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Preparation of two-dimensional titanium carbide (Ti3C2Tx) and NiCo2O4 composites

to achieve excellent microwave absorption properties

Tianqi Hou, Bingbing Wang, Mingliang Ma, Ailing Feng, Zhengyong Huang, Yi Zhang,
Zirui Jia, Guangxin Tan, Haijie Cao, Guanglei Wu
PII: S1359-8368(19)34646-3
DOI: https://doi.org/10.1016/j.compositesb.2019.107577
Reference: JCOMB 107577

To appear in: Composites Part B

Received Date: 9 September 2019

Revised Date: 28 October 2019
Accepted Date: 31 October 2019

Please cite this article as: Hou T, Wang B, Ma M, Feng A, Huang Z, Zhang Y, Jia Z, Tan G, Cao H, Wu
G, Preparation of two-dimensional titanium carbide (Ti3C2Tx) and NiCo2O4 composites to achieve
excellent microwave absorption properties, Composites Part B (2019), doi: https://doi.org/10.1016/
j.compositesb.2019.107577.

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Graphical Abstract:
 Preparation of two-dimensional titanium carbide (Ti3C2Tx)
and NiCo2O4 composites to achieve excellent microwave
absorption properties
Tianqi Hou1,#, Bingbing Wang1,#, Mingliang Ma2, Ailing Feng3, Zhengyong Huang4,
Yi Zhang5, , Zirui Jia1,*, Guangxin Tan1, Haijie Cao1, Guanglei Wu1,*
*

1
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, P. R. China;
2
Research Institute of Functional Materials, School of Civil Engineering, Qingdao
University of Technology, Qingdao 266033, P. R. China;
3
Institute of Physics & Optoelectronics Technology, Baoji University of Arts and
Sciences, Baoji 721016, P. R. China;
4
State Key Laboratory of Power Transmission Equipment & System Security and
New Technology, Chongqing University, Chongqing 400040, P. R. China;
5
School of Materials Science and Engineering, Henan University of Science and
Technology, Luoyang 471023, P.R. China;
*Correspondence: zhshgu436@163.com (Y. Zhang); jiazirui@mail.nwpu.edu.cn (Z.
Jia); wuguanglei@qdu.edu.cn/wuguanglei@mail.xjtu.edu.cn (G. Wu);
Tel./fax.: +86 532 85951496
#
contributed equally to this work.
Abstract
The appearance and development of two-dimensional titanium carbide materials
provide a new idea for our research on microwave absorption materials. Its excellent
electrical conductivity and surface functional groups allow it to be used as a
microwave absorber. In this study, Ti3C2Tx@NiCo2O4 composites were prepared by
simple hydrothermal method and subsequent annealing process. With the change of
annealing temperature, the state of composites is changed, so the structure and
properties of samples are further adjusted. When the annealing temperature is 350℃,
an optimal reflection loss value of -50.96dB can be obtained at 2.18mm. The excellent
microwave absorption performance is not only caused by polarization behavior, but
also related to multiple reflections and multiple scattering produced by unique
structures. Therefore, the prepared Ti3C2Tx@NiCo2O4 is expected to be a promising
microwave absorber with thin thickness and high absorption intensity.
Keyword: MXene, Interface Polarization, Microwave absorption, Multiple
Reflections, Transition metal oxide

