Materials and Design 195 (2020) 108942

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Co/CoS nanofibers with flower-like structure immobilized in carbonated

porous wood as bifunctional material for high-performance
supercapacitors and catalysts
Chuanyin Xiong a,⁎, Bingbing Li a, Weihua Dang a, Wei Zhao a, Chao Duan a, Lei Dai a, Yonghao Ni a,b
a
Shaanxi University of Science and Technology, Coll Bioresources Chem & Mat Engn, Shaanxi Prov Key Lab Papermaking Technol & Specia, Xi'an 710021, China
b
University of New Brunswick, Limerick Pulp & Paper Ctr, Fredericton, NB E3B 5A3, Canada

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Co/CoS nanofibers immobilized in car-

bonization wood as bifunctional hybrid
for supercapacitor and electrocatalyst.
• The porous wood and the pores formed
by cross-linked CoS nanofibers contrib-
ute a high areal power density of 192
mW cm−2.
• The high capacitance provided by Co
and CoS endows wood-based compos-
ites with a high areal energy density of
610 μWh cm−2.
• The hybrid shows a high oxygen reduc-
tion reaction onset potential of 0.9 V,
close to commercial Pt / C.

a r t i c l e i n f o a b s t r a c t

Article history: As a kind of green renewable resource from trees, wood has abundant porous structure, which makes it have
Received 30 March 2020 great potential in the field of energy storage. However, poor conductivity and limited energy storage capacity hin-
Received in revised form 1 July 2020 der the application of wood in the field of energy storage. Here, a novel carbonization lignin-free wood (CLFW)@
Accepted 3 July 2020
Co-CoS hybrid is designed and fabricated by a combination of vacuum filtration and carbonization. The CLFW@
Available online 10 July 2020
Co-CoS hybrid assembled into wood-based supercapacitor presents a high areal energy density of 610 μWh
Keywords:
cm−2, meanwhile maintaining a high areal power density of 192 mW cm−2. There are two main reasons for
Carbonization lignin-free wood@Co-CoS the excellent capacitance characteristics: one thing is that wood has a natural and abundant porous structure,
Bifunctional which provides more space and channels for the storage and transport of electrolyte ions. The other thing is
Porous that CoS and Co can provide high capacitance, and numerous new pores are created by the interweaving of
Nnanofibers CoS nanofibers with flower-like structure. Additionally, Co nanoparticles attached to CoS and wood have more
Supercapacitor active sites, which endows the hybrid with excellent ORR properties. Thus, this bifunctional material with excel-
ORR lent electrochemical performance and outstanding ORR properties has huge potential in the field of energy stor-
age and catalysis.
© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

⁎ Corresponding author.
E-mail address: xiongchuanyin@26.com (C. Xiong).

