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Energy, Environmental, and Catalysis Applications

Improving the Electro-catalytic Activity and Durability of
La0.6Sr0.4Co0.2Fe0.8O3-# Cathode by Surface Modification
Huijun Chen, Zheng Guo, Lei A Zhang, Yifeng Li, Fei Li, Yapeng Zhang, Yu Chen, Xinwei Wang,
Bo Yu, Jian-min Shi, Jiang Liu, Chenghao Yang, Shuang Cheng, Yan Chen, and Meilin Liu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b14693 • Publication Date (Web): 29 Oct 2018
Downloaded from http://pubs.acs.org on October 30, 2018

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Page 1 of 28 ACS Applied Materials & Interfaces

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Improving the Electro-catalytic Activity and
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Durability of La0.6Sr0.4Co0.2Fe0.8O3-δ Cathode by
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Surface Modification
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14 Huijun Chen,1 Zheng Guo,2 Lei A Zhang,3 Yifeng Li,4 Fei Li,1 Yapeng Zhang,1 Yu Chen,3 Xinwei Wang,2
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16 Bo Yu,4 Jian-min Shi,5 Jiang Liu,1 Chenghao Yang, 1 Shuang Cheng, 1 Yan Chen 1 ,6 *and Meilin Liu 3*
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20 Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Institute, School
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22 of Environment and Energy, South China University of Technology, Guangzhou510006, China
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25 2 School of Advanced Materials, Shenzhen Graduate School, Peking University, Shenzhen 518055,
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China
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3 Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245, USA
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34 4 Institute of Nuclear and New Energy Technology (INET), Tsinghua University, Beijing 100084, China
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37 5 Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang
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40 621000, China
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43 6 Guangdong Engineering and Technology Research Center for Surface Chemistry of Energy Materials,
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45 School of Environment and Energy, South China University of Technology, Guangzhou, 510006, PR
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48 China
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51 KEYWORDS: surface engineering, oxygen reduction reaction, oxygen defects, electrodes, oxide
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53 hetero-structures
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ABSTRACT: Electrode materials with high activity and good stability are essential for
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3 commercialization of energy conversion systems such as solid oxide fuel cells or electrolysis cells at the
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5 intermediate temperature. Modifying existing perovskite-based electrodes surface to form a hetero-
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7 structure has been widely applied for rational design of novel electrodes with high performance. Despite
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many successful developments in enhancing electrode performance by surface modification, some
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12 controversial results are also reported in the literature and the mechanisms are still not well understood.
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14 In this work, the mechanism of how surface modification impacts the oxygen reduction reaction (ORR)
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activity and stability of perovskite-based oxides were investigated. We took La0.6Sr0.4Co0.2Fe0.8O3
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19 (LSCF) as the thin-film model systems and modified its surface with additive PrxCe1-xO2 layers of
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21 different thicknesses. We found a strong correlation between surface oxygen defects and the ORR
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23 activity of hetero-structure. Inducing higher oxygen vacancy concentration compared to bare LSCF,
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26 PrO2 coating is proved to greatly facilitate the rate of oxygen dissociation, thus significantly enhancing
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28 ORR activity. Due to low oxygen vacancy density introduced by Pr0.2Ce0.8O2 and CeO2 coating, on the
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30 one hand, it does not boost the rate of ORR, but successfully suppresses surface Sr segregation, leading
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to an enhanced durability. Our findings demonstrate the vital role of surface oxygen defects and provide
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35 with important insights for rational design of high-performance electrode materials through surface
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37 defect engineering.
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41 1.INTRODUCTION
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43 Due to the high efficiency for chemical-to-electrical energy conversion, excellent fuel flexibility,
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and the capability to produce fuels from electricity or solar energy, high-temperature electrochemical
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48 systems have attracted great attentions, including solid oxide fuel cells, solid oxide electrolysis cells,
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50 oxygen separation membrane, and solar-thermal H2O/CO2 splitting systems.1, 2 However, broader
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52 commercialization of these systems is hindered by the lack of electrode materials with high performance
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55 and long lifespan.3 Modifying existing perovskite based electrode surface with a secondary phase to
