nanomaterials

Article
Preparation and Characterization of Epoxy Resin
Filled with Ti3C2Tx MXene Nanosheets with Excellent
Electric Conductivity
Ailing Feng 1 , Tianqi Hou 2 , Zirui Jia 2, *, Yi Zhang 2 , Fan Zhang 3, * and Guanglei Wu 2,4, *
1 Institute of Physics & Optoelectronics Technology, Baoji University of Arts and Sciences, Baoji 721016, China;
ailing@mail.xjtu.edu.cn
2 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, China;
qdhoutq@163.com (T.H.); zhangy@njtech.edu.cn (Y.Z.)
3 School of Materials Sciences and Engineering, East China Jiaotong University, Nanchang 330013, China
4 Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, Harbin University of
Science and Technology, Harbin 150080, China
* Correspondence: jiazirui@mail.nwpu.edu.cn (Z.J.); zhang_fan2003@126.com (F.Z.); wuguanglei@qdu.edu.cn
or wuguanglei@mail.xjtu.edu.cn (G.W.); Tel./Fax: +86-532-85951496 (G.W.)




Received: 14 December 2019; Accepted: 14 January 2020; Published: 17 January 2020


Abstract: MXene represents new kinds of two-dimensional material transition metal carbides and/or
carbonitrides, which have attracted much attention in various applications including electrochemical
storage devices, catalysts, and polymer composite. Here, we report a facile method to synthesize
Ti3 C2 Tx MXene nanosheets and prepare a novel electrically conductive adhesive based on epoxy
resin filled with Ti3 C2 Tx MXene nanosheets by solution blending. The structure, morphology, and
performance of Ti3 C2 Tx MXene nanosheets and epoxy/Ti3 C2 Tx MXene nanosheets composite were
investigated. The results show that Ti3 C2 Tx MXene possesses nanosheet structure. Ti3 C2 Tx MXene
nanosheets were homogeneously dispersed in epoxy resin. Electrical conductivity and mechanical
properties measurements reveal that the epoxy/Ti3 C2 Tx MXene nanosheet composite exhibited both
good electrical conductivity (4.52 × 10−4 S/m) and favorable mechanical properties (tensile strength
of 66.2 MPa and impact strength of 24.2 kJ/m2 ) when the content of Ti3 C2 Tx MXene nanosheets is
1.2 wt %. Thus, Ti3 C2 Tx MXene is a promising filler for electrically conductive adhesive with high
electric conductivity and high mechanical performance.

Keywords: MXene; epoxy resin; electrical conductivity; mechanical properties

1. Introduction
With the progression of science and technology, electronic units are developing towards the
direction of miniaturization, portability, and high integration [1–5]. Therefore, the electronic packaging
industry demands interconnect bonding technology, which could offer excellent electrical conductivity,
good flexibility, and satisfied mechanical strength [6–9]. Besides, it should be cost effective and
environmentally benign. In this regard, electrical conductive adhesives (ECAs) are regarded as one of
the most feasible alternative interconnection materials for future applications due to low processing
temperature, fine pitch interconnect, and environmental friendliness [10–13].
ECAs consist of polymer (such as, acrylate resin, silicone, or epoxy resin) and electrical conductive
fillers (such as, Ag, Au, Ni, or carbon materials). The polymer resin provides interconnect bonding
properties while conductive fillers conduct electricity in ECAs. This polymer is widely used because
of its low density, high specific strength, dimensional stability, and chemical resistance [14–18].

Nanomaterials 2020, 10, 162; doi:10.3390/nano10010162 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 162 2 of 11

Many researches have studied epoxy-based ECAs [19]. The formation of effective conductive paths
in the ECAs is the key to obtain high electrical conductivity. Several conductive fillers have been
studied in ECAs; these include cobalt nanoparticles [20], zinc complexes [21,22], cadmium [23], metal
oxide [24], and so on. However, there are some issues such as aggregation and poor interconnect
between conductive fillers with polymer resin, which need to be solved.
MXenes is a new kind of transition metal carbide/nitride two-dimensional material with
graphene-like structure. Their chemical formulas are Mn+1 Xn , where M is an early transition metal,
X is C and/or N, and n represents the number of X (1, 2, or 3). MXenes are promising conductive
fillers due to intrinsic high conductivity and unique structure [25–27]. Carbon materials (graphene
or carbon nanotube) have to be oxidized to introduce oxygen-containing functional groups, which
prevent carbon materials aggregating in the polymer resin and assist binding between graphene/carbon
nanotube and EP resin. However, the appearance of some functional groups decreases the electronic
conductivity. MXene does not require any pretreatment to composite with other materials, as the
surface atomic of MXenes is Ti, which can easily bind the O atomic of EP resin. Therefore, MXenes
could well be dispersed in the polymer resin and provide high electric conductivity.
Herein, we report on the structure and performance of EP/MXene ECAs. Ti3 AlC2 was used as
the MAX precursor to prepare Ti3 C2 Tx MXene nanosheets. The crystal structure and morphology
of Ti3 C2 Tx MXene nanosheets were characterized by scanning electron microscope (SEM), X-ray
diffraction (XRD), and transmission electron microscopy (TEM). Different amounts of Ti3 C2 Tx MXene
nanosheets were introduced into ECAs to study the effect of Ti3 C2 Tx MXene nanosheets on the electrical
properties and mechanical performance of the EP/Ti3 C2 Tx MXene nanosheet ECAs. The results show
that the electrical property and mechanical performance of the EP/Ti3 C2 Tx MXene nanosheets ECAs
could be improved compared to pure EP resin. Our work may shed lights on the development of ECAs
with high electric conductivity and high mechanical performance in the electronic industry.

