Carbon: Sciencedirect
Carbon: Sciencedirect
Carbon: Sciencedirect
Carbon
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a r t i c l e i n f o a b s t r a c t
Article history: Developing low-cost and highly efficient electrochemical materials toward supercapacitor applications is
Received 25 November 2019 crucial for energy conversion systems. In the present work, dual S, N-doped activated CoFe2O4@CNTs was
Received in revised form successfully synthesized using carbamide and sodium thiosulfate as N and S precursors and CNTs as a
11 February 2020
substrate via a convenient two-step hydrothermal activation procedure, which presents good perfor-
Accepted 17 February 2020
Available online 18 February 2020
mance for supercapacitor. The characterization results indicate that activity S and N atoms can be suc-
cessfully doped into the framework of CoFe2O4@CNTs with little impact on the inner morphology and
structure. However, the electrode material of N2S1eCoFe2O4@CNTs exhibits a superior electrochemical
Keywords:
CoFe2O4/CNTs
performance with 1053.60 F g1 at 1 A g1 in KOH electrolyte due to synergistic effects between spinel-
S type metal oxides, heteroatoms and sp2 lattice of graphitic carbon. In addition to high energy and power
N-doped densities, the capacitance retention of charging-discharging reaches 93.15% at a current density of
Binder-free 30 A g1 after 5000 cycles, exhibiting an outstanding cycle stability and potential lifetime in an alkaline
Electrode material electrolyte.
Supercapacitor © 2020 Elsevier Ltd. All rights reserved.
1. Introduction has provoked great interest in recent years for use as electrodes
in SCs, due to its high specific surface area (SSA), low cost, high
In modern society, pursuing more powerful electric power and electrical conductivity, excellent cyclic stability, wide operating
green sustainable energy resources have become global challenges temperature and superior mechanical [9e11]. So far, shaped
with the increasing depletion of fossil fuel and the serious envi- carbon nanomaterials (SCNMs), such as graphene, carbon fibres
ronmental pollution [1e4]. In the circumstance, electrochemical (CF), carbon sphere (CS) and carbon nanotubes (CNTs), have been
supercapacitors (SCs) are highly important energy storage systems widely explored as alternative supports due to unavailability of
with long cycle life, rapid charge-discharge rate, large power den- active site on some supports coupled with the poor interactions
sity and high rate capacity compared with batteries, thus has again between reactants and active sites [12]. In the case of CNTs, one-
attracted significant interest in the past a few years in energy dimensional allotrope of carbon, has notably shown short ion
storage devices, such as emergency power supplies, pulse energy diffusion distance, larger surface area and high interface areas,
for laser weapons, vehicle starting power and short-term power which is helpful for fast electron transport and tuneable when
boosters,etc [5e8]. employed as support.
Carbon, one of the most promising energy storage materials, Recently, the spinel-type metal oxides nanoparticles (NPs)
have been introduced as the supported pseudocapacitive mate-
rials, showing substantial enhancement in capacitance storage
performance due to their high energy density at a high charge-
* Corresponding author. 29 Guangrong dao, hongqiao District, Tianjin, 300130,
China.
discharge rate, robustness at the higher potential and reversible
E-mail address: mengfanbin8832@163.com (F. Meng). and rapid Faradaic surface reactions [5,13]. Further, carbons
https://doi.org/10.1016/j.carbon.2020.02.050
0008-6223/© 2020 Elsevier Ltd. All rights reserved.
