Highlighting a study on oxidation-resistant titanium

carbide MXene films by a group of researchers led As featured in:

by Dr Chi Won Ahn and Dr Yonghee Lee from National
Nanofab Center, and Prof. Yury Gogotsi from Drexel
University.

Oxidation-resistant titanium carbide MXene films.

Oxidation-resistant titanium carbide MXene films are

demonstrated. After hydrogen annealing, the stability
against oxidation of the MXene film under harsh
conditions (either underwater or under 100% RH at 70°C)
is dramatically improved. Besides, large recovery in the
electrical conductivity of oxidized Ti3C2 MXene films is
observed after hydrogen annealing. We also demonstrate
an electric heater made of oxidation-resistant MXene film, See Yonghee Lee,
Chi Won Ahn et al.,
which was capable of stable operation in air under highly
J. Mater. Chem. A, 2020, 8, 573.
oxidizing conditions (70°C, 100% RH).

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Oxidation-resistant titanium carbide MXene films†

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Cite this: J. Mater. Chem. A, 2020, 8, Yonghee Lee, ‡*a Seon Joon Kim,‡§bc Yong-Jae Kim,d Younghwan Lim,e
573 Yoonjeong Chae,a Byeong-Joo Lee,a Young-Tae Kim,f Hee Han,a Yury Gogotsi b

and Chi Won Ahn *a

Received 1st July 2019
Accepted 14th November 2019
DOI: 10.1039/c9ta07036b
rsc.li/materials-a
Two-dimensional transition metal carbides (MXenes) have attracted much attention due to their excellent
electrical conductivity and outstanding performances in energy storage, telecommunication, and sensing
applications. It is known that MXene flakes are readily oxidized in either humid air or aqueous
environments. While the chemical instability of MXenes may limit their use in applications involving
ambient environments and long-term operation, oxidation behaviour of MXene films has not been
addressed. In this work, we demonstrate a hydrogen annealing method to increase the oxidation stability
of Ti3C2 MXene in two different aspects: (1) dramatic improvement in the oxidation stability of pristine
MXene films against harsh conditions (100% relative humidity, 70
C), and (2) large recovery in the
electrical conductivity of previously oxidized Ti3C2 MXene films. We also demonstrate an electric-field-
induced heater capable of stable operation under highly oxidizing conditions, based on the oxidation-
resistant MXene film. A total loss of heat generation ability was observed for the as-prepared MXene film,
while the hydrogen-annealed one maintained its bright infrared radiation, under the highly oxidizing
conditions. This work offers a solution to industrial applications of unprotected MXene films, securing
their stable and long-term operation in humid conditions.

to days, leading to diminished electrical properties through the

Introduction
Two-dimensional (2D) metal carbides and nitrides, known as
MXenes, continue to be investigated in energy storage,1–3
sensing,4,5 plasmonic,6,7 and catalytic applications8,9 because of
their unique properties, which include excellent electro-
chemical activity, extensive surface functionality, high conduc-
tivity, and good processability in aqueous dispersions.10,11
Single-layer MXene akes are readily oxidized in either humid
air or aqueous environments on a time scale from several hours
a
Global Nanotechnology Development Team, National Nano Fab Center (NNFC),
Daejeon 34141, South Korea. E-mail: cwahn@nnfc.re.kr; yhlee@nnfc.re.kr
b
Department of Materials Science and Engineering, A.J. Drexel Nanomaterials
Institute, Drexel University, Philadelphia, PA 19104, USA
c
Wearable Platform Materials Technology Center, Korea Advanced Institute of Science
and Technology (KAIST), Daejeon 34141, South Korea
d
Department of Chemical and Biomolecular Engineering (BK-21 PLUS), Korea
Advanced Institute of Science and Technology (KAIST), 291, Daehak-ro, Yuseong-gu,
Daejeon 34141, Republic of Korea
e
Department of Materials Science and Engineering, Korea Advanced Institute of Science
and Technology (KAIST), 291, Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of
Korea
f
Graduate School of Green Energy Technology, Chungnam National University, 99
Daehak-ro, Yuseong-gu, Daejeon 305-764, Republic of Korea
† Electronic supplementary information (ESI) available. See
10.1039/c9ta07036b
‡ These authors contributed equally to this work.
§ Present address: Materials Architecturing Research Center, Korea Institute of
Science and Technology (KIST), Seoul 02792, Republic of Korea.
formation of titanium dioxide (TiO2)12,13 and limiting their use
in applications involving exposure to an oxygen-containing
aqueous environment and long-term operation.
In recent years, researchers have investigated the oxidation
stability of MXenes, including the factors governing oxidation
of MXenes in solution, and have proposed methods to lower the
oxidation rate.12–15 Zhang et al., demonstrated an improved
chemical stability of MXene by developing a method for storing
Ti3C2 MXene colloidal solutions in Ar-lled bottles at low
temperatures, and they also found that the degradation of
MXene begins at the edges and that small akes are less stable
than larger ones.13 In addition, if one strictly controls the
storage conditions of MXene such as the amount of water
molecules and the temperature, the oxidation rate of the
Ti3C2Tx akes can be slowed down.15 However, these previous
studies are limited to controlling the storage conditions. Very
recently, some papers were published presenting approaches to
suppress the oxidation of colloidal MXene nanosheets by
introducing additives.16–18 Along with the stability of MXene
sheets in water, the stability of thin MXene lms that are typi-
cally used in applications such as transparent conducting
lms,19,20 antennas,21,22 heaters,23 electromagnetic shielding,24,25
and sensors,4,26 needs to be studied. A. Lipatov et al., demon-
DOI:
strated that Ti3C2Tx MXene lm-based eld-effect transistor
suffered from environmental degradation in humid air during
operation.27 Thus, the development of MXene lms with high