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57 form a hetero-structure has been widely used to improve the electrodes activity and stability.4, 5-6 Such
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secondary phases include perovskite-based oxides,7-11 alkaline earth metal oxides,12 transition metal
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3 oxides,13-17-18 lanthanides oxides19 and their composites phases.20 Despite many successful developments
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5 in enhancing electrode performance by surface modification, some controversial results are also
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7 reported in the literature. For instance, the decoration of CoOx was reported to improve the ORR activity
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of (La,Sr)CoO3 (LSC)14 and La0.8Sr0.2FeO3 electrode,15 but show little impact on that of LSCF16 and
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12 (La,Sr)MnO3 (LSM)/ yttria stabilized zirconia (YSZ) electrode.17 Mutoro et al.12 showed that the
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14 decoration of SrOx nano-particles on LSC surface greatly enhanced the oxygen surface exchange
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kinetics, while Rupp et al.14 reported a severe deactivation effect of sub-monolayer of SrOx on the LSC.
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19 The proposed mechanisms for enhancement in catalytic activity arisen from surface modification are
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21 still controversial. 21-24
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24 It is well known that oxygen defects play an essential role in determining the activity and stability
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27 of oxide electrodes.13, 25-30 For many perovskite with high electronic and ionic conductivity such as LSC,
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29 LSCF, and BSCF, more oxygen vacancies on the surface are reported to lead to higher surface oxygen
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31 exchange coefficient. 31, 32 Consistently, perovskite oxides with a higher O 2p band center energy level,
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which are associated with lower oxygen vacancy formation energy, are reported to have better ORR
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36 activity.27 On the other hand, high concentration of oxygen vacancies on the surface is claimed to
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38 destabilize perovskite oxide surface,13, 29 attributed to the electrostatic interaction between positively
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charged oxygen vacancies on the surface and negatively charged cation dopant such as Sr, Ca, and Ba.29
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43 Such interaction can lead to cation segregation and separation on the surfaces, which is one major cause
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45 for the degradation of perovskite oxide materials.4 For oxide hetero-structure electrodes, the oxygen
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47 vacancies in the surface coating layer are found to influence the activity and stability of electrodes.13, 20,
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50 The mechanism for such influence, however, is still unclear.
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53 In this work, praseodymium doped ceria (PrxCe1−xO2) modified La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) thin
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55 films synthesized by Pulsed Laser Deposition (PLD) were used as the model hetero-structure electrodes.
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The controversial reports about the impact of surface modification in literature, as mentioned above, in
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3 many cases originated from the inability to control the coating's thickness, microstructure, density,
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5 composition and uniformity. The use of PLD technique in this study ensures that the surface coating has
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7 a well-defined thickness, composition, and morphology, enabling a systematic investigation into the
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impact of surface modification. PrxCe1−xO2−δ was chosen as the modification layer due to its tunable
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12 oxygen defect chemistry.34-37 The objective is to provide critical insight into the mechanism of how
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14 surface modification impacts the ORR activity and stability of perovskite-based oxides. Particularly, we
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focus on understanding the impact of oxygen defect in the modification layer on the overall ORR
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19 performance. We found that PrO2 modified LSCF showed much higher ORR activity compared with
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21 bare LSCF, which were attributed to the high oxygen vacancy concentration in the top layer that
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23 facilitated the oxygen dissociation process. In contrast, Pr0.2Ce0.8O2 (PCO) and CeO2 modified LSCF
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26 only showed moderate enhancement in ORR activity, but presented much better long-term stability. We
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28 believe this can be related to the high oxygen formation energy and low Sr solubility in the top layer,
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30 which suppress Sr segregation to LSCF surface during high temperature operation. Our results provide a
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guide line for the rational design of oxide hetero-structure through surface oxygen defects engineering.
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36 2. EXPERIMENTAL SECTION
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39 Highly textured LSCF (001) films with ~25 nm thickness were prepared by PLD on YSZ (001)