Y. Li et al. / Carbon 162 (2020) 124e135 125
doped by heteroatoms (e.g., N, S, and so on) are considered as 2.3. Synthesis of NxSy-CoFe2O4@CNTs
one of the promising candidates for electrode materials, since C
atom in the sp2 lattice of graphitic carbon substituted by het- In order to obtain the N1S1eCoFe2O4@CNTs, 3.723g of
eroatoms can change the electronic arrangement and tailor their Na2S2O3$5H2O and 0.3003g CH4N2O with different quality were
electron donor property effectively [14e19]. In addition, dual dissolved in 40 ml of ultrapure water, followed by being added
heteroatom-doped with different electronegativity can further 0.12g prepared CoFe2O4@CNTs powders and stirred for 2h. Af-
improve the electrochemical performance as synergistic effects terwards, the mixture was transferred to a 100 ml Teflon-lined
are able to create unique electronic coupling structure on the sp2 stainless steel autoclave, sealed tightly, and heated at 180 C
hybridized carbon. Especially, sulfur and nitrogen with strong for 16 h. Finally, the obtained black hydrogel was subsequently
synergistic effects have successfully attracted extensive attention washed with distilled water for several times, filtered and dried
due to their superior ability to replace carbon atoms [20e23]. to obtain N1S1eCoFe2O4@CNTs nanocomposites.
Inspired by these factors, herein, we have developed the N Similarly, the samples were named based on the molar ratio of
and S co-doped into the framework of CoFe2O4@CNTs as an nitrogen and sulfur, such as N2S1eCoFe2O4@CNTs, N3S1eCoFe2O4
efficient and durable electrode material for supercapacitor with @CNTs, N1S2eCoFe2O4@CNTs and so on.
power densities and high capacitance retention due to the
cooperative effect between spinel-type metal oxides, hetero-
atoms and sp2 lattice of graphitic carbon. The framework of
binder-free CoFe2O4@CNTs is fabricated by the hydrothermal 2.4. Characterization
activation procedure, followed by annealing in argon atmo-
spheres. It has been found that the spinel-type CoFe2O4 were The X-ray diffraction (XRD, CuKa, l ¼ 0.15406 Å, Bruker D8
deposited on the surface of CNTs uniform and extensive without Advance) patterns were characterized at a scanning speed of 6 /
surfactant, while a negligible and loose CoFe2O4 forms detach- min in the 2 q range from 10 to 90 . Raman spectra of the sam-
ment the substrate. Subsequently, the N and S doping ratio, level ples were acquired by a DXR Microscope Raman spectrometer. The
and form in the CoFe2O4@CNTs as secondary template can be chemical vibration mode was determined by Fourier transform
readily tuned by a simple control of molar ratio of reactants. As infrared spectroscopy (FTIR) (Bruker, Vector 22, Germany) in the
prepared NxSy-CoFe2O4@CNTs exhibits the superior enhanced range of 400 cm1 to 4000 cm1 by means of KBr disc technique.
stability and bifunctional activity than the CoFe2O4@CNTs, Surface functional groups and bonding characterization were
CoFe2O4, CNTs and some other materials [24e26]. As a result, the characterized by X-ray photoelectron spectroscopy (XPS,
NxSy-CoFe2O4@CNTs nanocomposites are one of the most suitable ESCALAB-250Xi, America) system using monochromatized AI-Ka
electrode materials with desirable specific capacitance, X-ray source. The morphology observation and crystalline struc-
outstanding stability and excellent redox supercapacitive per- ture of the as-obtained products were investigated by field
formances, indicating it a promising electrode for supercapacitor. emission scanning electron microscopy (FESEM, NovaNano-
SEM450, American FEI Company) and transmission electron mi-
croscopy (TEM, JEM-2010FEF, Japan JEOL), respectively. The
2. Experimental
correlative elemental analysis was performed with an energy
dispersive X-ray spectroscope (EDS) attached to the FESEM. The
2.1. Materials
magnetic properties were investigated by vibrating sample
magnetometer (VSM, 7407, America LakeShore) running under
Cobalt acetate (C4H6CoO4$4H2O, purity: 99.5%), ferric acetate
20,000 Oe field, respectively. The thermal gravimetric analysis
(C4H7FeO5, purity: 98.5%), sodium thiosulfate (Na2S2O3$5H2O, pu-
(TGA) curves were obtained using instrument of LLCSDTQ-600
rity: 99.0%), carbamide (CH4N2O, purity: 99.95%), sodium borohy-
(America TA Instruments-water) at a heating rate of 5 C/min
dride (NaBH4, purity: 98%) and sodium dodecylbenzenesulphonate
from room temperature to 1000 C in flowing air.
