Ceramics International xxx (xxxx) xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Enhanced pseudocapacitive performances of eco-friendly co-precipitated

Fe-doped cerium oxide nanoparticles
Chae Eun Lee a, 1, Seo Hyun Choi a, b, c, 1, Hyun Young Kim a, Sun Sook Lee b, Seong K. Kim a, *,
Ki-Seok An b, **
a
Department of Advanced Materials and Chemical Engineering, Hannam University, 70 Hannamro, Daejeon, 34400, Republic of Korea
b
Thin Film Materials Research Center, Korea Research Institute of Chemical Technology (KRICT), Yuseong Post Office Box 107, Daejeon, 34114, Republic of Korea
c
School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, 16419, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, we report a method to enhance the performance of environmentally friendly cerium oxide (CeO2)
Cerium oxide based pseudocapacitive electrode materials synthesized by a facile and safe co-precipitation method. Although
Pseudocapacitive material co-precipitation can be considered as one of the most safe and facile procedures for the preparation of metal
Energy storage
oxide nanoparticles, co-precipitated CeO2 often exhibits substantially reduced specific capacitance. However, by
Supercapacitor
simply doping Fe into CeO2, we observed a notable enhancement in the performance of the CeO2 electrode.
Co-precipitation
Although co-precipitated CeO2 demonstrates a specific capacitance of 121.0 F g-1 at 1 A g-1, the performance of
the CeO2 electrode increased by 4.6 times to 559.0 F g-1 after 10 at.% Fe doping (10FDC). The specific capac­
itance of 10FDC at a high rate (10 A g-1) significantly increased by 8.9 times compared to that of CeO2 (21.6 F g-1
for CeO2 and 192.7 F g-1 for 10FDC). In addition, 10FDC exhibited excellent cycling stability, and less than 5%
decrease in its specific capacitance was observed even after 7,300 charging and discharging cycles. The mech­
anism behind the capacitance enhancement was investigated via electrochemical analysis, which suggested that
the contribution of the surface-capacitive limited process and the electrical conductivity of the electrode
enhanced after Fe doping. Our study proposes a new possibility for the development of high-performance eco-
friendly energy storage materials via the modification of electrical properties and introduction of defects by facile
acceptor doping.

1. Introduction demonstrate high specific capacitances when used as electrode materials

for pseudocapacitors and hybrid capacitors [5,8–11]. However, most of
Nowadays, studies related to energy conversion and storage are the high-performance electrode materials are either scarce in nature or
receiving considerable attention because of the importance of devel­ based on environmentally harmful materials; thus, they are not suitable
oping new energy systems. To store electrical energy, electrochemical for establishing a truly sustainable future energy system. In contrast,
energy storage devices, such as rechargeable batteries (secondary bat­ cerium oxide (CeO2) is one of the few environmentally friendly pseudo­
teries) and supercapacitors, are being actively investigated. Secondary capacitive materials with low toxicity (definite cases of bio­
batteries based on electrochemical redox reactions demonstrate high logical/environmental damage caused by Ce compounds have not been
energy densities with a stable supply of electrical energy, and electric reported to date); thus, CeO2 can be an appropriate material for a sus­
double-layer supercapacitors (EDLCs) exhibit high power densities with tainable future energy system [12–14]. Furthermore, although Ce is
fast charge/discharge rates [1–3]. In addition to these, pseudocapacitors considered as a rare-earth element, it is actually the most abundant
and hybrid supercapacitors comprising the advantages of both batteries element in the lanthanide series [15–18]. In fact, the concentration of Ce
and EDLCs, have been extensively studied [1,4–8]. in the Earth’s crust is as high as 66 ppm, which makes Ce almost as
Several metal oxides (RuO2, MoO2, MnO2, etc.) are reported to abundant as Cu (with a concentration of 68 ppm in the Earth’s crust) [18].