https://doi.org/10.1016/j.matdes.2020.108942
0264-1275/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 C. Xiong et al. / Materials and Design 195 (2020) 108942
1. Introduction
In recent years, with the continuous development of the society, the
environmental and resource problems are attracting more and more at-
tention, advocating green and sustainable development are increasingly
popular [1–8]. Thereinto, the development of green and sustainable en-
ergy is closely related to people's lives. Researchers from all over the
world are particularly concerned about this. As a kind of high-power
green energy, supercapacitor can better meet people's demand for fast
life rhythm compared with other energy storage devices. To the best
of our knowledge, the energy storage performance of supercapacitor
mainly depends on the electrode material which is one of its compo-
nents [9]. Generally speaking, electrode materials can be divided into
three categories according to the categories of materials: carbon mate-
rials [10,11], metal oxides [12–14] and conductive polymers [15–17].
These three types of electrode materials have their own advantages
and disadvantages [15]. Therefore, most researchers use the combina-
tion of them to develop their strengths and avoid their weaknesses, sup-
plemented by the microstructural design, so as to obtain the energy
storage device with outstanding comprehensive energy storage perfor-
mance [15]. As a kind of green renewable resource from trees, wood has
rich natural pore structure, which makes it have great potential in the
field of energy storage. However, poor conductivity limits the use of
wood in energy storage [18]. Carbonized wood is one of the common
means to improve the electrical conductivity of wood [18,19]. Although
carbonized wood has abundant porous structure, which can facilitate
the rapid transport of electrolyte ions, and thus facilitate the acquisition
of high power density, as a kind of carbonaceous material, carbonized
wood can provide limited energy storage capacity, which limits its en-
ergy density. Therefore, it is an effective strategy to introduce other
components into the carbonized wood, and improve the power and en-
ergy density of wood-based energy storage devices by using the synergy
effect among different components [20–22]. Hu et al. reported a kind of
carbonized wood loaded with Ru nanoparticles hybrid used as a mate-
rial for energy storage, and the hybrid presents excellent electrochemi-
cal performance [18]. Of course, besides metal nanoparticles can be
served effective components introduced into carbonized wood, there
are still numerous other components with various structure such as
metal compound [23], conducting polymer [24] etc. also can be added
into carbonized wood to obtain energy storage materials with outstand-
ing comprehensive performance. Thereinto, metal sulfides have large
pseudocapacitance, and different structures of metal sulfides will
bring different energy storage effects [25–31]. Yaddanapudi et al. [25]
devised a facile method to fabricate nickel/carbonized wood nanocom-
posite for environmentally friendly supercapacitor electrodes, and it is
found that the hybrid shows excellent comprehensive energy storage
performance. Kim et al. [30] prepared dense cloud-like tiny bundles
consisting of CuS nanoparticles, and the as-obtained material was
used as an efficient electrode material for high-performance
supercapacitors. Furthermore, Kim et al. [26] also designed a mixture
of Co and Ni sulfides to be used as the cathode of the asymmetric
supercapacitor, and the assembled supercapacitor shows a superhigh
energy density of 75.65 Wh kg−1. These studies show that metal sul-
fides have the potential to become electrode materials for high perfor-
mance supercapacitors. Recently, flower like CoS not only inherits the
excellent properties of metal sulfide, but also increases the effective
contact area with electrolyte ions due to its special flower like structure,
which is also conducive to better transport of electrolyte ions. Therefore,
such a flower like structure CoS has attracted wide attention from re-
searchers [32,33].
In this research, natural wood with lignin removed is selected as an
original substrate to immense into the mixed solution of CoCl26H2O and
thiourea, and then conduct vacuum pumping through double row pipes
to obtain wood loaded with a mixture of CoCl26H2O and thiourea. Next,
the as-obtained lignin-free wood (LFW)@CoCl26H2O-thiourea hybrid is
further treated by carbonization to fabricate the final carbonization
lignin-free wood (CLFW)@Co-CoS product. The as-synthesized CLFW@
Co-CoS hybrid has the following characteristics: i) the removal of lignin
wood has more connected channels, which is conducive to the rapid
transmission of electrolyte ions, and also provides numerous channels
for the storage and transport of electrolyte ions. Moreover, the porous
wood pipe structure not only provides space for the loading of CoS
and Co nanoparticles, but also plays a role of template and confinement,
facilitating the formation and size control of CoS nanofibers. ii) CoS
nanofibers with flower-like structure not only contributes large capaci-
tance, but also creates a lot of new pores from the cross-liked nanofibers
network and flower-like structure, which is also beneficial for the stor-
age and transport of electrolyte ions. iii) Co nanoparticles immobilized
in the CoS nanofibers with flower-like structure and CLFW can not
only enhance the conductivity of the hybrid, but also provide some
part of capacitance, as well as provide numerous active sites for
electrocatalysis. Based on the above advantages of the synergistic effect
of these components, the hybrid presents a high areal energy density of
610 μWh cm−2, meanwhile maintaining a high areal power density of
192 mW cm−2. Additionally, the hybrid also displays outstanding oxy-
gen reduction reaction (ORR) catalytic performance.
2. Experimental section
2.1. Material
Light wood (Taobao), sodium chlorite (Tianjin Damao Chemical Re-
agent Factory), glacial acetic acid (Tianjin Damao Chemical Reagent Fac-
tory), cobalt chloride hexahydrate (magelin), thiourea (magelin).
2.2. Preparation of LFW
Light wood is cut into 4 cm long and 1 cm wide strips, and put them
into a beaker containing a mixture solution of 0.3 g sodium chlorite, 0.1
mL glacial acetic acid and 30 ml deionized water with a stirring rate of
100 rpm, and then heat the beaker at 80 °C for 12 h to remove the lignin
in the wood to obtain porous wood. Finally, the treated wood is put into
the refrigerator for 6 h, and then freeze dry it.
2.3. Fabrication of CLFW@Co-CoS hybrid
The preparation process of the CLFW@Co-CoS hybrid is shown in
Fig. 1. A mixed solution of 6 mol L−1 of CoCl26H2O and 2 mol L−1 of thio-
urea are prepared and treated by ultrasound with cell pulverizer. The
lignin removed wood is put into the above mixed solution, and then
bright green transparent wood@CoCl26H2O-thiourea composite is ob-
tained by bubbling the mixed solution into the wood channel with assis-
tance of double row pipe. Next, the wood@CoCl26H2O-thiourea
composite is put into the refrigerator for 6 h and then freeze-dried. Fi-
nally, the as-obtained material is put into the tubular furnace to heat
to 260 °C for 6 h, and then to 800 °C for 6 h. After the temperature
drops to room temperature, the CLFW@Co-CoS hybrid is obtained. As
a comparison, the CLFW@Co hybrid is also prepared by dipping wood
into the solution of CoCl26H2O, and then the rest of the steps are the
same as above.
2.4. Characterizations
The morphologies of the as-fabricated samples are detected by scan-
ning electron microscopy (SEM, JMS-6400), transmission electron mi-
croscopy (JEOL-2011, Japan) at 200 KV. EDS is obtained on the SEM,
using a 20 kV accelerating voltage. The chemical compositions of sam-
ples are revealed by powder X-ray diffraction (XRD, D8 Advance,
Bruker). XPS studies are carried out with ESCALAB 250Xi. Electrochem-
ical measurements are performed based on a two-electrode system in
Li2SO4 aqueous electrolyte by CHI760E electrochemical workstation.
 C. Xiong et al. / Materials and Design 195 (2020) 108942 3

Fig. 1. Displays the fabrication procedure of the CLFW@Co-CoS hybrid.