2. Experimental

2.1. Material
Epoxy resin and hardener tetrahyelrophthalic anhydride were purchased from Sigma-Aldrich.
The titanium carbide (TiC) powders were obtained from Alfa Aesar. Commercially available Ti2 AlC
was obtained from Kanthal Co., Ltd., Stockholm, Sweden; 36% hydrochloric acid (HCl) and lithium
fluoride (LiF, 98%) were bought from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China.

2.2. Preparation of EP/Ti3 C2 Tx MXene Nanosheets ECAs

The Ti3 AlC2 was prepared by mixing Ti2 AlC and TiC powders in a 1:1 M ratio, followed by
ball-milling at 300 rpm for 18 h. After being milled, the mixture was heated to 1350 ◦ C at 5 ◦ C/min in
an Al2 O3 tube furnace under Ar atmosphere. Then, the mixture was reacted at 1350 ◦ C for 2.0 h before
cooling again. The resulting product is Ti3 AlC2 .
First, 0.66 g LiF was added in 6 M HCI solution; 1.0 g Ti3 AlC2 powders were immersed in 50 mL
LiF/HCl solution. The mixture was stirred for 48 h at 40 ◦ C. The resulting suspension was washed
using distilled water five times and centrifuged to separate the powder from the supernatant. Then,
the obtained powder was sonicated for 2.0 h and rinsed three times with deionized water. Ti3 C2 Tx
MXene nanosheets were collected and dried in vacuum at 80 ◦ C for 24 h.
The resin mixture was uniformly mixed at the epoxy resin and curing agent (methyl
tetrahyelrophthalic anhydride) mass ratio equal to 100:32. Then, different amounts of Ti3 C2 Tx MXene
nanosheets added into resin mixture. To achieve uniform dispersion of Ti3 C2 Tx MXene nanosheets in
the epoxy resin, the mixture was mixed with a Flacktek Speed mixer at a speed of 2000 rpm for 0.5 h.
The curing process took place at 100 ◦ C for 2 h, 120 ◦ C for 2 h and 160 ◦ C for 4 h. After cooling to room
temperature, the resulting EP/Ti3 C2 Tx MXene nanosheets composites were obtained. The schematic
illustration of preparation of EP/Ti3 C2 Tx MXene nanosheets composites is illustrated in Figure 1.
 Nanomaterials 2020, 10, x FOR PEER REVIEW 3 of 12

schematic2020,
Nanomaterials illustration
10, 162 of preparation of EP/Ti3C2Tx MXene nanosheets composites is illustrated3 in
of 11
Figure 1.

Figure Theschematic
1.1. The
Figure schematic illustration
illustration forsynthetic
for the the synthetic procedure
procedure of 3Cthe
of the EP/Ti EP/Ti3 Cnanosheets
2Tx MXene 2 Tx MXene
nanosheets composites.
composites.

2.3.2.3.
Characterization
Characterizationand
andMeasurement
Measurement
The surface
The surfacemorphology
morphologyof ofTi Ti33AlC andTi
AlC22 and Ti33CC2T2xTMXene
x MXene nanosheets
nanosheets andand
the the fracture
fracture surfaces
surfaces of
of pure
pure EP,
EP, EP/Ti
EP/Ti33C
C22TTxx MXene
MXenenanosheets
nanosheetscomposites
compositeswere werecharacterized
characterized byby
SEMSEM (FEI,
(FEI, Quanta
Quanta 250,250,
Washington, WA, USA). The element contents
Washington, WA, USA). The element contents in Ti3C in Ti C T MXene
3 2T2x MXene
x nanosheets were characterized
nanosheets were characterized by
by energy-dispersive
energy-dispersiveX-ray X-ray (EDX,
(EDX, FEI,FEI, Quanta
Quanta 250).250). The phase
The phase structures
structures of 2Ti
of Ti3AlC 3 AlC
and Ti32Cand Ti3 C2 Tx
2Tx MXene

