Composites Part B 192 (2020) 107980

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Construction of multiple electromagnetic loss mechanism for enhanced

electromagnetic absorption performance of fish scale-derived
biomass absorber
Xinfeng Zhou a, 1, Zirui Jia a, 1, Ailing Feng b, Jiahao Kou a, Haijie Cao a, Xuehua Liu a,
Guanglei Wu a, *
a
Institute of Materials for Energy and Environment, State Key Laboratory of Bio-fibers and Eco-textiles, College of Materials Science and Engineering, Qingdao University,
Qingdao, 266071, PR China
b
Institute of Physics & Optoelectronics Technology, Baoji University of Arts and Sciences, Baoji, 721016, PR China

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

Keywords: Biomass-derived porous carbon materials have attracted considerable attention as promising electromagnetic
Core-shell Co@Co3O4 (EM) wave absorbers due to their lightweight characteristic, ultra large surface area as well as high dielectric
Porous carbon loss. However, the dielectric loss alone is difficult to achieve high EM wave absorption performance. In this work,
Fish scale
core-shell Co@Co3O4/porous carbon composites are designed and synthesized by a facile hydrothermal and
Impedance matching
subsequent pyrolysis process through using fish scale as carbon precursor, Co(NO3)2⋅6H2O as Co source, aiming
EM wave absorption
to offer more loss mechanism and achieve high EM wave absorption performance. As expected, the as-prepared
composite showed strong absorption ( 89.3 dB at 2.4 mm) with broadened bandwidth (11.92–18 GHz at 2 mm).
Such excellent absorption performance could be attributed to the reasonable design of composite. Special porous
structure not only is beneficial to the impedance matching to allow EM wave to enter absorber as much as
possible, but also could offer a conductive path for electronic, booming conductive loss. Besides, the designed
unique core-shell structure provides Co-Co3O4 interfaces along with Co3O4-C, C-void interfaces are propitious to
enhance interface polarization loss. Moreover, Co@Co3O4 nanoparticles could also supply the magnetic loss to
composites to further absorb EM wave from another point. Although there are many previous works about
Co@Co3O4 have been reported, little works have been done on the composites of biomass porous carbon with
core-shell Co@Co3O4 with such excellent EM wave absorption performance. This work indicates that the as-
obtained core-shell Co@Co3O4/C could be a candidate for dealing with the increasing EM wave pollution.

1. Introduction
Currently, the increasing development of electronic devices has
brought great convenience to our daily life. However, it also causes
many undesired problems especially electromagnetic (EM) wave inter­
ference. The critical pollution not only affect the normal use of elec­
tronic instruments but also threatens people’s health [1–3].
Consequently, it has been a hotspot to fabricating EM wave absorber to
attenuate or even eliminate the negative radiation of EM wave [4]. The
absorbers with excellent absorbing performance, low density, and
resistance to corrosion are in great demand [5].
During the past years, different carbonaceous materials especially
graphite and carbon nanotube (CNT) have been considered as ideal EM
wave absorber because of their merits of high electrical conductive,
special micro-structure, and lightweight [6,7]. Large amount of reports
about graphite and CNT have emerged in recent years. However, such
materials are suffered from the expensive raw materials (e.g., fossil) or
complex and diffuse syntheses process (e.g., hummers methods and
chemical vapor deposition (CVD)) [8]. It limits their application to a
large extent. Consequently, developing novel carbonaceous materials
with easy-available raw materials and simple process have been on the
agenda for a long time.
Recent years, biomass-derived carbon material has attracted
increasingly attention. As a novel carbon material, it has the

* Corresponding author.
E-mail addresses: wuguanglei@mail.xjtu.edu.cn, wuguanglei@qdu.edu.cn (G. Wu).
1
Contributed equally to this work.