2.5. Electrochemical behavior
A CHI 760E electrochemical workstation (Shanghai, Chenhua)
was used to check the electrochemical properties of the resultant
hybrid in an electrolyte containing 1.5 M Li2SO4 at room temperature.
The electrochemical experiment was carried out based on a two-
electrode system. The samples were directly acted as a working
electrode and a counter electrode, and separated by separators to
assemble supercapacitors. Cyclic voltammetry (CV) test were finished
at speeds of ranging from 10 to 200 mV s−1. The galvanostatic charge/
discharge (GCD) test was completed at current densities of ranging
from 3 to 10 A g−1. EIS was conducted in a frequency range of 100
kHz to 0.01 Hz. Specific capacitance Cm (F g−1), energy density W
(Wh kg−1) and power density P (kW kg−1) were calculated from CV
curves according to the equations as follows [12]:
, particles are made up of the CoS nanoflowers (Fig. 2 (i)) and Co nano-
R V2
jIjdV
Cm ¼ V1
2mνΔV
2
. spacing of the lattice fringes of the Co-CoS mixture. Apparently, there
W ¼ Cm ΔV
2 are two kinds of lattice spacing, 0.21 and 0.25 nm, shown in the inset
 of Fig. 2 (i), corresponding to the (111) and (101) planes of Co [34]
P¼W Δt
where I is the current of CV, m is the total mass of CLFW@Co-CoS in two-
electrode system, Δt is the discharge time, and ΔV is the potential win-
dow during the CV test process.
3. Results and discussion
3.1. Structure and morphology
Fig. 2 (a-c) show the cross and longitudinal section of SEM images of
the CLFW, and its internal structure. Obviously, there are many tubes
and pores in CLFW, which can not only provide a lot of space for the
loading and chemical reaction of other components, just like a minia-
ture reactor, but also provide an environment for the transport and stor-
age of electrolyte ions. In addition, the tubes wall of CLFW also act as a
kind of template for the growth of CoS nanofibers by CoS nanoflowers
gathering. Therefore, the CLFW can be used as an ideal substrate to in-
troduce other components, such as CoCl26H2O-thiourea. Fig. 2 (d,
e) exhibit the SEM images of the CLFW after introduction of the mixture
of CoCl26H2O and thiourea, where it is found that the tubes inside the
CLFW is filled by the mixed solution, just like water flowing into a
pipe. By further magnification, it is clear that the rough tubes inside
the wood are completely covered by the mixed solution. Furthermore,
by carbonization of the LFW@CoCl26H2O-thiourea hybrid, the final
CLFW@Co-CoS hybrid is obtained as shown in Fig. 2 (f-i). It is found
that the cross-linked CoS nanofibers with loading numerous Co nano-
particles (Fig. 2 (h)) due to the template and confinement effect of the
ð1Þ
tubes of the CLFW. Furthermore, to determine the composition of the
hybrid more clearly, the HRTEM is used to measure the interplanar
ð2Þ
ð3Þ and CoS [35], respectively, which further confirms the composition of
the reaction products. This novel structure combines the inherent po-
rous characteristics of biomass materials with the advantages of ac-
quired pores formed by metallic monomers and their sulfides, as well
as bring extra-large capacitance from the Co-CoS mixture.
Furthermore, the elemental mappings test of CLFW@Co-CoS hybrid
is used to determine whether the elements in the hybrid are consistent
with the analysis in SEM. From the overlay image of the hybrid pre-
sented in Fig. 3 (a), it can be seen that there are mainly C and Co ele-
ments in the hybrid, which can also be proved from the Fig. 3 (b) and
(f). Moreover, C and Co elements from CLFW and Co-CoS mixture are
evenly distributed in the hybrid. Besides, there are a small amount of
4 C. Xiong et al. / Materials and Design 195 (2020) 108942

Fig. 2. The SEM morphologies of (a-c) CLFW (Cross section); (b) CLFW (Longitudinal section); (c) CLFW (Internal structure); (d, e) CLFW@CoCl26H2O-thiourea (Internal structure) under
different magnification; (f-i) CLFW@Co-CoS under different magnification. The inset shown in Fig. 2 (i) represents the interplanar spacing of the lattice fringes of the Co-CoS mixture.

N, S and O elements, which are mainly from thiourea and wood. Fur-
thermore, it can be further confirmed by the EDS spectra exhibited in
Fig. 3 (g), where it can be prove that there are indeed five elements
such as Co, C, N, S and O in the hybrid. Moreover, from the element con-
tent of S and Co, it can be preliminarily inferred that there is a mixture of
CoS and Co elements.
In addition, in order to further confirm the form of Co in the hybrid,
the XRD patterns of the FLW, CLFW, CLFW@Co and CLFW@Co-CoS hy-
brid are exhibited in Fig. 4, respectively. It can be observed that the
FLW presents a distinct characteristic peak at 2θ = 22.5°, corresponding
to the (002) lattice plane of cellulose as reported in the previous work
[36]. After carbonization of FLW, a new peak of 26.3° is observed due
to the production of graphite carbon [1], which is helpful to enhance
the conductivity of the material. In addition, as a comparison, the
XRD pattern of CLFW@Co displays two new characteristics peaks at
2θ = 44° and 51° corresponding to (111) and (200) lattice planes of
metallic Co (JCPDS card No. 15–0806) [37]. Furthermore, the XRD pat-
tern of CLFW@Co-CoS hybrid shows another new peaks at 2θ = 35.3°
and 74.4° corresponding to (101) and (202) lattice planes of CoS
(JCPDS card No. 65–8977) [32] compared with that of the CLFW@Co hy-
brid. These results are in line with the above results of HRTEM, and
prove that the metallic Co and CoS co-exist in the final CLFW@Co-CoS
sample.
Furthermore, in order to further support the above analysis results,
the XPS measurement is used as an efficient tool to reveal the valence
state of Co in the CLFW@Co-CoS hybrid. Initially, it can be seen clearly
from the XPS survey spectrum of the CLFW@Co-CoS hybrid as shown
in Fig. 5 (a) that there are five elements in the hybrid including Co, C,
N, S and O. The C 1 s spectrum is shown in Fig. 5 (b), where a peak ap-
peared at 284.6 eV represents the presence of sp2-hybridized carbon
atoms from CLFW. In addition, it is proved that there are mainly metallic
Co, Co2+ and S2− in the CLFW@Co-CoS hybrid as shown in Fig. 5 (c, d),
where it can be found that the main peaks are located at the lower bind-
ing energy values (782.6 and 798.4 eV) for Co 2p and the two peaks for
S 2p at 162.8 and 164.12 eV, respectively as reported in the previous lit-
erature [32,33,38,39]. All these analysis results indicate that metallic Co
co-exists with CoS in the CLFW@Co-CoS hybrid, matching well with the
HRTEM and XRD results discussed above. Of course, there are still a
small number of N and O elements from thiourea and CLFW.
3.2. Supercapacitive performance
To investigate the electrochemical properties of the wood to detect
whether the CLFW@Co-CoS hybrid has potential for supercapacitor
storage. Firstly, the CV and GCD curves of the hybrid under different
scan rates and current densities are studied. It is clearly seen that from
the Fig. 6 (a) the curves of the hybrid presents obvious reversible
redox peaks derived from the pseudocapacitance of CoS, which is the
same as the previous literature reports [33,35]. Because of the existence
of redox peaks of CoS, the current densities get larger, thus having larger
 C. Xiong et al. / Materials and Design 195 (2020) 108942 5

Fig. 3. The EDS images of CLFW@Co-CoS hybrid with elemental mappings for (a) corresponding overlay image; (b) Co; (c) C; (d) S; (e) N; (f) O; (g) the EDS of the hybrid.

