CHAPTER 3

TITANIUM CARBIDE MXene

3.1 Introduction

MXene’s, the gem stone in the crown of flatland, it all started with Titanium car-
bide (Naguib et al., 2011).The discovery of the MXene’s was discussed in detail in
the chapter-2. Titanium carbide MXene’s added to its credit as most researched and
reported MXene’s so far in diverse applications such as supercapacitor (Babu et al.,
2016),battery (Ahmed et al., 2016),fuel cell (Ling et al., 2016) environmental applica-
tions such as heavy metal removal and dye degradation (Mashtalir et al., 2014), Electro-
magnetic interference (EMI) shielding (Raagulan et al., 2019), dipole antennas (Chaud-
huri et al., 2018; Sarycheva et al., 2018a) etc. Titanium carbide MXene are derived by
etching the “A” layer from the parental Titanium aluminium carbide MAX phase, it
exists in three phases namely 211- T i2 AlC2 (Ahmed et al., 2016),312-T i3 AlC2 (Zhen
et al., 2005), 413-T i4 AlC3 (Lane et al., 2012). Follows the standard formula of MAX
phase.
Mn+1 AXn (3.1)

where

• ”M” is titanium.

• ”A” is aluminium.

• ”X” is carbon.

Titanium carbide MXene has a unique set of properties as electrically conducting met-
als and (Feng et al., 2017) mechanical strength, heat tolerance as ceramic materials
(Barsoum and El-Raghy, 2001; Zhen et al., 2005).It was experimentally proved that the
mechanical properties of these materials varied from brittle to pseudo plastic under the
influence of temperature around 1100 degree centigrade (Barsoum and Radovic, 2011;
Ghidiu et al., 2015).Temperature has a inversely proportional influence on the strength
of the materials (Merzhanov, 2004),the mechanical properties ranging towards pseu-
doductile with strains to failure/ fault in both compression and tension exceeding 25%

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(Zhang et al., 2015). The synthesis of this titanium carbide MXene is quite challenging
as there are different methods of synthesis such as microwave heating method (Guan
and Sun, 2016; Vadchenko et al., 2015), leading to the different properties of the mate-
rials (Cooper and Hansler, 1963),synthesis via Self propagating high temperature syn-
thesis (Sutham, 2013; Levashov et al., 2017), Molten salt synthesis (Wan et al., 2017;
Moore and Feng, 1995), aluminothermic reduction process (Hendaoui et al., 2008),
exchange reaction (Cuskelly et al., 2016; Mishra et al., 2011).
Here we employed a two step synthesis method i.e. synthesis of MAX phase fal-
lowed by HF etching for the synthesis of MXene.In this chapter the deals with the
synthesis of titanium carbide by simple ball milling of T iO2 , aluminium and graphite
powders, which was later converted to titanium aluminium carbide at a high tempera-
ture. By selective optimizing on the experimental parameters, two kinds of MXenes are
prepared viz. T i3 C2 and T i2 C by a simple ball milling technique without the need of
any high temperature set up. Later the aluminium was etched by using HF,as confirmed
by powder XRD; FESEM and TEM confirmed the morphological changes at various
stages of the investigation. TGA confirmed the materials stability, and further, the ma-
terial was tested for its electrochemical behaviour towards supercapacitor applications.

3.2 Synthesis

3.2.1 Synthesis of titanium aluminium carbide MAX phase

The powders of elemental Titanium (Ti), aluminium (Al),graphite(C) was ball milled a
charge ratio of 10:1 with different stoichiometric ratios in order get different phases of
titanium aluminium carbide. Since the elemental powders of titanium are expensive, we
have used Titanium di oxide (T iO2 ). The ball milled samples were heated at 1200o C
for 2 hours in a tubular furnace with a ramping rate of 5o C/ minute in the presence of
inert atmosphere. The stoichiometric equations are given as fallows.