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Journal of Materials Chemistry A
chemical stability in humid air as well as at high temperature is
strongly desired.
In this study, we demonstrate a hydrogen annealing method
to increase the oxidation stability of MXenes lms. Oxidation
resistance of pristine MXene lms increased, and the recovery
of the electrical characteristics of the oxidized MXene lms was
achieved. Sheet resistance, representing a typical electrical
characteristic of a lm, can be recovered for the oxidized Ti3C2
MXene lms through the hydrogen annealing. Further, the
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stability against oxidation of the MXene lm under harsh
conditions (100% relative humidity (RH), 70
C) was dramati-
cally improved by hydrogen annealing. We applied the annealed
MXene lms to heaters to show their stable and long-term
operation in humid and high-temperature conditions. Very
recently, people started to study Ti3C2 MXene-based heater due
to the excellent electrical characteristics as well as good thermal
stability of Ti3C2 MXenes.28,29 Heaters can be used in car seats
and smart textiles, as well as for de-icing of windshields.
Results and discussion
Ti3C2 MXene was obtained by etching Ti3AlC2 MAX powders
with LiF/HCl as the etchant, as described in previous
reports.15,30 Ti3C2 MXene lms were subsequently prepared on
SiO2/Si wafer substrates via spin-coating, where the thickness of
the lms was approximately 60 nm. Films of the same thickness
were used throughout the entire study. Hydrogen annealing was
performed at a temperature ranging from 300
C to 900
C for
30 min in a vacuum chamber with hydrogen gas owing
through the chamber.
Fig. 1a shows the X-ray diffraction (XRD) patterns of Ti3C2
lms annealed under hydrogen at 300
C, 500
C, and 900
C for
30 min. The main peak which is corresponding to the (002)
plane of the stacked MXene lm was found to shi to higher
angles as the annealing temperature was increased as presented
in Fig. 1b. The interlayer spacing of the as-prepared MXene lm
was measured as 12.4 Å (corresponding to 8.8
), which was
reduced to 10.4 Å at 300
C, 10.2 Å at 500
C, and 10.1 Å at
900
C, as all water molecules between the akes were gradually
volatilized (Fig. 1b),31 and functional groups were partially
removed.32 These results are consistent with previous reports
that internal water molecules are sufficiently removed from
Ti3C2 MXene lms aer thermal annealing at temperatures
greater than 300
C.33 Surely, it is expected that such a decrease
in interlayer spacing leads to improved electrical junctions and
a lower contact resistance between MXene akes. In the
previous studies, it was found that structural phase transition
from Ti3C2 to cubic TiC may occur at annealing temperatures
greater than 900
C.34 In our study, however, no such phase
transition to cubic carbides was observed in our experiments,
even in the case of annealing at 900
C, which might be
attributed to that the reaction time was insufficient (30 min) for
crystalline phase transitions to occur. Phase transitions were
not observed even aer repeated annealing at 900
C for 30 min
(Fig. S1†), indicating that the oxidation stability of the MXene
lms aer the treatment does not originate from other titanium
carbide phases. Also, no obvious difference was observed in the
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Raman spectra of MXene lms annealed at high temperatures,
showing that the evolution of titanium oxides is negligible
(Fig. S2†).
To investigate the evolution of surface morphology of MXene
lm aer hydrogen annealing, we performed SEM (scanning
electron microscopy) analysis, as shown in Fig. 1c. In the as-
prepared sample, the MXene akes are well dispersed in the
lm, with distinct ake boundaries. On the other hand, the
boundaries of the MXene akes are more indistinct aer
hydrogen annealing, implying that the MXene akes formed
a tightly packed network via the partial sintering of akes at
high temperatures. It was turned out by HRTEM (high resolu-
tion transmission electron microscopy) that the partial sinter-
ing occurred in MXene akes in the hydrogen-annealed sample,
while a periodic atomic arrangement was shown in the as-
prepared sample (Fig. 1d, e and S3†). Contact angle measure-
ments further support the tight packing of akes aer hydrogen
annealing. The as-prepared MXene lms showed a contact
angle of 44
immediately aer placement of the water droplet;
however, the contact angle decreased to 10
aer 10 s, implying
that the water droplet permeated through the loosely stacked
Ti3C2 MXene layers (Fig. 1f and S4†). However, for the hydrogen-
annealed lm, the contact angle maintained its initial value
(42
) for more than 1 min, demonstrating resistance to water
permeation.
Hydrogen annealing also changed the surface functional
groups of the MXene, as investigated using O 1s X-ray photo-
electron spectroscopy (XPS). As shown in the peak deconvolu-
tion analyses in Fig. S5,† aer hydrogen annealing, the relative
number of –OH terminations on the surface decreased, whereas
the number of –O terminations increased, accompanied by
a decrease in the amount of Ti–H2O species. The trans-
formation of surface functional groups can be expressed as35
Ti3C2(OH)wFx / Ti3C2OyFx + aH2O (1)
In addition, the ratio between –F and –OH species decreased
from 0.31 to 0.06, as shown in Fig. S5c.† The Ti3C2 MXenes lose
–F terminations with increasing annealing temperature,
resulting in the formation of Ti3C2Ox, as expressed in the
equation
Ti3C2OyFx / Ti3C2Oy + bF2 (2)
The details of elemental analysis by XPS for as-prepared and
H2-annealed in Ti, O, C, and F regions are summarized in Table
S2.†36
To study the oxidation stability of hydrogen-annealed MXene
lms, we measured the changes in the sheet resistance over
time of MXene lms annealed under various conditions and
subjected to harsh oxidizing conditions of 70
C and 100% RH.
For the as-prepared Ti3C2 MXene lm, the relative sheet resis-
tance (R/R0) increased by 162.7 times in 8.5 h and by 105 times
in 13 h; it was measured as “out of range” aer 1 day of
oxidation under the harsh conditions (Fig. 2a). The XRD
patterns in Fig. 2b show that the as-prepared Ti3C2 MXenes were
transformed into titanium dioxides (a mixture of rutile and
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Fig. 1 (a) XRD patterns and (b) the interlayer spacing of the (002) planes of the as-prepared sample and the annealed samples (300
C, 500
C,
and 900
C). (c) SEM images of as-prepared and hydrogen-annealed (900
C) samples. (d) HRTEM images of hydrogen-annealed (900
C)
sample (inset: the corresponding diffraction patterns), and (e) the corresponding intensity profile of hydrogen annealed MXene layers (sintered,
and non-sintered part). (f) Results of contact angle measurements for as-prepared and hydrogen-annealed (900
C) samples.