specific capacitance. Moreover, the CV curves exhibit symmetrical

shapes similar to rectangle, which should be ascribed to the existence
of Co nanoparticles enhancing the overall conductivity of the hybrid.
Fig. 6 (b) presents the GCD curves of the CLFW@Co-CoS hybrid under
various current densities, where the curves display symmetrical triangle
shapes with a little deviation from the synergistic effect of the
pseudocapacitance of CoS and high conductivity of Co nanoparticles.
Moreover, a longer discharging time is still obtained even at a high cur-
rent density of 3 A g−1, which demonstrates that the introduction of CoS
brings about large pseudocapacitance as expected. Furthermore, to
check the different effects from the various component of the hybrid
In the process of electrochemical energy storage, it is very necessary
to compare the electrochemical performance of the CLFW, CLFW@Co
and CLFW@Co-CoS samples. Fig. 6 (c) shows the comparison of the CV
curves of the CLFW, CLFW@Co and CLFW@Co-CoS at a scan rate of 10
mV s−1. Apparently, all of them display a symmetrical triangle shapes
but compared with the CLFW sample, the curves of the CLFW@Co
shows a larger CV area due to the introduction of the Co nanoparticles
Fig. 4. The XRD patterns of LFW, CLFW, CLFW@Co and CLFW@Co-CoS.
6 C. Xiong et al. / Materials and Design 195 (2020) 108942
Fig. 5. (a) XPS survey spectrum, and the high resolution spectra of (b) C 1 s; (c) Co 2p; (d) S 2p, (e) O 1 s and (f) N 1 s elemental states of CLFW@Co-CoS hybrid.
that offer extensive electrochemical active sites with highly accessible
surface area for more electrolyte ions to store [38], thus obtaining a
larger specific capacitance. Furthermore, the curves of the CLFW@Co-
CoS electrode presents a much larger CV area than that of the CLFW@
Co electrode due to the pseudocapacitance generated from the revers-
ible redox peaks of the CoS nanoflowers. Moreover, some pores formed
by the cross-linked CoS nanoflowers also provide numerous space for
the electrolyte ions to enter and store, which also brings about a part
of capacitance. Unanimously, the expected results of the GCD curves
of the three samples at a current density of 3 A g−1 shown in the
Fig. 6 (d) display the same trend as the CV curves. Specifically, the
discharging time at the same current density gradually increases
when the electrode is changed from CLFW to CLFW@Co then from
CLFW@Co to CLFW@Co-CoS, which demonstrates that the existence of
the Co nanoparticles and CoS nanoflowers indeed have a positive effect
on enhancing the whole capacitance of the hybrid as discussed in the CV
curves. Moreover, the GCD curves of the CLFW@Co-CoS shows a sym-
metrical shape with a slight deviation from an idea triangle implying
the existence of reversible redox peaks from the CoS nanoflowers,
which also matches well with the results of the CV curves. In addition,
to detect the dynamic transfer process of charge and electrolyte ions
in the electrode, EIS measurements are also investigated as shown in
the Fig. 6 (e). In view of the comparison of all EIS responses, some fea-
tures are worth of being investigated. Firstly, the intersections of all
curves and real axis (Z`) are close to 0 at the very high frequencies. As
we all known, the intersections represents a combinational resistance
(Rs) of electrolyte ionic, intrinsic substrate, and interface contact resis-
tance from the active material and current collector [12]. Here, the
CLFW is served as the intrinsic substrate and current collector. So the in-
tersections are close to 0 indicating the CLFW has a great potential in
acting as an excellent lightweight substrate and collector due to its
natural porous structure. Furthermore, in the high frequencies regions,
some small arcs represent the charge-transfer resistance (Rct), induced
by the Faradaic reactions and the double-layer capacitance (Cdl) on
the surface of the active electrode material [40]. Moreover, there is no
obvious change in these small arcs even after introduction of Co nano-
particles and CoS nanoflowers, which demonstrates that there is no ob-
vious blocking of the natural porous structure of CLFW after
introduction of Co nanoparticles and CoS nanoflowers. Of course, the ac-
quired porous structure formed from the cross-linked CoS nanoflowers
also provide numerous easy paths for the movements of the electrolyte
ions. In the middle frequencies regions, straight lines with a 45° slope,
known as a Warburg resistor (ZW), occur as a result of the frequency de-
pendence of the diffusion/migration of ions to the electrode surface in
the electrolyte [41]. In the low frequencies regions, straight lines close
to 90° appear, reflecting the limit capacitance (CL) of electrode material
[40]. Moreover, all of the curves show nearly straight lines close to 90︒,
indicating outstanding capacitance behavior. Based on the above analy-
sis and discussion, the equivalent circuit fit the Nyquist plots is provided
as shown in the inset of Fig. 6 (e). Consequently, from all the above anal-
ysis results, it can be proved that the CLFW@Co-CoS hybrid possesses
outstanding charge-discharge performance and porous structure. Fur-
thermore, the cycle stability, rate performance, gravity (area) specific
capacitance and energy efficiency of the CLFW@Co-CoS hybrid are in-
vestigated in terms of practice application as shown in Fig. 6 (f-i). As a
comparison, the CLFW@Co and CLFW@Co-CoS hybrid showing much
higher specific capacitance are selected as research object to study.
Fig. 6 (f) gives the comparison of cycle stability of both hybrid, where
it can be seen clearly that the CLFW@Co-CoS hybrid possesses better
cycle stability than that of the CLFW@Co hybrid after experiencing
3000 cycles at a scan rate of 100 mV s−1. This is mainly ascribed to the
formed cross-linked network from the CoS nanoflowers help to stabilize
 C. Xiong et al. / Materials and Design 195 (2020) 108942 7

