Enhancement of oxygen evolution reaction activity and durability of Ba0.5Sr0.5Co0.8Fe0.2O3-δ by CO2 thermal treatment

doi:10.1016/j.jmst.2019.01.005

材料科学与技术 ›› 2019, Vol. 35 ›› Issue (6): 1184-1191.DOI: 10.1016/j.jmst.2019.01.005

收稿日期:2018-11-14 修回日期:2018-11-25 接受日期:2018-12-10 出版日期:2019-06-20 发布日期:2019-06-19

Enhancement of oxygen evolution reaction activity and durability of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ by CO₂ thermal treatment

Fengli Liang^a^*(), Ziqiong Yang^a, Haipeng Deng^a, Jaka Sunarso^b^*(), Lili Yang^a, Junkui Mao^a

^aCollege of Energy and Power Engineering, Jiangsu Province Key Laboratory of Aerospace Power System, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
^bResearch Centre for Sustainable Technologies, Faculty of Engineering, Computing and Science, Swinburne University of Technology, Jalan Simpang Tiga, 93350 Kuching, Sarawak, Malaysia

Received:2018-11-14 Revised:2018-11-25 Accepted:2018-12-10 Online:2019-06-20 Published:2019-06-19
Contact: Liang Fengli,Sunarso Jaka
About author:
¹ These authors contributed equally to this work.

摘要/Abstract

Abstract:

This work demonstrates that in situ formation of carbonate layer on the surface of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ (BSCF) obtained by exposure to CO₂ during heating between 500 °C and 700 °C can provide enhanced oxygen evolution reaction (OER) performance and durability in an alkaline solution relative to the original BSCF. Three temperatures, i.e., 500 °C, 600 °C, and 700 °C were chosen to perform the CO₂ thermal treatment, resulting into BSCF-500, BSCF-600, and BSCF-700 samples. The OER was enhanced in the order of BSCF-500 < BSCF-700 < BSCF-600. BSCF-600 showed the best OER performance, i.e., a low overpotential of 0.36 V required to attain 10 mA cm^-2 current density as well as a mass activity of 74.14 $ Ag_{cat}^{-1} $ and a specific activity of 5.04 mA $ Ag_{cat}^{-2} $ at an overpotential of 0.4 V. The OER performance durability of BSCF-600 was highlighted by its ability to maintain a stable potential of around 1.61 V vs. RHE (RHE: reversible hydrogen electrode) when charged at a constant current density of 10 mA cm^-2 throughout the 800 min continuous chronopotentiometry test. The enhanced OER performance for BSCF-600 relative to the original BSCF is attributed to three factors: (i) higher electrochemically active surface area; (ii) faster charge transfer rate and higher electrical conductivity; and (iii) modified oxidation state of cobalt ions. The formation of thin carbonate layer in BSCF-600 appears to suppress the durability issue observed in BSCF.

Key words: Carbonate, Electrocatalysis, Oxygen evolution reaction, Perovskite, Water splitting

. [J]. 材料科学与技术, 2019, 35(6): 1184-1191.

Fengli Liang, Ziqiong Yang, Haipeng Deng, Jaka Sunarso, Lili Yang, Junkui Mao. Enhancement of oxygen evolution reaction activity and durability of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ by CO₂ thermal treatment[J]. J. Mater. Sci. Technol., 2019, 35(6): 1184-1191.

图/表 8

Fig. 1. Schematic illustration of the effect of heat treatment under CO2 exposure on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF).

Fig. 2. (a) Powder XRD patterns and (b) X-ray photoelectron spectroscopy (XPS) spectra of BSCF, BSCF-500, BSCF-600, and BSCF-700.

Fig. 3. SEM images of (a) BSCF-500, (b) BSCF-600, (c) BSCF-700, and (d) BSCF.

Fig. 4. (a) HRTEM images of BSCF-600 and (b) CO2-TPD profiles of BSCF, BSCF-500, BSCF-600, and BSCF-700 when heated from 50 °C to 1000 °C at 10 °C min-1 ramping rate in flowing argon gas at 20 mL min-1 flow rate.

Fig. 5. (a) LSVs over OER portion for BSCF, BSCF-600, BSCF-S, IrO2, BSCF-6-HCl, and SrCO3 obtained using rotating disk electrode at 5 mV s-1 scan rate and 1600 rpm rotation rate in an O2-saturated 0.1 mol L-1 KOH solution. All profiles were taken from the second scan profiles, (b) Tafel plots for BSCF-600, BSCF and IrO2 between 0.1 and 0.5 mA cm-2, (c) powder XRD patterns of BSCF, BSCF-6-HCl, and (d) powder XRD patterns of BSCF-600 before and after long term CP test.

Table 1 Summary of OER performance indicators for BSCF, BSCF-500, BSCF-600, and BSCF-700.

Sample	BET(m² g^-1)	Overpotential at J of 10 mA cm^-2(V)	Onset potential (V)	MA at η of 0.4 V (A g^-1)	SA at η of 0.4 V (mA cm^-2)	Tafel slope (mV dec^-1)
BSCF	0.44	0.450	1.52	18.78	4.27	73
BSCF-500	0.61	0.507	1.52	13.10	2.15	88
BSCF-600	1.47	0.357	1.47	74.14	5.04	63
BSCF-700	3.17	0.416	1.49	36.12	1.14	92

Fig. 6. (a) Time-dependent potential profile from CP test of BSCF-600, BSCF, and IrO2 obtained using carbon cloth as catalysts support upon maintaining a constant current density of 10 mA cm-2 in an O2-saturated 0.1 mol L-1 KOH solution and (b) LSVs of BSCF-600 using RDE at 1600 rpm rotation rate after CVs at the 1st, 500th, 1000th and 1500th cycle scans.

Fig. 7. (a) CV profiles of BSCF-600 in an O2-saturated 0.1 mol L-1 KOH solution at different scan rates of 20, 40, 60, 80, 100, 120, 140, and 160 mV s-1, (b) plot of the half of current density difference at 1.2 V vs. RHE vs. scan rate for BSCF-600 and BSCF, (c) EIS of BSCF-600 and BSCF obtained at an overpotential of 0.7 V and AC bias potential of 10 mV, and (d) Co 2p and Ba 3d XPS spectra of BSCF-600 and BSCF (Z′: real part of impedance; Z′′: imaginary part of impedance; Sat: satellite peak).

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Enhancement of oxygen evolution reaction activity and durability of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ by CO₂ thermal treatment

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