https://doi.org/10.1016/j.compositesb.2020.107980
Received 11 January 2020; Received in revised form 12 March 2020; Accepted 13 March 2020
Available online 19 March 2020
1359-8368/© 2020 Elsevier Ltd. All rights reserved.
X. Zhou et al.
characteristic of conventional carbon material, such as low-density and
high dielectric loss. Moreover, it has its own advantages, including eco-
friendly nature, low cost, convenience in preparation and favorable
porous structure [8]. Hence, biomass-derived carbon material has been
regarded as a sustainable method to handle the EM pollution.
Previous reports have illustrated that porous structure could not only
provide the media for EM wave reflection but also decrease the density
[9]. However, the build process of porous structure (e.g.,
template-etching method) would involve strong acid or alkali, which
suffers from long-term and high risk. Thus, developing simple and safe
methods is the hotspot. Many biomass-derived materials could be
directly converted into porous carbon materials through a concise
carbonization process [10]. Several biomasses like rice [11], Spinach
stem [10], walnut [12] and eggshell membrane [13] have shown their
potential in attenuating EM wave. The porous structure act as dominate
role and is explained as following: The porous structure can be accepted
as a solid media (host)-air composite. Three typical models including
Bruggeman 1/3 power law, Landauer-Brugge-man effective medium
approximation (EMA) and Maxwell-Garnet (MG) theory are be well
accepted to elaborate the porous materials [8]. The MG theory which is
� �
listed as follows is widely used [14,15]. εMGeff ¼ ðε2 þ2ε1 Þ fr ðε2 ε1 Þ ε1 , in
ðε2 þ2ε1 Þþ2fr ðε2 ε1 Þ
which ε1 is the soild permittivity and ε2 is the permittivity of s air, fr
represents the air volume fraction in porous structure. It can be deduced
that the existence of porous structure could effectively adjust complex
permittivity. The impedance matching is an essential consideration
when synthesis EM wave absorber which could be expressed as: [16,17]
qffiffiffi qffiffiffi
Zin =Z0 ¼ με00 μεrr , where ε0 is the relative complex permittivity while the
μ0 implies the vacuum permeability. The change of εr could cause the
Zin/Z0 to 1 which indicates that more EM wave will enter the absorber
and then provide more opportunities for absorber to consume EM wave.
Hence, the building of porous structure would be a reasonable and
effective strategy when design EM wave absorber.
However, the loss mechanism of biomass-derived carbon material is
limited to unilateral dielectric loss, which is insufficient to obtain proper
impedance matching. In this case, the majority of the EM wave may be
easily reflected from the surface of absorber, rather than be attenuated.
Therefore, impedance matching should be given priority. Introducing
magnetic materials into the carbon system is demonstrated to be a useful
method to regulate the values of absorber’s complex permittivity and
permeability, resulting in enhanced impedance matching and superior
absorbing performance [18]. For instance, Zhao [11] and his co-worker
prepared the Ni doping porous through a simple dipping and sintering
method from rice. With the addition of Ni, the magnetic loss of com­
posites has been improved, however, too much Ni led to the impedance
mismatch of composites. In the end, the excellent reflection loss (RL)
was up to 52.0 dB with the broadest effective absorption bandwidth
(EAB) of 5.0 GHz. Huang [13] and his co-worker successfully synthe­
sized porous carbon and obtained C@CoFe2O4 composites. The
enhanced magnetic loss originating from CoFe2O4 nanoparticles endow
the composites excellent performance which the excellent reflection loss
is 49.6 dB at 2.5 mm. Thus, it is necessary for the dielectric loss and
magnetic loss to be considered when fabricating absorbing materials. As
a kind of ferromagnetic metal, cobalt possesses high Curie point (1130
�
C) and large saturation magnetization, and it can offer intensive mag­
netic loss thus effectively attenuate microwaves.
In previously research, we successfully prepared carbon sphere/
Fe3O4-Fe quantum dots. During the high-temperature treatment, the
carbon exhibited reductivity which reduces Fe3O4 to Fe. Finally the
composites displayed excellent performance [19]. This work provided a
new thought taking amorphous carbon as reductant when fabricating
materials. Upon the prophase work, in this work, we chose scales as the
raw material of porous carbon. The role of fish scales (Fs) are usually
neglected because it was often discarded in daily life. After hydrother­
mal and a simple physical mixing, the precursor was obtained. During
2
Composites Part B 192 (2020) 107980
the heat-treatment, the formed carbon could reduce the cobalt metal salt
to cobalt and meanwhile the intrinsic oxygen atoms provide the oxygen
source for further oxidation of cobalt. Finally, a series different
Co@Co3O4 loading composites was obtained. However, although pre­
vious works have already reported about the Cobalt-carbon composites
like Co3O4/Co@RGO [20], Co3O4/Co@NMC [21], Co/CO3O4@C [22]
and so on, the complex synthesis process, expensive raw-materials of
carbonaceous would limit their further applications. Using fish scale as
raw-materials not only simplify the synthesis process, but also make full
use of the bio-diversity of biomass materials. There are few reports about
the composite of biomass materials with Co and Co3O4. The SEM char­
acterizations illustrate the change of morphology. The HR-TEM revealed
the core-shell structure that the Co3O4 acting as “shell” wrap cobalt.
Moreover, the pore size could be tuned which could influence the
impedance matching. Besides, abundant interface, suitable conductivity
as well as porous carbon skeleton endow the interface polarization loss
and conductive loss to eliminate EM wave energy. Finally, S-1.2 exhibits
outstanding EM wave absorption performance. The excellent RL reveals
89.3 dB with the matching thickness of 2.4 mm and the widest EAB
reach 6.08 GHz in 2.0 mm. This work provides a new thought when
fabricating composites without any addition reductant and oxidant.
2. Experimental section
2.1. Raw materials
Fs was obtained from common carp. Cobalt nitrate hexahydrate (Co
(NO3)2⋅6H2O), Potassium hydroxide (KOH) were obtained from Sino­
pharm Reagent Co., Ltd. The concentration of hydrochloric acid (HCl)
was 9 mol/L. Water is the deionized water (DI, 18.25 MΩ).
2.2. Preparation of core-shell Co@Co3O4/C composites
The Fs was cleaned with deionized and dried at 80 � C. Then cut the
scales and set aside. The preparation process is shown in Scheme 1.
Typically, 4 g Fs was added into KOH solution containing 60 mL DI and
4 g KOH and stirring to obtain homogeneous solution. Then the system
was transferred into Teflon-lined autoclave at 180 � C held for 24 h. After
cooling down to room temperature naturally, the pale-yellow clarifying
solution was obtained through vacuum filtration. Subsequently, the pH
of solution was adjusted to 7 by 9 mol/L HCl. After that, 0.5 mmol Co
(NO3)2⋅6H2O were added into 45 mL solution (pH ¼ 7) and stirring to
obtain homogeneous solution. After being freeze-dry, the power was
heat-treatment at 800 � C for 1 h under Ar atmosphere (heating rate: 2
�
C/min). The black power were washed with deionized and dried at 80
�
C for a night. For comparison, addition amount of Co(NO3)2⋅6H2O
varied from 0.5 mmol to 1.0 mmol, 1.2 mmol, 1.5 mmol and 2.0 mmol.
The samples gained from different Co(NO3)2⋅6H2O were marked as S-
0.5, S-1.0, S-1.2, S-1.5 and S-2.0, respectively.
2.3. EM wave absorption measurements
The samples were mixed with paraffin with the weight ratio of 1:5
and pressed into a toroidal-shaped pipe (ϕin ¼ 3:04 mm, ϕout ¼
7:00 mm). The height of toroidal-shaped pipe was about 2.0 mm. The
weight ratio of sample to paraffin is 1:5. The EM parameters (εr and μr)
were obtained by coaxial-line method on Agilent N5222A vector
network analyzer under the frequency of 2–18 GHz. The RL values in
different matching thickness were worked out with transmission line
theory [23,24]:
rffiffiffiffi �� � �
Zin ¼ Z0
μr � 2πfd pffiffiffiffiffiffiffiffi�
tanh��j εr μr �� (1)
εr c
� �
�Zin Z0 �
RLðdBÞ ¼ 20log�� � (2)
Zin þ Z0 �
X. Zhou et al. Composites Part B 192 (2020) 107980