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (S.K. Kim), [email protected] (K.-S. An).
1
These authors contribute equally to this work.

https://doi.org/10.1016/j.ceramint.2021.04.217
Received 22 March 2021; Received in revised form 20 April 2021; Accepted 23 April 2021
Available online 24 April 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Chae Eun Lee, Ceramics International, https://doi.org/10.1016/j.ceramint.2021.04.217
 C.E. Lee et al. Ceramics International xxx (xxxx) xxx

Due to Ce’s non-toxicity, high natural abundance, and great redox prop­ pestle and then calcined in a furnace at 700 ◦ C for 2 h to obtain CeO2 and
erty, Ce containing materials, such as CeO2 and CeS2, have been applied in FDC nano-powders.
a broad range of applications and research fields including various
biomedical applications [19,20], photocatalysis/photo-thermocatalysis 2.2. Characterization of the prepared materials
[12], gas purification [21], radical scavenging [22,23], high tempera­
ture solid electrolyte/cathodic interlayer for solid oxide fuel cell [24–26], Structures of the fabricated CeO2 and FDCs nanopowders were char­
and energy storage electrodes. Specifically, various CeO2 nanostructures acterized using X-ray diffraction (XRD). XRD patterns were measured
(e.g. nano-particles, flakes, stars, and flowers) and composites containing from 20 to 80◦ using a Rigaku D/Max-2200V X-ray diffractometer at a
Ce have been synthesized, and their performances as pseudocapacitive slow-rate in a step-scan mode. The obtained XRD patterns were further
materials have been examined [16,27–34]. However, to synthesize and analyzed using the Scherrer equation to estimate the domain size of the
construct high performance CeO2 nanostructures with large surface areas, synthesized nanoparticles [46,47].
complex synthesis procedures, such as hydrothermal method, are often Shapes and sizes of CeO2 and FDC nanoparticles were examined by
utilized, which are rather unsafe and unsuitable for large-scale industrial scanning electron microscopy (SEM, TESCAN VEGA-II LSU). Energy
production [16,27–34]. Accordingly, simpler, safer, and more dispersive X-ray spectroscopy (EDS) was performed using a Bruker
industrially-applicable synthesis procedures (including co-precipitation) Quantax 200 energy dispersive X-ray spectrometer coupled with TES­
have also been considered. Nevertheless, CeO2 prepared by a simple CAN VEGA-II LSU to analyze the composition of the prepared materials.
co-precipitation method typically exhibits low specific capacitances be­
tween 60 and 120 F g-1, probably due to the comparably low surface area 2.3. Electrochemical measurements
of the sphere-shaped nanoparticles and inherently low capacitance of
cubic CeO2 [31,34–37]. For electrochemical measurements, initially, the synthesized CeO2
For this reason, we attempted to enhance the performance of CeO2 and FDC nanoparticles were fabricated into electrodes. For electrode
synthesized via co-precipitation as pseudocapacitor electrodes by fabrication, the active material (CeO2 or FDCs) was mixed with activated
doping, specifically Fe doping. Fe is a well-known transition metal with carbon (YP-50F, Kurary Chemical Co. Ltd.) and polyvinylidene fluoride
multiple common oxidation states (2+ or 3+ in nature); thus, Fe con­ (PVDF, Mw = ~534,000; Sigma-Aldrich) at 8:1:1 ratio, respectively,
taining metal oxides, sulfides, and hydrides are often utilized in various using 1-methyl-2-pyrrolidinone (NMP, > 99%; Sigma-Aldrich) as a sol­
electrochemical and electrocatalytic applications [36–39]. When CeO2 vent to form slurries. The slurries containing CeO2, 1FDC, 5FDC, and
was doped with Fe and other transition metals, its electrical properties 10FDC were loaded onto Ni foams, which were used as the working
are expected to change. In particular, the electrical properties at in­ electrodes for electrochemical measurements. After completely drying
terfaces (for example grain boundaries) and surfaces are reported to the electrodes, the masses of the active materials loaded onto the elec­
alter significantly [40–42]. Therefore, the surface/interfacial redox re­ trodes were between 1 and 5 mg cm-1.
action can be substantially promoted. Simultaneously, Frenkel defects, For electrochemical characterization, cyclic voltammetry (CV), gal­