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single crystals substrates (CTMwafer, China) with GDC as a buffer layer. A surface modification layer
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44 of PrO2, Pr0.2Ce0.8O2 (PCO) and CeO2 with two different thicknesses (~2nm and ~6 nm) was deposited
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46 subsequently on top of LSCF/GDC/YSZ(001) thin film hetero-structure. The PLD growth was carried
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48 out at 600 °C under oxygen pressure of 10 mTorr. A KrF excimer laser with wavelength of 248 nm,
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51 energy of 300 mJ per pulse and a pulse frequency of 10 Hz were used for the deposition. The target
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53 substrate distance was set to be 10 cm. The films were cooled down to room temperature in 2 torr
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55 oxygen pressure with a cooling rate of 5 oC/min. PrO2 , PCO and CeO2 reference samples were
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deposited on to YSZ substrate with GDC buffer layer using the same PLD condition for comparison.
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3 The procedure to make PLD target can be found in Supporting Information Section 1.
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6 X-ray diffraction (Bruker D8 Advance, Germany) was used to confirm that all the powders and
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8 targets are the right phase. HRXRD 2θ−ω scans were performed to determine the orientation and the
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crystallinity of the thin films synthesized by PLD. The HRXRD measurements employed a high-
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13 resolution four-circle diffractometer with a two-bounce Ge(022) channel-cut monochromator and a
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15 scintillation counter, using Cu Kα1 radiation(Rigaku SmartLab, Japan). XPS measurement was
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performed for surface chemistry analysis, using Thermo Scientificinstrument (ESCALAB 250Xi) with
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20 monochromated Al Kα (15kV) X-ray radiation equipped with charge neutralization. The C 1s peak at
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22 284.6 eV was used as the internal reference peak for calibrating binding energies. The local cation
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24 composition on the surface was quantified by AES (PHI-700 , ULVAC-PHI) with energy resolution of
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27 1‰. Surface morphologies were investigated using a SEM (ZEISS SUPPRA 55VP, German) with ET
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29 secondary electron detector, and AFM using Asylum Research instrument (MFP-3D-S). High resolution
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31 transmission electron microscope(HRTEM) , high angle annular dark field scanning TEM (HAADF-
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STEM) and energy dispersive spectroscopy (EDS) elements linear scanning was performed by a JEOL
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36 JEM -3200FS machine to determine the interface structure. Focus ion Beam (FIB, FEI, Scios) milling
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38 technique was used for HRTEM sample preparation.
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The ORR activity and stability of modified LSCF and reference samples were evaluated by EIS
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44 using Zahner Im6 System. The EIS test was carried in frequency from 10 kHz to 5 mHz with an
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46 excitation voltage of 10 mV.
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49 First-principles calculations were carried out in Vienna Ab-initio Simulation Package (VASP) 38.
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52 Generalized gradient approximation parameterized by Perdew, Burke and Ernzerholf 39 with spin-
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54 polarization was adopted to describe the unpaired f electrons in Pr and Ce ions. Plane-wave basis set
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56 with energy cutoff 400 eV and a 4 × 4 × 4 and 2 × 2 × 2 Monkhorst-Pack 40 k-points were used for
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the fluorite conventional unit cell and the 40-atom supercell. To overcome the delocalization tendency
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3 of DFT method in describing small polarons, local lattice distortions surrounding them were created by
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5 using Ce_3 and Pr_3 pseudo-potentials prior of spin-polarized calculations.
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8 3. RESULTS AND DISCUSSION
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Using PLD, bare LSCF thin films and LSCF with a ~2nm (thin) and ~6nm (thick) coherent coating
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14 of PrO2, Pr0.2Ce0.8O2−δ (PCO) and CeO2 were grown on Yttrium stabilized Zirconia (YSZ) (001) single
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16 crystal substrates to serve as model systems. A Gd-doped CeO2 (GDC) layer buffer layer was grown
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between LSCF and YSZ substrate to avoid undesired reaction between electrode and electrolyte. High
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21 resolution X-ray diffraction (HRXRD) results showed that the LSCF, the PrxCe1−xO2−δ coating, and the
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23 GDC buffer layers were all highly textured in (001) orientation. Representative HRXRD results for the
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25 LSCF, the thick CeO2 (~6nm) modified LSCF are shown in Figure 1a. More detailed HRXRD results
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28 are shown in Figure S2. All the as prepared samples presented very smooth surface with roughness of
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30 less than 1 nm (Figure 1b, Figure S4).
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34 LSCF (b)
YSZ (002)