Scheme 1. Schematic illustration of the preparation of core-shell Co@Co3O4/C composites.

where f is the corresponding frequency, c represents the speed of light,

d represents the thickness of sample, and Zin is the input impedance,
while Z0 is air impedance.

2.4. Characterization

The morphology and element mapping of samples were obtained by

Field emission scanning electron microscope (SEM, JEOL JSM-7800 F),
and lattice spacing was observed on Transmission electron microscope
(TEM, JEOL JEM-2100). The Raman spectra of samples were collected
by using a renishaw inVia Plus Micro-Raman spectroscopy system
equipped with a 50 mW DPSS laser at 532 mm. The stage of elements in
the surface of composites was chartered by X-ray photoelectron spec­
troscopy (XPS) on Thermo Fisher ESCALAB 250Xi spectrometer with an
Al Ka X-ray source (1486.6 eV). The Brunauer-Emmett-Teller (BET) of
samples were tested by a Quantachrome Autosorb iQ3 at 77 K. The pore
sizes of as-obtained samples were calculated by Density Functional
Theory (DFT) method. Using a LakeShore 7404 (LakeShore, USA)
vibrating sample magnetometer (VSM) to detect the magnetic hysteresis
loop of samples.
Fig. 1. (a) Full XPS spectrum and high-resolution C 1s (b), O 1s (c), and Co 2p
3. Results and discussion (d) of S-1.2.

Fs, which is considered as trash when cooking, is selected as raw
materials to fabricating carbon materials. The whole system has no
additive reductant, but cleverly uses carbon itself to reduce cobalt salt.
Meanwhile, the break of oxygen group in precursor naturally could
provide necessary condition for the generation of Co3O4 [25,26]. To
further reveal the element chemical state on the surface of composites,
XPS spectrum of S-1.2 was provided in Fig. 1. The full spectrum shows
several distinct peaks located in 258 eV [27], 532 eV [23], 780 eV, and
797 eV [28], which are the characteristic peak of C 1s, O 1s, Co 2p3/2,
and Co 2p1/2. From Fig. 1b, the high resolution of C 1s could be divided
into three peaks in 284.6 eV, 285.7 eV, and 288.6 eV, which corresponds
C (sp2)-C (sp2) [29], C-O [30], and O-C¼O [27] bonds, respectively. As is
shown in Fig. 1c, O 1s was resolved into three peaks. Thereinto, the peak
located in 533.2 eV could be O-C bonds [31], and the peak at 531.2 eV is
the binding energy of -OH/-COOH [32]. Moreover, there is a peak
occurred at 529.7 eV, which is the characteristic peak of oxygen in
Co3O4 (Fig. 1c) [33]. For Co 2p spectrum (Fig. 1d), two peaks repre­
senting Co 2p3/2 and Co 2p1/2 are deconvoluted into several peaks. The
peak at 779.9 eV could be corresponding to the peak of Co0. The peaks at
796.7 eV and 782.4 eV represents Co3þ 2p3/2 and Co3þ 2p1/2, respec­
tively. Besides, the peaks located at 781.0 eV and 795.2 eV are
originated from Co2þ. Moreover, in the Co 2p spectrum, two satellite
peaks in 786.3 eV and 804.7 eV are appeared, which is the evidence of
the coexistence of Co2þ and Co3þ in the composites [34]. The result of
Co 2p spectrum indicated that part of cobalt is gradually converted to
Co3O4 during high-temperature treatment. All XPS spectrum confirms
that the composite is successfully synthesized and the cobalt and Co3O4
are coexistence inside composites.
The components of composites could be worked out by Raman
spectra as well. Fig. 2 shows the Raman shift of the composites. Two
typical peaks located at around 1350 cm 1 for D peak and 1580 cm 1 for
G peak could be observed. Generally, D peak is the defects or disorder or
limited size crystal of graphite, while G peak symbolise for ordered
structure of graphite carbon [35]. Consequently, the graphitization de­
gree could be stated by the intensity ratio (ID/IG) between D and G peak.
For S-0.5, S-1.0, S-1.2, S-1.5, and S-2.0, the ID/IG values were calculated
to be 0.934, 0.951, 0.969, 0.982, and 0.990, respectively. The decrease
trend was reported by many previous researches. Based on the
Three-Level Model proposed by Ferrari and Robertson [36], the upward
trend of ID/IG could be attributed to the transition from non-crystalline
carbon to nanocrystalline graphite. The formation of nanocrystalline