MXene
were were characterized
characterized by X-ray bypowder
X-ray powder
diffractiondiffraction (XRD, Rint-2000,
(XRD, Rint-2000, Rigaku,
Rigaku, Berlin, Berlin,using
Germany) Germany)
Cu
Kα Cu
using radiation (λ = 1.5418
Kα radiation (λ =Å)1.5418
operated at a voltage
Å) operated at of 30 kV and
a voltage of a30current
kV and ofa10 mA. Fourier
current transform
of 10 mA. Fourier
infraredinfrared
transform spectrum (FTIR, (FTIR,
spectrum IRpresitge-21 model,model,
IRpresitge-21 Tokyo,Tokyo,
Japan)Japan)
was wasusedused
to record
to recordthethe
Fourier
Fourier
transform
transform infraredspectra
infrared spectra ofof Ti
Ti33AlC
AlC 2 and
2
Ti
and C
3Ti2TCx MXene.
3 2 T x MXene.The internal
The morphology
internal of
morphologyTi 3C2Tof
x MXene
Ti 3 C2 Tx
nanosheets
MXene were studied
nanosheets using transmission
were studied electronelectron
using transmission microscope (TEM, JEOL,
microscope (TEM,JEM-2100 HT, Tokyo,
JEOL, JEM-2100 HT,
Japan). There are four methods (Volt-Ampere, double bridge, direct current
Tokyo, Japan). There are four methods (Volt-Ampere, double bridge, direct current four probe, and four probe, and digital
multimeter)
digital to measure
multimeter) the conductivity
to measure of composites.
the conductivity We usedWe
of composites. digital
usedmultimeter (830/F-33 (830/F-33
digital multimeter model,
Beijing Jiaxin Instrument, Ltd., Beijing, China) to test the resistance (R) of EP/Ti3C2Tx MXene
model, Beijing Jiaxin Instrument, Ltd., Beijing, China) to test the resistance (R) of EP/Ti3 C2 Tx MXene
nanosheets composites. Composite circles with a diameter of 20 mm and a thickness of 2 mm were
nanosheets composites. Composite circles with a diameter of 20 mm and a thickness of 2 mm were
prepared. Then we calculated the resistivity (ρ) of composite based on the diameter and thickness of
prepared. Then we calculated the resistivity (ρ) of composite based on the diameter and thickness of
samples. Electrical conductivity (K) is the reciprocal of resistivity (ρ) as follows: K = 0.0637/R (S/cm).
samples. Electrical conductivity (K) is the reciprocal of resistivity (ρ) as follows: K = 0.0637/R (S/cm).
The mechanical properties of EP/Ti3C2Tx MXene nanosheets composites were tested using tensile
The mechanical properties of EP/Ti3 C2 Tx MXene nanosheets composites were tested using tensile
testing machine (UTM-2460 model, Hebei JInjian Co., Ltd., Tangshan, China).
testing machine (UTM-2460 model, Hebei JInjian Co., Ltd., Tangshan, China).
3. Results and Discussion
3. Results and Discussion
3.1. The Structure and Morphology of Ti3AlC2 and Ti3C2Tx MXene
3.1. The Structure and Morphology of Ti3 AlC2 and Ti3 C2 Tx MXene
The SEM images of Ti3AlC2, Ti3C2Tx, and Ti3C2Tx nanosheets are shown in Figure 2. SEM images
The SEM images of Ti AlC2 , Ti3 C2 Tx , and Ti3 C2 Tx nanosheets are shown in Figure 2. SEM images
(Figure 2a,b) show that 3Ti3AlC 2 display a solid bulk morphology with uneven sizes. The smaller
(Figure 2a,b) show that Ti 3 AlC 2 display a solid bulk morphology with uneven sizes. The smaller
Ti3AlC2 MAX is about 2 μm while the larger one is about 20 μm. After HF etching, Ti3C2Tx show a
Ti3loosely
AlC2 MAX is about
packed 2 µm
structure whileofthe
consist larger oneTi
multilayered is3C
about 20 µm. After HF etching, Ti3 C2 Tx show
2Tx nanosheets, which had typical diameters of a
loosely packed structure consist of multilayered
2 μm (Figure 2c,d). The interlayer space of multilayered Ti C
3 2 Tx nanosheets, which had typical diameters
Ti3C2Tx is ~200 nm. This morphology is
of 2because
µm (Figure 2c,d).treatment
the LiF/HF The interlayer
removes space of multilayered
Al layers from Ti3AlCTi 3 C2 TxBy
2 MAX. issonication,
~200 nm. This morphology
the loosely packed is
because
Ti3C2Tthe LiF/HF
x MXene is treatment
converted removes Al layers
to nanosheets from
(Figure Ti3The
2e,f). AlC2TiMAX. By sonication,
3C2Tx MXene the loosely
nanosheets packed
have smooth
Ti3surface,
C2 Tx MXene is converted to nanosheets (Figure 2e,f).
which show a structure similar to that of graphene. The The Ti C T
3 thin MXene nanosheets have smooth
2 x sheet is of ~10 nm thick, which
surface, which to
corresponds show a structure
roughly 5 Ti3C2Tsimilar to that of graphene. The thin sheet is of ~10 nm thick, which
x layers.

corresponds to roughly 5 Ti3 C2 Tx layers.

To study the elements of Ti3 C2 Tx nanosheets, energy dispersive X-ray (EDX) analysis were carried
out. Figure 3 reveal EDX spectrum and SEM-EDX element mappings of Ti3 C2 Tx MXene nanosheets.
As shown in Figure 3a, Ti3 C2 Tx MXene thin nanosheets have diameters of 3 µm. In the EDX spectrum
(Figure 3b), four strong peaks are belonged to C, Ti, O, and F, whereas a weak peak assigns to Al.
As shown in Figure 3c, the uniform C, Ti, O, and F elemental distributions are observed. The composition
of Ti3 C2 Tx nanosheets, as calculated from EDS analysis, is shown in Table 1. The results showed that
the Ti3 C2 Tx MXene contains 11.0 wt % C, 69.0 wt % Ti, 11.1 wt % O, 7.8 wt % F and 1.1 wt % Al. The F
and O elements are attributed to presence of –F, –OH, and –COOH.
Nanomaterials 2020, 10, 162 4 of 11
Nanomaterials 2020, 10, x FOR PEER REVIEW 4 of 12