anatase phases) aer 1 day of harsh oxidation. The formation of
oxides was also clearly observed in the XPS spectra (Fig. S6†). By
contrast, the sheet resistance of lms annealed under hydrogen
at 900
C barely increased aer harsh oxidation; specically the
R/R0 was only 1.9 even aer 2 days of oxidation, which is
a surprising result. Also, crystalline phase transformations were
not detected in the XRD pattern. Thus, the hydrogen annealing
at 900
C imparted dramatic oxidation resistance to the Ti3C2
MXene lm, which is known to be very vulnerable to oxidation
in its pristine state.12–14 The annealed Ti3C2 MXene lms
exhibited improved oxidation stability even in water; the sheet
resistance of the lm was almost unchanged aer the lm had
been immersed in water for 1 day (Fig. S7†).
SEM images of the top surface were taken to observe the
change in morphology aer harsh oxidation. As shown in
Fig. 2c, the surface of the hydrogen-pretreated lms aer
oxidation was very smooth and lacked any notable features,
preserving the original texture. However, as shown in Fig. 2d,
the as-prepared lm aer oxidation exhibits a very rough
surface, with porous features evident in the magnied image.
These results show that the lm network was broken and that
the majority of the surface was transformed into titanium
dioxides. SEM images of cross-sections prepared using
a focused ion beam (FIB) also show a substantial difference
between the as-prepared lms and the hydrogen-annealed
lms. When the as-prepared lms were oxidized, their
internal regions were clearly distorted compared with their
pristine state (Fig. 2e and f). However, the inner structure of the
hydrogen-annealed lms did not change aer harsh oxidation,
demonstrating their outstanding stability (Fig. 2g and h). XPS
analysis results also show that the inner Ti3C2 layers remained
intact in the hydrogen-annealed lms, although a very thin layer
of TiO2 (approximately 5 nm thick) was detected at the outer-
most Ti3C2 MXene layer (Fig. S8†).36
The oxidation stability of lms annealed under hydrogen at
lower temperatures was also studied. The results show that
lms annealed at 300
C exhibited a 6.3  104-fold increase in
R/R0 aer 13 h of oxidation, which is similar to the R/R0 of the
as-prepared lms not subjected to the hydrogen treatment.
Even aer a longer annealing time of 3 h (at 300
C) to suffi-
ciently remove the internal moisture,31 the oxidation stability
was not improved despite the similarity of the interlayer spacing
to that of the lm annealed at 900
C (Fig. S9†). Because the
oxidation of Ti3C2 MXene into titanium dioxides typically
requires water as the oxygen source,13,15 this result indicates that
water molecules can re-penetrate into the interlayer gaps of the
lms annealed at 300
C. Thus, the reduction of hydroxyl
surface functional groups, which have a high affinity for water,
and partial sintering at high temperatures (e.g., 900
C) are
required to impart oxidation resistance to the Ti3C2 MXene
lms. Changes in the surface functional groups might be also
responsible for the improved oxidation stability. Fu et al., who