3
X. Zhou et al.
Fig. 2. Raman shift of the as-prepared samples.
graphite is inspired by Co@Co3O4 nanoparticles, which result in the
increase of ID/IG value. Another possible reason could be that the pres­
ence of Co@Co3O4 nanoparticles could introduce more defects. Similar
results could be found in previous literatures [37,38], so the introduce of
the Co@Co3O4 nanoparticles is another significant factor to cause the
decrease trend of the samples. Moreover, the four peaks centered at
around 185.6 cm 1, 468.0 cm 1, 516.1 cm 1, and 673.3 cm 1 are
ascribed to the F2g, Eg, 2F2g, and A1g vibrational modes of Co3O4 [39].
However, the vibration peaks caused by Co nanocrystallites were not
detected which is agree with previous reports [40].
The surface morphology and micro structure of as-obtained
Fig. 3. (a–e) SEM images of S-0.5, S-1.0, S-1.2, S-1.5, and S-2.0, respectively. (f) specific details of S-1.2,(g) elements mapping of a selected area of S-1.2.
4
Composites Part B 192 (2020) 107980
composites are characterized by SEM and TEM, respectively. SEM im­
ages of Fs were shown in Figs. S1a and b. The block structure consisting
of “mushroom bag” could be observed, which is obviously different from
the structure of composites. For S-0.5, pore of the carbon have not yet
been exhibited and just some fold formed (Fig. 3a). With further
increasing the amount of cobalt salts (see in Fig. 3b-f), well-defined
porous structure was gradually formed and large amount of nano­
particles were evenly distributed in the carbon skeleton. As is shown in
Fig. 3c, the nanoparticles were homogeneously embedded in the inner
and outer walls of the carbon skeleton. As is shown in Fig. 3f, the
diameter of nanoparticles was uniformly about 150 nm and the pore size
was about 1 μm. Generally speaking, the incident EM wave’s wavelength
is far longer than the cell size of pore, thus the porous structure will not
cause multi-reflection and scattering of EM wave. However, the unique
carbon skeleton could be favoring for the conductive loss to attenuate
EM wave. Moreover, plenty of interfaces could also give rise to interface
polarization, boosting high EM wave absorption performance. From
Fig. 3d and e, certain amounts of nanoparticles were entering the pore
and gather together, especially in S-2.0. To illustrate the importance of
Co@Co3O4 nanoparticles in the formation of porous structure, the SEM
of neat fish scale without cobalt source was shown in Figs. S1c and d. It
could be found that no distinct porous structure was observed compared
to S-1.2. Consequently, the Co@Co3O4 exhibits a significant role in the
formation of porous structure.
The elements mapping was carried out to indicate the elements
distribution of S-1.2 and shown in Fig. 3g. The Co elements from Co3O4
and cobalt and O elements originating from Co3O4 and carbon material
were uniformly distributed in the composites and exhibited a homoge­
neous dispersion state.
Fig. S2 illustrate the atomic ratio of C, O, and Co element in the
samples analyzed by EDS. It could be clearly seen that the Co elements
increase from S-0.5 to S-2.0, which in accordance with the experiment
X. Zhou et al.
section.
The detailed structure evolutions of the samples were examined by
TEM and exhibited in Fig. S3 and Fig. 4. It can be evidently draw a
conclusion that the amount and corresponding size of the nanoparticles
simultaneously increased with the growing amount of cobalt salt. As is
shown in Fig. 4a, the porous structure with the nanoparticles anchored
on it could be observed of S-1.2 which in accord with SEM image.
Moreover, the enlarged image in Fig. 4a reveals the core-shell structure
of nanoparticle. To further identify the structural composition of com­
posites, the HR-TEM image were carried out and shown in Fig. 4b. The
planar spacing of the core of nanoparticles was 0.17 and 0.20 nm, cor­
responding to the (200) and (111) crystal plane of Co, respectively. On
the other hand, the planar spacing of 0.46 nm for (111) plane of Co3O4,
0.24 nm for (311) plane of Co3O4, and 0.23 nm for (222) of Co3O4 were
observed in the shell of nanoparticles. Fig. 4c displayed the selected-area
electron diffraction (SAED) image of S-1.2. Five diffraction rings could
be corresponding to the (111), (311), (220), (422), and (511) planes of
Co3O4, while two rings for (111) and (220) planes of Co could be
observed as well. Based on above observation, it can be known that the
nanoparticles with core-shell structure are well-defined, with Co as cores
and thin Co3O4 as shells. The formation of Co3O4 shell is due to the
oxidation of cobalt under high temperature. Furthermore, the shell
thickness of Co@Co3O4 gradually increases with the size of the particle,
shown in Fig. 4d. Based on the date of Fig. S2 and Fig. 4d, the content of
C, Co and Co3O4 could be calculated when thinking the nanoparticles as
a ball and shown in Table S1. It could be found that the content of C
displayed a decrease trend from S-0.5 to S-2.0, while the Co and Co3O4
exhibited an upward trend, which is corresponding to the experimental
section well. Besides, the increase of Co and Co3O4 would introduce
more EM wave loss mechanism like magnetic loss, interface loss and so
on to attenuate the EM wave energy.
To illustrate the nanopore distributions of as-obtained samples, the
N2 adsorption-desorption isotherms and pore diameter were displayed
in Fig. 5a and b. It could be found from Fig. 5a that with the cobalt
Fig. 4. (a) TEM, (b) HR-TEM images and (c) SAED patterns of S-1.2, (d) the thickness statistics of shell and diameter of samples. The inset two images in Fig. 4(a) is
the high magnification image of nanoparticles, the HR-TEM inset image in Fig. 4(b) is from the edge of a nanoparticle.
5
Composites Part B 192 (2020) 107980
source increasing, the isotherms gradually tend to the IV-type isotherm
with the hysteresis loop, implying the presence of mesopores. Besides,
from Fig. 5b it could be found that the pore diameter of S-0.5 was lower
than 2 nm, which is the characteristic of micropore. In addition, with the
increasing of cobalt source, S-1.0, S-1.2, S-1.5 and S-2.0 exhibited the
mesopore especially S-2.0 with the pore diameter of 4 nm. However, the
pore type of S-1.0 to S-2.0 is mainly micropore.
The static magnetic properties of composites were tested at room
temperature by VSM and the field-dependent magnetization curves were
displayed in Fig. 6. The magnetic saturation of the applied magnetic
field is about 15 KOe. Fig. 6a exhibits the typical hysteresis loops
implying the ferromagnetic behavior of the as-synthesized composites.
The saturation magnetization (Ms) and intrinsic coercivity (Hc) values of
as-obtained samples are measured and listed in Table 1. All Ms values
are lower than 30, much lower than that of cobalt, which is owing to the
existence of the Co3O4 shell. Moreover, the presence of large amount of
nonmagnetic carbon materials is another reason for the small Ms values.
Besides, the Ms values of five composites are 25.1, 24.9, 23.7, 22.8, and
19.8 emu g 1, respectively. The decreasing trend of Ms could be
explained by the increasing thickness of Co3O4 shell although the mass
fraction of Co elements exhibited increasing trend (see in Fig. S2).
Absorber with high Hc value usually leads to a high frequency resonance
[41]. In this case, the S-1.2 (229.26 Oe) and S-1.5 (233.87 Oe) possess a
higher Hc value, while the S-0.5 and S-2.0 show the value of 199.17 Oe
and 116.51 Oe, respectively. The S-1.0 exhibits the lower Hc value of
81.81 Oe. The low Hc values of the as-prepared samples illustrate the
nature of their soft magnetic materials.
The complex permittivity (εr ¼ ε’ jε’’) and complex permeability
(μr ¼ μ’ jμ’’) of composites were measured and shown in Fig. 7.
Typically, the real part and imagine part in complex permittivity are in
accordance with the storage and dissipation capacity of the electric
energy in EM energy, while the μ’ and μ’’ are in accordance with the
storage and dissipation capacity of the magnetic energy, respectively
[42,43]. It can be observed from Fig. 7a that ε’ values of composites
X. Zhou et al. Composites Part B 192 (2020) 107980