(a) RMS 0.21nm

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YSZ (004)

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LSCF (001)

GDC (002)

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GDC (004)

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LSCF as-prep.
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CeO2(004) GDC (004)
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YSZ (004)

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LSCF (001)

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LSCF (002)

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Figure 1.(a) HRXRD pattern of as prepared LSCF, thick CeO2 (~6 nm)/LSCF (CeO2 thick). The peaks
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3 of top CeO2 layer overlap with the GDC buffer layer . All the layers are highly textured in (001)
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5 orientation. AFM images of (b)as prepared LSCF, (c) thick CeO2/LSCF. The surface roughness of
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7 LSCF and thick CeO2/LSCF were 0.21 nm and 0.45 nm, respectively.
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The ORR activity of the LSCF and the modified LSCF electrodes at different temperatures and
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13 oxygen partial pressures were evaluated using electrochemical impedance spectroscopy (EIS) performed
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15 on model cells with the thin-film electrode as the working electrode, YSZ substrate as the electrolyte,
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and porous Ag-YSZ as the counter electrode (Figure 2a). Representative EIS spectra are shown in
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20 Figure 2b for the bare LSCF and the LSCF with a thick modification layer (~6 nm) tested at 600 oC in
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22 air. Since the contribution of the counter electrode (porous Ag-YSZ) to the total impedance of the cell is
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24 much smaller than that of the dense thin-film working electrode (Figure S3), the Nyquist plots are
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27 dominated by a semicircle attributed to the surface oxygen exchange process of the thin-film electrode.
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29 Using the equivalent circuit shown in Figure 2b, the ORR area specific resistance (ASR) of the LSCF
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31 and the modified LSCF at different temperatures in air are obtained (Figure 2c-d). Oxygen exchange
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coeffient kq can be calculated from the ORR ASR using equations (1-2).
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37 kq=kBT/4e2ASR co (1)
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40 co =(3-δ)/Vm (2)
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where kB is Boltzmann constant, T is the absolute temperature, e is the electron charge. The lattice
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46 oxygen concentration co is calculated based the bulk molar volume Vm and oxide ion vacancy content δ
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48 of LSCF at 873K reported by Niwa et al41.
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51 Among the samples tested, PrO2/LSCF shows the most pronounced enhancement in ORR kinetics.
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54 The ORR kinetic of the thick PrO2/LSCF is nearly 6 times faster than that of the bare LSCF at 600 °C in
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performance of the PCO/LSCF was between that of the PrO2/LSCF and that of the CeO2/LSCF
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3 electrode. The effect of the modification layer thickness was also studied. For both PrO2 and PCO
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5 modification, the ORR kinetics increased with the thickness of the modification layer, leading to higher
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7 kq value for a thicker layer (Figure 2 c and d). In contrast, for the CeO2 modification, the performance
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became worse with the increasing thickness of the top CeO2 layer.The dependence of kq on oxygen
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12 partial pressure of the modified LSCF and corresponding single phase were fitted using the following
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14 equation
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kq ∝ p𝑂𝑚
2 (3)
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21 where pO2 is the oxygen partial pressure. The exponent m can provide information about the
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23 species involved in the rate limiting step (RLS) of the ORR.
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Considering a simple mode for the ORR, the reaction steps and the corresponding exponent m are
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32 O2,gas ⇔ O2,ads; m=1 (4)
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O2,ads ⇔ 2Oads; m=0.5 (5)
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39 O2, ads  4e -  2 V'O'  2 OOx ; m=0.25 (6)
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31 Figure 2. (a) Schematics of the EIS measurement setup. (b) Nyquist plot for the bare LSCF and the
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thick (~6nm) PrO2, PCO and CeO2 modified LSCF measured in air at 600 °C. The inset figure shows
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36 the equivalent circuit for the fitting of EIS data. (c-d) Temperature dependence of oxygen surface
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38 exchange coefficient, kq for the bare LSCF and the LSCF coated with a thin (c) and a thick (d)
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modification layer
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17 Figure 3. The oxygen partial pressure dependence of the kq for (a) PrO2/LSCF, (b) PCO/LSCF, (c)
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19 CeO2/LSCF and corresponding reference samples at 600 oC. The test pressure ranges from 1 bar to 10-3
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22 bar. (a) PrO2/LSCF, (b) PCO/LSCF (c) CeO2/LSCF. Thin and thick are referred to the thickness of the
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24 decoration layer, which are 2 nm and 6 nm, respectively. Pure is referred to bare PrxCe1−xO2−δ films
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After surface modification, the dependence of kq on oxygen pressure showed noticeable changes.
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32 For bare LSCF, m was close to 0.5 (Figure 3), indicating that the dissociation of molecular oxygen to
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34 atomic oxygen is likely to be RLS (O2,ads ⇔ 2Oads).42-45 This result is consistent with previous report for
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mixed ionic and electronic conductors (MIEC) such as LSCF and LSC, which have sufficiently high
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39 electronic and ion conductivity.31, 32 The m value for the PrO2 modified LSCF was between 0.5 and 0.25,
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41 implying that the rate of ORR may be limited by both oxygen dissociation and charge transfer process.
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43 The m value for the PCO and the CeO2 modified LSCF electrode were close to 0.25, indicating that the
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46 charge transfer process ( O2, ads  4e -  2 V'O'  2 OOx ) may be the rate-limiting step of ORR. It needs to
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48 note that the ORR reaction steps proposed above may contain several elemental steps. Determining the
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51 exact elemental step as the RLS is beyond the scope of this work. Our EIS results, however, provided
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53 evidence that surface modifications critically influence the mechanism and kinetics of ORR, due to the
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Besides the initial ORR activity, long-term stability of bare LSCF and modified LSCF were also
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3 compared. The kq of all samples at 600 oC in air as a function of operation time are shown in Figure 4.
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5 The kq of the bare LSCF reduced continuously with operation time, becoming more than 6 times lower
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7 than the initial value after 60 hours operation. In contrast, all surface modified electrodes showed
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enhanced stability. In particular, the LSCF electrode coated with a 6 nm thick CeO2 layer showed much
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LSCF
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q

