Author’s Accepted Manuscript

Synthesis of CoNi/SiO2 core-shell nanoparticles

decorated reduced graphene oxide nanosheets for
enhanced electromagnetic wave absorption
properties

Xudong Liu, Ying Huang, Na Zhang, Suhua Zhou

www.elsevier.com/locate/ceri

PII: S0272-8842(18)32430-1
DOI: https://doi.org/10.1016/j.ceramint.2018.08.337
Reference: CERI19372
To appear in: Ceramics International
Received date: 21 July 2018
Revised date: 20 August 2018
Accepted date: 29 August 2018
Cite this article as: Xudong Liu, Ying Huang, Na Zhang and Suhua Zhou,
Synthesis of CoNi/SiO2 core-shell nanoparticles decorated reduced graphene
oxide nanosheets for enhanced electromagnetic wave absorption properties,
Ceramics International, https://doi.org/10.1016/j.ceramint.2018.08.337
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Synthesis of CoNi/SiO2 core-shell nanoparticles decorated reduced

graphene oxide nanosheets for enhanced electromagnetic wave

absorption properties
Xudong Liu, Ying Huang*, Na Zhang, Suhua Zhou

MOE Key Laboratory of Material Physics and Chemistry under Extraordinary Conditions, Ministry of Education,

School of Science, Northwestern Polytechnical University, Xi’an 710072, People’s Republic of China

Abstract

In this research, the nanocomposites, CoNi/SiO2 core-shell nanoparticles decorated

reduced graphene oxide (RGO) nanosheets, are successfully synthesized via

liquid-phase reduction reactions combined with a sol-gel route. The structures,

morphologies, chemical composition and magnetic properties of CoNi nanoparticles,

CoNi/SiO2 core-shell nanoparticles and RGO/CoNi/SiO2 nanocomposites have been

investigated in exhaustive detail. The electromagnetic (EM) parameters of

RGO/CoNi/SiO2 nanocomposites are measured using a vector network analyzer. The

results reveal that the RGO/CoNi/SiO2 nanocomposites display enhanced EM wave

absorption properties with the maximum reflection loss (RL) of -46.3 dB at 6.2 GHz

with a matching thickness of 4.2 mm. Additionally, the absorption bandwidth

corresponding to the RL less than -10 dB is up to 14.3 GHz (3.7-18.0 GHz) with a

matching thickness range of 2.0-5.0 mm. To comprehensively consider the absorption

bandwidth and the maximum RL, the integrational method which defines S as the

integration area of RL (RL  -10 dB) and RE as EM wave absorption efficiency is

adopted to reveal that the RGO/CoNi/SiO2 nanocomposites exhibit the excellent

absorption properties with the matching thickness of only 2.0 mm. Accordingly, the

as-prepared RGO/CoNi/SiO2 nanocomposites could be applied as promising EM

*
Corresponding author. Tel.: +86 29 88431636.
E-mail addresses: liuxudongnwpu@163.com (X.D. Liu), yingh@nwpu.edu.cn (Y. Huang).

1
wave absorption materials.

Keywords: EM wave absorption properties, Integrational method, Nanocomposites,

CoNi/SiO2 core-shell nanoparticles

1. Introduction

With the rapid development of electronic and communication devices, the problems

of EM interference not only influence civil and military applications but also do harm

to the human health [1-3]. Plentiful efforts have been devoted to the synthesis of

various EM wave absorption materials with thin thickness, lightweight, strong

absorption properties and broad absorption bandwidth to satisfy the growing demands

of EM wave absorption [4-6]. Due to dissipation effects for electrons by periodic

boundary conditions of nanostructures, magnetic nanocomposites are considered as a

kind of outstanding EM wave absorption materials [7]. Herein, we report the synthesis

of the EM wave absorption material which adopts graphene nanosheets as substrates,

loads with CoNi/SiO2 core-shell nanoparticles and analyze its absorption properties.

As a two-dimensional emerging material, graphene has been studied in lots of

fields of electronics, sensors and energy storage owing to its high surface area,

remarkable thermal conductivity, excellent electronic conductivity and mechanical

properties [8-11]. The graphene also can be considered as a promising candidate of

EM wave absorption materials. However, the properties of pure graphene only depend

on the dielectric loss lacking magnetic loss, which leads to its poor impedance

matching characteristic, and it is still a challenge to prepare an excellent absorber

based on graphene [12, 13]. Song et al. [14] developed the absorption material with a

broad bandwidth of 4.2 GHz covering the whole X band (8.2-12.4 GHz) via the route

of in-situ growing ZnO nanowires on the three-dimensional hierarchical RGO foams.

In Zhang’s study [15], 3D ferromagnetic graphene nanocomposites (decorated with

2
Fe3O4 nanoparticles and ZnO nanorods) with great impedance matching property

were synthesized by a facile solvothermal process combined with a co-decorated

route and the maximum RL reached -57.0 dB at 13.5 GHz with a matching thickness

of 2.0 mm. To improve the absorption properties of pure graphene, it is effective to

decorate graphene nanosheets with semiconductors or magnetic particles, which can

get improved impedance matching and reach ideal absorption properties.

CoNi alloy, as a kind of ferromagnetic alloy, has been attracted considerable

interest as an EM wave absorber owing to its high saturation magnetization, high

Snoek’s limit and high magnetocrystalline anisotropy [16, 17]. There are lots of

crucial factors such as particle size, surface structures and composition for the

properties of CoNi alloys to achieve adjustable physical structures and chemical

composition [18]. Many researches have focused on the size and morphologies of

materials. Feng et al. [19] fabricated a kind of EM wave absorption hybrids,

CoNi/nitrogen-doped graphene, showing the maximum RL of -22 dB with a matching

thickness of 2.0 mm. The size of spherical CoNi nanocrystals is only 70-170 nm. Liu

et al. [7] reported that the CoNi flowers of different sizes and hierarchical structures

exhibit great potential for the utilization of excellent magnetic EM wave absorption

properties. CoNi flowers with 2.5 m achieve the maximum RL of -28.5 dB with a

matching thickness of 2 mm at 6.8 GHz and in the meanwhile the flowers with 0.6

m have a broad absorption bandwidth of 6.5 GHz below -10 dB. In Wang’s research

[20], highly porous flower-like NiO@graphene composites with lightweight were

investigated and the absorption bandwidth (RL  -10 dB) was 4.24 GHz (12.48-16.72

GHz) with a matching thickness of 1.7 mm. Thanks to their specific structure, good

impedance and polarization, the composites with a filler loading of 25 wt% showed

outstanding properties for Ku-band EM wave absorption. An in situ transformation

3
was adopted in Ding’s report [21] to fabricate uniform core-shell Co@C microspheres

from Co3O4@phenolic resin precursor. The introduction of carbon shells can not only

regulate the complex permittivity but also suppress the skin effect to produce stronger

magnetic loss. Moreover, the shells such as C or SiO2 can avoid oxidation and

corrosion of metal elements. The core-shell structured composites have the advantage

of the combined functionalities of cores and shells, which promote the EM wave

absorption properties compared with single-component absorbers [22].

In this paper, we adopt graphene as a substrate decorated with CoNi/SiO2 core-shell

nanoparticles via liquid-phase reduction reactions combined with a sol-gel route. The

EM absorption measurements reveal that RGO/CoNi/SiO2 nanocomposites exhibit

enhanced absorption properties contrast with CoNi and CoNi/SiO2 core-shell

nanoparticles. The maximum RL of -46.3 dB is reached at 6.2 GHz with a matching

thickness of 4.2 mm and the absorption bandwidth (RL  -10 dB) is up to 14.3 GHz

(3.7-18.0 GHz) with a matching thickness range of 2.0-5.0 mm. Thus, the

RGO/CoNi/SiO2 nanocomposites become a potential candidate in the field of EM

wave absorption materials.

2. Experimental section

2.1 Preparation of CoNi nanoparticles

The CoNi nanoparticles are prepared as follows: 3.75 mmol CoCl2·6H2O, 3.75

mmol NiCl2·6H2O and 0.15 g PVP (K30) are dissolved in an ethylene glycol solution

(140 mL) and ultrasonicated for 2 h at room temperature. Then an ethylene glycol

solution (15 mL) composed of 1 g NaOH and 1.5 mL hydrated hydrazine is added

into the above solution which is heated to 80 C. The mixture is kept at 80 C and

reacted for 40 min. The products are washed in deionized water and absolute ethanol

for several times and separated by a magnet. Finally, the black CoNi nanoparticles are

4
dried at 50 C for 10 h under vacuum for subsequent steps.

2.2 Preparation of CoNi/SiO2 core-shell nanoparticles

The CoNi nanoparticles are coated with SiO2 by a Stöber sol-gel process. Briefly,

the dried CoNi nanoparticles (0.2 g) and 0.01 g CTAB are evenly dispersed into the

mixture of 40 mL ethanol and 10mL deionized water by ultrasonication. 1 mL

ammonia and 0.2 mL TEOS are added successively with mechanical stirring and

reacted for 10 h at room temperature. The CoNi/SiO2 core-shell nanoparticles are

separated and dried by similar procedures of CoNi nanoparticles.

2.3 Preparation of RGO/CoNi/SiO2 nanocomposites

Graphene oxide (GO) is prepared based on a modified Hummer’s method [23]. The

obtained CoNi/SiO2 core-shell nanoparticles (0.12 g) are dispersed in GO solution

(0.5 mg/mL, 100 mL), stirred and heated to 80 C for 30 min, then 50 mL deionized

water in which 0.3 g NaBH4 dissolved is added, dropwise, into the above suspension

solution and reacted at 80 C for 2 h. The products are similarly washed in deionized

water and absolute ethanol for several times and collected by a magnet, then dried at

50 C under vacuum for 10 h.

2.4 Characterization

The crystal structure properties of three as-prepared products are investigated by

X-ray diffraction (XRD, Rigaku, Cu K). The sizes and morphologies are observed

by a transmission electron microscopy (TEM, Tecnai F30 G2) and a field-emission

scanning electron microscope (FESEM, Quanta 600 FEG). The surface elemental

composition of samples is characterized by X-ray photoelectron spectroscopy

measurements (XPS, ESCALAB 250 Thermofisher Co). A vibrating sample

magnetometer (VSM, Riken Denshi, BHV-525) is used to analyze the hysteresis loop

and magnetic properties. A vector network analyzer (NA, HP8720ES) is applied to

5
measure the EM parameters in the frequency range of 2.0-18.0 GHz. The as-prepared

products are well mixed with paraffin by heating, then moved into a toroidal mold

with an inner diameter of 3.04 mm, outer diameter of 7.0 mm based on the mass ratio

1:1 of each sample to paraffin.

3. Results and discussion

Fig. 1 vividly displays the prepared procedure of RGO/CoNi/SiO2 nanocomposites.

In brief, the CoNi nanoparticles are reduced from cobalt chloride and nickel chloride

through a liquid-phase reduction reaction and coated with SiO2 via sol-gel process

using TEOS. Then, the GO are reduced to RGO by NaBH4 and decorated with

CoNi/SiO2 core-shell nanoparticles at the same time.

The crystal structures of as-prepared products are characterized by XRD. Figure 2

shows the XRD patterns of CoNi nanoparticles, CoNi/SiO2 core-shell nanoparticles

and RGO/CoNi/SiO2 nanocomposites. It is observed from the three patterns that all

diffraction peaks centered at 44.4, 51.7 and 76.3 generally match with (111), (200)

and (220) crystal planes of Co (JCPDS No. 15-0806) and Ni (JCPDS No. 04-0850),

which agree with the face center cubic structure [24-26]. Since no impurity diffraction

peaks are found, the as-prepared nanocomposites are confirmed of high purity.

Meanwhile, there is no other extra peak appeared in the XRD patterns of CoNi/SiO2

core-shell nanoparticles and RGO/CoNi/SiO2 nanocomposites, revealing that the

structure of SiO2 shell is amorphous and the self-restacking of graphene nanosheets in

the composites is prevented effectively by the introduction of CoNi/SiO2 core-shell

nanoparticles [27].

The surface structure and morphology of as-prepared materials are investigated at

different amplification ratio by SEM (Fig. 3). In Fig. 3a-b, it is seen that CoNi

nanoparticles disperse appropriately with an approximate diameter of 80 nm. After the

6
sol-gel process, the surface of CoNi/SiO2 core-shell nanoparticles (Fig. 3c) becomes

smooth and the size is also increased, which confirms the silica is coated on CoNi

nanoparticles successfully. Moreover, the core-shell nanoparticles arise aggregation

and adhesion to some extent due to the small particle size and larger surface energy.

The SEM image of RGO/CoNi/SiO2 nanocomposites is presented in Fig. 3d. Single

CoNi/SiO2 core-shell nanoparticles or clusters are distributed on graphene which

display a crumpled structure due to deformation during restacking process. TEM

images at different magnifications shown in Fig. 4a-b further characterize the

structure of RGO/CoNi/SiO2 nanocomposites. It is evident that the RGO with plenty

of folds are decorated with CoNi/SiO2 core-shell nanoparticles, indicating that the

core-shell nanoparticles are successfully loaded on graphene nanosheets. The SAED

patterns (Fig. 4c) of RGO/CoNi/SiO2 nanocomposites reveal that the lattice spacing of

2.0 Å, 1.7 Å, 1.2 Å and 1.06 Å, which result from the radiuses of the diffraction rings,

can be indexed to the (111), (200), (220) and (311) planes of the face center cubic

structure of CoNi crystal nanoparticles [28]. We can conclude that the above results

agree well with the XRD patterns in Fig. 2.

The surface elemental composition of RGO/CoNi/SiO2 nanocomposites is

measured by XPS and the results are displayed in Fig. 5. The wide scan spectrum of

the RGO/CoNi/SiO2 nanocomposites is shown in Fig. 5a. It reveals that the main

peaks marked in the figure correspond to Si 2p, C 1s, O 1s, Co 2p and Ni 2p,

respectively. Fig. 5b shows the C 1s spectrum of the nanocomposites, the high

resolution XPS spectrum can be deconvoluted into three main composition: the

binding energy at 284.6 eV, 286.4 eV and 288.3 eV are assigned to the C-C/C=C, C-O

and C=O groups, respectively [29-32]. O 1s spectrum (Fig. 5c) is also divided into

three peaks with the binding energy at 531.5 eV, 532.7 eV and 533.2 eV, which are in

7
accordance with O-Si, O-H and C-O/C=O groups [33]. In Fig. 5d-e, the binding

energy peaks at 781.2 eV and 797.5 eV are relevant to the Co 2p3/2 orbital and the Co

2p1/2 orbital as well as the peaks at 855.7 eV and 873.7 eV are relevant to the Ni

2p3/2 orbital and the Ni 2p1/2 orbital [34-36]. Both spectra show the satellite peaks

indicating the partially surface oxidation of cobalt and nickel [16]. Also, the Si 2p

orbital at 102.1 eV (Fig. 5f) are assigned to the silica shell of CoNi/SiO2 core-shell

nanoparticles, revealing the generation of SiO2 on the surface of CoNi nanoparticles

[37, 38]. It can be concluded from the results of XPS that CoNi nanoparticles are

coated with silica and the CoNi/SiO2 core-shell nanoparticles are successfully loaded

on the graphene nanosheets.

The magnetic hysteresis loops of CoNi nanoparticles, CoNi/SiO2 core-shell

nanoparticles and RGO/CoNi/SiO2 nanocomposites are measured by VSM at room

temperature and shown in Fig. 6. All samples exhibit ferromagnetic behavior [39, 40].

The saturation magnetization values (Ms) of three samples are 65.16, 44.41 and 17.45

emu/g, respectively. The decreasing of saturation magnetization mainly results from

the addition of non-magnetic silica shell and graphene nanosheets. The Ms is still

relatively high although the nonmagnetic components (graphene and silica) are

introduced in the nanocomposites. It is attributed to the CoNi nanoparticles, the

mainly cause of magnetic loss, which have the advantage of further improving the EM

wave absorption properties [27, 41].

The absorption properties of the RGO/CoNi/SiO2 nanocomposites are influenced

by four constants: the relative complex permittivity (r = -j), the relative complex

permeability (r = -j), the dielectric tangent loss (tan E = /) and the magnetic

tangent loss (tan M = /) [42]. The real parts ( and ) represent the storage

capability of the EM energy, while the imaginary parts ( and ) represent the

8
energy dissipation [43-45]. Therefore, the EM parameters of the RGO/CoNi/SiO2

nanocomposites are measured by a vector network analyzer and the complex

permittivity and permeability changing with frequency (2.0-18.0 GHz) are displayed

in Fig. 7.

In Fig. 7a-b, the  values show a gradual decreasing from 9.5 to 6.3 while  values

approximately maintain around 2.8 in the frequency of 2.0-18.0 GHz. Moreover, the

 values show a sharp drop from 1.6 to 1.1 during 2.0-5.9 GHz following with a slow

decreasing to 1.0 during 5.9-18.0 GHz while  values increase from 0.17 to the

maximum value of 0.32 at 3.8 GHz and decrease from 0.32 to 0. As shown in Fig. 7c,

the values of tan E are bigger than tan M in general and both below 1.0. The former

shows a slow increasing from 0.3 to 0.4 in 2.0-18.0 GHz and the latter increases in

2.0-4.2 GHz then decreases with several fluctuations in 4.2-18.0 GHz with the

maximum value of 0.24. It indicates that the dielectric loss plays a chief role in all

frequencies. Furthermore, the image of values of C0 (C0 = ()-2f-1) changing with

frequency is shown in Fig. 7d. If the magnetic loss mainly results from eddy current

effect, the C0 will be equal to a constant instead of changing with frequency. However,

the values of C0 in Fig. 7d cannot remain constant, which indicates that the magnetic

loss of RGO/CoNi/SiO2 nanocomposites does not exclusively result from the eddy

current effect. The natural resonance caused by small size effect of CoNi/SiO 2

core-shell nanoparticles becomes the major contribution to the magnetic loss [46-48].

The EM wave absorption properties of three samples (CoNi nanoparticles,

CoNi/SiO2 core-shell nanoparticles, RGO/CoNi/SiO2 nanocomposites) are evaluated

and compared by mixing with the paraffin matrix (50 wt%). The owned relative

complex permittivity and the relative complex permeability at a specific frequency

and thickness are used to calculate the values of RL according to the transmission-line

9
theory. The equations are given as follows [49, 50]:

RL (dB)  20 log Zin  Z o  Zin  Z 0  (1)

Zin  Z o ur  r tanh[ j 2fd c  ur r ] (2)

Where Zin is the input characteristic impedance of the absorber, Z0 is the impedance

of free space, f is the frequency, c is the velocity of EM wave, d is the thickness of the

nanocomposites, while r is the complex permittivity, r is the complex permeability.

Fig. 8 shows the calculated RL of CoNi nanoparticles, CoNi/SiO2 core-shell

nanoparticles and RGO/CoNi/SiO2 nanocomposites. In Fig. 8a-b, the maximum RL of

CoNi nanoparticles and CoNi/SiO2 core-shell nanoparticles are respectively -19.8 dB

at 5.9 GHz with the matching thickness of 2.0 mm and -14.6 dB at 11.5 GHz with the

matching thickness of 2.0 mm. In the range of 2.0-5.0 mm, the frequency bandwidth

(RL  -10 dB) of CoNi nanoparticles and CoNi/SiO2 core-shell nanoparticles are 3.2

GHz (4.2-7.4 GHz) and 2.9 GHz (10.3-13.2 GHz). The values of RL peaks and

absorption bandwidths slightly reduce and shift towards higher frequency due to the

coating of non-conductive and non-magnetic silica shell, indicating that CoNi

nanoparticles can be used as a lower frequency absorber while CoNi/SiO2 core-shell

nanoparticles can be used as a higher frequency absorber. Moreover, when the

CoNi/SiO2 core-shell nanoparticles are used to decorate graphene nanosheets, the

obtained RGO/CoNi/SiO2 nanocomposites become a kind of strong absorption and

wide frequency bandwidth absorption materials. In Fig. 8c, the maximum RL of

RGO/CoNi/SiO2 nanocomposites reaches -46.3 dB at 6.2 GHz with the matching

thickness of 4.2 mm. The frequency bandwidth (RL  -10 dB) is up to 14.3 GHz

(3.7-18.0 GHz) with a matching thickness range of 2.0-5.0 mm. Fig. 8d shows the

three-dimensional RL of RGO/CoNi/SiO2 nanocomposites. The absorption

bandwidths (RL  -10 dB) are marked by a red line while RL  -20 dB by a black line
10
in the projection section with matching thickness from 2.0 to 5.0 mm. It is evident that

RGO/CoNi/SiO2 nanocomposites can achieve enhanced absorption properties over a

wider frequency range compared with CoNi nanoparticles and CoNi/SiO2 core-shell

nanoparticles, revealing the RGO/CoNi/SiO2 nanocomposites can be utilized as

effective broadband EM wave absorption materials.

The comparison of frequency bandwidths (RL  -10 dB) for three materials is

generalized in Fig. 9a with the matching thickness range of 2.0-5.0 mm. When the

thickness varies from 2.0 to 5.0 mm, the absorption bandwidths of RGO/CoNi/SiO2

nanocomposites are about 5.8, 5.0, 3.8, 3.1, 2.8, 2.6 and 2.5 GHz, which evidently

surpass CoNi nanoparticles and CoNi/SiO2 core-shell nanoparticles. Furthermore, Fig.

9b shows the maximum RL at different thickness of the three absorption materials. It

shows that the RGO/CoNi/SiO2 nanocomposites possess the strongest absorption

properties comparing with the other samples. Above all, the RGO/CoNi/SiO2

nanocomposites exhibit the advantages in both aspects of absorption bandwidth and

the maximum RL.

To further study the relationship between RL and thickness, also explain the

absorption mechanism of RGO/CoNi/SiO2 nanocomposites, the quarter-wavelength

matching model is used in Fig. 10. Briefly, when the EM wave is incident on the

absorption material backed by a metal plate, it is partially reflected from air-absorber

interface while partially reflected from absorber-metal interface [51, 52]. At an

appropriate frequency point, the both reflected waves extinct with each other due to

the phase difference of 180 and the thickness of absorbers satisfy the quarter-wave

thickness criteria [53-55]:

t m  nc (4 f m  r  r ) (3)

This criterion illustrates that when the thickness (tm) coincides the above equation,

11
the RL of RGO/CoNi/SiO2 nanocomposites will reached at the maximum value at a

specific frequency (fm). The thickness (tmexp) obtained from the maximum RL in Fig.

10a are marked with colorful points in Fig. 10b. Then the black line shows the values

of tm calculated by the equation and named as tmfit. It is found that the calculated

values (tmfit) basically agree with the experimental results (tmexp), which illustrates that

the quarter-wavelength model can be used to explain the mechanism of EM wave

absorption exactly.

Additionally, it is of importance to weaken the reflection of EM wave at the

interface of air-absorber. Therefore, as the following equation expressing, the

impedance matching characteristics also have an influence on the RL [56, 57]:

Z  Z in Z o  u r  r tanh[ j 2fd c  u r  r ] (4)

When the values of Z are approximately equal to 1, the EM wave can enter the

inside of absorption materials easily and then be converted to heat or weaken by

interference process, achieving enhanced absorption properties. For the

RGO/CoNi/SiO2 nanocomposites, the values of Z are shown in Fig. 10c. It is seen that

on the quarter-wavelength model, when the frequency is 6.2 GHz and the thickness of

the absorption material is 4.2 mm, the value of Z is close to 1 and the maximum RL

reaches at -46.3 dB in the meantime. It illustrates that the excellent impedance

matching characteristic also facilitates the improvement of EM wave absorption

properties of RGO/CoNi/SiO2 nanocomposites.

For the RGO/CoNi/SiO2 nanocomposites, when the thickness is 4.2 mm, the

maximum RL reaches at -46.3 dB with the bandwidth (RL  -10 dB) of 2.6 GHz.

However, when the thickness is 2.0 mm, the maximum RL is only -28.4 dB with a

broad bandwidth (RL  -10 dB) of 5.8 GHz (Fig. 8c). It is difficult to satisfy the

maximum RL and broad bandwidth simultaneously at a certain thickness. Hence, we

12
cannot evaluate the best thickness to achieve the most excellent absorption properties.

For this problem, Zhao et al. [58] use a method of integration to synthetically evaluate

the absorption properties. Firstly, S is defined as the integration area of RL when the

RL  -10 dB. Secondly, the EM absorption efficiency RE is defined as RE = S/d.

Therefore, the value of RE is a comprehensive evaluation indicator of absorption

properties. Based on this method, we can calculate the value of S and RE of

RGO/CoNi/SiO2 nanocomposites (corresponding to the Fig. 8c). Table 1 summarized

the maximum RL, bandwidth, S and RE of RGO/CoNi/SiO2 nanocomposites at

different thickness. When the thickness is 2.0 mm, the values of S and RE are 41.59

dBGHz and 20.80 dBGHz/mm respectively. With the increasing of thickness from

2.0 mm to 5.0 mm, both indicators show a decreasing trend in general. Fig. 11 shows

the integration area with the thickness of 2.0, 2.5, 3.0 and 4.2 mm. The corresponding

S values are 41.59, 32.64, 28.63 and 20.07 dBGHz, and RE values are 20.80, 13.06,

9.54 and 4.78 dBGHz/mm, respectively. In summary, we can conclude that the best

EM wave absorption properties are achieved with the material thickness of 2.0 mm.

4. Conclusion

All in all, the RGO/CoNi/SiO2 nanocomposites are successfully prepared by

liquid-phase reduction reactions combined with a sol-gel route. The CoNi/SiO2

core-shell nanoparticles are distributed on the graphene nanosheets. And the

RGO/CoNi/SiO2 nanocomposites exhibit excellent EM wave absorption properties.

The maximum RL achieves -46.3 dB with the matching thickness of 4.2 mm, while

the frequency bandwidth corresponding to the RL less than -10 dB covers 14.3 GHz

(3.7-18.0 GHz) with a thickness range of 2.0-5.0 mm. Furthermore, according to the

integration area S of RL (RL  -10 dB) and the comprehensive evaluation indicator

RE, the RGO/CoNi/SiO2 nanocomposites achieve the enhanced absorption properties

13
with the thickness of only 2.0 mm (S = 41.59 dBGHz and RE = 20.80 dBGHz/mm).

Hence, the RGO/CoNi/SiO2 nanocomposites show quite excellent prospect and great

potential as EM wave absorption materials.

Acknowledgement

We appreciate the financial support by National Natural Science Foundation of China

(51672222), Spaceflight Innovation Foundation of China and Spaceflight Foundation

of China (2014-HT-XGD).

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Figure Caption

Fig. 1. Prepared procedure of RGO/CoNi/SiO2 nanocomposites.

Fig. 2. XRD patterns of CoNi nanoparticles, CoNi/SiO2 core-shell nanoparticles and

RGO/CoNi/SiO2 nanocomposites.

19
Fig. 3. SEM images of CoNi nanoparticles (a and b) at different magnifications, CoNi/SiO2

core-shell nanoparticles (c) and RGO/CoNi/SiO2 nanocomposites(d).

Fig. 4. TEM images (a and b) at different magnifications and SAED pattern (c) of

RGO/CoNi/SiO2 nanocomposites.

20
Fig. 5. Wide scan (a), C 1s (b), O 1s (c), Co 2p (d), Ni 2p (e) and Si 2p (f) XPS spectra for

RGO/CoNi/SiO2 nanocomposites.

21
Fig. 6. Magnetic hysteresis loops of CoNi nanoparticles, CoNi/SiO2 core-shell nanoparticles and

RGO/CoNi/SiO2 nanocomposites.

Fig. 7. The curves of r and r (a and b), tan  (c) and C0 (d) of the RGO/CoNi/SiO2

nanocomposites changing with frequency.

22
Fig. 8. RL of CoNi nanoparticles (a), CoNi/SiO2 core-shell nanoparticles (b) and RGO/CoNi/SiO2

nanocomposites (c) with various thickness in the frequency of 2.0-18.0 GHz; three-dimensional

RL figure (d) of RGO/CoNi/SiO2 nanocomposites.

Fig. 9. The EM wave absorption bandwidth with the RL value below -10 dB (a) and the

comparison of the maximum RL value (b) of CoNi nanoparticles, CoNi/SiO2 core-shell

nanoparticles and RGO/CoNi/SiO2 nanocomposites with different thickness.

23
 Fig. 10. The RL values with various material thickness changing with frequency (a); simulated

values of material thickness (tm) and the frequency (fm) based on the /4 model (b); the values of Z

changing with the frequency (c) for the RGO/CoNi/SiO2 nanocomposites.

24
 Fig. 11. The integration area of RL of RGO/CoNi/SiO2 nanocomposites with different thickness:

2.0 (a), 2.5 (b), 3.0 (c) and 4.2 mm (d).

Table 1. The maximum RL, bandwidth, S and RE of RGO/CoNi/SiO2

nanocomposites with different thickness.

Bandwidth
Thickness Maximum RL S RE
(RL  -10 dB)
(mm) (dB) (dBGHz) (dBGHz/mm)
(GHz)

2.0 -28.4 5.8 41.59 20.80

2.5 -28.0 5.0 32.64 13.06

25
3.0 -32.1 3.8 28.63 9.54

3.5 -39.6 3.1 27.03 7.72

4.2 -46.3 2.6 20.07 4.78

5.0 -31.7 2.5 18.92 3.78

26