3T iO2 + 5Al + 2C = T i3 AlC2 (M AXphase) + 2Al2 O3 (3.2)

6T iO2 + 11Al + 3C = 3T iAlC(M AXphase) + 4Al2 O3 (3.3)

3.2.2 Synthesis of titanium carbide MXene

To convert the synthesised MAX phase in to MXene, 2g of synthesised MAX phase
either T i2 AlC or T i3 AlC2 were carefully added in to 20 ml of conc.HF (40-50%) and
set undisturbed for 10 hrs.After that the etched MXene were washed with deionized
water and vacuum filtered using a polypropylene filter and dried at 80o C for 24 hrs;then
pealed from the filter.The etching reactions are as follows

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 T i3 AlC2 + 3HF = AlF3 + 3/2(H2 ) + T i3 C2 (M Xene) (3.4)

T i2 AlC + 2HF = AlF2 + H2 + T i2 C(M Xene) (3.5)

Fig. 3.1 Photograph of beakers showing the etching processes-Top view

3.3 Material characterization

The structural and phase properties of the synthesised MAX phase and MXenes were
investigated by XRD.The Fig.3.3 and 3.4 displays the XRD patterns of the T i3 AlC2 ,
T i3 C2 and T i2 AlC,T i2 C respectively. As evident from the XRD patterns, there is
a presence of the T i3 AlC2 , T i3 C2 , T i2 AlC, T i2 C and trace peaks of Al2 O3 and few
unidentified peaks. After HFetching the intensity of Al2 O3 intensity was reduced and
only peaks penetrating to T i3 C2 were mainly observed, which confirms that the etching
process was successful and element “Al” was removed completely .The peak angle at 2θ
value of 39o almost decreased, which indicates that the Al atoms present in the crystal
structure of the parental MAX phase T i3 AlC2 . It is also noted that the peaks are shifted
to lower values after the etching. the obtained results were in accordance with the
existing literature(Li et al., 2016). The same has be noted in case of the T i2 AlC, after
HF etching aluminium was removed from the parental MAX phase T i2 AlC,though it
contains other mixed phases as well.

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 Fig. 3.2 Photograph of beakers showing the etching processes-Side view

Fig. 3.3 XRD diffractogram spectrum of (a) T i3 AlC2 b(MAX phases) and(b)T i3 C2 (MXene)

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Fig. 3.4 XRD diffractogram spectrum of (a)T i2 AlC (MAX phase) and (b)T i2 C (MXenes)

Fig. 3.5 Raman spectroscopy of the MAX phase (a) T i2 AlC and MXene (b) T i2 C

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 Fig. 3.6 Raman spectroscopy of the MAX phase (a)T i3 AlC2 and MXene (b)T i3 C2

The Raman spectrum of the synthesised samples were shown in Fig.3.5 3.6 which
were in agreement with the earlier reports. as clearly seen in the spectrum the parental
MAX phases possess four vibrational modes around 153.3, 260.9, 270.3, 358.7cm−1
respectively for the both samples of T i3 AlC2 and T i2 AlC respectively .The most in-
tense modes viz. ω1 , ω2 , ω3 , ω4 . are associated with Titanium (Ti) and Aluminium
(Al),whereas two more intense modes of ω5 ,ω6 were reported in literature correspond-
ing to the carbon sub lattice due to the ultra pure systems (Lane et al., 2012).which were
absent in our synthesised sample due to the presence of the mixed phases of T iC and
Al2 O3 . Despite the absence of ω5 , ω6 modes corresponds to carbon and aluminium, it
still effects the raman vibrational modes(Hu et al., 2016).the spectrum of the aluminium
etched samples show us that the aluminium was etched keeping the Hexagonal structure
undisturbed and it evident that the aluminium etching has not eliminated these modes
ω1 , ω2 , ω3 , ω4 but pushed them to the lower frequencies.
The FESEM micrograph of the samples immediately after ball milling, parental
MAX phases and MXene were given in the Fig.3.8 and 3.9. The FESEM images of
the ball milled samples show that the powders of titanium dioxide, aluminium and
graphite were mixed properly and different types of plates like structures are seen in
the Fig.3.8(a1 a2 ),3.9(a1 a2 ).The images of T i3 AlC, T i2 AlC 3.6,3.7(b1 b2 ) shows the
transition of the morphology to layered solids and minor amount of other shapes also