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Fig. 2 (a) Time evolution of the sheet resistances of Ti3C2 MXene thin films subjected to oxidation stability tests in 100% relative humidity and at
70
C, both before and after the films were annealed under hydrogen. (b) XRD patterns of an as-prepared sample and a hydrogen-annealed
sample (900
C) before and after oxidation for 1 day. SEM images of (c) a hydrogen-annealed and (d) an as-prepared sample after the sample was
kept at 70
C and 100% RH for 1 day. Cross-sectional SEM images of the as-prepared sample (e) before and (f) after oxidation and those of
a hydrogen-annealed sample (900
C) (g) before and (h) after oxidation. Gold layers are deposited on top of MXene layers to obtain better cross-
sectional images.

investigated thermodynamic stabilization of Ti3C2 MXenes with
various functional terminations, reported that oxygen-
terminated Ti3C2 MXene (Ti3C2O2) exhibited greater thermo-
dynamic stability than hydroxyl- and uorine-terminated
MXene because the oxygen groups hindered the deformation
of the Ti–C structure, whereas the other terminating species
resulted in bond instability modes.37
To study the inuence of hydrogen post-annealing on the
recovery of the electrical characteristics of the Ti3C2 MXene
lms, the lms were rst oxidized to the desired extent by
exposure to a humid environment, as described in a previous
study.15 The oxidation reaction caused by water is described as13
Ti3C2O2 + 4H2O / 3TiO2 + 2C + 4H2 (3)