1. Introduction

With the rapid advancement of radio technology and modern science, many
high-power electronic devices are widely used in our life. At the same time,
microwave radiation has caused tremendous damage to our environment and people.
Therefore, researchers are increasingly concerned about the progress in the field of
microwave absorbing materials [1-5]. By using an ideal microwave absorber to absorb
excess electromagnetic waves, it is possible to meet the requirements [6,7]. The ideal
microwave absorbing material should exhibit the characteristics of light weight, high
absorption efficiency and large effective absorption bandwidth.
According to previous reports, graphene [8,9] RGO [10,11] carbon nanotubes
[12] etc. which all have good dielectric constants are widely investigated in the study
of microwave absorption. As a kind of material with two-dimensional structure
composed of carbides and nitrides of transition metals, MXene was first reported by
Yury Gogotsi et al in 2011 [13]. Ti3C2Tx was obtained by etching Ti3AlC2 and it was
one of the most studied members of the MXene series. It is obtained by selectively
etching Al element from the three-dimensional lamellar maximum phase. It has the
general formula of Mn+1XnTx, in which M only represents early transition metals (e.g.
Mo, Nb, and Ti), n=1, 2 or 3, and X is -O, -OH or –F [14]. Ti3C2Tx has the potential of
microwave absorption due to its special layered structure, good conductivity, high
dielectric constant, dielectric loss matching with ohmic loss and other characteristics.
These characteristics are beneficial to electromagnetic microwave absorption.
Therefore, Ti3C2Tx was selected as part of the composite material. According to the
relevant report [15,16],etching the Ti3AlC2 at room temperature with different
concentrations of hydrofluoric acid can result in an accordion-like multilayer structure
with different etching degrees. Subsequent addition of some intercalating agents, such
as DMSO, TMAOH, etc. can bring to a greater lamellar spacing of the layered
structure. When the solution of the intercalant is added by centrifugation, a large-sized
Ti3C2Tx sheet can be prepared by a hand-shake method.
In recent years, MXene (Ti3C2Tx) has been used in solar cells, supercapacitors,
catalysis and electromagnetic shielding [17-20]. Similarly, MXene (Ti3C2Tx) has also
been widely studied in microwave absorbers. Yin et al. prepared a layered C/TiO2
hybrid by calcining at 800 in a carbon dioxide atmosphere using Ti3C2Tx as a raw
material. When the thickness of the prepared absorber is 1.7 mm, the value of
minimum reflection loss is -36 dB, and the effective bandwidth reaches 5.6 GHz [21].
Because of multiple reflection and polarization relaxation, the aerogel composites
exhibit preferable microwave absorbing performance with the low density. And when
the corresponding thickness is 2mm, the minimum reflection loss of the material is
-43.4dB at 11.2GHz, and the effective bandwidth is 4.5GH [22]. Xu et al. synthesized
MXene/Fe3O4 composites by a special hydrothermal method and then annealed to
obtain C/TiO2/α-Fe composites, wherein the minimum reflection loss is -45.1dB at 3.9
GHz and effective bandwidth about 3.5GHz, with a thickness of 3.5mm [23]. Wu et al.
successfully prepared NiCo2O4-CoNiO2 hybrid material. When the calcination
temperature reaches 450 , the hybrid materials have excellent MA performance,
which can be attributed to the current role of double polarization and polarization of
the sample. The minimum reflection loss of the hybrid material calcined at 450 is
-42.13dB at 11.84GHz with the corresponding thickness of 1.55mm, and the effective
bandwidth is 3.92GHz (13.12-17.04GHz) [24]. He and Zhou et al. designed a
three-dimensional layered TiO2/Ti3C2Tx/RGO composite aerogel, wherein the
minimum RL value of obtained absorber – is 65.3dB at 10.2GHz with the thickness of
2.5mm and the effective bandwidth is 4.3GHz [25]. All the above results show that
MXene (Ti3C2Tx) is an effective MA material and has great potential in microwave
absorption. Nevertheless, due to the defects of electronic conduction and impedance
matching, pure MXene (Ti3C2Tx) is difficult to be used as microwave absorbing
material. As is known to all, cobalt-nickel oxides (such as NiCo2O4) are widely used
in the field of electrochemistry due to their excellent electrochemical properties. So
far, they haven't reported much on microwave absorption. Especially the
Ti3C2Tx@NiCo2O4 composite.
In this study, we have successfully prepared MXene@NiCo2O4 composites by
simple solvothermal method and studied their microwave absorbing properties. The
results show that Mxene@NiCo2O4 composites have excellent MA performance,
which is owing to the fact that a few layers of MXene can achieve multiple reflection
effect. Meanwhile, the spherical NiCo2O4 has core-shell structure and can effectively
absorb microwave. The minimum reflection loss (RL) can reach -50.96 dB at 12.24
GHz, and the effective absorption bandwidth ranged from 11.76 GHz to 12.64 GHz at
a thickness of 2.18 mm. It is not hard to find that two-dimensional titanium carbide
(Ti3C2Tx) and NiCo2O4 composites meets our requirements as an ideal absorbers.

2. Experimental section

2.1. Materials
Lithium fluoride (LiF, Alfa Aesar, 98.5%), hydrochloric acid (HCl, Fisher
Scientific, 37.2%), Ti3AlC2 powers were purchased from Jilin 11 Technology
Company Limited. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O), Nickel nitrate
hexahydrate (Ni(NO3)2·6H2O), Glycerol, Isopropyl alcohol. Other reagents are
analytical reagents, which can be used without further purification. They are
purchased from Chemical Reagents Company Limited of China Pharmaceutical
Group.
2.2. Synthesis of Ti3C2Tx
The synthesis of Ti3C2Tx has been improved by previous reports [15]. First, 1.5g
LiF was dissolved into 30 ml 6M hydrochloric acid under stirring. After the LiF
powder was completely dissolved, the Ti3AlC2 powder of 1g was added to the above
solution. Then, the mixed solution was maintained for 48 hours at 40 . And
centrifugation was adopted to wash the mixed solution several times with deionized
water until the pH of the solution is higher than 6. It is worth mentioning that it takes
2-4 minutes to shake hands before each centrifugation. Finally, the supernatant was
reserved after centrifuged at 3500 rpm for 1 hour.
2.3. Synthesis of MXene(Ti3C2Tx)@NiCo2O4 Composites
Spherical NiCo2O4 was prepared by simple solvothermal method. 0.0072g cobalt
nitrate hexahydrate, 0.0036g nickel nitrate hexahydrate and 6ml glycerol were
dissolved in 40ml isopropanol and stirred for 15 minutes with a glass rod until the
solution was bright pink. The above solution was transferred to 100ml PTFE liner and
maintained for 6h at 180 . After the reaction, the solution was washed to PH=6 or so,
and evenly mixed with mxene supernatant by magnetic stirring. The precipitate was
collected by vacuum filtration and dried under vacuum at 80°C for 12 hours. Finally,
in order to obtain samples, the dry powder was annealed at various temperatures
(350°C, 400°C, 450°C and 500°C) for 2 hours in an argon atmosphere at a heating
rate of 1°C/min. The obtained samples can be labeled as S1, S2, S3 and S4
respectively.
2.4. Characterization and measurements
The Powder X-ray diffraction (XRD) was performed on a Rigaku Ultima IV with
Cu-Ka radiation (λ = 0.154178 nm). Field emission scanning electron microscopy
(F-SEM; JEOL JSM-7800F) and transmission electron microscopy (TEM; JEOL
JEM-2100) were carried out to obtain morphology and nanostructure of all samples.
Raman spectral patterns were obtained using a Renishaw inVia Plus Micro-Raman
spectroscopy system using a 50 mW DPSS laser at 532 nm. The X-ray photoelectron
spectroscopy (XPS) patterns were collected on a Thermo Fisher ESCALAB 250Xi
spectrometer with an Al Ka X-ray source (1486.6 eV). The Fourier transform infrared
spectroscopy (FT-IR, Nicolet iS50) was chosen to study the surface structure of the
sample.
2.5. Electromagnetic parameters
Since paraffin does not affect the complex permittivity and complex permeability
of the material, paraffin wax is selected as the matrix material to study the microwave
absorption properties of the synthesized sample. The composites for measuring
microwave absorption properties were prepared by mixing paraffin wax with 50 wt%
Ti3C2Tx, and pressing them into rings with a thickness of about 2 mm. The complex
dielectric constant (εr=ε'-jε") and magnetic permeability (µr=µ'-jµ") were measured by
a vector network analyzer (E5080A, Key Sight) using the set parameters in the range
of 2.0-18.0 GHz. The weight ratio of the composite to paraffin wax is 1:1. The RL
values can be calculated according to the generalized transmission line theory using
the following formulas [26-29]:

µγ  2πfd 
Z in = Z 0 tanh j   ε γ µγ (1)
εγ  c 

Z in − Z 0
RL(dB) = 20 log (2)
Z in − Z 0

Where Zin in the formula stands for the normalized input impedance of the
absorber, Z0 indicates the characteristic impedance in free space, f corresponds to the
electromagnetic wave frequency, d represents the thickness of the absorber, and c is
the velocity of the electromagnetic wave in free space. When the value of RL is less
than -10dB, it means that 90% of the electromagnetic wave can be absorbed by the
absorber, and the frequency range corresponding to the RL value below -10dB is the
effective absorption bandwidth of the absorber.

3. Results and discussion

3.1 process flow of the MXene and NiCo2O4 Composites

Scheme 1 reveals the preparation process of Ti3C2Tx@NiCo2O4 composites. In
the course of the synthesis, the bulk Ti3AlC2 was in-situ etched using lithium fluoride
and hydrochloric acid, followed by hand-peeling to prepare a few layers of Ti3C2Tx
sheets (Schema 1a).Then, the NiCo–glycerate are dried and annealed in air. Results
the above process can obtain spherical NiCo2O4 (Schema 1b).
As can be seen from previous reports, MXene has a strong surface energy, and its
surface has a very rich functional group, such as -O, -OH and -F, which are beneficial
to some substances adsorbed on its surface. The annealed spherical NiCo2O4 was
added to the Ti3C2Tx supernatant and continuously stirred and sonicated. NiCo2O4
spheres adsorbed on the surface of Ti3C2Tx due to the interaction between the
oxygen-containing functional groups on the surface of Ti3C2Tx and NiCo2O4 or the
van der Waals interaction between Ti3C2Tx and NiCo2O4 beads. Finally, we got the
Ti3C2Tx@NiCo2O4 composite we are craving (Schema 1c).

Scheme.1. A Flow Chart Embodying Sample Preparation.

3.2 Micro-morphology and composition of MXene (Ti3C2Tx)@NiCo2O4
composite
To understand the crystal construction of the composites, X-ray diffraction was
used to characterize the composites. As shown in Fig. 1a, the corresponding
characteristic peak of Al in Ti3AlC2 at 2θ = 39°, disappeared, which means that Al
elements in Ti3C2Tx were successfully etched. Furthermore, it can be clearly seen
from the figure that the characteristic peak corresponding to the (002) crystal plane of
Ti3AlC2 is shifted from 9.48° to 6.08°, which also proves the disappearance of Al
intercalation [30]. As shown in Fig. 1b, the XRD pattern of composites clearly shows
the diffraction peak of the corresponding Ti3C2Tx (002) crystal plane at 2θ = 6°. After
a simple mixing of Ti3C2Tx and NiCo2O4 spheres, the diffraction peaks representing
NiCo2O4 phase (JCPDS No. 20-0781) were observed at 2θ= 31.14°, 36.69°, 44.62°,
55.43°, 59.09° and 64.98° for all Ti3C2Tx@NiCo2O4 composites. This means the
successful formation of NiCo2O4. In addition, the diffraction peaks of calcined
samples become sharper with the increase of calcination temperature, which is due to
the larger crystal size of the samples. At the same time, the characteristic peaks of the
samples increased significantly with the increase of calcination temperature, which
can be attributed to the agglomeration of the crystals.

Fig. 1. XRD images of (a) Ti3AlC2, Ti3C2Tx and (b) Ti3C2Tx@NiCo2O4.