Fig. 6. The comparison of the (a) CV curves of the CLFW@Co-CoS hybrid under different scan rates; (b) GCD curves the CLFW@Co-CoS hybrid under various current densities; (c) CV curves
of the CLFW, CLFW@Co and CLFW@Co-CoS at a scan rate of 10 A g−1; (d) GCD curves of the CLFW, CLFW@Co and CLFW@Co-CoS at a current density of 3 A g−1; (e) EIS measurements of the
CLFW@Co and CLFW@Co-CoS hybrid; (f) the cycle stability of the CLFW@Co and CLFW@Co-CoS hybrid at a scan rate of 100 mV s−1 after experiencing 3000 cycles; (g) the change of
capacitance retention of the CLFW@Co and CLFW@Co-CoS hybrid with the increase of scan rates; (h) the gravity specific capacitances and area specific capacitance of the CLFW@Co
and CLFW@Co-CoS hybrid under various current densities; (i) the gravity specific capacitances and energy efficiencis of the CLFW@Co and CLFW@Co-CoS hybrid under various current
densities. The inset presented in Fig. 6 (e) represents the equivalent circuit of the Nyquist plots. The inset presented in Fig. 6 (f) shows the SEM image of the CLFW@Co-CoS hybrid
microstructure after cycling test.

the CLFW and Co nanoparticles. Moreover, it can be seen that there is no
obvious change in the microstructure of the graphene hybrid after cy-
cling test, and it still maintains a kind of cross-linked network formed
by the CoS nanoflowers with loading Co nanoparticles as shown in the
inset of Fig. 6 (f). It demonstrates that the CLFW@Co-CoS hybrid has ex-
cellent structural stability during the cycling test. Furthermore, the ca-
pacitance retention of both under various scan rates are explored to
reflect the dependence of capacitance on sweep speed, which is com-
monly referred to as the rate performance (Fig. 6 (g)). Apparently, in
the presence of the Co nanoparticles and CoS nanoflowers, the CLFW@
Co-CoS hybrid displays better rate performance, and even at a high
scan rate of 200 mV s−1, the CLFW@Co-CoS hybrid still shows a
high capacitance retention of ~95%, which further proves the existence
of excellent porous structure of the CLFW@Co-CoS hybrid. Moreover,
it can be found that the gravity specific capacitances change from
~800 to ~600 F g−1 meanwhile the areal specific capacitance from 6
to 4 F cm−2 when the current densities are altered from 1 to 10
A g−1 (Fig. 6 (h)). These specific capacitance values are much higher
than that of the CLFW@Co hybrid, and most previous work [42–44].
In addition, energy efficiency as another important parameter that
measuring the discharge efficiency of material is also investigated. It
can be observed from the Fig. 6 (i) that the CLFW@Co-CoS hybrid
shows high specific capacitance values between 600 and 800 F g−1,
and energy efficiency between 70 and 80% being comparable with
most others' work [1,10], which implies that the CLFW@Co-CoS hybrid
is an efficient energy storage material. Furthermore, in terms of prac-
tical application of supercapacitor, the energy and power density
(gravity and area) are important parameters that determine the prac-
tical performance of supercapacitor devices. Therefore, it is very im-
portant to investigate the relationship between energy and power
density of supercapacitors assembled with the as-fabricated CLFW@
Co-CoS hybrid electrode, and compare its corresponding performance
with others' work. Fig. 7 (a, b) display the comparison map of the en-
ergy and power density (gravity and area) of such assembled
supercapacitor, where it can be seen cleanly that our work shows an
outstanding energy and power density compared with most of previ-
ous work [20,33,43–50]. To sum up, the excellent comprehensive elec-
trochemical storage properties of the hybrid are mainly attributed to
the fact that the CLFW@Co-CoS hybrid not only preserves the porous
structure of natural biomass material, but also introduces the acquired
porous structure of CoS nanoflowers, as well as gets huge additional
capacitance from the Co nanoparticles and CoS nanoflowers. The syn-
ergistic effect of these factors greatly improves the electrochemical en-
ergy storage of material.
8 C. Xiong et al. / Materials and Design 195 (2020) 108942

Fig. 7. The comparison map of the energy and power density of the supercapacitor (a) Gravity; (b) Areal.

3.3. ORR catalytic properties
Furthermore, the as-prepared CLFW@Co-CoS hybrid is used as
electrocatalyst, and the results of the corresponding ORR performance
tests are shown in Fig. 8. An ORR activity test of the CLFW@Co-CoS hy-
brid in O2 and N2 saturated KOH solution (0.1 M) is displayed in Fig. 8
(a), where a notable peak appears at a potential of ~0.85 V in
O2-saturated KOH solution due to the reduction of O2 from the
CLFW@Co-CoS hybrid, reflecting an outstanding ORR catalytic perfor-
mance of CLFW@Co-CoS hybrid. Fig. 8 (b) presents a shows the compar-
ison of polarization curves between the hybrid and the commercial Pt/C
electrode. The ORR onset and half-wave potential of the CLFW@Co-CoS
hybrid can reach up to approximately 0.9 and 0.83 V, respectively,
which is close to the level of commercial Pt/C. Furthermore, the stability