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The sheet resistance of the oxidized lms Rox increased to
three to ve times the initial sheet resistance R0 (i.e., 3 # Rox/R0
# 5), presumably because of the degradation of the Ti3C2
MXene and the formation of titanium dioxides. The oxidized
lms were subsequently placed in a high-vacuum chamber and
annealed at temperatures ranging from 100
C to 900
C under
owing hydrogen gas. Fig. 3a shows the sheet resistance of the
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MXene lms aer they were post-annealed in a hydrogen
atmosphere at various temperatures. The results show that the
sheet resistance recovered upon hydrogen post-annealing,
where the degree of sheet-resistance recovery increased with
increasing annealing temperature. The value of (Rox  Rre)/(Rox
 R0) (Rre is the recovered sheet resistance aer reduction),
which represents the degree of recovery (Rre/R0) versus the

Fig. 3 (a) Changes in the sheet resistances of Ti3C2 MXene thin films upon hydrogen post-annealing at various temperatures. (b) The degree of
recovery (Rox  Rre) versus the degree of oxidation (Rox  R0) of the sheet resistances with respect to the annealing temperature. (c) Changes in
sheet resistance upon hydrogen post-annealing, for several MXene films with various degrees of oxidation. (d) The degree of reduction (Rre) as
a function of the degree of oxidation (Rox/R0) for two H2 post-annealing temperatures (500
C and 900
C). SEM images of (e) the oxidized in the
ambient condition for 5 day and (f) the hydrogen post-annealed thin films (insets: magnified views of the corresponding images). Component
peak-fitting for the Ti 2p XPS spectra of the (g) oxidized and (h) hydrogen post-annealed Ti3C2 MXene.