Figure
2. SEM2. SEM images
images ofofTiTi3 AlC
3AlC2 MAX (a) at a lower magnification, (b) at a higher magnification; SEM
Figure 2 MAX (a) at a lower magnification, (b) at a higher magnification;
images of accordion-like multi-layered
SEM images of accordion-like multi-layered Ti3CTi2T x (c) at a lower magnification, (d) at a higher
3 C2 Tx (c) at a lower magnification, (d) at a higher
magnification); SEM images of Ti3C2Tx nanosheets (e) at a lower magnification, and (f) at a higher
magnification); SEM images of Ti3 C2 Tx nanosheets (e) at a lower magnification, and (f) at a higher
magnification).
Nanomaterials 2020, 10, x FOR PEER REVIEW 5 of 12
magnification).
To study the elements of Ti3C2Tx nanosheets, energy dispersive X-ray (EDX) analysis were
carried out. Figure 3 reveal EDX spectrum and SEM-EDX element mappings of Ti3C2Tx MXene
nanosheets. As shown in Figure 3a, Ti3C2Tx MXene thin nanosheets have diameters of 3 μm. In the
EDX spectrum (Figure 3b), four strong peaks are belonged to C, Ti, O, and F, whereas a weak peak
assigns to Al. As shown in Figure 3c, the uniform C, Ti, O, and F elemental distributions are observed.
The composition of Ti3C2Tx nanosheets, as calculated from EDS analysis, is shown in Table 1. The
results showed that the Ti3C2Tx MXene contains 11.0 wt % C, 69.0 wt % Ti, 11.1 wt % O, 7.8 wt % F
and 1.1 wt % Al. The F and O elements are attributed to presence of –F, –OH, and –COOH.

Figure
Figure 3. SEM
3. (a) (a) SEM image
image of of
Ti3Ti
C32CT2Tx x nanosheets,
nanosheets, (b)
(b)energy-dispersive
energy-dispersiveX-ray spectroscopy
X-ray (EDX)(EDX)
spectroscopy
spectrum
spectrum of Tiof
C 3C2Tx nanosheets, and (c) element mappings of Ti3C2Tx nanosheets.
TiT nanosheets, and (c) element mappings of Ti C T nanosheets.
3 2 x 3 2 x

Table 1. Element content of Ti3C2Tx MXene nanosheets.

Element Atomic % Weight %

C 27.4 11.0
Ti 40.8 69.0
O 19.0 11.1
F 11.6 7.8
Al 1.2 1.1

The structural properties of Ti3AlC2 and Ti3C2Tx MXene were tested using XRD and Fourier
Nanomaterials 2020, 10, 162 5 of 11

Table 1. Element content of Ti3 C2 Tx MXene nanosheets.

Element Atomic % Weight %

C 27.4 11.0
Ti 40.8 69.0
O 19.0 11.1
F 11.6 7.8
Al 1.2 1.1

The structural properties of Ti3 AlC2 and Ti3 C2 Tx MXene were tested using XRD and Fourier
transform infrared spectroscopy (FTIR), as shown in Figure 4. The diffraction pattern (Figure 4aA)
has eleven broad peaks at 9.5◦ , 19.0◦ , 34.0◦ , 36.8◦ , 38.8◦ , 41.9◦ , 45.1◦ , 48.5◦ , 52.7◦ , 56.6◦ , and 60.2◦ ,
corresponding to (002), (004), (101), (103), (104), (105), (106), (107), (108), (109), and (110) of Ti3 AlC2
MAX (JCPDS No. 52-0875) [28,29], respectively. It can be seen in the XRD patterns that the crystallinity
and structural order of Ti3 AlC2 decrease after HF treatment. As shown in Figure 4aB, no characteristic
diffraction peaks of at 2θ = 36.9◦ , 38.9◦ , 42.0◦ belonged to Ti3 AlC2 are observed (Figure 4aA) because
of the removal of Al layers from Ti3 AlC2 MAX. Moreover, the characteristic (002) peak at 2θ = 9.5◦
shifted to a lower value (2θ = 8.3◦ ) and became broadened, displaying an increase in c-spacing when
the Al atoms are removed away and replaced by –F and –OH. The FTIR spectra of Ti3 AlC2 MAX and
Ti3 C2 Tx MXene nanosheets are shown in Figure 4b. There is no obvious peak in Ti3 AlC2 MAX curve,
which means there is no organic functional groups on Ti3 AlC2 MAX. From Figure 4b, the obvious
band at 3490 cm−1 is indicative of the presence of obvious strongly hydrogen-bonded –OH on the
surface of Ti3 C2 Tx MXene nanosheets. A weak peak at 1216 cm−1 can be observed. This weak peak is a
characteristic of covalent C–F bond stretching vibrations [30]. FTIR result confirmed that Al atoms are
replaced by2020,
Nanomaterials –F, –OH, and
10, x FOR –COOH
PEER functional groups, which is consistent with the XRD result. 6 of 12
REVIEW

Figure 4. (a)XRD
4. (a) XRDpatterns
patternsof of
Ti3Ti
AlC3 AlC 2 MAX
2 MAX (A) and
(A) and Ti3C2Ti
Tx3 C 2 Tx nanosheets
nanosheets (B). (b)(B).
FTIR(b)spectra
FTIR spectra ofx
of Ti3C2T
Ti 3 C2 Tx nanosheets.
nanosheets.