such as oxygen vacancies, would be formed to account for the disturbed vanostatic charge-discharge measurements, and EIS were conducted.
charge neutrality caused by doping Fe into CeO2 [40–44]. For these measurements, a three-electrode setup comprising 3 M po­
For the above mentioned reasons, herein, we synthesized Fe-doped tassium hydroxide (KOH, Sigma-Aldrich) as the electrolyte, Ag/AgCl
CeO2 (FDC) with various Fe doping concentrations to investigate the (ALS Co. Ltd.) as the reference electrode, and a Pt electrode as the
effect of Fe doping on the electrochemical properties of co-precipitated counter electrode was used. CV was performed between 0 and 0.5 V vs.
CeO2 for its application as a supercapacitor electrode. Specific capaci­ Ag/AgCl at various scan rates (10, 20, 30, 40, 50, 100, 200, 500 mV s-1).
tance of 10 at.% FDC (10FDC) was more than 4.6 times that of co- Galvanostatic charge-discharge measurements were conducted between
precipitated CeO2 nanoparticles at 1 A g-1 (559.0 F g-1 vs. 121.0 F g-1, 0 V and 0.4 V at the constant charging/discharging current densities of
respectively). 10FDC also demonstrated excellent stability, maintaining 1, 2, 3, 4, 5, and 10 A g-1 to examine the capacitance of the electrodes.
95% of its initial capacitance even after 7,300 cycles of charging and EIS was performed for the CeO2 and 10FDC electrodes from 1 MHz to
discharging. To examine the mechanism of capacitance enhancement, 100 mHz by applying ac-potential with an amplitude of 10 mV with and
electrochemical analysis was performed, which indicated significant without an applied dc-bias potential of 400 mV.
enhancement in the contribution of the surface-capacitive limited en­
ergy storage process. Further investigation by electrochemical imped­ 3. Results and discussion
ance spectroscopy (EIS) suggested that the electrical conductivity of the
CeO2 electrode was enhanced upon Fe doping, which might have 3.1. Structures of the synthesized CeO2 and FDCs nanoparticles
accelerated the pseudocapacitive redox reaction of CeO2 nanoparticles.
CeO2, 1FDC, 5FDC, and 10FDC nanoparticles were fabricated by a
2. Experimental Methods facile co-precipitation method (Fig. S1 in the Supporting Information)
[45]. A detailed description of the synthesis method is provided in
2.1. Synthesis of CeO2 and Fe doped CeO2 Experimental Methods. Compared with the hydrothermal method, the
co-precipitation method is a relatively simple and safer method for the
CeO2 1 at.% FDC (1FDC), 5 at.% FDC (5FDC), and 10% Fe-CeO2 preparation of CeO2 nanoparticles. In addition, the co-precipitation
(10FDC) were synthesized by the co-precipitation method [40]. Calcu­ method allows the synthesis of various acceptor- and donor-doped
lated amounts of iron nitrate nonahydrate (Sigma Aldrich) and cerium CeO2, via which various properties including electrical and electro­
nitrate hexahydrate (Sigma-Aldrich) were mixed in distilled water fol­ chemical properties of CeOx can be tuned. In this study, FDCs were
lowed by stirring until all nitrates were completely dissolved. To the fabricated by the co-precipitation method because (1) Fe doping is
nitrate solution, a relatively dilute ammonium carbonate (Sigma-Al­ known to modify the electrical properties of CeO2, and (2) Frenkel de­
drich) solution (pH = ~10) was added dropwise to prevent particle fects (such as O vacancies as shown in Fig. 1a) can be intentionally
growth. Upon the addition of ammonium carbonate solution to the ni­ introduced into the system by adding an acceptor (Fe3+) as the dopant.
trate solution, precipitates were formed. After completion of precipita­ Owing to the introduction of O vacancies via Fe doping, the synthesized
tion, the precipitates were collected using a centrifuge. The collected iron doped cerium oxides (FDCs) are expected to be formed as Fex
precipitates were washed several times with de-ionized water and Ce1-xO2-x/2, where x indicates the amount of Fe3+ substitutionally doped
ethanol. After washing, the precipitates were dried overnight in a drying into the Ce sites. The amount of Fe doped into 1FDC, 5FDC, and 10FDC
oven at 80 ◦ C. The dried powder was finely ground using a mortar and was confirmed by EDS, as shown in Fig. S2 in the Supporting