FTIR spectrum of Ti3C2Tx and Ti3C2Tx@NiCo2O4 are given in Fig. 2a. Among
the five curves in the figure, the stretching bands at 1398 cm-1, 2300 cm-1and 3415
cm-1 can be attributed to hydrogen bonding (O-H), hydroxyl (-OH) and adsorbed
water molecule [31]. The characteristic peak at 1629 cm-1 is the result of C=O tensile
vibration. At the same time, the characteristic peak at 651 cm-1 is the absorption peak
of oxide for composites calcined at different temperatures. Furthermore, the peak of
Ti3C2Tx appears at 566cm-1, which can be attributed to the stretching vibration of Ti-O
[32,33]. This also confirms the conclusion of XRD image and the successful
fabrication of composite materials. On the other hand, the peaks of S1 and S2 at 1398
cm-1 migrated to low wavenumber, which may be caused by different interactions
between the bonds. Furthermore, it can be seen from the infrared spectra that no
characteristic peaks appear or disappear in the oxide composites prepared at different
calcination temperatures, indicating that they are relatively stable at the corresponding
temperatures. For further study of prepared samples, Raman spectroscopy was also
studied. The Raman spectrum images of pure Ti3C2Tx and composites are given in Fig
2(b). For pure Ti3C2Tx, a very distinct characteristic peak was observed around 200
cm-1 which represents the A1g mode of Ti3C2O2 [34]. The other two peaks around 380
cm-1 and 600 cm-1 are attributable to the vibration model of the non-stoichiometric
titanium carbide phase. The characteristic suits of the composite at 523 cm-1 and 651
cm-1 were formed by vibrations of octahedron/Ni2+ and octahedron/Co3+, respectively
[35]. Incidentally, the difference in peak strength of the four samples at 523cm-1 and
651cm-1 is due to the mass of the samples. Further, lattice disorder caused by
octahedral elements sharing edges and substitution of Ni2+ leads to the generation of
dipole polarization, improving the microwave absorption performance. At the same
time, the characteristic peak of Ti3C2Tx can also be observed in the curve of the
composite material, which is completely consistent with the previous assumption.

Fig. 2. (a) FT-IR spectra of Ti3C2Tx and Ti3C2Tx@NiCo2O4(b) Raman spectra of

Ti3C2Tx@NiCo2O4.
The chemical composition of Ti3AlC2 and Ti3C2Tx was characterized by XPS
analysis. As is easily seen from Fig. 3(a), Ti3AlC2 is composed of O, Ti, C, and Al
elements. In the curve of the Ti3C2Tx obtained by etching, the peak of the Al element
disappears, which is consistent with the result of the previous XRD. The Ti2p spectra
of Ti3C2Tx is shown in Fig 3(b). The five curves fitted in the spectrum, each of which
is a component of Ti2p 1/2 and Ti2p 3/2. Ti2p can be divided into 5 pairs of peaks,
corresponding to Ti-C (454.6eV), Ti( ) (455.6eV), Ti( ) (456.6eV), TiO2 (458eV)
and Ti-F (458.6eV), respectively. These peaks are quite consistent with those
previously reported [37]. For the O1s spectrum in Fig. 3(c), characteristic peaks at
positions 529.8eV, 530.5eV, 531.8eV and 533eV can be assigned to O-Ti, TiO2,
Ti-OH, Ti-H2O [38]. The curve of C1s in Fig. 3(d) is fitted by four peaks, among
them, 281.6eV corresponds to C-Ti, which is formed due to the introduction of defects
during etching. 284.6eV and 285.7eV correspond to C-C and C-O. And the former
formation can be attributed to the etching process. The selective dissolution of Ti in
the latter may be the reason why the material is exposed to the atmosphere during the
preparation process. Finally, 289.9eV corresponds to the characteristic peak
contributed by O-C=O.