Figure 55 show
Figure show TEMTEMimage
imageand andthe thecorresponding
corresponding selected-area
selected-area electron
electron diffraction
diffraction (SAED)
(SAED) of
of Ti C T MXene nanosheets. Figure 5a indicates a typical low-magnification
Ti3C23Tx 2 MXene nanosheets. Figure 5a indicates a typical low-magnification TEM image of
x TEM image of the
the
synthesized Ti
synthesized Ti33C TxxMXene,
C22T MXene,in inwhich
whichthinthinnanosheet
nanosheet morphology
morphology formed,
formed, and and the
the thin
thin nanosheet
nanosheet hashas
five layers,
five layers, which
which is is consistent
consistent with
with the
the SEM
SEM result.
result. HRTEM
HRTEM waswas used
used toto characterize
characterize the
theTi
Ti33CC22T
Txx
MXene nanosheets (Figure 5b). The Ti C T MXene sample shows the characteristic
MXene nanosheets (Figure 5b). The Ti33C22Txx MXene sample shows the characteristic spacings of 0.31 spacings of 0.31
nm for
nm for the
the (110)
(110) lattice
lattice planes
planesofofTi
Ti33C
C22T [31]. The
Txx [31]. The SAED
SAED pattern
pattern of
of Ti C22TTxxMXene
Ti33C MXenenanosheets
nanosheets showed
showed
a hexagonal arrangement at the atomic scale, revealing the typical hexagonal crystalline
a hexagonal arrangement at the atomic scale, revealing the typical hexagonal crystalline structure of structure of
Ti C T phase.
Ti33C22Txxphase.
synthesized Ti3C2Tx MXene, in which thin nanosheet morphology formed, and the thin nanosheet has
five layers, which is consistent with the SEM result. HRTEM was used to characterize the Ti3C2Tx
MXene nanosheets (Figure 5b). The Ti3C2Tx MXene sample shows the characteristic spacings of 0.31
nm for the (110) lattice planes of Ti3C2Tx [31]. The SAED pattern of Ti3C2Tx MXene nanosheets showed
a hexagonal2020,
Nanomaterials arrangement
10, 162 at the atomic scale, revealing the typical hexagonal crystalline structure
6 of of
11
Ti3C2Tx phase.

5. (a) TEM image

Figure 5. image ofof Ti
Ti33C
C22Txx nanosheets,
nanosheets, (b) HRTEM image of
of Ti
Ti33C22Txx nanosheets,
nanosheets, and
and (c)
diffraction (SAED)
selected-area electron diffraction (SAED) of Ti33C22Txx nanosheets.
of Ti nanosheets.

3.2. The Structure

3.2. The Structure of
of EP/Ti
EP/Ti33C
C22TTxx MXene
MXeneNanosheets
NanosheetsECAs
ECAs
Figure
Figure 66 shows
shows XRD XRD patterns
patternsof ofthe
theepoxy
epoxy(a),
(a),TiTi3 C
3C22T
Txx MXene
MXene nanosheets
nanosheets(b), (b),EP/Ti
EP/Ti33CC22TTxx MXene
MXene
nanosheets composite containing 0.4 wt % Ti C T (c), EP/Ti
nanosheets composite containing 0.4 wt % Ti3C2Tx (c), EP/Ti3C2Tx MXene nanosheets composite
3 2 x 3 C 2 T x MXene nanosheets composite
containing
containing 1.0 1.0 wtwt % % TiTi33C
C22TTxx (d),
(d), and
and EP/Ti C22TTxx MXene
EP/Ti33C MXene nanosheets
nanosheets composite
composite containing
containing 1.6 1.6 wt
wt %%
Ti C22TTxx (e).
Ti33C (e). The
Theepoxy
epoxyhas has aa broad
broad peak
peak at 2θ =
at 2θ ◦
16.8 , whereas
= 16.8°, whereas Ti Ti33C C22TTxxMXene
MXene nanosheets
nanosheets have
have peaks
peaks
at 2θ = 8.8 ◦ , 60.2◦ belonged to (002) and (110) planes. For EP/Ti C T MXene nanosheets composite,
at 2θ = 8.8°, 60.2° belonged to (002) and (110) planes. For EP/Ti33C22Txx MXene nanosheets composite,
the
the characteristic
characteristic (002) (002) peak
peak of of Ti
Ti33C Txx MXene
C22T MXene nanosheets
nanosheets shiftedshifted to to aa lower
lower value.
value. The
The EP
EP composite
composite
containing
containing 0.4 wt % filler did not give any discernible (002) or (110) peaks (Figure 6c), most likely
0.4 wt % filler did not give any discernible (002) or (110) peaks (Figure 6c), most likely
because
because the the TiTi33CC22TTx xloading
loadingwas wasnotnotsufficient
sufficienttoto yield
yield anyany signal.
signal. At At a higher
a higher loading
loading fraction
fraction of
of 1.0
1.0
wt wt%, %, thethe composite
composite had hadthethe (110)peak
(110) peakand andalso
alsoaasimilar
similar (002)
(002) peak
peak shift.
shift. The
The EP
EP composite
composite
containing 1.6 wt % still had the (110) peak which become
containing 1.6 wt % still had the (110) peak which become broad. Explanation for this mightbroad. Explanation for this might be
be that
that EP polymer molecular chains are incorporated
EP polymer molecular chains are incorporated in the Ti3C2Tx MXene in the Ti C T MXene layers which
3 2 xlayers which make the d-spacing make the
d-spacing
increase. increase.
Nanomaterials 2020, 10, x FOR PEER REVIEW 7 of 12

6. XRD
Figure 6. XRD patterns
patterns of
ofepoxy
epoxy(a),(a),TiTi 3C
3C22TTxx MXene
MXene nanosheets
nanosheets (b),
(b),EP/Ti
EP/Ti3 C
3C22T
Txx MXene nanosheets
containing 0.4
composite containing 0.4 wt
wt %% TiTi33CC2T2 T (c),EP/Ti
(c),
x x EP/Ti
3C32C
Tx2 TMXene
x MXene nanosheets
nanosheets composite
composite containing
containing 1.0
1.0
wt %wtTi
%3CTi2T
3C 2 Tx and
x (d), (d), and EP/Ti
EP/Ti 3C2T3xC 2 Tx MXene
MXene nanosheets
nanosheets composite
composite containing
containing 1.6 wt 1.6%wt
Ti3%
C2Ti
Tx3 C 2 Tx (e).
(e).