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39 Figure 4. The kq of bare LSCF and modified LSCF at 600 oC in air for about 60 hours. The thin and
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42 thick are referred modification layer with the thickness of ~2nm and ~6nm.
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45 To understand the mechanism for the enhancement in stability of the surface modified LSCF, we
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47 have characterized the detailed surface morphology and composition of the bare LSCF and the surface
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modified LSCF electrodes before and after annealing at 600 oC in air. As shown in Figure 1b and
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52 Figure 5a, as prepared LSCF films presented very smooth surface. Auger Electron Spectroscopy (AES)
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54 results from different locations of the as-prepared LSCF surface did not show any noticeable difference
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(Figure 5b), indicating a chemically homogeneous surface. After annealing in air at 600 oC for 3 hours,
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the LSCF surface became very rough, with particles presented on the surface (Figure 5c). HRXRD
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3 results showed no secondary phase form in bulk (Figure S6). As shown in AES element mapping of Sr
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5 on annealed LSCF, the particles that form on surface were Sr enriched phases with low concentration of
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7 Fe and Co. (Figure 5d, Figure S7) Further increasing the annealing temperature to 750 oC resulted in
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even larger Sr-enriched particles on the LSCF surface (Figure S8). Such preferential segregation of Sr
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12 to the surface after high temperature annealing have been widely observed in perovskite-based
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14 materials,4 such as (La,Sr)MnO3, 29, 46-48 Sr(Ti,Fe)O3,49 (Ba,Sr)(Co,Fe)O350 and (La,Sr)2CoO4.51 Due to
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the insulating nature of the Sr enriched particles, they physically block the active sites for oxygen
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19 reduction reaction and impede the paths for ionic and electronic transport. Therefore, we believed the
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21 segregation and separation of Sr cation on the surface is the reason for the degradation of LSCF at 600
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23 oC (Figure 4).
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26 0302.8.map: Company Name
27 2017 Mar 2 10.0 kV 0 nA FRR 10.92 min
28 (a) Sr1
(b) RSF

29 2
Intensity

70.3
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La Fe Co Sr
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LSCF 600 oC Sr mapping
0.200 ?m