Fig. 5. (a) N2 absorption-desorption isotherms and (b) pore size of as-obtained samples.

Fig. 6. Magnetic hysteresis loops of the S samples at room temperature.

increases. So the dipolar orientation polarization could be ignored as

Table 1
well [45,48]. The interface polarization could be attributed to the
The Ms and Hc values of samples.
interface of Co3O4, Co porous carbon materials, air, and paraffin in this
Sample Ms(emu/g) Hc(Oe) case. Co is a good conductor, and the cross-linked networks which could
S-0.5 25.1 199.17 be beneficial to the transport of electron are built in nanoparticles [45].
S-1.0 24.9 81.81 Besides, the porous carbon skeleton could provide a conductive path for
S-1.2 23.7 229.26
the transport of electron, booming conductive loss. Based on the free
S-1.5 22.8 233.87
S-2.0 19.8 116.51
electron theory [14],

ε’’ ¼ 1=2ε0 πρf (3)

show decreasing trend with the increasing frequency, known as fre­
quency dispersion behavior [44]. However, when the frequency in­
creases, ε’’ curves also exhibit decreasing trend with several resonant
peaks. (Fig. 7c), which is the characteristic of the existence of dielectric
loss behaviors. According to previous reports [45,46], the dielectric loss
behaviors could be divided into polarization loss (e.g. dipolar orienta­
tion polarization, interface polarization, ionic polarization, and electric
polarization etc.) and conductivity loss. Generally, the ionic polarization
and electric polarization generate at a higher frequency (103–106 GHz),
so they could be removed easily [47]. Besides, the ε’’ values showed
slightly increase trend with the frequency increasing, which imply that
the dipole can be reoriented quickly enough to respond to the applied
electric field as the frequency of the incident electromagnetic wave
where ε0 , ρ, f are permittivity of the vacuum, resistivity, and frequency
of the EM wave, respectively. So it can be concluded that the high
electronic conductivity could result in high ε’’ values. Therefore, the
higher ε’’ values of S-0.5 and S-2.0 can generate higher conductivity,
which easily causes greater mismatch of permittivity and permeability.
Such mismatch is unfavorable to attenuate EM wave energy.
According to the Debye theory and free electron theory, the con­
ductively loss could be beneficial to the attenuation of EM wave energy.
The ε’ and ε’’ could be expressed by the following equation on the basis
of Debye theory [49,50]:

6
X. Zhou et al. Composites Part B 192 (2020) 107980

Fig. 7. (a) real part and (c) imaginary part of complex permittivity of composites; (b) real part and (d) imaginary part of complex permeability of composites; (e)
dielectric loss tangent and (f) magnetic loss tangent of composites; (g) Cole-Cole plots of S-1.2 and (h) C0 curve of the composites.

7
X. Zhou et al.
ε’ ¼ ε∞ þ
εs ε∞
(4)
1 þ ð2πf Þ2 r2
2πfrðεs ε∞ Þ
ε’’ ¼ (5)
1 þ ð2πf Þ2 r2
where εs , is the static dielectric constant and ε∞ represents optical
dielectric constant, f is the matching frequency, r is the polarization
relaxation time. On the basic of eq. (4) and eq. (5), Cole-Cole equation
could be expressed as:
� εs þ ε∞ �2 �ε ε∞ �2
(6)
s
ε’ þ ðε’’ Þ2 ¼
2 2
According to eq. (6), one semicircle (named Cole-Cole semicircle)
represents a relaxation process. It could be found from Fig. 7g and
Fig. S4 that several Cole-Cole semicircles are occurred, implying more
dielectric loss in attenuating EM wave. Moreover, it can be seen that the
amount of Cole-Cole semicircles exhibited a significantly increase trend,
implying more dielectric loss mechanism occurred to attenuate EM wave
energy. The reason on the increase of Cole-Cole semicircles could be
ascribed to the increasing amount of Co@Co3O4 nanoparticles. In pre­
vious discussion, the Co and Co3O4 would increase from S-0.5 to S-2.0.
The increase of Co and Co3O4 could lead into more interfaces, which is
beneficial to the enhance of interface polarization loss.
The μ’ and μ’’ of composites were drawn and shown in Fig. 7b and d.
Dramatic fluctuate along with several peaks were occurred in curves in
2–18 GHz for all the composites. Generally speaking, when generate the
relaxation process in magnetization, the magnetic loss could be divided
into eddy current and resonance including domain wall resonance,
natural resonance, exchange resonance [51]. Thereinto, the domain wall
resonance can be not considered for it just occurs in low frequency [51].
Based on the obtained μ’ and μ’’ values, the eddy current could be
calculated as following equation [52,53]:
C0 ¼ μ’’ ðμ’ Þ 2 f 1
¼ 2πμ0 d2 σ (7)
When the magnetic loss stems from eddy current loss, C0 values
would keep a constant from 2 to 18 GHz. It could be seen from Fig. 7h
that all the curves almost remained constant when the frequency was
from 9 to 14 GHz. Consequently, the eddy current loss should be the key
source of the magnetic loss in 9–14 GHz, while in the other frequency
ranges (2–9 GHz and 14–18 GHz), natural and exchange resonance are
the dominant magnetic loss mechanism [51]. Based on previous reports,
the fluctuate peak at the frequency of 2–9 is natural resonance and
14–18 GHz could belong to exchange resonance, respectively. It is
noteworthy that the amplitude of curve fluctuation of S-1.0 is much
lower than the other four samples, the reason could be attributed to it
possesses smallest Hc value among five composites.
Generally speaking, the dielectric loss tangent value (tanδE ¼ ε00 /ε0 )
and magnetic loss tangent (tanδM ¼ μ00 /μ0 ) value mean the capacity to
the attenuation of EM wave [54,55]. Fig. 7e to f shows the tanδE and
tanδM curves of composites. It could be observed that all the tanδE value
of S-1.0, S-1.2, S-1.5, and S-2.0 are larger than 0.2 while the tanδM values
are smaller than 0.2, implying in 2–18 GHz the dielectric loss plays a
more important role in attenuating EM waves.
Generally speaking, the value of Reflection Loss (RL) is a vital
indictor to assess EM wave absorption performance [56,57]. Besides, the
RL value below than 10 dB (RL � 10 dB) implies that 90% EM wave
can be absorbed by EM absorber which could satisfy with practical
application. And the EAB is defined as the frequency range covered by
RL value less than 10 dB [58,59]. The RL values of the composites at
the frequency from 2 to 18 GHz in the matching thickness of 0.1–5 mm
were calculated and draw 3D color map displayed in Fig. 8. As to S-0.5,
the porous structure has not yet been constructed due to inadequate
cobalt salts, the EM wave would be reflected from the surface of com­
posites because of the poor impedance matching according to the MG
theory. S-0.5 shows the minimum RL value of 26.7 dB at the thickness
8
Composites Part B 192 (2020) 107980
of 1.8 mm and the corresponding EAB is 4.72 GHz, covering the fre­
quency of 12.96–13.52 GHz and 13.84–18 GHz. Moreover, the widest
EAB of 6.4 GHz covering 11.6–18 GHz is obtained when the thickness is
2.0 mm in which the minimum RL value is 20.7 dB. By increase the
addition amount of cobalt source, S-1.0 initially exhibits porous struc­
ture but the pore size is not uniform. Compared with S-0.5, S-1.0 shows
the enhanced EM wave absorption capacity with minimum RL of 55.9
dB at 1.7 mm. S-1.2 exhibits wonderful EM wave performance. The
minimum RL value is up to 89.3 dB at 2.4 mm and the corresponding
EAB is 4.56 GHz (9.52–14.68 GHz). Moreover, the widest EAB is 6.08
GHz, ranging from 11.92 to 18 GHz. As for the S-1.5, the minimum RL
value of S-1.5 dropped to 51.7 dB and the matching thickness increase
to 4.7 mm. Besides, the widest EAB obtained at 1.9 mm is reduced to
5.28 GHz (12.72–18 GHz) as well. However, for S-2.0, the minimum RL
values could hardly to exceed 30 dB in different thickness.
Moreover, it could be found that with the matching thickness
increasing, the corresponding frequency of minimum RL value gradually
converts into the low frequency region. The relationship of matching
thickness and the frequency could be expressed by quarter-wavelength
matching model as following [60–62]:
tm ¼
nλ nc
¼ pffiffiffiffiffiffiffiffiffiffiffiffiffi ðn ¼ 1; 3; 5Þ (8)
4 4fm jμr jjεr j
where tm fm represent the matching thickness andthe frequency of the
minimum RL value, jμr j and jεr j are the modulus of the μr and εr ,
respectively. c is the light speed in free space. The EM wave from the air-
absorber and absorber-paraffin interface is out of phase by 180� when
the matching thickness satisfies the equation [61]. The extinction effect
could be got which result in a dissipation in the air-absorber interface
and leading to augmented EM wave absorption performance [61].
Fig. 9a and Fig. S5 display the simulation of the thickness versus RL
value peak frequency of composites. The black stars were the optimal
matching thickness which was obtained from 3D RL map, while the
brown line was obtained from the equation. It could be found that the
black stars are almost on the line, implying that the sterling EM ab­
sorption performance could be explained by the quarter-wavelength
theory.
Based on the previous elaborate, the impedance values (Z ¼ Zin/Z0)
were calculated in 0.1–5 mm in 2–18 GHz and shown in Fig. 9b and
Fig. S6. The Z values between 0.9 and 1.1 were lined in white lines and
the area between two white lines are calculated to 0.73, 4.25, 6.32, 5.34
and 1.98 corresponding to S-0.5, S-1.0, S-1.2, S-1.5 and S-2.0, respec­
tively. It could be found that S-1.2 exhibited largest region among the as-
obtained samples, agreeing with its outstanding EM wave absorption
ability. Apart from impedance matching index, the attenuation constant
α which indicate the capacity to attenuate EM wave inside the absorber
is an important index as well. The attenuation constant α could be ob­
tained by following equation [63]:
pffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiq
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2πf
α¼ ðμ’’ ε’’ μ’ ε’ Þ þ ðμ’’ ε’’ μ’ ε’ Þ2 þ ðμ’ ε’’ þ μ’’ε’Þ2 (9)
c
Fig. 9c exhibits the α values of the samples. It could be found that
though the α values of S-1.0 are the lowest, the performance is not the
poorest. On the contrary, S-2.0 and S-0.5 possess relatively higher α
values, but they exhibit unsatisfactory EM wave absorption perfor­
mance. The reason could be explained that S-1.0 possessed prefer
impedance than that of S-2.0 and S-0.5, implying S-1.0 has more op­
portunity to attenuate EM wave. Hence, compared to attenuation con­
stant, impedance matching dominates in influencing EM wave
absorption performance.
To sum up, the EM wave absorption mechanism was summarized and
shown in Fig. 10. The synergistic effect of dielectric loss and magnetic
loss was beneficial to the attenuation of EM wave energy. Based on the
MG theory, the prefer porous structure by reasonable construction
provide a guarantee of the impedance matching to make the EM wave to
X. Zhou et al. Composites Part B 192 (2020) 107980