Fig.3. (a) Survey spectra of Ti3AlC2 and Ti3C2Tx. XPS spectra of (b) Ti 2p, (c) O 1s,
and (d) C 1s for Ti3C2Tx.
The detailed element composition of Ti3C2Tx@NiCo2O4 composite was further
characterized by XPS (Fig. 4). The total spectrum of Ti3C2Tx@NiCo2O4 composite
proves that there are five typical peaks corresponding to Ni 2p, Co 2p, Ti 2p, O 1s and
C 1s respectively (Fig. 4a). The Ni 2p spectrum corresponds to two spin dipole
orbitals of Ni2+ and Ni3+. Among them, the peaks located at 853.6eV and 872.8eV
belong to Ni2+, and the peak stood for Ni3+ center at 854.9eV. The peaks at 861eV and
879eV can be attributed to the two satellite oscillation peaks of nickel (Fig.4b). It can
be seen from Fig. 4c that there are two main peaks in the spectrum of Co 2p, which is
namely Co 2p3/2 centered at 779.3 eV and Co 2p1/2 centered at 794.9 eV.
Fig.4. (a) Survey spectra of Ti3C2Tx/NiCo2O4. High-resolution XPS spectra of (b) Ni
2p, (c) Co 2p, (d) Ti 2p, (e) C 1s and (d) O 1s.
As the calcination temperature reaches 350℃, part of Co3+ is reduced to Co2+. A
large amount of Co2+ will cause disordered arrangement of the crystal lattice, thus
forming oxygen vacancy. Interestingly, The presence of oxygen vacancies will bind
the surrounding electrons and act as electron donors, improving charge transfer and
promoting charge separation. The polarization center generated by charge separation
is beneficial to electromagnetic wave absorption. However, with the continuous
increase of temperature, Co2+ is oxidized, which leads to the decrease of Co2+, and the
performance of the composite material is reduced. Fig 4d shows the XPS spectrum of
Ti 2p. The Ti 2p spectrum can be divided into three peaks, which correspond to Ti(IV)
(458.1eV), Ti-F (458.6eV) and TiO2 (464.0eV). The C 1s spectrum of the composite
discloses the peak located at 284.8 eV is C-C, the peak located at 286.1 eV is C-O and
a peak situated at 288.6eV is O-C=O (Fig 4e). As shown in Fig. 4f, the characteristic
peaks appear at four positions of 529.1 eV, 530.3 eV, 531.5 eV and 533.2 eV, which
correspond to metal oxygen bonds, titanium oxide formed by slight oxidation, oxygen
vacancies, and water adsorbed by physical and chemical methods.
The microstructure of pure Ti3C2Tx was analyzed by SEM and TEM. As shown
in Fig. 5(a), the prepared Ti3C2Tx layer whose surface is relatively smooth is about 10
µm. Fig. 5(b) shows the thin layer structure of Ti3C2Tx, which is consistent with the
results of SEM (Fig. 5(a)). Fig. 5(c) displays the HRTEM of Ti3C2Tx with interplanar
spacing d=0.25nm and 0.23nm, corresponding to (006) and (103) crystal planes,
respectively [39]. The crystal structure of Ti3C2Tx is further confirmed by electron
diffraction of the selected region (Fig. 5(d)), and the image shows the hexagonal
arrangement of atoms.

Fig.5. (a) SEM images of Ti3C2Tx. (b) TEM and (c) HRTEM images of Ti3C2Tx. (d) is
the corresponding SAED pattern.
The microstructure and morphology of Ti3C2Tx@NiCo2O4 composites were
characterized by scanning electron microscopy (SEM). Fig. 6a, b, c, and d correspond
to SEM images of composites prepared by calcining spherical NiCo2O4 at four
different temperatures. As shown in Fig. 6(a), the NiCo2O4 particles calcined at 350 °
C have a smooth surface and are relatively uniformly distributed on the surface of the
Ti3C2Tx sheet. And the diameter of the NiCo2O4 particle is approximately 200 nm. In
Fig. 6(b), the NiCo2O4 spheres are mainly distributed around the Ti3C2Tx sheets, and
the particles have irregular shapes with the increase of the calcination temperature,
and some even have cracks. Fig. 6(c) clearly shows that most of particles in S3 are
gathered together and the specific surface area is reduced, which may result in a
decrease in the MA performance of the sample.

Fig.6. SEM images of (a) S1, (b) S2, (c) S3, (d) S4.
In Fig. 6d, although there is no significant agglomeration, the size of the particles
is no longer regular and the extent of the crack is more severe than S2. In addition, the
elemental mapping of the Ti3C2Tx @NiCo2O4 composite is also shown. Fig. 7a-e
show the elemental distribution of Ti, O, Co and Ni in the composite, confirming the
uniformity and integrity of the composite. The EDS image of the composite further
demonstrates the above results (Fig. 7f).
 Fig.7. (a) SEM image of Ti3C2Tx@NiCo2O4 composite material and corresponding
element mapping images of (b) Ti, (c) O, (d) Co and (e) Ni elements. (f) The EDS
pattern of Ti3C2Tx@NiCo2O4 composite.
The prepared two-dimensional titanium carbide (Ti3C2Tx) and NiCo2O4
composites were further characterized by TEM. Fig. 8a, d, f, h show the structures of
S1, S2, S3, and S4, which are consistent with the results of SEM. Fig. 8a confirms the
uniform distribution of NiCo2O4 beads on the MXene sheet. Then, the interplanar
spacing of 0.47 nm and 0.24 nm corresponds to the (111) and (311) crystal planes of
NiCo2O4, respectively (Fig. 8b). The selected area electron diffraction pattern (SAED)
of Fig. 8c exhibits the polycrystalline structure of NiCo2O4, which is well matched to
the previous XRD results. From the TEM image of S2 (Fig. 8d), few small spheres
have a core-shell structure (Marked in Red circle), but their surfaces have already
exhibited significant folds. The TEM images (Fig. 8f, h) corresponding to S3 and S4
exhibit very rough surfaces, which are associated with many small nanoparticles. It is
agglomerated and the size is slightly different from It can be seen from the HRTEM
image of (Fig 8g, i) that the interplanar spacing of 0.28nm and 0.47nm corresponds to
the (220) and (111) crystal planes of NiCo2O4. Although the morphology of the four
samples did not be changed significantly, it could be seen from SEM and TEM images
that the spherical structure of NiCo2O4 was destroyed with the increase of calcination
temperature. At the same time, TEM images also show the subtle changes inside the
spherical NiCo2O4 as the calcination temperature increases. All these will affect the
mechanism of microwave absorption such as interface polarization and multiple
scattering. Thus the electromagnetic constant of the composite material is affected.