Fig. 8. Oxygen reduction reaction performance of CLFW@Co-CoS. (a) CV curves in N2- and O2-saturated KOH solution (0.1 M). (b) The comparison of polarization curves of commercialized
Pt/C and CLFW@Co-CoS. (c) The stability of polarization curves of the CLFW@Co-CoS hybrid. (d) Polarization curves of CLFW@Co-CoS measured with different rotation speed.
 C. Xiong et al. / Materials and Design 195 (2020) 108942
of polarization curves of the CLFW@Co-CoS hybrid is explored as shown
in Fig. 8 (c). Apparently, the polarization curve of the hybrid basically
does not change significantly after 1000 cycles implying an excellent
stability. Additionally, the electrocatalytic kinetics of CLFW@Co-CoS hy-
brid in ORR is also studied through polarization curves change under
various rotation speed as displayed in Fig. 8 (d). It can be observed
that current densities increase along with the increase of rotate speeds
due to the shorter O2 diffusion length, and convenient path from porous
CLFW for O2 access. The above results prove that the CLFW@Co-CoS hy-
brid has the potential to become an efficient catalyst.
4. Conclusion
In a word, a novel CLFW@Co-CoS bifunctional material with out-
standing supercapacitive and ORR properties has been devised by
means of vacuum filtration, and carbonization. The as-fabricated
CLFW@Co-CoS hybrid has the following merits: i) There are many nat-
ural pipes inside the wood, which can provide numerous channels for
the storage and transport of electrolyte ions. Moreover, the porous
wood pipe structure not only provides space for the loading of CoS
and Co nanoparticles, but also plays a role of template and confinement,
facilitating the formation and size control of CoS nanofibers. ii) CoS
nanofibers with flower-like structure not only contributes large capaci-
tance, but also creates a lot of new pores from the cross-liked nanofibers
network and flower-like structure, which is also beneficial for the stor-
age and transport of electrolyte ions. iii) Co nanoparticle immobilized in
the CoS nanofibers with flower-like structure and CLFW can not only
enhance the conductivity of the hybrid, but also provide some part of ca-
pacitance as well as provide numerous active sites for electrocatalysis.
To sum up, because of the synergistic effect of these components, the
CLFW@Co-CoS hybrid displays presents a high areal energy density of
610 μWh cm−2, meanwhile maintaining a high areal power density of
192 mW cm−2. In addition, the hybrid also presents outstanding ORR
catalytic performance. Last but not least, the design ideas in this study
are expected to provide more references and possibilities for the con-
struction and application of multifunctional and renewable wood-
based composites.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by Supported by the fund of the China
Postdoctoral Science Foundation (2019M653853XB); Natural Science
Foundation of Shaanxi Province (2020JQ-729); Opening Project of
Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution
Control (2019KF21); Natural science advance research foundation of
Shaanxi University of Science and Technology (2018QNBJ-03); National
Demonstration Center for Experimental Light Chemistry Engineering
Education (Shaanxi University of Science & Technology); High-level
Foreign Experts Project (GDT20186100425), and Biomass Chemistry
and Materials Acadamician Workstation Project in SUST (134090002).
References
[1] C.Y. Xiong, Q. Yang, W.H. Dang, M.R. Li, B.B. Li, J. Su, Y. Liu, W. Zhao, C. Duan, L. Dai,
Y.J. Xu, Y.H. Ni, Fabrication of eco-friendly carbon microtubes @ nitrogen-doped re-
duced graphene oxide hybrid as an excellent carbonaceous scaffold to load MnO2
nanowall (PANI nanorod) as bifunctional material for high-performance
supercapacitor and oxygen reduction reaction catalyst, J. Power Sources 447
(2020) 227387.
[2] M.X. Shen, K. Gao, F.K. Xiang, B.B. Wang, L. Dai, L.Q. Zheng, F. Baker, C. Duan, Y.H.
Zhang, S.H. Sun, Y.H. Ni, Nanocellulose-assisted synthesis of ultrafine co
9
nanoparticles-loaded bimodal micro-mesoporous N-rich carbon as bifunctional ox-
ygen electrode for Zn-air batteries, J. Power Sources 450 (2020) 227640.
[3] C.Y. Xiong, B.B. Li, H.G. Liu, W. Zhao, C. Duan, H.W. Wu, Y.H. Ni, Smart porous wood
supported flower-like NiS/Ni conjuction with vitrimer co-effect as multifunctional
material with reshaping, shape-memory and self-healing for highperformance
supercapacitors, catalysts and sensors, J. Mater. Chem. A 8 (2020) 10898–10908.
[4] W.S. Chen, H.P. Yu, S.Y. Lee, T. Wen, J. Li, Z.J. Fan, Nanocellulose: a promising
nanomaterial for advanced electrochemical energy storage, Chem. Soc. Rev. 47
(2018) 2837.
[5] C.Y. Xiong, M.R. Li, S.X. Nie, W.H. Dang, W. Zhao, L. Dai, Y.H. Ni, Non-carbonized po-
rous lignin-free wood as an effective scaffold to fabricate lignin-free Wood@
Polyaniline supercapacitor material for renewable energy storage application, J.
Power Sources 471 (2020) 228448.
[6] L. Wang, B. Wen, X.Y. Bai, C. Liu, H.B. Yang, NiCo alloy/carbon nanorods decorated
with carbon nanotubes for microwave absorption, ACS Appl. Nano Mater. 12
(2019) 7827–7838.