Fig. 8. Reflection Loss in the frequency of 2–18 GHz for the S-0.5 (a), S-1.0 (b), S-1.2 (c), S-1.5(d), and S-2.0(e), respectively.

9
X. Zhou et al. Composites Part B 192 (2020) 107980

Fig. 9. (a) Dependence of matching thickness (tm) on matching frequency (fm) of S-1.2 at a wavelength of λ/4; The frequency-dependent (b) normalized input
impendence (Zin/Z0) of S-1.2 and (c) attenuation constants of the prepared samples.

Fig. 10. The EM wave absorption mechanism of composites.

be absorbed as much as possible. Besides, the booming dielectric loss
originated from Co@Co3O4 and porous carbon skeleton play a dominant
role in attenuating EM wave, which could be listed as following: (I) the
unique porous structure of carbon skeleton could provide a path for the
transport of electric, benefiting to the conductive loss; (II) the abundant
interfaces (i.e, Co-Co3O4, Co-C, C-void interfaces) could generate
interfacial polarization environment, providing intense dielectric loss
with conductive loss originated from carbon conductive network, which
supplies an effective way to transfer the electromagnetic energy into
heat energy. Moreover, the Co@Co3O4 nanoparticles could provide
magnetic loss to attenuate EM waves as well. Hence, the prefer imped­
ance matching, excellent dielectric loss and magnetic are great contri­
bution to the superior absorbing performance of S-1.2.
Fig. 11 lists several RL values and EAB of Co-based composites and
bio-materials [12,13,64–69]. It could be found that the S-1.2 in this
work not only possesses outstanding RL value at a relatively thin
thickness (<2.5 mm) but also the EAB is superior among the absorbers.
Consequently, Co@Co3O4/C composites would be a promising candi­
date for dealing with EM wave interference problem.

10
X. Zhou et al.
Fig. 11. The RL value and wide EAB compared between different Co-materials
and bio-materials with S-1.2.
4. Conclusions
In this work, Co@Co3O4/C composites were successfully synthesized
through a facile hydrothermal and subsequent pyrolysis process using
fish scale as precursor. During the pyrolysis process, the Co nano­
particles were obtained by the reduction of amorphous carbon. Subse­
quently, the oxygen atom derived from the amorphous material provides
conditions for the formation of Co3O4 shell. Finally the core-shell
Co@Co3O4/C composites were obtained. Besides, by adjusting the
amount of cobalt salt, both the pore size and the size of the nanoparticles
could be modified. The as-prepared composites showed enhanced EM
wave absorption performance, compared with Co-based absorber and
bio-materials. When the filler ration is about 16.7 wt%, the RLmin of S-
1.2 is as low as 89.3 dB at 2.4 mm. The widest EAB are above 6 GHz,
which have bright prospect in practice application. Such excellent ab­
sorption performance could be attributed to the reasonable design of
composite. Special porous structure which is beneficial to impedance
matching and conductive loss, core-shell Co@Co3O4 which provide
extra interface polarization loss and magnetic loss to further attenuate
EM wave energy to other form energy. Although plenty literatures about
Co@Co3O4 have been reported, little works have been done to used
metal salt source to construct porous structure on biomass materials
with such excellent EM wave absorption performance. This work in­
dicates that the as-obtained core-shell Co@Co3O4/C composites could
be a candidate for dealing with the increasing EM wave pollution.
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.
CRediT authorship contribution statement
Xinfeng Zhou: Writing - original draft. Zirui Jia: Writing - original
draft. Ailing Feng: Visualization, Investigation. Jiahao Kou: Writing -
original draft. Haijie Cao: Software, Validation. Xuehua Liu: Formal
analysis. Guanglei Wu: Writing - original draft.
Acknowledgments
This work was financially supported by the Natural Science Foun­
dation of Shandong Province (No.ZR2019YQ24), the Qingchuang
11
Composites Part B 192 (2020) 107980
Talents Induction Program of Shandong Higher Education Institution
(Research and Innovation Team of Structural-Functional Polymer
Composites), National Natural Science Foundation of China
(No.51407134, No.51801001), China Postdoctoral Science Foundation
(No.2016M590619, No.2016M601878), Provincial Key Research and
Development Program of Shaanxi (No. 2019GY-197), The authors
acknowledge the support from The Thousand Talents Plan, The World-
Class University and Discipline, The Taishan Scholar’s Advantageous
and Distinctive Discipline Program of Shandong Province and The
World-Class Discipline Program of Shandong Province.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compositesb.2020.107980.
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