3.3. Electrical Conductivity and Mechanical Performance

The electrical conductivity (K) of the EP/Ti3C2Tx MXene nanosheets composite under various
mass fractions of Ti3C2Tx MXene nanosheets is illustrated in Figure 7. From Figure 7 we can observe
that the electrical conductivity of the EP/Ti3C2Tx MXene nanosheets composite increases gradually as
Nanomaterials 2020, 10, 162 7 of 11

3.3. Electrical Conductivity and Mechanical Performance

The electrical conductivity (K) of the EP/Ti3 C2 Tx MXene nanosheets composite under various
mass fractions of Ti3 C2 Tx MXene nanosheets is illustrated in Figure 7. From Figure 7 we can observe
that the electrical conductivity of the EP/Ti3 C2 Tx MXene nanosheets composite increases gradually
as the increasing of Ti3 C2 Tx MXene nanosheets filler content. When the content of Ti3 C2 Tx MXene
nanosheets is lower than 0.4 wt %, the electrical conductivity slowly increases with increasing content
ofNanomaterials 2020, 10,nanosheets.
Ti3 C2 Tx MXene x FOR PEER REVIEW
When the content of Ti3 C2 Tx MXene nanosheets increases to 0.6 wt 8 of%,
12
the electrical conductivity of the EP/Ti3 C2 Tx MXene nanosheets composite increases significantly.
composite
The is about of
critical content 0.28 volis%regarded
filler (0.85 wt %). Thepercolation
as the percolationthreshold.
threshold of EP/Ti
Thus the3Cpercolation
2Tx MXene nanosheets
threshold
composite (0.85 wt %) is higher than that of aligned multi-wall carbon nanotube/EP
of the EP/Ti3 C2 Tx MXene nanosheets composite is ~0.85 wt %. The electrical conductivity of composite (0.0025
the
wt %) because aligned CNT by an injection CVD method overcome the obstacle
−6 of
EP/Ti3 C2 Tx MXene nanosheets composite in percolation threshold is 1.81 × 10 S/m, that is, ten orders aggregation and
ofshow higherhigher
magnitude electrical
thanconductivity [32].
that of the pure However,
epoxy usually
resin (about 1.03CNT is easy
× 10−16 S/m).toAfter
aggregate inelectrical
that, the polymer
conductivity of the EP/Ti3 C2 Tx MXene nanosheets composites also increases as the content of Ti3of
composites, which hamper their high electrical conductivity. So the percolation threshold C2our
Tx
composite is lower than that of usual CNT-based polymer composite
MXene nanosheets increases. However, its electrical conductivity increases slowly. [33].

Figure7.7.The
Figure Theelectrical
electricalconductivity
conductivity(K,
(K,S/m)
S/m)ofofthe
theEP/Ti3 C3C
EP/Ti 2 T2T
x xMXene
MXenenanosheets
nanosheetscomposite
compositeunder
under
various mass fractions of Ti3 C2 Tx MXene nanosheets.
various mass fractions of Ti3C2Tx MXene nanosheets.

The percolation theory was applied for the calculation of the percolation threshold of composites.
The mechanical properties (tensile strength and impact strength) of the EP/Ti3C2Tx MXene
The dependence of the electrical conductivity of EP/Ti3 C2 Tx MXene nanosheets composite on Ti3 C2 Tx
nanosheets composite are tested with electronic tensile testing machine. The dependencies of tensile
MXene content can be described in σm = σn (P-Pc)β , where σn is the conductivity of Ti3 C2 Tx MXene
strength (a) and impact strength (b) of the EP/Ti3C2Tx MXene nanosheets composite on the content of
nanosheets, σm is the electrical conductivity of EP/Ti3 C2 Tx MXene nanosheets composite, P is the
the Ti3C2Tx MXene nanosheets are shown in Figure 8. Figure 8 shows that the tensile strength and
volume fraction of Ti3 C2 Tx MXene nanosheets, Pc is the percolation threshold, β is the conductivity
impact strength of the EP/Ti3C2Tx MXene nanosheets composite first increases with the content of
exponent which is approximately 1.3 and 2.0 for three-dimensional and two-dimensions randomly
Ti3C2Tx MXene nanosheets increasing. When the content of Ti3C2Tx MXene nanosheets increases to
distributed nanocomposites, respectively, in the percolation model [32]. The density of the Ti3 C2 Tx
1.2 wt %, the tensile strength and impact strength of composite arrive at the highest value of 66.2 MPa
MXene nanosheets is ~5 greater than the EP polymer. Therefore, we calculate that the conductivity
and 24.2 kJ/m2, which is better than that in some papers [34]. After that, the tensile strength and
exponent for EP/Ti3 C2 Tx MXene nanosheets composite as β = 0.84. The Ti3 C2 Tx MXene nanosheets
impact strength of composite then gradually decreases. It is known that the tensile strength and
electrical conductivity is about 24 S/cm which is much higher than conventional non-conductive
impact strength of polymer resin is related to the rigidity of the polymer chains. As the content of
polymer (~10−16 S/cm) and the Ti3 C2 Tx MXene nanosheets have a large aspect ratio (~100–500),
Ti3C2Tx MXene nanosheets increase, the rigidity of the EP/Ti3C2Tx MXene nanosheets composite
which can be observed in the SEM photograph of the Ti3 C2 Tx MXene nanosheets. Such an extreme
increases due to Ti3C2Tx MXene nanosheets that connect many single EP polymer chains by –F, –OH,
geometry might be a factor contributable to the high electrical conductivity and low conductivity
and –COOH functional groups. However, when the content of Ti3C2Tx MXene nanosheets is more
exponent. We can infer that the percolation threshold of EP/Ti3 C2 Tx MXene nanosheets composite is
than 1.2 wt %, the EP/Ti3C2Tx MXene nanosheets composite possesses more Ti3C2Tx MXene
nanosheets agglomeration, reducing their tensile strength and impact strength.
Nanomaterials 2020, 10, 162 8 of 11

about 0.28 vol % (0.85 wt %). The percolation threshold of EP/Ti3 C2 Tx MXene nanosheets composite
(0.85 wt %) is higher than that of aligned multi-wall carbon nanotube/EP composite (0.0025 wt %)
because aligned CNT by an injection CVD method overcome the obstacle of aggregation and show
higher electrical conductivity [32]. However, usually CNT is easy to aggregate in polymer composites,
which hamper their high electrical conductivity. So the percolation threshold of our composite is lower
than that of usual CNT-based polymer composite [33].
The mechanical properties (tensile strength and impact strength) of the EP/Ti3 C2 Tx MXene
nanosheets composite are tested with electronic tensile testing machine. The dependencies of tensile
strength (a) and impact strength (b) of the EP/Ti3 C2 Tx MXene nanosheets composite on the content of
the Ti3 C2 Tx MXene nanosheets are shown in Figure 8. Figure 8 shows that the tensile strength and
impact strength of the EP/Ti3 C2 Tx MXene nanosheets composite first increases with the content of
Ti3 C2 Tx MXene nanosheets increasing. When the content of Ti3 C2 Tx MXene nanosheets increases to
1.2 wt %, the tensile strength and impact strength of composite arrive at the highest value of 66.2 MPa
and 24.2 kJ/m2 , which is better than that in some papers [34]. After that, the tensile strength and
impact strength of composite then gradually decreases. It is known that the tensile strength and impact
strength of polymer resin is related to the rigidity of the polymer chains. As the content of Ti3 C2 Tx
MXene nanosheets increase, the rigidity of the EP/Ti3 C2 Tx MXene nanosheets composite increases due
to Ti3 C2 Tx MXene nanosheets that connect many single EP polymer chains by –F, –OH, and –COOH
functional groups. However, when the content of Ti3 C2 Tx MXene nanosheets is more than 1.2 wt %, the
EP/Ti3 C2 Tx MXene nanosheets composite possesses more Ti3 C2 Tx MXene nanosheets agglomeration,
reducing their
Nanomaterials 2020,tensile strength
10, x FOR and impact strength.
PEER REVIEW 9 of 12

Figure 8.
Figure Thetensile
8. The (a) tensile strength
strength and (b)strength
and impact impact of
strength of 3the
the EP/Ti C2TxEP/Ti
MXene3 C2 Tx MXene nanosheets
nanosheets composite
composite under various contents of the Ti3 C 2 Tx MXene
under various contents of the Ti3C2Tx MXene nanosheets. nanosheets.