[7] C.Y. Xiong, M.R. Li, W. Zhao, C. Duan, L. Dai, M.X. Shen, Y.J. Xu, Y.H. Ni, A smart
Paper@Polyaniline nanofibers incorporated vitrimer bifunctional device with
reshaping, shape-memory and self-healing properties applied in high-
performance supercapacitors and sensors, Chem. Eng. J. 396 (2020) 125318.
[8] A.L. Dang, T.H. Li, C.Y. Xiong, T.K. Zhao, Y.D. Shang, H.G. Liu, X.D. Chen, H. Li, Q.
Zhuang, S.Z. Zhang, Long-life electrochemical supercapacitor based on a novel hier-
archically carbon foam templated carbon nanotube electrode, Compos. Part B Eng.
141 (2018) 250–257.
[9] M. F, Y.L. Shao, R.B. Kaner, Graphene for batteries, supercapacitors and beyond, Nat.
Rev. 1 (2016) 1.
[10] C.Y. Xiong, X. Lin, H.G. Liu, M.R. Li, B.B. Li, S.S. Jiao, W. Zhao, C. Duan, L. Dai, Y.H. Ni,
Fabrication of 3D expanded graphite-based (MnO2 nanowalls and PANI nanofibers)
hybrid as bifunctional material for high-performance supercapacitor and sensor, J.
Electrochem. Soc. 166 (2019) A3965.
[11] X.L. Zhang, Q.L. Lin, X.Q. Zhang, K.P. Peng, A novel 3D conductive network-based
polyaniline/graphitic mesoporous carbon composite electrode with excellent elec-
trochemical performance, J. Power Sources 401 (2018) 278.
[12] C.Y. Xiong, T.H. Li, A.L. Dang, T.K. Zhao, H. Li, H.Q. Lv, Two-step approach of fabrica-
tion of three-dimensional MnO2-graphene-carbon nanotube hybrid as a binder-free
supercapacitor electrode, J. Power Sources 306 (2016) 602.
[13] C.L. Xiang, Q.Y. Wang, Y.J. Zou, P.R. Huang, H.L. Chu, S.J. Qiu, F. Xu, L.X. Sun, Simple
synthesis of graphene-doped flower-like cobalt–nickel–tungsten–boron oxides
with self-oxidation for high-performance supercapacitors, J. Mater. Chem. A 5
(2017) 9907.
[14] M.A.A. Mohd Abdah, N.H.N. Azman, S. Kulandaivalu, Y. Sulaiman, Review of the use
of transition-metal-oxide and conducting polymer-based fibres for high-
performance supercapacitors, Mater. Des. 186 (2020) 108199.
[15] C.Y. Xiong, B.B. Li, X. Lin, H.G. Liu, Y.J. Xu, J.J. Mao, C. Duan, T.H. Li, Y.H. Ni, The recent
progress on three-dimensional porous graphene-based hybrid structure for
supercapacitor, Compos. Part B Eng. 165 (2019) 10.
[16] C.Y. Xiong, T.H. Li, Y.C. Zhu, T.K. Zhao, A.L. Dang, H. Li, X.L. Ji, Y.D. Shang, M. Khan,
Two-step approach of fabrication of interconnected nanoporous 3D reduced
graphene oxide-carbon nanotube-polyaniline hybrid as a binder-free
supercapacitor electrode, J. Alloy. Compd. 695 (2017) 1248.
[17] H.Y. Chu, C. Fu, J.J. Xu, W.Y. Li, J. Qian, W. Nie, X.H. Ran, Carbon-doped inorganic
nanoassemblies as fillers to tailor the dielectric and energy storage properties in
polymer-based nanocomposites, Mater. Des. 188 (2020) 108486.
[18] H.Y. Song, S.M. Xu, Y.J. Li, J.Q. Dai, A. Gong, M.W. Zhu, C.L. Zhu, C.J. Chen, Y.N. Chen,
Y.G. Yao, B.Y. Liu, J.W. Song, G. Pastel, L.B. Hu, Hierarchically porous, Ultrathick,
“breathable” wood-derived cathode for lithium-oxygen batteries, Adv. Energy
Mater. 8 (2018) 1701203.
[19] S. Teng, G. Siegel, W. Wang, A. Tiwari, Carbonized wood for supercapacitor elec-
trodes, ECS Solid State Lett. 3 (2014) M25–M28.
[20] C.J. Chen, Y. Zhang, Y.J. Li, J.Q. Dai, J.W. Song, Y.G. Yao, Y.H. Gong, I. Kierzewski, J. Xie,
L.B. Hu, All-wood, low tortuosity, aqueous, biodegradable supercapacitors with
ultra-high capacitance, Energy Environ. Sci. 10 (2017) 538.
[21] C. Wan, Y. Jiao, J. Li, Core–shell composite of wood-derived biochar supported MnO2
nanosheets for supercapacitor applications, RSC Adv. 6 (2016) 64811–64817.
[22] S. Teng, G. Siegel, M.C. Prestgard, W. Wang, A. Tiwari, Synthesis and characterization
of copper-infiltrated carbonized wood monoliths for supercapacitor electrodes,
Electrochim. Acta 161 (2015) 343–350.
[23] D.P. Dubal, N.R. Chodankar, D.-H. Kim, P. Gomez-Romero, Towards flexible solid-
state supercapacitors for smart and wearable electronics, Chem. Soc. Rev. 47
(2018) 2065.
[24] S. Park, S.G. Thangavel, G.K. Parida, K.S.H. Li, P.S. Lee, A stretchable and self-healing
energy storage device based on mechanically and electrically restorative liquid-
metal particles and carboxylated polyurethane composites, Adv. Mater. 31 (2019),
1805536. .
[25] H.S. Yaddanapudi, K. Tian, S. Teng, A. Tiwari, Facile preparation of nickel/carbonized
wood nanocomposite for environmentally friendly supercapacitor electrodes, Sci.
Rep. 6 (2016) 33659.
[26] C.V.V.M. Gopi, R. Vinodh, S. Sambasivam, I.M. Obaidat, S. Singh, H.J. Kim, Co9S8-
Ni3S2/CuMn2O4-NiMn2O4 and MnFe2O4-ZnFe2O4/graphene as binder-free cathode
and anode materials for high energy density supercapacitors, Chem. Eng. J. 381
(2020) 122640.
[27] C.V.V.M. Gopi, S. Ravi, S.S. Rao, A.E. Reddy, H.J. Kim, Carbon nanotube/metal-sulfide
composite flexible electrodes for high-performance quantum dot-sensitized solar
cells and supercapacitors, Sci. Rep. 7 (2017) 46519.
[28] C.V.V.M. Gopi, P.J.S. Rana, R. Padma, R. Vinodh, H.J. Kim, Selective integration of hi-
erarchical nanostructured energy materials: an effective approach to boost the
10 C. Xiong et al. / Materials and Design 195 (2020) 108942
energy storage performance of flexible hybrid supercapacitors, J. Mater. Chem. A 7