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Journal of Materials Chemistry A
degree of oxidation (Rox/R0), approaches 1 for lms annealed at
900
C, indicating that the sheet resistance was fully recovered
(Fig. 3a and b). By contrast, increasing the annealing time from
30 min to 60 min reduced the degree of recovery of the sheet
resistance (Fig. S10†).
To determine whether hydrogen post-annealing could lead
to recovery of the electrical properties of severely oxidized
MXene lms, we varied the degree of oxidation by controlling
the air exposure time at 70
C prior to hydrogen post-annealing.
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As shown in Fig. 3c, the sheet resistances of oxidized lms (Rox/
R0 ¼ 3.19, 4.68, 6.74, 29.04, 109.96) were reduced (to Rre/R0 ¼
0.93, 1.24, 1.66, 3.00, 4.37, respectively) aer hydrogen post-
annealing. The changes in the sheet resistances of the lms
are detailed in Table S1.† The Rre value approached 1 for the
samples with a low degree of oxidation. We speculate that, in
the early stage of annealing, the electrical characteristics were
partially recovered as water and gas molecules that had initially
adhered to the surface of the MXene lm from the ambient
atmosphere were volatilized from the surface.38 The value of Rre
decreased for the samples with a high degree of oxidation,
implying that a substantial amount of Ti3C2 MXene akes were
transformed into titanium dioxides (Fig. 3c and S11†).
Fig. 3e and f shows SEM images of an oxidized Ti3C2 MXene
lm (Rox/R0 z 5.0) before and aer hydrogen post-annealing at
900
C, respectively. The oxidized lm exhibits a large number
of TiO2 particles on its surface, whereas the surface of the
reduced lm is surprisingly smooth, indicating that nearly all of
the TiO2 particles were removed aer hydrogen post-annealing.
We used XPS to further characterize the chemical state of the
Ti3C2 MXene surface. The Ti 2p regions in the spectra of the
oxidized Ti3C2 MXene akes and their hydrogen-annealed
counterparts were t by components representing moieties
such as TiC, Ti–X, TixOy, and TiO2 (Fig. 3g and h). The results
clearly show that the fraction of peak from the oxidized Ti3C2
MXene, as identied by the TiO2 components at 458.6 eV and
464.2 eV, was reduced from 24.4% to 13.0% aer hydrogen
annealing. To investigate the inuence of hydrogen gas on the
recovery of the sheet resistance during thermal annealing, we
carried out a control experiment in which Ti3C2 MXene was
annealed at a high temperature in the absence of hydrogen (Ar
100%). As shown in Fig. S12,† the sheet resistance recovered to
a great extent for lms annealed under owing hydrogen (Rox
3.19 to Rre 0.93) compared to owing Ar (Rox 3.04 to Rre 1.53).
The authors of previous studies have reported that TiO2 nano-
particles can be reduced at high temperatures under a hydrogen
atmosphere, as expressed by the following formula.39
O2 + 2Ti4+ + H2 / VO + 2Ti3+ + H2O (4)
VO + H2O + O2 / 2OH (5)
(VO: O vacancy)
Also, it was reported that the reduction of TiO2 can be
accelerated in the presence of a carbon layer.40 Therefore, the
greater recovery of the sheet resistance is attributable to the
effective hydrogen-induced elimination of poorly conductive
TiO2 nanoparticles on the surface. The reduction and
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elimination of such TiO2 nanoparticles can be especially
important for MXene lms, as TiO2 nanoparticles tend to form
along the ake edge sites during oxidation.13 In conductive
lms composed of 2D akes, inter-ake electrical conductivity
(edge to edge electron transfer) plays an important role in
determining the total electrical conductivity of the lm.
Therefore, eliminating the non-conductive TiO2 particles at the
edge of the lm is critical in restoring the electrical conductivity
of the entire lm. Furthermore, hydrogen gas produces surface
oxygen vacancies, and the oxygen vacancies create two hydroxyl
groups by reacting with neighboring water molecules, resulting
in a decrease in the water content of the lm.40
To demonstrate the outstanding electrical properties of the
hydrogen-annealed MXene lms, we fabricated Ti3C2 MXene-
based heaters, which generate heat through joule heating,
expressed as41
P ¼ VI ¼ I2R (6)
Potentials from 10 to 25 V were applied to the MXene lms,
and the temperature was measured and recorded as a function
of time. Fig. 4a shows the heating properties of as-prepared
Ti3C2 MXene lms, where higher applied voltages are clearly
observed to result in higher temperatures; the temperature
reached a maximum of 183.3
C when 25 V was applied. For
comparison, the heating properties of oxidized MXene lms
were also measured; the results are shown in Fig. 4b. The
maximum temperature attained at 25 V substantially decreased
to 108.8
C because of the increased sheet resistance of the
oxidized lm (279.2 U sq1) compared with that of the as-
prepared lm (71.4 U sq1). Aer the oxidized lm was post-
annealed under hydrogen at 900
C, the maximum tempera-
ture of the heater was also restored to 158.9
C at 25 V because
the sheet resistance was reduced to 105.9 U sq1 (Fig. 4c). The
summarized results (Fig. 4d) clearly show that, although
oxidation of the MXene lms greatly degrades their heating
properties, the hydrogen post-annealing treatment restores the
original properties to a large extent.
The recovery of the heating properties of MXene lms that
had been oxidized to different degrees was also investigated
(Fig. 4e and f). For more severely oxidized MXene lms, the
highest temperature was reduced to 53
C aer oxidation but
increased to 162.7
C aer the hydrogen post-annealing treat-
ment. At the same time, the sheet resistance recovered from
990.1 U sq1 to 62.5 U sq1 aer hydrogen post-annealing.
Through hydrogen annealing, the sheet resistance of Ti3C2
MXene lm was reduced due to the improved junction charac-
teristics, and this change was reected in the heater characteris-
tics. The temperature proles of the heaters based on the as-
prepared Ti3C2 MXene lm and the hydrogen-annealed lms are
shown in Fig. 4g and Table S3.† Because of the improved electrical
characteristics aer the hydrogen annealing of the lms, higher
temperatures were observed in lms, despite a sheet resistance
similar to that of the as-prepared sample. The Ti3C2 MXene-based
heaters shown in our work are comparable in the driving voltage
and the steady state temperature to other nanomaterials-based
heaters such as graphene, and AgNW (Table S4†).
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Fig. 4 Temperature profiles of Ti3C2 MXene-based heaters under different applied voltages, where the heaters were fabricated using (a) as-
prepared, (b) oxidized, and (c) hydrogen-annealed (900
C) Ti3C2 MXene. (d) Temperatures obtained from Ti3C2 MXene heaters represented in
(a–c), as measured at 150 s. (e) Temperatures measured at 150 s under an applied potential of 20 V and the sheet resistances of the samples
represented in (a–c). (f) The temperature measured at 150 s under an applied potential of 20 V and the sheet resistances of the samples with
higher oxidation degrees. (g) The temperature profiles of the as-prepared and the hydrogen-annealed MXene thin films with various sheet
resistances (measured at 150 s). (h) The temperature measured at 25 V and 150 s and (i) infrared images of the MXene-based thin-film heaters
(fabricated using as-prepared and hydrogen-annealed samples) before and after the oxidation stability test (100% RH, 70
C) for 1 day.