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Fig. 1. (a) General structure of FDC showing the formation of O vacancies upon Fe doping. (b) XRD patterns of CeO2 and FDCs, and (c) average domain sizes
calculated from the XRD patterns. SEM images of (d) CeO2 and (e) 10FDC, and (f) the corresponding particle size distributions. (g) Average particle sizes and particle
size distributions of CeO2 and FDCs obtained from the corresponding SEM images.

Information. The XRD patterns of all the samples are shown in Fig. 1b. 3.2. Performances of the co-precipitated FDC nanoparticles
The XRD patterns of the prepared CeO2 nanoparticles were similar to
those typically exhibited by cubic fluorite CeO2 without any secondary After the structural and chemical characterization of CeO2 and FDCs,
phase (Fig. 1b). The XRD patterns of all FDC nanoparticles were almost electrodes were fabricated using CeO2 and FDCs nanoparticles as the
identical patterns to that of CeO2; this indicated that the cubic fluorite active materials. To evaluate the performance of the samples as elec­
structure of CeO2 was well-maintained in al FDCs without the formation trodes of a pseudocapacitor, galvanostatic charge–discharge experi­
of secondary phases. Using the Scherrer equation, the crystal domain size ments were performed at constant current densities between 1 and 10 A
was calculated from the XRD patterns (Fig. 1c), and crystal domains with g-1. To attain the specific capacitances (Cg) of the electrodes, the applied
sizes of 12–25 nm were observed. According to the calculations, the charging and discharging current densities were calculated using the
crystal domains of all FDCs were similar to or smaller than those of CeO2. mass of the active material in the fabricated electrodes. Electrodes were
tFig. 1d, 1e, and Fig. S3 show the SEM images of CeO2 and FDCs. As charged up to 0.4 V and discharged to 0 V. Cg was calculated from the
shown in the SEM images, the shapes of the CeO2 and FDC nanoparticles charge–discharge curves using Eq. (1).
were nearly spherical, and the nanoparticles agglomerated in all the sam­ /
Cg = (Ig × Δt) ΔV (1)
ples. Compared with other previously reported CeO2 nanostructures syn­
thesized by the complex methods such as hydrothermal and solvothermal
where Ig is the applied current density in A g-1, Δt is the time taken to
[48–50], co-precipitated CeO2 or FDC nanoparticles probably cannot offer
completely discharge the sample, and ΔV is the potential difference
a higher surface area. However, the co-precipitation method enables uni­
between the charged and discharged states. Fig. 2a–d show the char­
form synthesis of nanoparticles, as demonstrated by the highly intense and
ge–discharge curves for CeO2, 1FDC, 5FDC, and 10 FDC, respectively.
clean XRD patterns and the uniformly shaped and sized nanoparticles in
From the results shown in Fig. 2a–d, Cg of each sample was calculated
the SEM images. The sizes of the nanoparticles were measured from the
and is plotted in Fig. 2e. As clearly shown in Fig. 2e, the highest Cg was
SEM images, and the obtained particle size distributions are plotted in
observed for 10FDC, followed by 5FDC, 1FDC, and CeO2. For CeO2, the
Fig. 1f and Fig. S3. For each sample, the size distribution plots were ac­
Cg at 1 A g-1 is approximately 121.0 F g-1, which is substantially lower
quired by conducting at least 50 repeated measurements on randomly
than the theoretical specific capacitance of CeO2 (estimated to be 520 F
selected particles in the SEM images. Regardless of the Fe concentration, all
g-1 [32]). However, according to the results reported in previous studies,
samples presented similar average particle sizes with narrow particle size
the CeO2 nanoparticles synthesized using co-precipitation method
distributions. For CeO2, the mean particle size was 34.1 nm with standard
generally exhibit low Cg values near or below 100 F g-1 [31,34–37],
deviation of 10.09 nm. Moreover, the mean particle sizes and size distri­
which are consistent with our result. Although our nominally pure CeO2
butions for 1FDC, 5FDC, and 10FDC were 33.7 nm, 32.0 nm, and 32.6 nm
nanoparticles demonstrated unsatisfactory performance, doping CeO2
and 7.99 nm, 7.36 nm, and 6.61 nm, respectively, indicating the synthesis
with Fe significantly increased the performance of the corresponding
of relatively uniform nanoparticles for all samples. A comparison between
electrode. Even after 1 at.% Fe doping, the Cg of the electrode increased
the crystal domain sizes determined from XRD and the particle sizes
by more than 30%. When charged and discharged at 1 A g-1, the 1FDC,
calculated from the SEM images, implies that the CeO2 particles are highly
5FDC, and 10FDC electrodes exhibited the Cg values of 160.5 F g-1,
likely to be composed of 1–2 crystal domains (single- or bi-crystal parti­
320.8 F g-1, and 559.0 F g-1 (which is 4.6 times the capacitance of CeO2),
cles), whereas the FDCs appears to be composed of 2–3 crystal domains (i.
respectively. In our case, the performance increase was not caused by
e. most of the particles are polycrystalline).
the formation of a composite/hybrid material or a change in the