Fig.8. (a) TEM image, (b) HRTEM image, (c) the SAED pattern of S1,TEM and
HRTEM images of S2(d,e),S3(f,g) and S4(h,i).
In order to show the relationship between frequency and RL value of Ti3C2Tx
with different thickness, a three-dimensional figure is drawn as shown in Fig. 9a.
When the frequency is 10.08GHz, the minimum reflection loss value is - 28.18dB at
2.1mm. But this can’t meet the requirements of our ideal absorber. The complex
permittivity and permeability of Ti3C2Tx are demonstrated in Fig. 9b and c. According
to previous reports, the storage capacity of electromagnetic energy is represented by
the real part of complex permittivity (ε') and complex permeability (µ'), and the
internal dissipation of electromagnetic energy is represented by the imaginary part (ε"
and µ") [40]. As shown in Fig. 9, the real and imaginary parts of Ti3C2Tx complex
permittivity are in the range of 16-6 and 6-9 respectively. Ti3C2Tx has a higher real
part compared with other similar materials, which is closely related to the excellent
conductivity of Ti3C2Tx. In addition, the peaks of imaginary part can be attributed to
polarization and related relaxation. Layer delamination of Ti3C2Tx leads to interfacial
polarization, while defects in the layer cause dipolar polarization. The real part of
complex permeability (µ') increases from 0.1 to 1, while the imaginary part decreases
from 0.6 to -0.6 (fig. 9c). The imaginary part (µ") can be used to explain the magnetic
loss of materials, while the three resonance peaks appearing in the imaginary part
curve can be attributed to multiple magnetic resonances. Fig. 9d shows the
relationship between dielectric loss angle tangent (tanδE) and magnetic loss angle
tangent (tanδM) with frequency of Ti3C2Tx. In the frequency range of 2-18 GHz, the
tangent value of tanδE increases from 0.4 to 1.5, which is due to the interfacial
polarization of Ti3C2Tx layer. On the other hand, magnetic loss occurs in the
megahertz frequency range [41, 42]. And the thickness of the actual sample is much
smaller than that of resonance. Therefore, the magnetic loss of Ti3C2Tx is almost
negligible.

Fig.9. (a) Three-dimensional representation of RL values for the Ti3C2Tx. Frequency

dependence on (b) complex permittivity curves, (c) complex permeability curves, (d)
dielectric loss tangent and magnetic loss tangent of Ti3C2Tx.
Fig. 10 shows a model of the three-dimensional reflection loss of four
composites. From Fig. 10 can get the conclusion that S1 is endowed with the
minimum RL value of -50.96dB at 12.24GHz and 2.18mm thickness. With the
increase of the calcination temperature of NiCo2O4 pellets, the RL value of the
corresponding composites shows a downward trend, which is related to the complex
dielectric constant of the composite material mentioned later as well as the complex
magnetic permeability. The minimum RL value of S2 is -43.15 dB with a thickness of
2 mm (Fig. 10b). The minimum RL value of S3 is -28.96 dB at the frequency of 5.92
GHz and the thickness of 4.9mm (Fig. 10c). For S4, although the RL value of -37.23
dB is obtained at 6.56 GHz, the corresponding thickness reaches 4.5 mm, which does
not meet the requirement of thin thickness absorbers.

Fig.10. Three-dimensional representation of RL values for the paraffin-based

composites : (a) S1, (b) S2, (c) S3 and (d) S4.
Fig. 11a-d further illustrate the relationship between RL value and frequency at a
particular thickness. The above two figures show that the Ti3C2Tx@NiCo2O4
composite has excellent MA behavior. It can be intuitively seen from Fig 10 and Fig
11 that, with the increase of calcination temperature, the RL value of the other three
samples decreased to a certain extent compared with S1. In combination with XRD
images and SEM images, with the increase of calcination temperature, although the
crystallinity of NiCo2O4 increased, the spherical structure of NiCo2O4 was destroyed,
which affected part of the microwave absorption mechanism of the composite
material, thus leading to a decrease in the performance of the composite.

