Abstract

INTRODUCTION While the alkaline water electrolysis (AWE) has the advantage of low cost and mass production, it has the issue of catalyst coated electrode degradation caused mainly by catalyst layer detachment due to reverse currents generated by the start and stop of variable renewable electricity. A previous study reported that heat treatment of a NiCo2O4 spinel catalyst-supported electrode (NiCo) on a Ni substrate suppress delamination of the catalyst layer with decrease in initial activity due to increase of electrode resistance. [1] In this study, in order to find optimize preparation for both initial activity and durability of the anode electrode catalyst, we compared and evaluated the degradation behavior of NiCo electrodes prepared various conditions. EXPERIMENTAL The accelerated durability test (ADT) was performed in a three-electrode cell with 7 M KOH aqueous solution as electrolyte at 25℃. RHE, Ni coil and 1 cm2 electrode of NiCo spinel catalyst supported on Ni mesh substrate prepared with 8 to 24 of layered thermal decomposition coating at various temperature are used as reference, counter and working electrodes, respectively. Here, the thickness of the coting was determined by Co loading measured with XRF. Constant current electrolysis at 1 A cm-2 for 2 hours was conducted as pretreatment at 80℃ before ADT. The ADT protocol consisted of three steps [2] (Fig.1): (1) constant current electrolysis at 600 mA cm-2 for 1 min, (2) potential scanning from open-circuit potential (OCP) to anodic potential E min (= 0.5 V vs. RHE) at sweep rate of -500 mV s-1, and (3) holding at constant potential of E min for 1 min. To evaluate the anode activity, CV (potential range: 0.5 to 2.0 V vs. RHE, sweep rate: 5 and 50 mV s-1, 3 cycles) and AC impedance measurements (bias potential: 1.6, 1.7 V vs. RHE, frequency range: 106-10-1 Hz, amplitude: 10 mV) were performed at every 200 ADT cycles in 2,000 cycles of ADT. RESULTS AND DISCUSSION As shown in Fig. 2 of the anode potential as a function of the ADT cycle, the potential of the 350°C prepared anode significantly increased around 800 cycles toward around 1.9 V vs. RHE, while the 450°C prepared anode showed slowly and constantly increase in potential.As shown in Fig. 3 of the redox peaks in cyclic voltammograms, the NiCo redox peaks around 1.2 V vs. RHE disappeared and the Ni redox peaks around 1.2 V vs. RHE appeared at the end of the ADT,. The NiCo redox peak of the 350°C prepared anode was significantly larger than the Ni redox peak in the initial period, whereas the Ni redox peaks became larger than the NiCo redox peak around 700 cycles. The charge of NiCo redox peak of the 450°C prepared anode gradually decreased and that of the Ni oxidation peak increased and they reversed for 8, 16, and 24 layered anodes at 1000, 1400, and 1600 cycles, respectively, but NiCo redox peak still remained. These results means that the consumption of the NiCo oxide electrocatalyst occurs during the ADT and the 450°C preparation suppress rapidly detachment of the 450°C prepared anode around 700 cycles.As shown in Fig. 4 of the polarization curves, the OER activity of the 8 layered at the 450°C prepared was almost same as that of the 350°C prepared anode at 200 cycles, and the 16 and 24 layered at 450°C prepared were higher activity than the 350°C prepared and the 8 layered at 450°C prepared. The Tafel slopes of the initial ADT (200 cycles) were almost the same for the 350°C and 450°C. The slope for the 450°C prepared anodes after 2000 cycles were almost same as the initial regardless of the number of applications, but the slope for the 350°C prepared increased. This result also suggests NiCo oxide of the 450°C prepared still remained at the end of the ADT and it dominates oxygen evolution reaction, while the 350°C prepared electrocatalyst completely consumed during the ADT. ACKNOWLEDGEMENTS This study was based on results obtained from the Development of Technologies for Realizing a Hydrogen Society (P20003) commissioned by the New Energy and Industrial Technology Development Organization (NEDO). REFERENCES [1] N. Todoroki, K. Nagasawa, H. Enjoji, S. Mitsushima., ACS Appl. Mater. Interfaces, 15, 20, 24399 24407 (2023).[2] A. Abdel Haleem, K. Nagasawa, Y. Kuroda, Y. Nishiki, A. Zaenal, S. Mitsushima., Electrochem., 89, 2, 186 191 (2021). Figure 1