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Fig. 2. Evaluation of specific capacitances for (a) CeO2, (b) 1FDC, (c) 5FDC, and (d) 10FDC. (e) Specific capacitances obtained at different discharge current
densities. (f) Stability of 10FDC during 8,000 cycles of repeated charging and discharging.

structure/phase, as reported previously [37–39], as the XRD results Similar charging and discharging potentials were observed for all FDCs,
clearly confirmed that FDCs were formed as single-phase particles with a which suggested that the electrochemical redox reaction between the
cubic fluorite structure. Thus, further investigation was necessary to electrode and K+ was similar for CeO2 and FDCs.
understand the mechanism of the enhancement of electrochemical Based on the CV results, the rate-limiting steps of the pseudocapa­
properties upon doping. citive redox reactions of CeO2 and FDCs were determined and compared.
Similar to the cases of most of other pseudocapacitive electrode Pseudocapacitive redox reaction is a two-step process; the first step in­
materials, the performance of the FDC nanoparticles considerably volves ion transfer between the electrolyte and the electrode, and the
decreased when the discharging current density was increased. Never­ second step comprises a redox reaction on the surface of the electrode. If
theless, the highest Cg was observed for 10FDC (192.7 F g-1 at 10 A g-1) at the kinetics of the pseudocapacitive reaction are limited by ion diffu­
all discharging current densities. In contrast, the CeO2, 1FDC, and 5FDC sion, the process is considered diffusion-controlled, for which the
nanoparticles showed the Cg values of only 21.6, 76.0, and 168.6 F g-1 at exponent b in Eq. (2) is approximately 0.5. However, if the reaction is
10 A g-1, respectively. Upon comparing the Cg values of CeO2 and limited by the redox reaction, the process is considered surface-
10FDC, the Cg of 10FDC was found to be 8.9 fold that of CeO2 at 10 A g-1, capacitive, for which b is 1 [4–6]. In Eq. (2), ip is the peak current (for
verifying that the high rate performance of CeO2 also was enhanced after the charging or discharging redox reaction peak), and a is a
10 at.% Fe doping. pre-exponent constant.
Stability of a material upon repeated charging and discharging is also
ip = a × υb (2)
important for its application as an electrode in pseudocapacitors or
hybrid capacitors. Fig. 2f shows the results of repeated charging and In general, surface capacitive process, which provides faster charging
discharging at 10 A g-1 for the 10FDC electrode. Even after 8,000 cycles and discharging rates, is favorable for pseudocapacitive electrodes,
of repeated charging and discharging, the performance of the electrode whereas diffusion-controlled process is often observed for battery ma­
degraded by less than 22%. More importantly, the 10FDC electrode terials with slower charging and discharging rates. In Fig. 3e, the ip
retained its performance for up to more than 7,300 cycles with less than values acquired during the discharging of each sample at different υ are
5% performance degradation. plotted as a log-log plot. From this plot, b can be obtained by estimating
the slope of the curve (details are provided in the Supporting Informa­
tion). Interestingly, all curves can be divided into two linear regions
3.3. Mechanism behind enhanced capacitance with different slopes. At low υ region (between 10 and 100 mV s-1), b was
above 0.75, whereas at high υ (above 100 mV s-1), b values were close to
To further investigate the mechanism behind the enhanced perfor­ or below 0.6. These results indicate that the energy storage mechanisms
mance of FDC nanoparticles, CV and EIS were performed. The results of of CeO2 and FDC electrodes are partially limited by the surface-
the CV measurements are shown in Fig. 3a-d and Fig. S4a–d in the capacitive process, specifically during relatively slow charging and
Supporting Information. CV curves were acquired at various scan rates discharging. In addition, the b values observed at low υ increased when
(υ) ranging from 10 to 500 mV s-1. For all samples, CV curves with Fe was doped into CeO2 (Fig. S5 in the Supporting Information). The b
pseudocapacitive redox peaks were achieved. With an increase in the Fe values at a slow rate (bS) were greater than 0.80 for all FDCs, which
concentration, the integrated area of the CV curve also increased, which suggests that the surface capacitive process significantly contributes to
indicated that the Cg of the electrode enhanced with an increase in the Fe the charging/discharging of FDCs. Using Eq. (3), the extent of the
concentration. For CeO2, redox peaks related to pseudocapacitive contribution of the surface-capacitive process was calculated and is
charging and discharging were observed near 0.4 and 0.3 V, respec­ shown in Fig. 3f.
tively, which were similar to the previously reported results [34–37].