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50000 X 10.0 keV 0.5 µm
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 3/2/2017
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3 Figure 5. (a) SEM image of as prepared LSCF (b) Representative AES spectra from different location,
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52 as marked in (a), on as prepared LSCF surface (c) SEM image of LSCF after annealing at 600oC in air,
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54 (d) AES mapping of Sr for annealed LSCF from the same location as for (c)). The brightness in (d)
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represents the intensity of Sr concentration.
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The PrxCe1-xO2 modified LSCF films presented very smooth surface in their as prepared states
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7 much less than that on bare LSCF. For annealed CeO2/LSCF, only a few scattered particles were
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observed on the surface (Figure 6 g-h). These results indicate that the modification layer on top of
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12 LSCF can suppress Sr segregation and phase separation on the LSCF surface, which explains the
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14 enhanced stability of modified LSCF.
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53 Figure 6. SEM images of the bare LSCF (a-b) and the LSCF modified by (c) thin PrO2, (d) thick PrO2,
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55 (e) thin PCO (f) thick PCO, (g) thin CeO2, and (h) thick CeO2 after annealing at 600°C in air for 3 hours;
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(i) Comparison of the Sr 3d XPS spectra for the bare LSCF and the modified LSCF in their as prepared
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3 state (left) and after annealing (right). The yellow and purple doublets are attributed to bulk coordinated
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5 Sr in LSCF lattice (Srlattice) and surface Sr species (Srnon-lattic). (j) Comparison of Srnon-lattic/Srlattice ratio for
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7 bare LSCF and modified LSCF.
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10
11
To further understand the influence of surface modification on the Sr segregation behavior in LSCF,
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13 we compared the chemical environment of Sr in the near surface for bare LSCF and modified LSCF. Sr
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15 3d spectra of the bare LSCF and the LSCF with a thin surface modification layer in their as prepared
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17
state and after 600 oC annealing are presented in Figure 6i. The Sr 3d spectra were deconvoluted with
18
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20 two sets of spin–orbit split doublets. The doublets located at lower binding energy (Srlattice) are attributed
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22 to Sr within LSCF lattice, while the ones located at higher binding energy are attributed to Sr-OH, Sr-
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24 CO3 and under coordinated Sr (Srnon-lattice).4, 49, 51-54 The Srnon-lattice / Sr lattice ratio reflects the extent of Sr
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26
27 segregation and separation in bare LSCF and modified LSCF. The Sr non-lattice/Sr lattice ratio of bare LSCF
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29 showed large increase after annealing (Figure 6i-j), indicating a strong Sr segregation towards the
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31 surface. This is consistent with the AES results for bare LSCF as shown in Figure 5. After covering
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34
LSCF with a thin modification layer, we can see non-lattice Sr becomes much less pronounced both for
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36 as prepared and annealed samples.
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39 The Srnon-lattice/Srlattice ratios are in the order of LSCF> PrO2/LSCF> PCO/LSCF> CeO2/LSCF
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(Figure 6j), suggesting that CeO2 modification is most effective for suppressing Sr segregation in LSCF
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43
44 (Figure 6j), which is consistent with SEM results (Figure 6g-h). As shown in Figure 6 c-f, the particle
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46 density on PCO/LSCF surface is larger than that on PrO2/LSCF, but the particles size is considerably
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48 smaller. Although SEM is a powerful tool to reveal surface morphology of thin films, it cannot provide
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51 a quantitative comparison of the coverage of these surface particles among different samples. The XPS
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53 results provide direct evidence that the PCO can more successfully suppress Sr segregation than PrO2,
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55 which is consistent with the better stability of PCO/LSCF than PrO2/LSCF shown in Figure 4. For the
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LSCF with a thick modification layer (~6nm), due to the detection depth limit of XPS, we were not able
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3 to probe the Sr environment. Therefore, instead of XPS measurement, we did High Resolution
4
5 Transmission Electron Microscopy (HRTEM) and Energy Dispersive Spectroscopy (EDS)
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7 characterization for the annealed thick CeO2/LSCF film. As shown in Figure 7, there was no clear Sr
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10
segregation and secondary phase formation near the interface of CeO2 and LSCF. Due to the surface
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12 damage introduced by FIB milling during sample preparation, we were not able to obtain the local
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14 structure information of Sr segregation on the top surface of bare LSCF with TEM measurement. Using
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Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS, Figure S10), the presence of Sr
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19 segregation on LSCF surface and the suppression effect of PCO coating were observed and were
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21 consistent with our XPS and SEM results.
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23
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25 Substr ate
26 (a) 0
27
(b) Fe Co Sr La Ce
28 YSZ 0.5 mm
LSCF

GDC
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CeO 2 20
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2 nm
Distance (nm)

33 GDC
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35 37.8 nm 40
36

LSCF
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39 60
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LSCF
25.0 nm
CeO 2

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43
CeO 2
(e)
44 5.6 nm 80
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46 Intensity (a.u.) Sur face
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Figure 7. (a) HRTEM images of thick (~6 nm )CeO2/LSCF thin film after annealing at 600 oC for 3
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52 hours in air; (b) EDS analysis from the substrate to the surface.
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55 Considering the essential role of oxygen vacancy for ORR activity and stability for LSCF, we
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hypothesize that the mechanism for the different improvement of ORR performance for PrO2, PCO and
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3 CeO2 modified LSCF are related to their very different oxygen defect chemistry. To provide more
4
5 insight into the underlying mechanism, we did theoretical computation of the oxygen vacancy formation
6
7 energy 𝐸𝑣𝑎𝑐 for PrO2, PCO and CeO2. The calculation details can be found in the Supporting
8
9
10 Information Section 2. As shown in Figure 8a, we found that 𝐸𝑣𝑎𝑐 decreased with the increase of Pr
11
12 dopant concentration in the CeO2 host materials, which are consistent with previous experiment and
13
14
theoretical work.20, 34, 35
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16
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18 The reason for the different improvement in ORR activity for PrO2, PCO and CeO2 modified LSCF
19
20 can be related their different oxygen defect concentration (Figure 8b). The oxygen vacancy formation
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22 energy (Evac) in PrO2 (0.91eV) is found to be much lower than that in LSCF (1.3-2.4 eV).20, 55
23
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25 Depositing a PrO2 layer onto LSCF can lead to higher concentration of oxygen vacancies on surface
26
27 compared with the bare LSCF, which strongly facilitate the dissociation and incorporation of oxygen
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29 molecular oxygen, leading to a significant enhancement of ORR activity for PrO2 coated LSCF.32, 56, 57
30
31
32
This interpretation is consistent with our previous near ambient XPS results. 20CeO2, on the other hand,
33
34 shows very high oxygen vacancy formation energy (3.7eV) (Figure 8 a). As a result, CeO2 single phase
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36 exhibited very low kq, which was also independent of oxygen partial pressure (Figure 3c). Covering
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LSCF with a CeO2 lead to a blocking effect for the absorption of oxygen gas molecular and charge
39
40
41 transfer process. Therefore, CeO2 modification showed the smallest improvement in ORR activity.
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43 Furthermore, due to the different oxygen vacancy concentration in the top layer, the ORR activity got
44
45 improve when PrO2 thickness increased, but decreased with CeO2 top layer thickness. The oxygen
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48 formation energy of PCO was between PrO2 and CeO2, leading to less improvement in ORR activity
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50 compared with PrO2/LSCF but better performance than CeO2/LSCF.
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53 Oxygen defect concentration on the top layer of modified LSCF can also impact the Sr segregation
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behavior of LSCF. This is why kq of the modified LSCF does not completely follow the order of oxygen
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vacancy formation energy of the modification layer after long time operation (Figure 4).Our recent
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3 results showed that the oxygen defect chemistry of perovskite oxides were strongly impacted by the
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5 presence of hetero-interfaces.58 A less reducible CeO2 on top of LSCF leads to a decrease in oxygen
6
7 vacancies on the LSCF surface. As a results, the electrostatic attraction between the positively charged
8
9
10
oxygen vacancy and negatively charge Sr dopant decreased, resulting in a decrease in the driving force
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12 for Sr to segregate to the surface.29 Therefore, CeO2/LSCF presents much less Srnon-lattice than the bare
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14 LSCF does. This effect is similar to the enhanced stability of LSC by surface modification of less
15
16
reducible oxides reported by Tsvetkov et al.13 By doping Pr into CeO2, the oxygen formation energy
17
18
19 decreases and surface oxygen concentration increases. As a result, PrO2 and PCO showed less apparent
20
21 effect in suppressing Sr segregation. The reason why a more reducible PrO2 on top of LSCF can still
22
23 improve the stability of LSCF is that the PrO2 layer physically blocks the direct contact of the LSCF
24
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26 with CO2 and H2O. As is well known, direct exposure of LSCF to CO2 and H2O in the air may facilitate
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28 the formation of insulating phases such as Sr(OH)2 and SrCO34, 49, 51 It needs to note that, besides
29
30 oxygen vacancy formation energy, the different substitution energy of Sr in PrO2, PCO and CeO2
31
32
33
(Figure 8) can also contribute to the variation of Sr segregation in LSCF. CeO2 with highest Sr
34
35 substitution energy can better suppress Sr segregated from the bulk of LSCF to the interface and surface
36
37 of hetero-structure. To compensate the charge difference, substituting Pr or Ce with Sr is normally
38
39
accompanied with the formation of oxygen vacancies. Therefore, the large Sr substitution energy in
40
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42 CeO2 is correlated with its high oxygen vacancy formation energy.
43
44
45 Our results demonstrate that surface oxygen vacancies have critical impact on the ORR kinetics and
46
47 stability of perovskite electrodes. While high oxygen vacancies promote the ORR reaction, it may
48
49
50 destabilize the surface by introducing more surface dopant segregation. Therefore, an ideal material
51
52 design can be the use of composite coating which can both block the Sr segregation and provide oxygen
53
54 defects on the surface to facilitate the reaction, as demonstrated in some of recent works.20, 33 It is also
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worth to emphasis that besides materials characteristics, the microstructure of the top layer also strongly
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impact on the ORR activity of the hetero-structure. For instance, we found the ORR activity of
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3 PrO2/LSCF and PCO/LSCF increased with the thickness of top layer. In contrast, a thicker the top CeO2
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5 lead to a worse ORR activity. Therefore, one reason for the large variation in performance of surface
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7 modified electrode in literature can be the different microstructure such as thickness and density of the
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9
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surface coating. Techniques such as atomic layer deposition 59 that can realize surface modification with
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12 well controlled thickness and composition are believed to be powerful tools for the synthesis of high
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14 performance electrode material.
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36 Figure 8. (a) Vacancy formation energy (Black square) and Sr substitution energy (Blue sphere) in
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CeO2, PCO (Pr0.25Ce0.75O2) and PrO2. PCO have two scenarios in Sr substituting Pr and Ce site. Dashed
39
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41 line is for the guiding of eyes. The inset figure shows the spin charge density of PCO with an oxygen
42
43 vacancy in the cell. (b) Illustration shows the critical impact of oxygen vacancies in the modification
44
45 layer on the performance of hetero-structure electrodes. High densities of oxygen vacancy in the top
46
47
48 layer can facilitate oxygen dissociation and incorporation on the surface, leading to high ORR activity,
49
50 as for the case of PrO2/LSCF. Low concentration oxygen in the top layer can help suppress Sr
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52 segregation to the surface, leading to better stability, as exampled by CeO2/LSCF.
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4. Conclusion
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In summary, we have systematically investigated the effect of surface modification on LSCF