The oxidation stability of the hydrogen-annealed MXene
lms also played a role in preserving the heating effect. The
sheet resistance of as-prepared MXene lm increased to 2.61 
107 U sq1 when the sample was stored under highly oxidizing
conditions (70
C, 100% RH) for 1 day (Fig. 4h). As with the
severe change in sheet resistance, a total loss of heat generation
ability (26.1
C) was also observed for the fully oxidized heating
devices (Fig. 4h and i). However, the oxidation-resistant Ti3C2
lm subjected to hydrogen annealing maintained a sheet
resistance less than twice its initial value under the same
oxidizing conditions, resulting in a maximum temperature of
203.5
C for the heating device, with the device still emitting
bright infrared radiation (Fig. 4h and i).
high temperatures. Furthermore, aer hydrogen annealing of
Ti3C2 MXene lms, the oxidation reaction under humid
conditions (100% RH, 70
C) was effectively retarded. We also
demonstrated an electric heater made of oxidation-resistant
MXene lm, which was capable of stable operation in air
under highly oxidizing conditions (70
C, 100% RH). This work
provides insight into the oxidation mechanism of Ti3C2 MXene
lms, offers a protection method and broadens the range of
potential applications of MXenes lms in open air, at high
humidity and elevated temperature.
Experimental sections
Preparation and characterization of Ti3C2 MXene lms

Conclusions Ti3C2 MXenes were prepared according to the synthetic method

described in the previous study.15 The aqueous dispersions of
We demonstrated that the sheet resistance of an oxidized Ti3C2 MXenes were spin cast onto plasma-treated Si/SiO2 substrates to
MXene lm can be recovered through hydrogen annealing at form uniform lms. For the oxidation of the MXene lms, the

This journal is © The Royal Society of Chemistry 2020 J. Mater. Chem. A, 2020, 8, 573–581 | 579

Journal of Materials Chemistry A
degree of oxidation was varied by controlling the air exposure
time at 70
C, as described in the previous study.15 For hydrogen
annealing, the lms were annealed at a desired temperature
(100 to 900
C) in a vacuum chamber through which a 10%
hydrogen gas mixture (Ar 90%) was owing. The temperature
was increased from RT to 900
C during 10 min. Therefore, the
heating rate was 1.5
C s1 (or 90
C min1). A four-point probe
measurement was performed to determine the sheet resistances
of the lms (AIT, CMT-100 MP). XPS (Thermo Fisher Scientic,
Published on 18 November 2019. Downloaded by University of Georgia on 1/2/2020 8:47:05 PM.
K-Alpha), Raman spectroscopy (NOST, FEX), and XRD (Smar-
tLab, Rigaku) were used to characterize the lm structures. A
scanning electron microscope (FEI, Sirion) and transmission
electron microscope (JEM-ARM200F) were used to investigate
the morphological changes in the lms. A contact angle
analyzer (Phoenix 300 Plus) was used to measure the contact
angle of the lms.
Fabrication of MXene-based heating devices
To fabricate Ti3C2 MXene-based heating devices, the aqueous
dispersions of MXene were spin cast onto plasma-treated quartz
substrates. A tip of Cu tape was used to connect the lms to
a DC power supply. The desired DC voltage (3 V to 25 V) was
applied to the lms with various sheet resistances. An infrared
radiation thermometer (FLIR E75) was used to monitor the
temperature proles of the MXene-based heaters.
Author contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the nal version of
the manuscript.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The authors acknowledge helpful discussions with Asia Sar-
ycheva and Dr Mykola Seredych (Drexel University). This
research was supported by the National Research Foundation of
Korea (NRF) funded by the Ministry of Education, Science and
Technology (MEST) (NRF-2015K1A4A3047100, NRF-
2015M3A7B6027973, and NRF-2015M3A7B7046618) and by the
Open Innovation Program funded by NNFC (PCOI1801M004).
This research was also supported by Nano-Material Technology
Development Program through the National Research Foun-
dation of Korea (NRF) funded by the Ministry of Science, ICT
and Future Planning (2009-0082580).
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