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Fig. 3. Results of cyclic voltammetry measurements for (a) CeO2, (b) 1FDC, (c) 5FDC, and (d) 10FDC. (e) Discharging peak current obtained from the CV curves vs.
scan rates, and (f) results of the energy storage mechanisms of CeO2 and FDC electrodes.

ip = k1 υ + k2 υ1/2 (3) demonstrated profound redox peaks typically associated with battery-
like materials, the energy-storing redox events were mostly capacitive
where k1 and k2 are the rate constants of the surface-capacitive and in nature.
diffusion-controlled processes, respectively. For all FDCs, the contribu­ Finally, EIS was conducted to further analyze the electrochemical
tions of the surface-capacitive process were above 70% at υ below 100 characteristics of the FDC electrodes (Fig. 4). Fig. 4b and 4c shows the
mV s-1 (denoted as “S”); this indicates that although the CV curves Nyquist plots obtained from the impedance measurements of CeO2 and

Fig. 4. Results of EIS. (a) Equivalent circuit used for EIS and Nyquist plots for (b) CeO2 and (c) 10FDC.

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C.E. Lee et al. Ceramics International xxx (xxxx) xxx

10FDC with and without an applied dc bias potential of 400 mV, and the transfer resistance; Qredox is also added to account for the pseudocapa­
equivalent circuit proposed for this analysis is shown in Fig. 4a. The citive redox behavior of the electrode materials [51]. When Vdc is
equivalent circuit consists of three main parts connected in a serial applied, changes in the impedance and capacitance at low frequencies
arrangement. The first serial component comprises a single resistive can be observed. To gain a better understanding of the low frequency
element (Rs) corresponding to the serial resistance of the cell, which in­ response, the impedance results were plotted as Bode plots (Fig. 5).
cludes the electric resistance of the electrode. For 10FDC, the Rs value was According to previous studies, the dependence of the low-frequency
approximately 2.8 W, whereas for the CeO2 electrode, Rs = ~3.9 W, impedance (Z′ and Z′′ ), capacitance (C′ and C′′ ), and/or phase angle (f)
which implied that the electrical conductivity of CeO2 increased upon Fe on the applied Vdc can be used to distinguish pseudocapacitve behavior
doping. For these measurements, all experimental parameters (including and battery materials. Battery materials exhibit a strong Vdc dependence
measurement set-up, and electrolyte condition) were carefully controlled; at low frequencies, whereas pseudocapacitive materials demonstrate a
thus, the difference between the Rs values of electrode materials was relatively small Vdc dependence at low frequencies. The absolute im­
mainly caused by the different electrical properties of these materials. pedances (|Z|) of both CeO2 and 10FDC showed frequency dependence,
The second component consists of a capacitive element (Ce) in par­ typically observed in the case of electrochemical energy storage mate­
allel with a resistive element (Re) and a Warburg element (ZW) in a serial rials. In addition, the low-frequency f of 10FDC showed small Vdc de­
arrangement. These elements correspond to the capacitance, resistance, pendencies, which indicate that both electrodes exhibit relatively fast
and the diffusional impedance from the electrolyte, respectively. The electrochemical redox reactions. These fast redox reactions are generally
third component comprises a capacitive element (Cedl) in parallel with a observed in pseudocapacitive materials. The Vdc dependence of 10FDC is
resistive element (Rct) and a constant phase element (Qredox). Cedl rep­ smaller (with Δφ = -1.81◦ ) than that of CeO2; this suggests that a faster
resents the electric double layer capacitance, and Rct signifies the charge redox reaction occurs in the case of 10FDC when compared with that in

Fig. 5. Bode plots obtained from the EIS measurements of (a) CeO2 and (b) 10FDC electrodes.

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C.E. Lee et al. Ceramics International xxx (xxxx) xxx

the case of CeO2 (Δφ = -12.51◦ ), which is also consistent with the result Appendix A. Supplementary data
shown in Fig. 3f. In addition, static and dynamic dielectric losses were
examined using the results of impedance measurements (Fig. S6 in the Supplementary data to this article can be found online at https://doi.
Supporting Information). For both CeO2 and 10FDC samples, relatively org/10.1016/j.ceramint.2021.04.217.
small static dielectric loss tangents <1 could be observed at low fre­
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