3.4. The Morphology of EP/Ti3 C2 Tx MXene Nanosheets Composite

3.4. The Morphology of EP/Ti3C2Tx MXene Nanosheets Composite
To understand the effect of the content of Ti3 C2 Tx Mxene nanosheets in NH2 –CF/MXene/EP
To understand the effect of the content of Ti3C2Tx Mxene nanosheets in NH2–CF/MXene/EP
composites on mechanical properties, SEM was used to observe the fracture surfaces of EP composites
composites on mechanical properties, SEM was used to observe the fracture surfaces of EP
after impact strength test. Figure 9a–d presents the fracture source of EP/Ti3 C2 Tx MXene nanosheets
composites after impact strength test. Figure 9a–d presents the fracture source of EP/Ti3C2Tx MXene
composite containing 0.4 wt %, 0.8 wt %, 1.2 wt %, and 1.6 wt % Ti3 C2 Tx MXene nanosheets.
nanosheets composite containing 0.4 wt %, 0.8 wt %, 1.2 wt %, and 1.6 wt % Ti3C2Tx MXene nanosheets.
The EP/Ti3 C2 Tx MXene nanosheets composite containing 0.4 wt % Ti3 C2 Tx MXene nanosheets display
The EP/Ti3C2Tx MXene nanosheets composite containing 0.4 wt % Ti3C2Tx MXene nanosheets display
comparatively slippery fracture (Figure 9a). The fracture surfaces of EP/Ti3 C2 Tx MXene nanosheets
comparatively slippery fracture (Figure 9a). The fracture surfaces of EP/Ti3C2Tx MXene nanosheets
composite containing 0.8 wt % or 1.2 wt % Ti3 C2 Tx MXene nanosheets are rougher. In Figure 9d,
composite containing 0.8 wt % or 1.2 wt % Ti3C2Tx MXene nanosheets are rougher. In Figure 9d, we
we can observe that there is apparent agglomeration on the fracture surface of EP/Ti3 C2 Tx MXene
can observe that there is apparent agglomeration on the fracture surface of EP/Ti3C2Tx MXene
nanosheets composite containing 1.6 wt % Ti3 C2 Tx MXene nanosheets. The agglomeration of Ti3 C2 Tx
nanosheets composite containing 1.6 wt % Ti3C2Tx MXene nanosheets. The agglomeration of Ti3C2Tx
MXene nanosheets could decrease the impact strength of the EP composites. So the SEM results are
consistent with the impact strength shown in Figure 8b.
composites after impact strength test. Figure 9a–d presents the fracture source of EP/Ti3C2Tx MXene
nanosheets composite containing 0.4 wt %, 0.8 wt %, 1.2 wt %, and 1.6 wt % Ti3C2Tx MXene nanosheets.
The EP/Ti3C2Tx MXene nanosheets composite containing 0.4 wt % Ti3C2Tx MXene nanosheets display
comparatively slippery fracture (Figure 9a). The fracture surfaces of EP/Ti3C2Tx MXene nanosheets
composite
Nanomaterials containing
2020, 10, 162 0.8 wt % or 1.2 wt % Ti3C2Tx MXene nanosheets are rougher. In Figure 9d,9 ofwe
11
can observe that there is apparent agglomeration on the fracture surface of EP/Ti3C2Tx MXene
nanosheets composite containing 1.6 wt % Ti3C2Tx MXene nanosheets. The agglomeration of Ti3C2Tx
MXene nanosheets
MXene nanosheets could could decrease
decrease the
the impact
impact strength
strength of
of the
the EP
EP composites. So the
composites. So the SEM
SEM results
results are
are
consistent with the impact strength shown in Figure
consistent with the impact strength shown in Figure 8b. 8b.

Figure 9. The fracture surfaces of the

the EP/Ti
EP/Ti33C22Txx MXene
MXene nanosheets
nanosheets composite
composite containing
containing 0.4 0.4 wt
wt %
%
Ti33C
C22TTxx MXene
MXene nanosheets
nanosheets (a),
(a), 0.8
0.8 wt % Ti
Ti33C22T
Txx MXene
MXene nanosheets
nanosheets (b), 1.2 wt
wt %
% Ti
Ti33C
C22Txx MXene
nanosheets (c), and 1.6 wt % Ti33C22TTxxMXene
MXenenanosheets
nanosheets(d).
(d).

4. Conclusions
In summary, a novel ECA based on EP resin filled with Ti3 C2 Tx MXene nanosheets was prepared
by a simple solution blending. Ti3 C2 Tx MXene is of nanosheet structure, which contains 11.0 wt % C,
69.0 wt % Ti, 11.1 wt % O, 7.8 wt % F, and 1.1 wt % Al. These –F, –OH, and –COOH functional groups
make Ti3 C2 Tx MXene nanosheets homogeneously disperse in EP resin. The electrical conductivity
of the EP/Ti3 C2 Tx MXene nanosheets composite increases gradually as Ti3 C2 Tx MXene nanosheets
content increases, and the percolation threshold of EP/Ti3 C2 Tx MXene nanosheets composite is
0.85 wt %. The electrical conductivity of EP/Ti3 C2 Tx MXene nanosheets composite in percolation
threshold is 1.81 × 10−6 S/m, which is ten orders of magnitude higher than that of the pure epoxy
resin (~1.03 × 10−16 S/m). The increase in Ti3 C2 Tx MXene nanosheets content may increase the tensile
strength and impact strength of epoxy/Ti3 C2 Tx MXene nanosheets composite when the content of
filler is low. When the content of filler is 1.2 wt %, the properties of epoxy/Ti3 C2 Tx MXene nanosheets
composite are optimum (electrical conductivity of 4.52 × 10−4 S/m, tensile strength of 66.2 MPa and
impact strength of 24.2 KJ/m2 ). This work presents more applications of MXene-polymer composites.

Author Contributions: A.F. conceived the idea of the paper; T.H. collected and classified the related literature; Z.J.
and G.W. also gave helpful advice during the writing process. Y.Z. and F.Z. also gave some great enlightenment
and helpful advices during calculating the percolation threshold and the revising process. A.F. wrote the paper.
All authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the Natural Science Foundation of Shandong Province
(No. ZR2019YQ24), the Qingchuang 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),
Qingdao Postdoctoral Application Research Project, Provincial Key Research and Development Program of
Shaanxi (No. 2019GY-197), Key Laboratory of Engineering Dielectrics and Its Application (Harbin University of
Science and Technology), Ministry of Education (No. KFZ1803), Key Project of Baoji University of Arts and Sciences
(No. ZK2018051), Baoji Science and Technology Project (No. 16RKX1-29) and Baoji Engineering Technology
Nanomaterials 2020, 10, 162 10 of 11

Research Center for Ultrafast Optics and New Materials (No. 2015CXNL-1-3). Feng AL is supported by The
Thousand Talents Plan for Young Professionals of Shaanxi Province.
Acknowledgments: The authors thank the colleagues in the laboratory for their support.
Conflicts of Interest: The authors declare no conflicts of interest.

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