39
seen which may be of T iC or Al2 O3 or other unidentified phases .The FESEM images
of the synthesised MXene samples were in stacked layers as can be seen in 3.8,3.9
(c1 c2 ).The TEM images of T i3 C2 is shown in the Fig.3.10 and from the images it is ev-
ident that clear exfoliation of flaky structures could be observed. Notably, regardless of
high atomic composition of titanium, ultra- thin films of the MXenes T i3 C2 transparent
to electrons are detected, as the layer number increased, the colour moved towards a
darker shade (Eames and Islam, 2014; Simon et al., 2014).

Fig. 3.7 Thermogravimetric analysis of T i3 AlC, T i2 AlC MAX phases, MXene T i3 C2 and T i2 C

Thermogravimetric analysisTGA was done for room temperature to 1200o c under

N2 atmosphere in order to estimate the stability of the synthesised MAX phases and
MXenes. In case of T i3 C2 the stability was more in comparison with theT i3 AlC2 ,as
weight decreased from 1% to less than 0.5% which conforms that the weak bonding of
the aluminium to titanium and carbon atoms where as for T i2 C. The weight loss has
increased from the 2.5% to 4% (Fig.3.7).

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Fig. 3.8 FESEM of T i2 AlC - a1 , a2 ( powders after ball milling); a3 , a4 (T i2 AlC MAX phases) and
a5 , a6 ( T i2 C MXene)

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Fig. 3.9 FESEM of T i3 AlC2 -b1 , b2 ( powders after ball milling); b3 , b4 (T i2 AlC MAX phases) and b5 , b6
(T i2 C MXene)

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Fig. 3.10 TEM of the MXene T i3 C2

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3.4 Electrochemical testing

3.4.1 Fabrication of electrode

The working MXene electrodes for the electrochemical testing were assembled by coat-
ing 1 mg of the active material on the carbon paper using 5% nafion mixture of lower
aliphatic alcohols as a binder. In this investigation a typical three electrode system
was used for all the electrochemical measurements with platinum wire as a counter
electrode and Ag/AgCl as a reference electrode (Zhu et al., 2016).All the measure-
ments were carried out using 6M KOH as aqueous electrolyte solution at room temper-
atures.cyclic voltammetry (CV),galvanostatic charge and discharge (CP) and electro-
chemical impedance spectroscopy (EIS) were measured by CHI660C electrochemical
workstation.CV curves are recorded as different scan rates from 1 mV/s to 100 mV/s
and charge and discharge studies were performed at different current densities within
the potential range of -0.25V to +0.25V respectively.EIS measurement were carried out
from 0.01 hertz (Hz) to 100 Kilo hertz (KHz).

3.4.2 Electrochemical testing

The electrochemical behaviour of the prepared MXenes is estimated using a three-
electrode system in 6M KOH as electrolyte. The CV of T i3 C2 at different scanrates
at a potential window of -0.25 V to + 0.25 V are presented in Fig.3.11 and Fig.3.12
respectively. the obtained CV graphs are nearly rectangular shape which resembles
the EDLC behaviour and shows high reversibility of capacitive behaviour(Lukatskaya
et al., 2013a).The broad area in CV loops might be due to the layered structure and
synergistic effect between the components.Excess of K+ cations could readily be inter-
calated between the layers of titanium carbide MXene. The enhanced performance of
the electrode material is inclusive of the other factors viz.higher specific surface area
and density because of its morphology and aligned flake like structure. Moreover, both
electrodes have stronger dependence on the scan rates. which is assumed that when
aligned parallel to the current collector increases path for ions as the electrode thick-
ness increases. interestingly as the scanrate decreases, the K+ ions moving deeper in
to the spacing between the layers of the exfoliated titanium carbide results in excess
current. In the earlier report by Lin, Barbara, Taberna, Van Aken, Anasori, Gogotsi and
Simon (2016).it was reported that in case of ionic liquid, interlayer spacing could be
increased or decreased reversibly depending on the voltage sweep. These phenomena
were observed in both T i2 C and T i3 C2 . The specific capacitance was estimated from
the CV measurements were calculated using the following equation

C = Imax /(mdv/dt) (3.6)

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 Where ”m” is the mass of the active MXene material/unit area and ”dv/dt” is the
scan rate.Both figures of CV show an increment in the current response with scan rate,
which constitutes ideal capacitor behaviour. A plot of specific capacitance (SP) Vs scan
rate is plotted in the Fig.3.13 and as obvious from the analysis, both MXene exhibits
excellent capacitance behaviour with a capacitance value of 450 F/g at 1 mV/s and
as seen in the analysis, T i3 C2 showed a higher capacitance nature of the fabricated
electrode. Overall T i3 C2 and T iC2 have provided a layered electrochemically active
surface area and thus high charge storage in capacitance applications.

Fig. 3.11 Cyclic voltammetry of MXene T i3 C2 at various scan rates Vs.Ag/Agcl

Fig.3.13 and 3.14 displays the CP testing of the prepared MXene electrode material
at different current densities, which were performed with three – electrodes systems in
the potentials windows of -0.2V to 0.2V vs Ag/AgCl to provides complimentary mea-
surements of specific capacitance from CV.The obtained charge-discharge curves are
triangular in shape demonstrating the excellent performance of the electrode materials
and concerning in an argument with CV graph. At higher current densities, the ions
that diffused from the electrolyte have enough time to gain access and penetrate deep
into the available gaps between MXene there by contributing to increase performance
of the MXene electrode, sheets in progressively diminished and secondarily the amount
of ions that diffuses from the electrolyte are very less and may be holding on loosely on
the top most layer of the synthesized MXene material leading to a faster discharge.
Further more, the EIS at a frequency range of 0.01 Hz to 1000Hz was employed to

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 Fig. 3.12 Cyclic voltammetry of MXene T i2 C at various scan rates Vs. Ag/AgCl

Fig. 3.13 A plot of Specific capacitance vs scan rate MXene T i3 C2 , T i2 C as calculated from CV graphs.

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Fig. 3.14 A Charge-Discharge Characteristics of MXene T i3 C2 measured at different current densities.

Fig. 3.15 Charge-Discharge Characteristics of MXeneT i2 C measured at different current densities.

study the kinetics of the prepared electrode MXene shown in the Fig.3.16 and 3.17,In
T i2 C,the presence of small semicircle at the high frequency range represents the charge

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transfer resistance across the electrode and electrolyte interface, where as it was not
clearly visible in the case of T i3 C2 ,which may be due to HF etching that had roughened
the surface of electrode strongly

Fig. 3.16 Nyquist plots of MXene T i3 C2 electrode by applying a sine wave with an amplitude of 0.1 V
over the frequency range from 0.01 Hz to 100 kHz. Inset: Enlargement of the Nyquist plots in the high
frequency region and its equivalent circuit.

3.5 Conclusion

2D titanium carbide MXenes were successfully synthesized by etching aluminium from

their counter MAX phases by using HF, and a simple ball milling route was employed
to synthesise titanium aluminium carbide . The exfoliated layered structures are con-
venient for the electrolyte to penetrate into the electrode material thereby providing the
path for penetration of ions into the electrode. The electrochemical investigation reveals
a specific capacitance around 447 F/g for T i3 C2 and 248 F/g T i2 C at 1 mV/s scan rate in
6M KOH electrolyte.These excellent properties imply that the electrode materials could
be exploited in supercapacitor applications. Overall, this work provides safe, effective,
and detailed investigation of titanium carbide as supercapacitor electrode materials.

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Fig. 3.17 Nyquist plots of MXene T i2 C electrode by applying a sine wave with an amplitude of 0.1 V
over the frequency range from 0.01 Hz to 100 kHz. Inset: Enlargement of the Nyquist plots in the high
frequency region and its equivalent circuit.

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