(2019) 6374–6386.
[29] C.V.V.M. Gopi, R. Vinodh, S. Sambasivam, I.M. Obaidat, H.J. Kim, Recent progress of
advanced energy storage materials for flexible and wearable supercapacitor: from
design and development to applications, J. Energy Storage 27 (2020) 101035.
[30] K.V.G. Raghavendra, C.V.V.M. Gopi, R. Vinodh, I.K. Durga, H.J. Kim, One-step facile
synthesis of dense cloud-like tiny bundled nanoparticles of CuS nanostructures as
an efficient electrode material for high-performance supercapacitors, J. Energy Stor-
age 27 (2020) 101148.
[31] M. Harilal, S.G. Krishnan, B.L. Vijayan, M.V. Reddy, S. Adams, A.R. Barron, M.M.
Yusoff, R. Jose, Continuous nanobelts of nickel oxide-cobalt oxide hybrid with im-
proved capacitive charge storage properties, Mater. Des. 122 (2017) 376–384.
[32] H. Chen, X. Zhu, Y. Chang, J. Cai, R. Zhao, 3D flower-like CoS hierarchitectures
recycled from spent LiCoO2 batteries and its application in electrochemical capaci-
tor, Mater. Lett. 218 (2018) 40.
[33] K.A. Kumar, A. Pandurangan, S. Arumugam, M. Sathiskumar, Effect of bi-functional
hierarchical flower-like CoS nanostructure on its interfacial charge transport kinet-
ics, magnetic and electrochemical behaviors for supercapacitor and DSSC applica-
tions, Sci. Rep. 9 (2019) 1228.
[34] Z.L. Chen, R.B. Wu, Y. Liu, Y. Ha, Y.H. Guo, D.L. Sun, M. Liu, F. Fang, Ultrafine co nano-
particles encapsulated in carbon-nanotubes-grafted graphene sheets as advanced
electrocatalysts for the hydrogen evolution reaction, Adv. Mater. 30 (2018)
1802011.
[35] S. Zhang, C. Li, H.Q. Xiao, G.J. Wei, Y. Zhou, Z.J. Wang, J. Zhang, C.H. An, Synthesis of
3D flower-like cobalt sulfide hierachitecture for high-performance electrochemical
energy storage, J. Nanopart. Res. 19 (2017) 202.
[36] Q.F. Zheng, Z.Y. Cai, Z.Q. Ma, S.Q. Gong, Cellulose nanofibril/reduced graphene oxide/
carbon nanotube hybrid aerogels for highly flexible and all-solid-state
supercapacitors, ACS Appl. Mater. Interfaces 7 (2015) 3263.
[37] Z.H. Li, H.Y. He, H.B. Cao, S.M. Sun, W.L. Diao, D.L. Gao, P.L. Lu, S.S. Zhang, Z. Guo, M.J.
Li, R.J. Liu, D.H. Ren, C.M. Liu, Y. Zhang, Z. Yang, J.K. Jiang, G.J. Zhang, Atomic co/Ni
dual sites and co/Ni alloy nanoparticles in N-doped porous Januslike carbon frame-
works for bifunctional oxygen electrocatalysis, Appl. Catal. B Environ. 240 (2019)
112–121.
[38] M. Ishaq, M. Jabeen, W.M. Song, L.Y. Xu, W.B. Li, Q.G. Deng, Fluorinated graphene-
supported nickel-cobalt-iron nitride nanoparticles as a promising hybrid electrode
for supercapacitor applications, Electrochim. Acta 282 (2018) 913.
[39] F.L. Luo, J. Lia, H.Y. Yuan, D. Xiao, Rapid synthesis of three-dimensional flower-like
cobalt sulfide hierarchitectures by microwave assisted heating method forhigh-
performance supercapacitors, Electrochim. Acta 123 (2014) 183.
[40] J. Yan, Z.J. Fan, T. Wei, W.Z. Qian, M.L. Zhang, F. Wei, Fast and reversible surface
redox reaction of graphene-MnO2 composites as supercapacitor electrodes, Carbon
48 (2010) 3825–3833.
[41] C.Y. Xiong, M.R. Li, W. Zhao, C. Duan, Y.H. Ni, Flexible N-doped reduced graphene
oxide/carbon nanotube-MnO2 film as a multifunctional material for high-
performance supercapacitors, catalysts and sensors, J. Mater. 6 (2020) 523–531.
[42] Y. Liu, J. Sun, S.Y. Lin, Z.K. Xu, L. Li, In-situ growth of interconnected NiS2/MoS2 nano-
wires supported on Ni foam as binder-free electrode for hybrid supercapacitor, J.
Alloy Compd. 820 (2020) 153113.
[43] S.C. Sekhar, G. Nagaraju, J.S. Yu, High-performance pouch- type hybrid
supercapacitor based on hierarchical NiO-Co3O4-NiO composite nanoarchitectures
as an advanced electrode material, Nano Energy 48 (2018) 81.
[44] S.C. Sekhar, G. Nagaraju, J.S. Yu, Conductive silver nanowires-fenced carbon cloth
fibers-supported layered double hydroxide nanosheets as a flexible and binder-
free electrode for high-performance asymmetric supercapacitors, Nano Energy 36
(2017) 58.
[45] Z. Yang, Q.X. Ma, L. Han, L.K. Tao, Design of Mo-doped cobalt sulfide hollow
nanocages from zeolitic imidazolate frameworks as advanced electrodes for
supercapacitors, Inorg. Chem. Front. 6 (2019) 2178.
[46] S.Q. Wang, Y.P. Song, Y. Ma, Z.Q. Zhu, C.H. Zhao, C.H. Zhao, C.J. Zhao, Attaining a high
energy density of 106 Wh kg−1 for aqueous supercapacitor based on VS4/rGO/
CoS2@co electrode, Chem. Eng. J. 365 (2019) 88.
[47] H. Li, Z.J. Li, Z.L. Wu, M.X. Sun, S.B. Han, C. Cai, W.Z. Shen, Y.Q. Fu, Nanocomposites of
cobalt sulfide embedded carbon nanotubes with enhanced supercapacitor perfor-
mance, J. Electrochem. Soc. 6 (2019) A1031.
[48] J.H. Shi, X.C. Li, G.H. He, L. Zhang, M. Li, Electrodeposition of high-capacitance 3D
CoS/graphene nanosheets on nickel foam for high-performance aqueous asymmet-
ric supercapacitors, J. Mater. Chem. A 3 (2015) 20619.
[49] Y. Ko, M. Kwon, W.K. Bae, B. Lee, S.W. Lee, J.H. Cho, Flexible supercapacitor elec-
trodes based on real metal-like cellulose papers, Nat. Commun. 8 (2017) 536.
[50] G.Q. Sun, H.S. Yang, G.F. Zhang, J. Gao, X.T. Jin, Y. Zhao, L. Jiang, L.T. Qu, A capacity re-
coverable zinc-ion micro-supercapacitor, Energy Environ. Sci. 11 (2018) 3367.