1
2
3 electrode performance, providing critical insight into the role of oxygen defect in the surface
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5 modification layer on the ORR activity and stability of oxide hetero-structure electrodes. In particular,
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7 LSCF thin-film electrodes with PrxCe1-xO2-δ (x=0, 0.2, 1) coating are synthesized by PLD to serve as the
8
9
10
model system with well-defined hetero-structures for fundamental studies. Among the coating materials
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12 studied, PrO2 modification displays the most pronounced enhancement in ORR activity, attributed
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14 largely to the high oxygen vacancy concentration of PrO2. Degradation in performance of a bare LSCF
15
16
electrode was due mainly to surface Sr segregation at high temperature during operation. Such Sr
17
18
19 segregation is successfully suppressed by the application of a surface coating, leading to greatly
20
21 improved stability. The effects of suppressing Sr segregation follow the order of CeO2/LSCF >
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23 PCO/LSCF > PrO2/LSCF, because oxygen vacancy formation energy and Sr substitution energy
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25
26 increases as the Pr content is reduced. Not only Sr solubility is the lowest in CeO2, its lowest oxygen
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28 vacancy concentration in CeO2 helps to suppress the Sr segregation to the surface. These results
29
30 demonstrate the vital role of surface oxygen defects and point to a potential direction for achieving high-
31
32
33
performance electrodes through surface defect engineering.
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35
36 ASSOCIATED CONTENT
37
38 Supporting Information.
39
40
The Supporting Information is available free of charge on the ACS Publications website at DOI:
41
42
43 Additional experimental data including pulsed Laser Deposition Target synthesis ;XRD patterns of PLD
44
45 target after sintering (S1); HRXRD patterns of modified LSCF and corresponding single phase
46
47 reference samples (S2);Resistance comparison between porous Ag-YSZ and LSCF(S3); SEM image of
48
49
50 the modified LSCF in their as prepared states (S4); Nyquist plot for modified LSCF(S5); HRXRD
51
52 patterns of thin film before and after annealing(S6);SEM and AES maps for LSCF(S7);XPS and EDS
53
54 analysis on annealed LSCF surface(S8);La 3d 5/2 and Ce 3d XPS spectra of PCO single phase and PCO
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modified LSCF (S9); TOF-SIMS pattern of modified LSCF and bare LSCF(S10) and DFT calculation
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of oxygen vacancy formation energy and Sr substitution energy; Summary of fitting parameters for Sr
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3 3d peak (Table S1).
4
5
6 AUTHOR INFORMATION
7
8
9
Corresponding Author
10
11
12
*(Y. C.)E-mail address: escheny@scut.edu.cn.
13
14
15 *(M. L.)E-mail address: meilin.liu@mse.gatech.edu.
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17
ORCID
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19
20 *Yan Chen : 0000-0001-6193-7508
21
22
23 *Meilin Liu: 0000-0002-6188-2372
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25
26 Notes
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28 The authors declare no competing financial interest
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30
31 ACKNOWLEDGMENT
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33
34 This work was supported by Guangzhou Science and Technology Program General Projects (No.
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36 201707010146), the Fundamental Research Funds for the Central Universities (2018MS40), Guangdong
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38
39
Innovative and Entrepreneurial Research Team Program (No. 2014ZT05N200), the National Natural
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41 Science Foundation of China (11605063, 91745203), the Science and Technology Planning Project of
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43 Guangdong Province, China (No. 2017B090916002), the Recruitment Program of Global Youth Experts
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45
of China. This research used resources of the National Energy Research Scientific Computing Center, a
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48 DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of
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50 Energy under Contract No. DE-AC02-05CH11231.
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