Bi0.15Sr0.85Co0.8Fe0.2O3-δ perovskite: A novel bifunctional oxygen electrocatalyst with superior durability in alkaline media

doi:10.1016/j.jmst.2021.09.027

Abstract

Abstract:

Perovskite-type oxides are considered as promising alternatives to the scarce and expensive precious metal-based electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Here, we report a Bi_0.15Sr_0.85Co_0.8Fe_0.2O_3-_δ (BiSCF) perovskite prepared by the conventional solid-state reaction method as a novel bifunctional oxygen electrocatalyst in alkaline media. BiSCF shows excellent electrocatalytic activities towards both OER and ORR with a low OER overpotential (${{\eta }_{\text{OER}10\text{mA}\ \text{c}{{\text{m}}^{-2}}}}$= 354 mV), good chemical reaction kinetics (Tafel slope = 94.21 mV dec^-1 and 72.8 mV dec^-1 for OER and ORR, respectively), and excellent durability (i.e., ${{\eta }_{\text{OER}10\text{mA}\ \text{c}{{\text{m}}^{-2}}}}$ increases from 354 mV to 404 mV within 24 h; better durability than the commercial 30 wt.% Pt/C at 0.4 V vs RHE regarding ORR). It also presents the best bifunctional property among the reported perovskites. The excellent electrocatalytic properties of BiSCF can be attributed to its abundant oxygen vacancies and rich oxidation states of Co and Fe. With high activities, excellent stability and easy fabrication, BiSCF is expected to be a promising bifunctional oxygen electrocatalyst for renewable energy conversion and storage devices.

Key words: Perovskite, Solid-state reaction, Oxygen evolution reaction (OER), Oxygen reduction reaction (ORR), Defect chemistry

Jing Li, Fan Yang, Yunzhu Du, Xiyang Cai, Qiaodan Hu, Junliang Zhang. Bi_0.15Sr_0.85Co_0.8Fe_0.2O_3-_δ perovskite: A novel bifunctional oxygen electrocatalyst with superior durability in alkaline media[J]. J. Mater. Sci. Technol., 2022, 108: 158-163.

Figures/Tables 6

Fig. 1. (a) Rietveld refinement of the XRD pattern of BiSCF. Red circles represent the observed pattern and the solid line shows the calculated fit. The reflection maker for the P4/mmm structure is shown as vertical lines with the difference pattern below the diffraction pattern. The quality of fit is indicated in Fig. 1(a). (b) Crystal structure visualized by VESTA and lattice parameters of BiSCF obtained from Rietveld refinement.

Fig. 2. OER electrocatalytic performances of BiSCF in O2-saturated 0.1 M KOH solution. (a-c) Polarization curve, overpotential at 10 mA cm-2 (rotation speed of 1600 rmp) and Tafel plot, respectively. Data for IrO2 and several well-known perovskite electrocatalysts evaluated at the same conditions are included for comparison. (d) LSV curves before and after 150 CV cycles and (e) OER stability measured by chronopotentiometry at 10 mA cm-2.

Table 1. OER electrocatalytic performances of BiSCF in comparison with IrO2 and other reported perovskites. ηOER represents the overpotential at 10 mA cm-2. Unless specified, data are all obtained in 0.1 M KOH.

Catalyst	η_OER (mV)	Tafel slope (mV dec^-1)	η_OER after durability test (mV)	Catalyst loading (mg cm^-2)
BiSCF, this work	354	94.21	406 (24 h)	0.255
BaSCF, this work	350	114.22	-	0.255
LFO, this work	508	135.65	-	0.255
LSC, this work	404	101.34	-	0.255
IrO₂, this work	280	74.40		0.255
LaCo_0.2Fe_0.8O_3-_δ³⁰*	440	-	-	0.255
SrFe_0.9Si_0.1O_3-_δ [31]	400	-	-	0.232
Bi_0.6Ca_0.4FeO₃ [32]	420	-	-	-
SrCo_0.9Ti_0.1O₃ [20]	500	-	500 (5 h)	0.32
IrO₂ [20]	360	-	390 (5 h)	0.32
BaSCF [21]	500	-	720 (5 h)	0.232
Sr₂FeMo_0.65Ni_0.35O₆ [21]	370	-	470 (5 h)	0.232
SrNb_0.1Co_0.7Fe_0.2O_3-_δ [33]*	450	-	470 (30 h)	0.232

Fig. 3. ORR electrocatalytic performances of BiSCF in O2-saturated 0.1 M KOH solution. (a) ORR polarization curves and (b) Eonset and E1/2 of BiSCF, BaSCF, LSC, LFO and Pt/C; (c) K-L plots and their linear fittings (rotation speed between 100 and 2500 rmp); (d) ORR stability of BiSCF in comparison to BaSCF and Pt/C measured by chronoamperometry at 0.4 V vs RHE.

Table 2. ORR and bifunctional performance of BiSCF in comparison with the commercial Pt/C and several perovskite-type oxygen electrocatalysts. All data are obtained in 0.1 M KOH solution.

Catalyst	E_onset (V)	E_1/2 (V)	Tafel slope (mV dec^-1)	△E (V)	Catalyst loading (mg cm^-2)
BiSCF, this work	0.81	0.698	72.5	0.885	0.255
BaSCF, this work	0.79	0.688	78.0	0.892	0.255
LFO, this work	0.80	0.664	63.0	0.94	0.255
LSC, this work	0.80	0.712	72.8	1.07	0.255
Pt/C, this work	1.04	0.897	78.8	-	0.255
MnO₂/La_0.7Sr_0.3MnO₃ [35]	-	-	-	0.893	0.236
La_0.3(Ba_0.5Sr_0.5)_0.7Co_0.8Fe_0.2O_3-_δ [36]	-	-	-	1	0.64
Nd_0.5Sr_0.5CoO_3-_δ [37]	-	-	-	1.26	-
La_0.95FeO_3-_δ [38]	-	-	-	1.26	0.232
La_0.5Sr_0.5CoO_3-_δ [39]	-	-	-	1.04	0.23
La_0.8Sr_0.2Mn_1-_xNi_xO₃ [40]	-	-	-	1.07	0.14
La_0.8Sr_0.2MnO₃ [41]	-	-	-	1.3	0.655

Fig. 4. XPS spectra of BiSCF: (a) Co 2p; (b) Fe 2p and (c) O 1 s.

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