Fig.11.Theoretical RL curves versus frequency and thickness of (a) S1, (b) S2, (c) S3,
and (d) S4
The relationship between complex permittivity and complex permeability with
frequency of MXene@NiCo2O4 composites is shown in Fig. 12a-f. Fig. 12 (a, b)
show the frequency dependence of the complex permittivity of different samples. For
S2, the real part of complex permittivity changes from 10 to 9, the imaginary part
increases from 1.5 to about 1.9 in the 2-18 GHz. The apparent peak near 12 GHz can
be understood as interfacial polarization and defect polarization. The real part of the
complex permittivity of S4 is similar to that of S1, which is relatively stable in the
whole frequency band. The appearance of vibrational peaks is the result of interfacial
polarization. The imaginary part of the complex permittivity of S4 increases from
about 0.5 to 0.9, indicating that its electromagnetic dissipation is not as good as that of
S1, which is consistent with the conclusion of the three-dimensional RL value model.
The ε' and ε" of the sample S3 are relatively stable in the range of 2-18 GHz, but there
are obvious fluctuations around 15 GHz, which can be understood as the related
polarization phenomena and relaxation behavior. Polarization phenomena include
interfacial polarization due to Ti3C2Tx multilayer structure and dipole polarization due
to external defects of NiCo2O4 sphere. The real part of the complex permittivity of S1
remained stable between 2 and 12 GHz, and there were five obvious vibration peaks
in the rest of the frequency. The formation of the peaks could be attributed to more
migration charges induced at the interface and the junction, which caused the interface
polarization. Furthermore, the free ions in NiCo2O4 are captured by the Ti3C2Tx
interface during the movement. Therefore, agglomeration of space charges is formed
in the interface region, and the motion of these charges generates an electric dipole
moment. [43-45]. Meanwhile, the ε" of the S1 increases from about 0.75 to 1.5, which
proves that S1 has strong electromagnetic dissipation ability that is conducive to the
improvement of electromagnetic microwave absorption. For the Ti3C2Tx@NiCo2O4
composite, multiple interfaces between Ti3C2Tx, NiCo2O4 and the cavity can improve
the microwave absorption behavior. Fig. 12c and d show the µ' and µ" of four
composite materials. The µ' of all samples have similar trends in the same frequency
range, which indicates that they have similar electromagnetic storage capacity. It can
be easily observed that there are obvious fluctuations in the frequency range of 5-6
GHz and 12-13 GHz, which may be attributed to small surface effect, size effect and
hysteresis resonance [46]. And their imaginary parts also have vibration peaks in the
same range, which can be understood as the role of magnetic resonance and eddy
current effect. According to previous reports, eddy current effects which usually
occurs in high frequency range may hinder electromagnetic wave penetration through
absorbers and negatively affect electromagnetic dissipation performance [47].
Because spheres in S1 are uniformly dispersed on the lamellae, the eddy current effect
is effectively limited, so the vibration peak is relatively small in the corresponding
range. For S3, the fluctuation of real part and imaginary part of permeability in the
frequency range of 2-18 GHz is smaller than that of other samples, which also proves
that its magnetic properties are very limited. Therefore, its microwave absorption
performance is lower than that of the other three samples. It is worth noting that all
samples produced resonance phenomena due to energy absorption of incident
electromagnetic waves in a specific frequency range and spinning effect [48]. In
addition, the dependence of tanδε and tanδµ on frequency of four samples is shown in
Fig. 12e, f. Generally, the tanδε and tanδµ correspond to the dielectric loss and
magnetic loss properties of the sample. Due to the existence of the resonance
phenomenon, the curve shows two distinct peaks. In most frequency ranges, the tanδµ
of the corresponding sample is larger than that of tanδε, which indicates that the
prepared MXene@NiCo2O4 composite is a kind of magnetic loss microwave
absorbing material.

Fig.12. Frequency dependence on (a, b) relative complex permittivity curves, (c, d)

relative complex permeability curves, (e) dielectric loss tangent, and (f) magnetic loss
tangent of S1, S2, S3 and S4.
To further explain the microwave absorption enhancement mechanism of the
MXene@NiCo2O4 composites, RL and characteristic impedance Z versus frequency
are presented in Fig. 13. The normalized characteristic impedance (Z=|Zin/Z0|) is one
of the important conditions for evaluating the MA properties of materials [24,49] It
can be seen from the image that the minimum reflection loss can be obtained when
the matching thickness and frequency are 2.18mm and 12.24 GHz. At the same time,
the corresponding Z is almost equal to 1, which shows that S1 possess outstanding
impedance matching.

Fig.13. The frequency dependence of RL values for the sample S1 and the modulus of
normalized input impendence (|Zin/Z0|) for the sample S1.
The strong attenuation constant are beneficial to improve EM absorption
behavior of the material. The attenuation constant alpha can be explained by the
following [50-52]:

2πf
α= (µ"ε "− µ ' ε ') + (µ"ε "− µ ' ε ')2 + (µ"ε "+ µ ' ε ')2 (3)
c

Generally, there is no fixed relationship between dielectric and magnetic loss and
alpha value. High dielectric loss and magnetic loss result in large alpha values, but
vice versa. This phenomenon is clearly shown in Fig. 14. The attenuation constant α
of S1, S2, S3 and S4 increases from 2.6 to 122.1, 3.3 to 127.7, 5.2 to 36.1 and 3.3 to
246.7. Although S4 has the largest attenuation constant α in the frequency range, S1
has the best MA performance and the impedance matching is optimal. Therefore, for
Ti3C2Tx@NiCo2O4 composites, impedance matching is the most important factor to
improve MA performance.

Fig.14. The attenuation constant α of S1,S2,S3,S4.