(SDBS, C18H29NaO3S, purity: 99.5%) were supplied by Aladdin
(China). All reagents materials were analytical-grade and used as
received without further purification. The CNTs (carbon content:
99.8%) were purchased from Cyberelectrochemical materials Co. Ltd
2.5. Electrochemical tests
(Tianjin, China).
All the electrochemical studies were evaluated employing a
2.2. Synthesis of activated CNTs and binder-free CoFe2O4@CNTs three-electrode system by an electrochemical workstation
(CHI660E, Chenhua, shanghai). The working electrodes were
The preparation procedures of CoFe2O4@CNTs and NxSy- fabricated as follows: a slurry containing the carbon black, pol-
CoFe2O4@CNTs are schematically illustrated in Fig. 1. In brief, 0.3g of yfluortetraethylene (PTFE) and active materials with a weight
CNTs were mixed in the SDBS solution (30 wt%; 50 mL), stirred for ratio of 1:1:8 was well mixed, and then was pressed on nickel
2 h, sonicated for 40 min, allowed to stand for 24 h, filtered, washed foams (1.0 cm 1.0 cm) and dried at 50 C for 48 h in vacuum.
and dried in a mild condition. Next, 0.382g of C4H7FeO5 and 0.249g The mass loading of active materials on each current collector
C4H6CoO4$4H2O were dissolved in 40 ml of ultrapure water. After was 3 mg. The electrochemical measurements were carried out in
thorough mixing, 0.12 g pretreated active CNTs were added to the 1 M KOH aqueous solution with a three-electrode system where
solution by continuously stirring for 1h under a magnetic stirrer, the modified nickel foam, platinum foil electrode and a standard
followed by being added NaBH4 solution (20 wt%; 5 mL) and stirred Hg/HgO electrode acted as working, counter and reference elec-
for 2h. After that, the mixture was transferred to a 100 ml Teflon- trode, respectively. Cyclic voltammetry (CV), galvanostatic
lined stainless steel autoclave, sealed tightly, and heated at 150 C charge-discharge (GCD) measurements and electrochemical
for 12 h. Then, the black precipitate was collected after washed and impedance spectroscopy (EIS, frequency ranging from 0.01 KHz
vacuum dried. Subsequently, the CoFe2O4@CNTs nanocomposites to 100 kHz at 5 mV amplitude) were investigated by the potential
were obtained by calcining the collected powders in shielding gas range of negative 1-0.1V. The corresponding specific capacitance
(Ar) atmosphere at 700 C for 2 h in a muffle furnace. was calculated based on the following equation:
126 Y. Li et al. / Carbon 162 (2020) 124e135
Fig. 1. Schematic illustrations of the preparation of CoFe2O4@CNTs and NxSy-CoFe2O4@CNTs nanocomposites. (a) CNTs were mixed in the SDBS solution and dried to obtain active
CNTs. (bec) fabrication of the CoFe2O4@CNTs nanocomposites by hydrothermal activation and high-temperature sintering procedure. (ced) the preparation process and structure of
NxSy-CoFe2O4@CNTs nanocomposites. . (A colour version of this figure can be viewed online.)
Fig. 2. XRD diffraction patterns of (a) CNTs, CoFe2O4, CoFe2O4@CNTs and (b) NxSy-CoFe2O4@CNTs samples. (c) Raman spectra of the as-prepared samples (200 cm1e2000 cm1). (d)
FTIR patterns of the as-prepared samples (400 cm1e4000 cm1). (A colour version of this figure can be viewed online.)
corresponded to the well-documented D and G bands of graphitic ratio of nitrogen and sulfur, representing the enhanced disorder
carbon, respectively. The prominent D-band is related to the vi- and defects with increasing ratios, which illustrates C atom in
bration of sp3 carbon atoms stemming from the degree of lattice graphitic carbon substituted by heteroatoms [31].
disorder and defects, while the G peaks is ascribed to the in-plane The constitutions of spinel structure and chemical properties of
stretching mode of sp2 carbon domains in a graphitic 2D hexagonal as-obtained CoFe2O4@CNTs and NxSy-CoFe2O4@CNTs were inves-
lattice. Generally, the integral intensity ratios of D-band to G-band tigated by FTIR spectra. As shown in Fig. 2(d), the strong peak at
(ID/IG) are usually used to evaluate the disorder degree of defect about 3440 cm1 in all as-obtained samples is assigned to the
density [28,29]. Furthermore, both NxSy-CoFe2O4@CNTs and typical eOH stretching vibration, which can result from surface
CoFe2O4 exhibit a series of small peaks at 288 cm1, 458 cm1 and absorption of water molecules. In addition, a characteristic peak of
665 cm1, corresponding to the characteristic peaks of metal ox- CNTs, CoFe2O4@CNTs and NxSy-CoFe2O4@CNTs at 1627 cm1 cor-
ides. In addition, there is also a distinct peak at 364 cm1 in all NxSy- responds to the typical bending vibrations of C]C, indicating the
CoFe2O4@CNTs samples, which is caused by the metal polysulfides graphitization of the as-prepared samples [32]. Furthermore, there
[27,30]. Compared with the CNTs, the ID/IG ratio of the is a strong absorption peak at about 585 cm1 of CoFe2O4,
CoFe2O4@CNTs varies from 0.391 to 0.804, indicating the great CoFe2O4@CNTs and NxSy-CoFe2O4@CNTs, corresponding to the
disordering of the crystal structure, which may be caused by the typical metal-oxygen bond in spinel type crystal structure. Notably,
introduction of Co and Fe inserted into the inside cavity with it the FTIR spectra of NxSy-CoFe2O4@CNTs also exhibit distinct ab-
deposited on the surface of the CNTs simultaneously. In addition, sorption peaks at 425 cm1, 1012 cm1, 1139 cm1 and 1383 cm1,
the values of intensities ratios of ID/IG are increased from 0.899, which are attributed to the CoS2 & FeS2, CeN stretching vibrations,
0.959 and 0.977 for N1S1eCoFe2O4@CNTs, N2S1eCoFe2O4@CNTs CeO deformation vibrations and CeS bending vibrations, respec-
and N1S2eCoFe2O4@CNTs after the doping of the different molar tively. The main unconspicuous band corresponds to the CeO
128 Y. Li et al. / Carbon 162 (2020) 124e135
Fig. 3. XPS spectra of N1S2eCoFe2O4@CNTs nanocomposites. (a) survey scan, (b,c,d,e,f) C 1s scan, Fe 2p scan, Co 2p scan, N 1s scan and S 2p scan. (A colour version of this figure can
be viewed online.)
deformation vibrations due to the residues of the incompletely atom in graphitic carbon bond with heteroatoms, indicating suc-
removed oxygen-containing functional groups of CNTs and the cessful coating surface of N and S on the CoFe2O4@CNTs.
incorporation of physicochemically adsorbed oxygen. Moreover, The bonding characteristics and functional groups of the
the characterization data of CeN and CeS have demonstrated C N1S2eCoFe2O4@CNTs were evaluated by XPS, which are shown in
Y. Li et al. / Carbon 162 (2020) 124e135 129
Fig. 4. FESEM and HRTEM images of samples. SEM images of (a) pristine CNTs, (b,c), (d) N1S1eCoFe2O4@CNTs at low magnification and high magnification. (e,f) HRTEM images of
N1S1eCoFe2O4@CNTs. (A colour version of this figure can be viewed online.)
Table S1 and Fig. 3. In brief, the spectra distinctly show the peaks of pyridinic-N doped in the CoFe2O4@CNTs, respectively [39,40].
C 1s, Fe 2p, Co 2p, N 1s and S 2p, which confirms the successful Additionally, the high-resolution S 2p can be assigned to five peaks
formation of CoFe2O4 nanoparticles on surface of CNTs and in- centered at 161.9 eV, 162.8 eV, 163.4 eV, 164.8 eV and 168.8 eV,
dicates the successful N and S doping with the hydrothermal associated with SeCo, SeFe, 2p3/2 CeSeC, 2p1/2 CeSeC and C-SOX-
method. The spectrum for a C 1s can be deconvoluted into three C, respectively, and further convinced the successful doping of N
peaks located at 284.7 eV, 285.8 eV and 287.4 eV, representing for and S atoms into the CoFe2O4@CNTs framework [41,42].
the sp2 CeC, CeS & CeO and CeN &C]O [33]. For the Fe 2p spectra, The morphology and microstructure features of the CNTs,
it can be divided into several peaks at 706.4 eV and 707.2 eV within CoFe2O4@CNTs and NxSy-CoFe2O4@CNTs were characterized by
Fe 2p3/2 region, and 718.3 eV, 720.5 eV and 711.3 eV within Fe 2p1/2 FESEM and FETEM in Fig. 4 and Fig. S1, respectively. As can be seen
and satellite peaks regions, which reveals the formation of CoFe2O4 from Fig. 4(a), the as-spun CNTs show 1D fibrous morphologies
[34e36]. Moreover, the deconvolution of Co 2p spectra can be with an average diameter of 150 nm and smooth surface. As shown
deconvoluted into binding energies of 779.6 eV, 780.2 eV, 782.3 eV in Fig. 4(b), the N1S1eCoFe2O4@CNTs inherits the continuously
and 785.6 eV within Co 2p3/2 and satellite peaks regions, and fibrous morphology of the as-spun CNTs with smooth surface and
794.6 eV, 795.5 eV, 798.3 eV and 803.6 eV within Co 2p1/2 and shows successful coating surface of N and S on the CoFe2O4@CNTs
satellite peaks regions [37,38]. In the N 1s spectra, the four fitted with slight detached CoFe2O4. In Fig. 4(c) and (d), the images of
peaks are assigned at 398.5 eV, 400.4 eV, 401.3 eV and 404.8 eV, N1S1eCoFe2O4@CNTs demonstrate a relatively muddledness and
indicating pyridinic-N, pyrrolic-N, graphitic-N and oxidized roughness appearance with several ultra-quantity small-sized
130 Y. Li et al. / Carbon 162 (2020) 124e135
Fig. 5. Elemental mapping images of N1S1eCoFe2O4@CNTs. (A colour version of this figure can be viewed online.)
Fig. 7. Electrochemical performance of the CoFe2O4@CNTs nanocomposites electrodes for supercapacitors. (a) CV curves at different scan rates and (b) GCD curves at different
current densities. (c,d) EIS spectra of as-prepared samples. (e) Corresponding specific capacitance as a function of current density. (f) cyclic stability of CoFe2O4@CNTs at a current
density of 20 A g1 for 5000 cycles. (A colour version of this figure can be viewed online.)
decrease of saturation magnetization for higher concentration of N, The electrochemical performances of CoFe2O4@CNTs were per-
S heteroatoms may be attributed to the formation of second phase, formed by cyclic voltammetry (CV) and galvanostatic charge-
which decreases the resultant magnetic moment and thereby the discharge (GCD) measurements at different scan rates
magnetzation [47]. (10 mV s1-200 mV s1) using 1 M KOH aqueous solution as
132 Y. Li et al. / Carbon 162 (2020) 124e135
Fig. 8. Electrochemical performance of the NxSy-CoFe2O4@CNTs nanocomposites electrodes for supercapacitors. (a) CV curves of N2S1eCoFe2O4@CNTs at different scan rates. (b) CV
curves at 100 mV s1 for CNTs, CoFe2O4, CoFe2O4@CNTs, N1S1eCoFe2O4@CNTs, N2S1eCoFe2O4@CNTs and N1S2eCoFe2O4@CNTs, respectively. (c) GCD curves of N2S1eCoFe2O4@CNTs
Y. Li et al. / Carbon 162 (2020) 124e135 133
electrolyte in a three-electrode system. As shown in Fig. 7(a), the CV symmetric charge-discharge curves were observed at all current
curve of CoFe2O4@CNTs exhibits nonrectangular-like shape, which densities, exhibiting excellent electrochemical capacitive property
may be result from the cooperation of pseudo-capacitance nature and outstanding electrochemical reversibility [54]. The GCD curves
and double-layer capacitance behavior. In addition, all the curves of all the samples are compared at a current density of 1 A g1 in
exhibit a dominant pair of redox peaks, indicating an obviously Fig. 8(d), indicating that the N1S2eCoFe2O4@CNTs electrode displays
faradaic redox reaction behavior occurring in the working process, improved capacitive performance, which is in accordance with that
which are the characteristics of the extraction and insertion of of CV curves.
protons, respectively [48]. The corresponding mechanism can be EIS tests were conducted to get the intrinsic mechanism of the as-
interpreted based on the following equation: prepared samples, as shown in Fig. 8(e) and Fig. S3(e). In addition,
Table S2 summarizes the specific capacitance (Cm), energy density (E),
CoFe2 O4 þ OH4CoOOH þ 2FeOOH þ e intrinsic ohmic resistance (Rs) and charge transfer resistance (Rct) of
all the electrode materials. The charge transfer resistance (Rct) of the
CoOOH þ OH4CoO2 þ H2 O þ e nanohybrid electrodes decrease slightly from 14.84 U to 2.46 U for
CNTs and N1S2eCoFe2O4@CNTs, demonstrating the enhanced elec-
Moreover, the area surrounded magnifies and remains a ho- trochemical performance with the CoFe2O4 and N, S co-doped into the
mologous shape with voltage sweep rate increasing, which means framework of CNTs, which is benefit from the combination of fast ion
the enhancement of the capacitance value and an excellent rate diffusion as well as low electron-transfer resistance [54]. Moreover,
capability with reversible and fast capacitive characteristics at high the slope of the straight line at low frequency is significantly steeper
sweep rate. The galvanostatic charge-discharge curves of for the N1S2eCoFe2O4@CNTs electrode than for the other electrodes,
CoFe2O4@CNTs at different current densities are shown in Fig. 7(b). clearly indicating a high electrolyte diffusion rate [55]. As shown in
Apparently, every discharge time is approximate to the charging the specific capacitances in Fig. 8(f), Fig. S3(f) and Table S3, the
time of GCD curves even at different current densities among N1S2eCoFe2O4@CNTs exhibits a high capacitance of 1213 F g1,
1 A g1 to 8 A g1, exhibiting no obvious ohmic drop for all dis- 1119 F g1, 1030 F g1, 978 F g1, 936 F g1, 913 F g1 and 900 F g1 at
charging curves [49]. 0.5 A g1, 1 A g1, 2 A g1, 3 A g1, 4 A g1, 6 A g1 and 12 A g1,
Electrochemical impedance spectroscopy (EIS) is an effective way respectively, which is mainly due to more electroactive site for
to get more information about electrochemical performances and diffusion efficient provided by the high surface area and optimal
capacitive behavior. As shown in the Nyquist plots of Fig. 7(c), the porous textures with the increase of N, S heteroatoms content.
charge transfer resistance (Rct) of CoFe2O4@CNTs is 7.78 U, indicating Encouragingly, the N1S2eCoFe2O4@CNTs electrode retains 80.4% of its
a favorable ion diffusion process and excellent charge-transfer ki- initial capacitance even at a very high current density of 12 A g1,
netic between residual oxygen-containing functional groups from implying excellent rate capability and high reversible redox reaction.
CNTs and the redox reactions of CoFe2O4 NPs [7,50]. Furthermore, the Additionally, the cyclic stability of different electrode materials at the
intrinsic ohmic resistance (Rs) is 2.11 U, demonstrating efficient same current density (20 A g1) are compared in Figs. S3(g and h) and
electron transportation with loading of CoFe2O4 NPs. As shown in Fig. S4. The N, S doping level of N1S3eCoFe2O4@CNTs and
Fig. 7(e), the specific capacitance of CoFe2O4@CNTs is 615.5 F g1, N3S1eCoFe2O4@CNTs are relatively high with a N/S ratio, which are
537.6 F g1, 488.2 F g1, 421.3 F g1, 417.8 F g1 and 412 F g1 with an the higher and closer to the value of 96.11% and 95.47%, implying that
increase of current density from 1 A g1 to 8 A g1. The charging and a superior electrochemical performance should possess a relatively
diffusion of ions get longer time at the lower current densities, which high ratio of doped N and S. Furthermore, as shown in Fig. 8(g), the
enables the most of the active surface area to get charged respective capacitance retention remains 93.92%, 93.15% and 92.7% of
to the discharging time, hence the capacitance gets increased with N1S2eCoFe2O4@CNTs, N2S1eCoFe2O4@CNTs and N1S1eCoFe2O4
the current density decreased [51]. Especially, the capacitance @CNTs asymmetric supercapacitor at a current density of 30 A g1 for
retention of charging-discharging retains 94.96% after 5000 cycles of 5000 cycles, respectively, revealing the excellent cycling stability and
20 A g1, exhibiting an excellent cyclic stability and potential lifetime potential lifetime in an alkaline electrolyte [52,56].
in an alkaline electrolyte [52].
Similarly, the electrochemical properties of the NxSy-
CoFe2O4@CNTs were evaluated in 1 M KOH under the same condi- 4. Conclusion
tions. As shown in Fig. 8(a) and Figs. S3(a and c), the CV curves of
N2S1eCoFe2O4@CNTs, N1eCoFe2O4@CNTs and S1eCoFe2O4@CNTs In summary, various molar ratio of nitrogen and sulfur Co-
display nonrectangular-like shape and a dominant pair of redox doped activated CoFe2O4@CNTs nanocomposites have been
peaks at scan rates of 10 mV s1-200 mV s1, demonstrating the directly synthesized by substrate-assisted hydrothermal activation
cooperation of pseudo-capacitance and double-layer capacitance procedure and high-temperature sintering technique. The satura-
nature of the charge-discharge process. The as-obtained CV curves at tion magnetization decreases along with the increase of N, S het-
scan rates of 100 mV s1 of CNTs, CoFe2O4, CoFe2O4@CNTs, eroatoms content, indicating that the tetrahedral sites and
N1S1eCoFe2O4@CNTs, N2S1eCoFe2O4@CNTs and N1S2eCoFe2O4 octahedral sites in spinel structure of CoFe2O4 NPs could be occu-
@CNTs are shown in Fig. 8(b). These results suggest that the as- pied by N, S heteroatoms, which decreases the resultant magnetic
prepared N1S2eCoFe2O4@CNTs nanocomposites electrodes could moment and thereby the magnetzation. However, the NxSy-
deliver high capacity and reversibility, showing that the content of CoFe2O4@CNTs electrode materials exhibit a high capacity, good
molar ratio of nitrogen and sulfur in the composite is most appro- rate capability and excellent cyclic stability with the increase of N, S
priate for the full utilization of CoFe2O4 and N, S heteroatoms [34,53]. molar ratios, demonstrating that dual heteroatoms synergistic ef-
Fig. 8(c) and Figs. S3(b and d) display the selected GCD curves for fects are able to create unique electronic coupling structure on the
N2S1eCoFe2O4@CNTs, N1eCoFe2O4@CNTs and S1eCoFe2O4@CNTs sp2 hybridized carbon and spinel-type metal oxides nanoparticles,
hybrid electrodes at different current densities. The approximately which can further improve the electrochemical performance.
at different current densities. (d) GCD curves of as-prepared samples at a current density of 1 A g1 and (e) corresponding EIS spectra of as-prepared samples. (f) specific capacitance
at various current densities and (g) corresponding cyclic stability in 30 A g1 for 5000 cycles of N2S1eCoFe2O4@CNTs, N1S1eCoFe2O4@CNTs and N1S2eCoFe2O4@CNTs. (A colour
version of this figure can be viewed online.)
134 Y. Li et al. / Carbon 162 (2020) 124e135
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