Ceramics International 47 (2021) 5998–6009

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

Hierarchically Fe-doped porous carbon derived from phenolic resin for high
performance supercapacitor
Xiaoxi Dong a, b, c, Jingyue Wang a, b, c, Meifang Yan b, c, Bin Ren b, c, Junfeng Miao a, b, c,
Lihui Zhang b, c, Zhenfa Liu a, b, c, *, Yuelong Xu b, c, **
a
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, 300000, China
b
Institute of Energy Resources, Hebei Academy of Sciences, Shijiazhuang, 050081, China
c
Hebei Engineering Research Center for Water Saving in Industry, Shijiazhuang, 050081, China

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

Keywords: Supercapacitors are promising for high power application in the recent years. In particular, the conversion of
Hierarchical porous carbon simple and available carbon materials into economic and high performance electrical devices receives excellent
K2FeO4 scientific and technological interest. This paper reports a one-step strategy for synthesizing hierarchical porous
Graphitization degree
carbon derived from phenolic resin (PR), which is then used to configure electric double-layer capacitors
Supercapacitor
(EDLCs). Here, a carbon material with a flexible porous structure, large specific surface area, and high graphi­
tization degree is prepared using potassium ferrate (K2FeO4) to catalytically activate PR and to realize syn­
chronous carbonization and graphitization. This method overcomes the disadvantage of time-consuming, high-
cost, and environmentally unfriendly. In addition, the as-prepared carbon material has a high specific surface
area (1086 m2 g− 1) and a large pore size (3.07 nm), which can increase the transfer rate of electrolyte ions. The
specific capacitance of the obtained electrode material is 315 F g− 1 at 1.0 A g− 1, and the optimized electrode
material has an ultra-long cycle lifetime (capacitance retention rate is 96.3% after 10,000 cycles). Thus, the
hierarchically Fe-doped porous carbon material derived from PR material is expected to realize high rate
capacitance for supercapacitor applications.

1. Introduction
Supercapacitors (also known as ultracapacitors), a type of reliable
electrical energy storage (EES), have immense potential because of their
advantages of high power density, short charging time, low cost, and
remarkable cycling life [1–4]. They can be categorized into
pseudo-capacitors and electric double-layer capacitors (EDLCs). In the
case of pseudo-capacitors, fast reversible faradaic reactions occur during
the charging and discharging processes, and the electrode materials are
generally metallic oxides and polymers. The metallic oxides, used as
positive electrode materials, include MnO2, NiOx, and V2O5, and the
conductive polymer materials include PPY, PTH, and PAn, which are
doped with p-, n-, or P/N-type material for electrode preparation [5–7].
On the other hand, for EDLCs, the energy store is an accumulation and
release of pure physical changes that occur on the electrode–electrolyte
interface [8,9]. As a typical electrode, carbon material can provide a
suitable pore structure and large specific surface area. In addition, the
heteroatoms (such as N [10], B [11], S [12], and P [13]) doped in the
carbon framework can improve the electrochemical performance.
Supercapacitors have many applications in the EES field. Chen et al.
[14], for example, reported a sensitive changeable device that can
display various colors based on the tungsten oxide material. Cai et al.
[15] presented a smart supercapacitor whose stored energy level can be
simultaneously monitored through a rapid and reversible color change.
As the regenerative braking system of a vehicle, a supercapacitor can
store the excess kinetic energy, so that the excess energy is not be wasted
when the driver is braking, thus improving the service life of the braking
system.
Recently, carbon-based supercapacitors have attracted considerable
research interest because of their fast kinetic process and excellent cycle
stability [16]. Carbon materials exist in many forms, such as active
carbon, carbon fiber, carbon aerogel, and graphene. Thus, carbon-based

* Corresponding author. Institute of Energy Resources, Hebei Academy of Sciences, Shijiazhuang, 050081, China.
** Corresponding author. Institute of Energy Resources, Hebei Academy of Sciences, Shijiazhuang, 050081, China.
E-mail addresses: a13292005986@126.com (X. Dong), wjy423130@163.com (J. Wang), yanmeifang525@sina.com (M. Yan), RENBINTS@126.com (B. Ren),
13731017560@163.com (J. Miao), lzf63@sohu.com (L. Zhang), zlhkxy@126.com (Z. Liu), xudalong.cool@163.com (Y. Xu).

https://doi.org/10.1016/j.ceramint.2020.10.175
Received 22 September 2020; Received in revised form 20 October 2020; Accepted 22 October 2020
Available online 27 October 2020
0272-8842/© 2020 Published by Elsevier Ltd.
X. Dong et al.
materials with a suitable pore structure and good electrical conductivity
are essential for high-power-density supercapacitors. The suitability of
the pore structure depends on the pore size. Micropores can increase the
specific surface area, which is beneficial for accommodating charged
ions and obtaining an electrical double layer. In addition, they facilitate
the electrolyte–electrode contact and provide a channel for transferring
charged ions [17,18]. Thus, well-structured carbon materials with a
micro/meso/macroporous system, called hierarchical porous carbon,
are a suitable alternative for improving the electrochemical
performance.
From the long-term and environmental-friendliness viewpoints, PR is
an appropriate alternative. It is selected as the carbon source because of
its high production output, which is attributed to the polymerization
stability and complex chemical structures of phenols and aldehydes. PR
is developed using chemical and physical activation methods, such as
soft and hard template methods. Activated PR-based porous carbon
exhibits a much higher specific surface area (1086 m2 g− 1) and wide
pore size distribution [19–22]. Hence, PR can be used as a promising
electrode material for supercapacitor, owing to its easy availability,
simple formation process, high yield, and low cost; moreover, it exhibits
good wettability/compatibility with oxide and graphite [23]. PR is used
as a carbon source to obtain high conductivity through the use of tran­
sition metals, such as Fe, Ni, and Co. The use of transition metal as a
catalyst can not only improve the graphitization degree of PR but also
reduce the carbonization temperature (below 1000 ◦ C), thereby yielding
high rate capability [24,25]. For example, Li et al. [26] used Prussian
blue (PB) as a precursor and PB-doped Fe nanoparticles as a catalyst at a
low carbonization temperature of 450 ◦ C to obtain a high graphitization
degree, resulting in excellent capacity performance (167 mAh g− 1 at 1.0
A g− 1). Yan et al. [27] prepared a porous polymer containing FeCl3, in
situ, on a porous corncob biomass carrier at a pyrolysis temperature of
800 ◦ C and a high-power graphitization of Fe in the pyrolysis process.
K2FeO4 can be used as activating agent and catalyst to improve the
graphitization degree of carbon materials. Some chemical reactions
have been observed between K2FeO4 and carbon materials during the
carbonization process [28].
Therefore, the Fe-doped hierarchical porous carbon derived from PR
material, with a suitable pore structure and high graphitization degree,
is expected to achieve a high capacitive rate for supercapacitor.
In this study, the Fe-doped hierarchical porous carbon derived from
PR is prepared using a one-step strategy and manufactured as an elec­
trode for EDLCs, where PR acts as a raw material, while potassium fer­
rate (K2FeO4) acts as a catalyst and an activating agent. Generally,
K2FeO4 is a new type of non-nitrogen efficient disinfectant, mainly used
for treating drinking [29]. In this study, it is used for synchronous
carbonization and graphitization. The obtained activated PR is a
spherical structure. As the results indicate, the activated PR has not only
a large specific surface area of 1086 m2 g− 1 but also a high degree of
graphitization. Benefiting from its suitable pore structure, the activated
PR exhibits the specific capacitance of 315 F g− 1as a electrode material
at 1.0 A g− 1. Thus, the low-cost PR and green catalytic activator K2FeO4
are considered ideal candidates for future large-scale production.
2. Experimental
2.1. Cured of phenolic resin
Phenolic resin is used as carbon precursor, ethanol as the solvent and
hexamethylenetetramine as the curing agent. These three materials are
first stirred mechanically for 30 min. The mixtures are then pre-cured at
70 ◦ C for 2 h and then successively are heated up to 150 ◦ C for 12 h. At
last, the cured sample is carbonized in N2 atmosphere at 900 ◦ C for 1 h.
2.2. Activation of phenolic resin
First, K2FeO4 (0.2 M) is dissolved into 50 mL deionized water, then,
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add 100 mg PR and stir continuously for 8 h. Finally, the mixed liquor is
transferred to an oven to dry overnight at 100 ◦ C. The solid mixture is
then carbonized in N2 atmosphere at 750, 850, and 950 ◦ C. The samples
collected are denoted as PR-x (x represents the carbonization tempera­
ture, and has values of 750, 850, and 950). After being cooled down to
25 ◦ C, the PR-x samples are washed with deionized water to remove
nanoparticles production, finally, dry in the oven at 80 ◦ C.
2.3. Characterization
The specific surface area and pore size distribution are measured at
77 K by using an ASAP2420 analyzer with N2 adsorption–desorption
isotherms. The PR-x samples are degassed at 523 K for 4 h. The specific
surface area is derived from the Brunauer–Emmett–Teller model and the
pore size distribution is calculated by using the Barrett–Joyner–Halenda
method. Scanning electron microscope (SEM, ZEISS sigma500) and
transmission electron microscope (TEM, JEM-2100) is observed the
morphology of the PR-x samples. The PR-x phases are characterized by
powder X-ray diffraction (XRD). The patterns use Cu Kα radiation (λ =
1.54 Å) with a step-scanning within 10–90◦ (2θ), being measured at 40
mA and 40 KV. The Raman is used to test the graphitization degree of the
Renishaw laser at 532 nm. The surface chemical states are identified by
X-ray photoelectron spectroscopy (XPS, Thermo SCIENTIFIC ESCALAB
250Xi).
2.4. Electrochemical measurements
Electrochemical performance is studied by the electrochemical
working station (GAMRY Interface 1000) in a classical three-electrode
system, where the electrolyte is 6 M KOH solution. The working elec­
trode is prepared by mixing PR-x with a polytetrafluoroethylene binder
and having a weight ratio 95:5 and adding 50 mL deionized water into
the mixture, and then stirring for 6 h. The mixture is then dried in an
oven at 105 ◦ C. The as-prepared electrode material is placed between
two pieces of nickel foams of diameter 14 mm and pressed at 15 MPa for
10 s. After vacuum-drying at 105 ◦ C for 3 h, the electrode material is
soaked in 6 M KOH. Besides, the reference and counter-electrodes are
Hg/HgO and Pt, respectively. Cyclic voltammetry (CV) measurement
and electrochemical impedance spectroscopy (EIS) are performed at a 1
mV s− 1 scan rate with a potential window of − 1.0 to 0 V and a frequency
ranging from 10 MHz to 0.1 MHz. A galvanostatic charge–discharge
(GCD) test is conducted at a current density of 1.0, 2.0, 3.0, 5.0, 8.0, 10,
and 20.0 A g− 1 with a voltage window of − 0.8 to 0 V. The specific
capacitance is calculated from the GCD curves, as follows [30]:
Cm = 2I Δt/ (mΔV)
Where Cm indicates the specific capacitance, I indicates the current
density, Δt indicates the discharge time, ΔV is the voltage window, and
m is the mass of the electrode material.
3. Results and discussion
3.1. Characterization of structure and morphology
The fabrication mechanism of hierarchically Fe-doped porous carbon
via one-step carbonization process utilizing K2FeO4 catalytic and acti­
vation is depicted in Scheme 1. The purchased phenolic resin is
carbonized to form pellets with micropores. The as-obtained spherical
PR is used as carbon precursor, K2FeO4 is used as activation agent to
achieve developed pore. During the carbonization process, K compounds
are reduced to metallic K, and C is oxidized to CO/CO2 and carbonate,
resulting in the developed micro/mesopores. Meanwhile, amorphous Fe
(Fe(OH)3, FeO(OH)) is reduced to Fe3O4, or even metallic Fe. The
reduced Fe serves as the catalyst to expedite the formation of graphitized
carbon and Fe-containing species result in the developed macropores.
X. Dong et al.
Scheme 1. Schematic illustrations of PR precursor via one-step carbonization
process and utilize K2FeO4 as catalytic and activation.
Finally, the obtained carbon materials are washed using deionized water
to remove nanoparticles production. Removing the voids left by these
nanoparticles increase more porosity to the structure of the PR material.
The N2 adsorption–desorption isotherms are exhibited in Fig. 1a.
From Fig. 1a, the PR presents an I-type isotherm based on the IUPAC,
due to the presence of micropores. But PR-x samples exhibit an IV-type
and show a hysteresis hoop. The results indicate that there are abundant
microporous and mesoporous in the PR-x samples. These pores may be
formed in the etching process by KOH. The reactions during carbonized
process are as follows [31]:
KOH + C→K + H2 + K2 CO3 (1)
K2 CO3 → K2 O + CO2 (2)
CO2 + C→CO (3)
It can be seen that the consumption of carbon and gas release (CO2
CO and H2) result in the abundant pores.
PR-850 has a larger specific surface area (SBET, 1086 m2 g− 1) than PR
(212 m2 g− 1). Besides, the total pore volume (Vtotal) is 0.83 cm3 g− 1,
which is favor of increasing the number of adsorptive active sites and
enhancing the ion diffusion [32,33]. As seen in Fig. 1b, PR-x samples
have a much wider PSD within the range 1–7 nm. In addition, the hi­
erarchical porous structure of PR-x, including micro/meso/macropores,
can be realized. Table 1 shows the pore structure characteristic of the
PR-x samples. Table 1 show that K2FeO4 can improve the specific surface
area. Meanwhile, the average pore width (Daverage) of PR-x gradually
increases with the activation temperature [34]. However, the total pore
Fig. 1. PR and PR-x for (a) N2 adsorption–desorption isotherms and (b) pore size distributions.
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Table 1
Structure characteristics of PR and PR-x.
Samples SBET (m2 g− 1) Vtotal (cm3 g− 1) Daver (nm)
PR 212 0.12 2.24
PR-750 581 0.33 2.26
PR-850 1086 0.83 3.07
PR-950 416 0.28 3.19
volume of PR-950 is lower than that of PR-850. This is because of the
destruction of the pore structure at an ultrahigh temperature [].
The XRD and Raman spectra are used to investigate the crystalline
phase and graphitization degree of PR and PR-x. The XRD sample pat­
terns are shown in Fig. 2a. PR shows two broad characteristic peaks at 2θ
of 23.5◦ and 43.8◦ corresponding to (002) and (101), which represent
amorphous carbon [36]. After being activated with K2FeO4, PR-x shows
the diffraction peak at 44.7◦ indexed to (001) plane (JCPDS No.
06–0696), indicating that not only the Fe metal reduction of Fe3+ but
also the Fe metal itself has a high catalytic effect on improving graphi­
tization [37]. Furthermore, the well-defined peaks of PR-x at 2θ 27.4◦ ,
43.2◦ , 65.1◦ , and 82.5◦ are appeared and assigned to (220), (400), (200),
and (211) planes of Fe3O4, respectively [38].
According to the XRD results, the conversion of the Fe species in
carbonization is based on following the equations:
Fe(OH)3 → FeO(OH)→Fe2 O3 (4)
Fe2 O3 + (H2 , C, CO)→Fe3 O4 (5)
Fe3 O4 + (H2 , C, CO)→Fe (6)
Amorphous Fe species (Fe(OH)3, FeO(OH)) are firstly transformed
into Fe2O3 at 673 K (equ (4)), and then are further reduced to Fe3O4 at a
temperature that higher than 973 K by reducing components (equ (5)).
The generation of metallic Fe is due to amorphous carbon further re­
duces Fe3O4 [39,40].
The difference in the graphitization degree of PR-x at different
carbonization temperatures can be further recognized by the Raman
spectrum. As shown in Fig. 2b, two clear peaks are located at ~1350
cm− 1 (D-band) and 1580 cm− 1 (G-band). The D-band represents
graphite structural defects or disordered carbon atoms, while the G-band
corresponds to the in-plane stretching vibration of sp2 hybridization of
carbon atoms. The degree of crystallization or structural graphitization
of carbon materials is usually characterized by the D/G intensity ratio
(ID/IG) [41]. In addition, PR-850 and PR-950 have a 2D band, where 2D
at the 2690 cm− 1 band indicates a higher graphitization degree. The
ID/IG value of PR is 1.66, and after being activated with K2FeO4, the
ID/IG values of PR-750, PR-850, and PR-950 decrease to 1.59, 1.42, and
X. Dong et al.
Fig. 2. PR and PR-x for (a) XRD patterns and (b) Raman spectra.
1.28, respectively. The results show that on the one hand, the graphi­
tization degree increases with temperature, and on the other hand, the
catalytic activation of K2FeO4 improves the graphitization degree to
improve the electronic conductivity. In the PR-950 Raman spectra, the
sharper G and 2D bands clearly demonstrate the creation of few-layer
graphene sheets and the crystalline PR is converted to amorphous car­
bon by high temperature treat [81]. In addition, PR-950 sample has the
smallest ID/IG value (ID/IG = 1.28). The catalytic graphitization of car­
bon follows the dissolution-precipitation mechanism when Fe nano­
particles are used as catalyst. Amorphous carbon is first dissolved in Fe
nanoparticles and then deposited on the surface of the catalyst as
graphite carbon. Under a high temperature of 950 ◦ C, the degree of
graphitization is significantly increased during the intense
dissolution-precipitation process [82]. Although PR-950 (1.28) has a
higher degree of graphitization than PR-850, the less disordered porous
structures result in a lower specific surface area, and therefore, weaken
the catalytic activity. Furthermore, the presence of defects is favorable
for increasing the active sites and ion diffusion. Therefore, carbon ma­
terials with a moderate ID/IG value reflect the balance between graphi­
tization and disorder, and can effectively improve the electrochemical
performance [42,43].
The morphology of the prepared carbon materials is explored by SEM
and EDS, and the pore structure is studied by the HR-TEM technique. PR
exhibits a smooth surface with no mesopores (Fig. 3a). For PR-850
(Fig. 3c), a successful activation is achieved by an abundant porous
structure on the PR structure, due to catalysis of Fe species (Fe, Fe3O4)
during the synchronous carbonization and graphitization process [44,
45]. In addition, an increase in the number of mesopores may improve
the specific surface area, which can offer more electrochemically active
sites. Compared to PR-850, the spherical quantity and diameter of
PR-950 are increased (Fig. 3d). This phenomenon indicates that high
temperatures can lead to nanoparticle agglomeration. In addition, the
agglomeration substantially reduces the exposure of active sites and
catalytic activity [35]. From the EDS mapping picture of PR-850
(Fig. 3e–h), the continuous distribution of the C element indicates a
carbon layer structure, the discrete distribution of Fe and O elements,
indicating that the Fe3O4 nanoparticles appear on the PR-850. In
particular, the mass fraction of the Fe element in PR-850 is 20.28%,
indicating that K2FeO4 successfully activates the PR material (Fig. 3i).
Furthermore, the TEM image of PR-850 (Fig. 4a) indicates the presence
of a graphitic structure. A high-resolution TEM image (Fig. 4b) of
PR-850 shows a clear lattice fringe of Fe3O4 attributed to the (220) (d =
0.30 nm) plane. Besides, the lattice spacing is 0.34 nm, which belongs to
the (002) plane of graphitic carbon.
To further elucidate the composition of the surface element and the
crystalline states of PR-850, an XPS measurement is performed, as
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illustrated in Fig. 5a–d. The XPS survey spectra results (Fig. 5a) present
the C, O, and Fe elements of PR-850, which are consistent with the EDS
analysis results. Fig. 5b shows the PR-850C1 spectrum, with four peaks
centered at 284.5, 288.9, 293.3, and 295.6 eV, matching C=C, COOH,
C=O, and O=C-O, respectively [46]. The fitting result shows that there
is a sharp carbon (C=C) peak at 284.5 eV, which demonstrates the
graphitic form of carbon in the PR-850 sample [47]. As shown in Fig. 5c,
the PR-850 O1 spectrum exhibits three peaks at 529.9, 531.4, and 532.5
eV, which are assigned to Fe-O, Fe-O-C, and C-OH, respectively [48,49].
The peak at 529.9 eV is a signal of Fe-O bond, indicating the presence of
Fe3O4 in the PR-850 [50]. The Fe-O-C bond is generally observed in
small particles with low oxygen coordination at the defect sites and is
related to pseudo-capacitance [51]. Furthermore, the Fe 2p spectrum
can be deconvoluted into four peaks, corresponding to Fe3O4 2p3/2
(711.5 eV), Fe 2p3/2 satellite (718.9 eV), Fe3O4 2p1/2 (724.9 eV), and Fe
2p1/2 satellite (733.5 eV) [52], as shown in Fig. 5d. The proportion of
Fe3O4 and Fe is 82.2% and 17.8%. The XPS results indicate that the
polar functional groups contribute to the formation of a porous graphitic
structure [53].
The electrochemical properties of the as-prepared samples with
different temperatures are measured using a three-electrode device, and
the CV parameters are found to lie within a potential range of − 1.0 to 0
V. As shown in Fig. 6a, the PR is rectangular, which demonstrates its
electrochemical dual-layer capacitance. After being activated with
K2FeO4, each curve exhibits a reduction peak and an oxidation peak,
indicating their pseudo-capacitive characteristic. Specifically, the
oxidation peak at − 0.65 V is attributable to Fe(OH)2 formation, the Fe
(OH)/FeOOH redox couple may be represented, while the other reduc­
tion peak is attributable to Fe3O4 at − 0.95 V. Thus, the following re­
actions of iron oxidation and reduction occur [54]:
Re / Ox : Fe3 O4 + 4H2 O + 2e− ⇄3Fe(OH)2 + 2OH−
Re / Ox : Fe(OH)2 + 2OH− ⇄FeOOH + H2 O + 2e−
The CV measurements of the PR-x composite indicate a synergistic
combination of EDLCs and a pseudo-capacitive behavior. Furthermore,
PR-850 has a larger area envelope than PR-750 and PR-950, indicating a
higher specific capacitance. This is attributed to an appropriate degree
of graphitization and a uniform porous structure, which enhances the
conductivity and improves the efficiency of charge transportation.
Increasing the carbonization temperature to 950 ◦ C will decrease the
electrochemical performance, probably due to the agglomeration of
Fe3O4 in the PR-950 surface texture and then decreae the active sites.
These results are consistent with those obtained for SEM measurements
conducted for PR-950.
Fig. 6b shows the GCD properties of PR, PR-750, PR-850, and PR-
X. Dong et al. Ceramics International 47 (2021) 5998–6009

Fig. 3. SEM images for (a) PR, (b) PR-750, (c) PR-850, and (d) PR-950. High-angle SEM image of (e) PR-850 with EDS elemental mapping of (f) C, (g) O, and (h),
(i) Fe.

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Fig. 4. HR-TEM images of PR-850.

Fig. 5. High-resolution XPS spectra for PR-850: (a) XPS survey, (b) C1s, (c) O1s, and (d) Fe 2p.

950, the capacitances are calculated as 88, 201, 315, and 109 F g− 1 at
1.0 A g− 1, respectively (Table 2). The samples display a nonsymmetrical
shape, with the discharging time exceeding the charging time, which
indicates an appropriate pseudo-capacitive behavior. In addition, all the
GCD curves are close to linear, indicating that the internal resistance of
the electrode system is very small [55]. Owing to the suitable
mesoporous structure, PR-850 exhibits the highest specific capacitance
performance at 315 F g− 1. The increase in the number of mesopores can
substantially enhance the efficient diffusion of electrode in electrolyte.
Moreover, the higher specific surface area can offer active sites for the
adsorption of electrolyte ions, thus improving their capacitive perfor­
mance [56,57]. The PR-850 GCD curves during the charging and

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Fig. 6. a) CV profiles at 1 mV s− 1, b) GCD curves at 1.0 A g− 1, c) GCD curves at different current densities of PR-850, d) specific capacitance versus current density, e)
cyclability of PR-x.

discharging processes at different current densities ranging from 1.0 to As shown in Fig. 6d, the specific capacitance of PR-850 decreases
20 A g− 1 are further investigated and presented in Fig. 6c. The typical with the current density. For example, the specific capacitance is 315 F
asymmetrical triangular shape can be maintained even at 20 A g− 1, g− 1 at 1 A g− 1, and the specific capacitance is 230 F g− 1 when the current
which indicates the perfect kinetics and reversibility [58]. density is 20 A g− 1. This result mainly dues to the rapid charge and

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Table 2 Table 4
Specific capacitance of PR and PR-x at a cur­ Comparison of electrochemical performance of different Fe activation methods.
rent density of 1.0 A g− 1 Sources Specific Cyclability Electrolyte Ref.
Sample C (F g− 1) capacitance

PR 88 Graphene, FeSO4 264 F g− 1 at 2.5 95.7% after 2 M KOH [64]

PR-750 201 A g− 1 5000 cycles
PR-850 315 Graphene, Fe 274 F g− 1 at 1.0 75.3% after 2 M KOH [65]
PR-950 109 (CO)5 A g− 1 100,000 cycles
Graphene, FeCl3 81.3F g− 1 at 1.0 – 0.5 M [66]
A g− 1 Na2SO4
discharge rates, resulting in increased resistance, and it is difficult for Graphene, Fe 268.4 F g− 1 at 95.79% after 1 M KOH [67]
(NO3)3 2.0 A g− 1 2000 cycles
the electrolyte ions diffusion [59]. Thus, the internal active sites cannot
Graphene, FeSO4 313.6 F g− 1 at 88.2% after 6 M KOH [68]
effectively maintain adsorption/desorption charges, resulting in 0.5 A g− 1 2000 cycles
decreased specific capacitance [60]. However, the capacitance is still ZnDTO, 128 F g− 1 at 0.5 87.1% after 1 M H2SO4 [69]
maintained at 73%, even at 20 A g− 1. As shown in Table 3, there is a Hemoglo-bin A g− 1 5000 cycles
Graphene, iron 194.44F g− 1 at 97.5% after 2 M KOH [70]
specific capacitance at various current densities. The composite material
foil 10 A g− 1 2000 cycles
exhibits high specific capacitance and the following characteristics: (ⅰ) PAN, FeCl3 237 F g− 1 at 10 – 6 M KOH [71]
the higher specific surface area is favorable for ion adsorption, (ⅱ) the A g− 1
uniform spherical structure can shorten the diffusion pathway between Chitosan, K2FeO4 212 F g− 1 at 20 94.3% after 6 M KOH [72]
the electrode and ions and promote electron transfer [61,62]. A g− 1 1000 cycles
C60, ferrocenylp- 216.1 F g− 1 at 6 M KOH [73]
In the practical application of electrode materials, a long cycle life is
–
yrrolidine 20 A g− 1
an important issue. To study the electrochemical stability of PR-x, the Phenolic resin, 315 F g− 1 at 1.0 96.3% after 6 M KOH This
GCD cycle is tested at 1 A g− 1, as shown in Fig. 6e. All profiles’ specific K2FeO4 A g− 1 10,000 cycles work
capacitance decreases as the number of cycles increases. The reactions of 261 F g− 1 at 10
intercalation-deintercalation and adsorption-desorption between the A g− 1
230 F g− 1 at 20
electrolyte and electrode material cause stress and induce the electrode A g− 1
structure unstable, resulting in a capacitance value decrease [54].
PR-850 exhibits a remarkably enhanced performance by retaining a
capacitance of 96.3% after 10,000 cycles, compared to its initial value, showed the percentage of capacitive and diffusive contribution of PR-
while the specific capacitance retention of PR-750 and PR-950 is 74.2% 850 electrode for CV curves at 1, 5, 10, 20, and 30 mV s− 1, and it can
and 50.5%, respectively, which show worse cyclability than that of be discovered that capacitive contribution of EDLC is 50.5, 61.1, 65.8,
PR-850. The superior stability results of PR-850 increase the ionic 76.2, and 84.8%, indicating that the double layer dominates the
accessibility of the electrode/electrolyte interface with cycle perfor­ capacitive of the PR-850 electrode. As displayed in Fig. 7f, the PR-850
mance. The excellent cycle stability of PR-850 is mainly owed to the electrode has a small diffusion contribution because of faradaic redox
homogeneous distribution of the pore, which can shorten the diffusion reaction (equ.(7)), leading to the extremely improve the specific
distance of the electrode ions, and then accelerate the Faradaic redox capacitance. Furthermore, it is noticeable that the PR-850 electrode
reaction and ensure a high specific capacitance [63]. Table 4 compares capacitive contribution increases with the increasing scan rates in Fig. 7f
the activation and electrochemical properties of different Fe activation and achieve to 84.8% at 30 mV s− 1, indicating the remarkable charac­
methods. It can be clearly observed that the K2FeO4 activation method teristics of the PR-850 electrode.
exhibits the best specific capacitance and good cycle retention. A more accurate analysis of the internal resistance of the electrode
For further expounding the capacitive behavior, dynamic is carried and dynamic ion diffusion is performed using EIS. The Nyquist plots of
out based on CV curve. In general, the capacitive relates to the ion all samples and the homologous equivalent electrical circuit (the inset)
adsorption-desorption and diffusion-controlled charge storage associ­ are shown in Fig. 8a. In the Nyquist plots, the semicircle take on the X-
ates with the faradaic redox reaction. According to Dunn method [74], axis represents the equivalent series resistance (Rs), resulting from the
the combination of capacitive contributions and diffusion-controlled can internal resistance which represent the length of transfer path between
be distinguished through analyzing the following equation: the ion and electron [75]. The semicircle diameter indicates the
charge-transfer resistance (Rct), which has values of 1.75, 1.21, 1.12,
i(V) = k1v + k2v1/2 and 1.67Ω for PR, PR-750, PR-850, and PR-950, respectively. The
Where k1v denotes capacitive control, k2v1/2 represents the diffusion straight line at low frequency is related to the diffusion impedance of K+.
control. For analysis purposes, the equation is reorganized as follows: The K+ diffusivity (DK+) and the exchange current density (J0) can be
calculated using the following equations [76,77]:
i(V)/ v1/2 = k1v1/2+ k2
R2 T 2
DK+ =
By plotting v1/2 versus i(V)/v1/2, k1 and k2 can be acquired from the σ
2A2 n4 F4 c2 2
slope and intercept of the fitting straight line. Thus the capacitive
contribution and diffusion contribution can be calculated. Fig. 7a–f J0 =
RT
n F Rct

Table 3 Where R represents the gas constant (8.314 J mol− 1 K− 1), T represents
Specific capacitance of PR and PR-x at different current densities. the room temperature in our experiment, A is the electrode material
Sample Electric current density (A g− 1) C (F g− 1) surface area (0.785 × 10− 4 m2), n is the number of electrons involved, F
is the Faraday constant (9.65 × 10− 4 C mol− 1), C is the concentration of
PR-850 1 315
2 309 K+ (6 × 103 mol m3), and σ is the Warburg factor which is related to Zre
3 302 obtained from the slope of the lines in Fig. 8b. Table 5 lists the values of
5 290 the Rct, the K+ ion diffusivity, and the exchange current density (J0) for
8 271 the PR-x. In general, Rct reflects the electrochemical reaction activity at
10 261
20 230
the interface and electron/ion conductivity. The PR-850 sample shows

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X. Dong et al. Ceramics International 47 (2021) 5998–6009

Fig. 7. Contribution ration of the capacitive and diffusion control of the PR-850 electrode at the scan rate of a) 1 mV s− 1, b) 5 mV s− 1, c) 10 mV s− 1, d) 20 mV s− 1,
and e) 30 mV s− 1. f) Capacitive and diffusion contribution of the PR-850 electrode at the scan rate.

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X. Dong et al. Ceramics International 47 (2021) 5998–6009

1/2
Fig. 8. a)Nyquist plots, inset: equivalent electrical circuit, b)Nyquist graph of Zre plotted against ω− of PR-x.

Acknowledgments
Table 5
Charge-transfer resistance (Rct) K+ ion diffusivity (DK+) and the exchange cur­
This work was financially supported by the Science and Technology
rent density (J0) of PR and PR-x.
Program of Hebei Academy of Sciences (20705, 20706 and 201503).
Sample Value

Rct (Ω) Dk+(cm2 s− 1) J0 (A cm− 2) References

PR 1.75 0.887 × 10− 15 1.46 × 10− 2

PR-750 1.21 6.77 × 10− 15 2.12 × 10− 2

PR-850 1.12 9.49 × 10− 15 2.29 × 10−
PR-950 1.67 1.35 × 10− 15 1.54 × 10−
low values Rct (Rct = 1.12Ω) and the highest K+ diffusion coefficient
(Dk+ = 9.49 × 10− 15 cm2 s− 1), suggesting that it displays the best
electrochemical performance because of its interconnection structure
shortening the ion transmission channel [78,79]. The exchange current
density indicates the rates of both oxidation and reduction at equilib­
rium: with the increase of exchange current density, the reaction rate of
intercalation/de-intercalation is faster [80]. In summary, PR-850 shows
a low Rct, high Dk+, and J0, which involve high capacitor performance.
Besides, at a higher temperature, the agglomerate of iron may hinder the
charge transfer, yielding lower electrochemical performance.
4. Conclusion
Hierarchical and graphitized porous carbons with a wide pore dis­
tribution are successfully prepared at 850 ◦ C activation temperature of
carbon derived from PR, using a low-cost and efficient strategy. Mean­
while, K2FeO4 is used as an activation agent and catalyst for asynchro­
nous graphitization and carbonization. The obtained mecroporous
carbon with a higher total pore volume (0.83 cm3 g− 1), lager specific
surface area (1086 m2 g− 1), and appropriate graphitization degree (ID/
IG = 1.42) exhibits a perfect charge storage capacity of 315 F g− 1 at 1.0A
g− 1 under a three-electrode system in the KOH electrolyte. Approxi­
mately 73% of the initial capacitance is retained under a current density
of 20 A g− 1. In addition, 96.3% capacitance retention is obtained after
long-time charge–discharge cycles (10,000 cycles). Hence, the PR-850
as component for advanced electrode materials with excellent capaci­
tive performance can provide a good choice for designing high perfor­
mance for supercapacitors.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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