The microwave absorption properties of Ti3C2Tx@NiCo2O4 composites and
other absorbing materials based on Ti3C2Tx and NiCo2O4 are compared in Table 1.
Compared with the listed materials [24, 53-57], it can be concluded that the prepared
Ti3C2Tx@NiCo2O4 composite can obtain excellent MA properties at a thin thickness.
Table 1.The comparison of MA properties of various absorption materials.
Microwave absorption Mass Ratio Minimum RL Thickness Reference

materials (wt%) (dB) (mm)

NiCo2O4-CoNiO2 50 -42.13 1.55 [27]

Ti3C2Tx/Ni0.5Zn0.5Fe2O4 5 -42.5 6.5 [53]

C/TiO2 hybrids 45 -36 2.2 [54]

Ti3C2Tx/ppy 25 -42.9 3.2 [55]
ZnO-MXene Ti3C2Tx 25 -26.3 4.0 [56]
PVB/Co2Z/Ti3C2 30 -46.3 2.8 [57]
Ti3C2Tx@NiCo2O4 50 -50.96 2.18 This work
Generally, the complex permittivity is mainly affected by the Debye relaxation
process. According to the Debye dipole relaxation, the εr can be expressed by the
following formula [58-63]:

εs − ε∞
εγ = ε∞ + = ε '− jε " (4)
1 + j 2πfτ

Where f and τ represent the frequency and polarization relaxation time, respectively,
and ε∞ and εr represent the optical permittivity and the static dielectric constant,
respectively. Further derivation according to the above formula is available:

εs − ε∞
ε '= ε∞ + (5)
1 + (2πf ) γ 2
2

2πfγ (ε s − ε ∞ )
ε "= (6)
1 + (2πf ) γ 2
2

ε + ε∞  ε −ε 
2 2

 ε '− s  + (ε ") =  s ∞ 
2
(7)
 2   2 
On the basis of Equation 7, it can be concluded that the ε' and ε" curves can form
a semicircle, which is collectively marked as Cole-Cole semicircle, and each
semicircle represents a sequential Debye relaxation process [64-67]. ε' versus ε"
curves for four samples is shown in Fig.15a-d. Obviously, it can be seen from the
figure that there is a Cole-Cole semicircle for each sample, that is, there is a dielectric
relaxation process for each sample. Since the small spheres in S1 are uniformly
dispersed on the sheet, bonding charge and interface polarization are formed at the
interface. These phenomena are manifested in ε' versus ε" curve of S1, in which there
are multiple semicircles. This indicates that S1 has multiple dielectric relaxation
phenomena compared to other samples. In addition, the semicircles of S1 are more
pronounced, and unlike the images of S2 and S4 in which many points are stacked
together.
 Fig.15. Typical Cole-Cole models (a) S1, (b) S2, (c) S3 and (d) S4.
Combined with the above analysis, improving the impedance matching as well as
the dielectric and magnetic loss of the absorber are important for enhancing the MA
behavior. The excellent MA properties of Ti3C2Tx@NiCo2O4 composites can be
attributed to good impedance matching properties and the synergistic effect between
magnetic NiCo2O4 particles and Ti3C2Tx. The microwave absorption mechanism of
composites is shown in Scheme 2. First, the layered structure of Ti3C2Tx can provide a
large number of interfaces, resulting in interface polarization and related relaxation
phenomena. At the same time, the oxygen vacancies disrupt the balance of the charge
distribution and cause dipole polarization. Secondly, void and bending of Ti3C2Tx
sheets as well as evenly arranged between the Ti3C2Tx sheet with particles will
produce a large specific surface area. When the microwave is injected into the sheet
structure, the large specific surface area will provide interface polarization, which
effectively dissipates the incident wave. Third, the magnetic loss caused by eddy
current effect and resonance effect is also beneficial to improve the performance of
MA [68-72].
 Scheme.2. Scheme of microwave absorption mechanism of the Ti3C2Tx@NiCo2O4

4. Conclusion

In summary, the Ti3C2Tx@NiCo2O4 composite was prepared using a simple

hydrothermal method and annealing treatment. The structure, morphology and
microwave absorption properties of the composites were studied in detail by various
characterization methods. The prepared Ti3C2Tx sheet has a side length of about 10
µm, the spherical NiCo2O4 has a diameter of about 200 nm. And S1 has a minimum
reflection loss (RL) value of -50.96 dB at 12.24 GHz with a corresponding thickness
of 2.18 mm. The excellent MA properties of composite materials can be understood as
high dielectric loss and magnetic loss, multiple reflections and scattering caused by
lamellar structures, interface polarization, and a large number of polarization
phenomena. Therefore, Ti3C2Tx@NiCo2O4 composite materials can be applied to as
high-performance microwave absorbers.

Acknowledgements

This work was financially supported by the National Natural Science Foundation
of China (No.51407134, No.51603108, No.51707016, No.51801001), Natural
Science Foundation of Shandong Province (No.ZR2019YQ24), China Postdoctoral
Science Foundation (No.2016M590619, No.2016M601878, 2018T110944),
Provincial Key Research and Development Program of Shaanxi (No. 2019GY-197)
and the Qingchuang Talents Induction Program of Shandong Higher Education
Institution (Research and Innovation Team of Structural-Functional Polymer
Composites). 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.

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 Highlight

1. The Few layer of Ti3C2Tx sheets was prepared by hand shake. And the

composite material is prepared by a simple method.

2. The microwave absorption mechanism of the composite material is

explained, for example, interfacial polarization, multiple reflection, and

the like.

3. The higher reflection loss value was obtained with thinner thickness.
Declaration of interests

☒ 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.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: