Journal of The Electrochemical Society, 2021 168 030531

1945-7111/2021/168(3)/030531/8/$40.00 © 2021 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited

A First-Principles Investigation on the Electronic and Mechanical

Properties of 1T TiSe2 Multilayers for Energy Storage
J. E. Antonio,1 J. M. Cervantes,1 J. L. Rosas-Huerta,2 J. Pilo,3 E. Carvajal,1,z and
R. Escamilla4
1
ESIME-Culhuacán, Instituto Politécnico Nacional, Ciudad de México, Santa Ana 1000, 04440, Mexico
2
Facultad de Ciencias, Universidad Nacional Autónoma de México, Ciudad de México, A.P. 70-360, Mexico
3
Catalan Institute of Nanoscience and Nanotechnology-ICN2, Universitat Autonoma de Barcelona, Bellaterra, Cerdanyola
del Valles 08193, Spain
4
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Ciudad de México, A.P. 70-360,
04510, México

In this work, the electronic and mechanical properties of bulk TiSe2 were studied, and the effects of confinement on the compound,
into mono-, bi-, and tri-layered systems, on the electronic and mechanical properties using DFT-based calculations within the
Generalized Gradient Approximation (GGA) using Perdew–Burke–Ernzerhof (PBE) exchange-correlation functional. Lithium
atoms were placed at different adsorption sites of the TiSe2 monolayer to study the consequences on the electronic and mechanical
properties and to identify the most favourable adsorption site for Li in the TiSe2 systems. Mono -, bi-, and tri-layered systems have
associated a metallic behaviour, similar to the bulk material. Young’s modulus for mono-, bi-, and tri-layered systems show similar
behaviour to the bulk case. On the other hand, monolayers with Li are metallic when Li atoms are placed at the surface; and this
behaviour could be favourable to facilitate electronic transport by the monolayer. Finally, the mechanical properties analysis
supported that the better adsorption sites are those labelled as Top and Hollow.
© 2021 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited. [DOI: 10.1149/1945-7111/
abed29]

Manuscript submitted December 26, 2020; revised manuscript received February 23, 2021. Published March 18, 2021.

The growing access to electronic devices, which requires materials, which are formed either by linear chains or layers, and
electrochemical support to operate, is linked to increasing demand the latter case is typical for dichalcogenides. For CDWs, electrons
for energy storage because those devices are used for more flow through linear chains in the material, having a similar effect to
demanding applications. Then, it is necessary to look for better superconductivity,24,25 and happens at transition temperatures of
materials for energy conversion and storage. Among multiple 200 K18,26 and 202 K.27 The TiSe2 monolayer has been synthesized
possibilities, 2D materials offer an excellent alternative; among the by the exfoliation of molecular beam epitaxy.26 Using the ARPES
latter, the transition metal dichalcogenides (TMDCs) are an example technique, the bandgap of 0.098 eV for a 2 × 2 monolayer was
of layered compounds that can be exfoliated as 2D systems as it was obtained, while the value of 0.092 eV was obtained by the HSE06
made for graphene.1–3 MX, MX2, M2X3, and M3X4 (M = transition functional.28 Also, this material has been used to form heterostruc-
metal and X = chalcogen) are different TMDCs structural formulae; tures with SnSe, having ionic bonds that stabilize the system.29,30 In
those have associated good energy density values (around 210/225 addition, the TiSe2 monolayer has 780 mAh g−1 at 0.18–1.43 eV.19
mAh g−1) and support a high number of charge/discharge cycles; The electronic and mechanical properties of the bulk TiSe2 and
then, these qualities make TMDCs remarkable candidates for use as the confinement effect on these properties by building up mono-, bi-,
battery cathodes.1,4–7 However, those compounds could be metals, and tri-layered systems were studied in this work. Besides, Li atoms
semiconductors, or insulators; the electric behaviour of TMDCs were placed at different layer’s adsorption sites (Top, Down,
depends on the ratio of transition metal (TM) d-electrons to Hollow, and Bridge31,32) to identify the most favorable one for
chalcogenide p-electrons. This ratio defines the TMDCs electronic lithium adsorption through the electronic and mechanical properties
properties and their possible application area.8–11 It has been study, to enhance the batteries performance since TiSe2 monolayers
reported that the TM d-electrons are responsible for the different could be used as a cathode. All calculations were made within the
TMDCs phases through coordination with the chalcogen in the Density Functional Theory (DFT) framework.
system.11 For energy storage applications, it has been shown that
TiSe2 must be used in magnesium-, sodium- (SIBs) and lithium-ion Model and Calculation Scheme
(LIBs) batteries: as a monolayers’ structure where Ti atoms are
Bulk material and some monolayers (MLs) were calculated in the
sandwiched at octahedral holes between Se planes.1,6,12–14
DFT framework, within the Generalized Gradient Approximation
TiSe2 is a semiconductor with a negligible gap between the
(GGA)33,34 by means of the Perdew–Burke–Ernzerhof (PBE)
conduction and valence band formed by the Ti-3d and Se-4p
exchange-correlation functional,34–36 as it is implemented in the
orbitals, respectively.15–17 Besides, TiSe2 shows excellent potential
CASTEP code.37,38 Those calculations were made using a cut-off
as a cathode in multivalent-ion batteries (MVIBs), where the atoms
energy value of 350 eV and ultrasoft pseudopotentials.39,40 The
are interlaced in the compound; the reported voltages are 2.0, 2.0,
Brillouin zone was sampled using 3 × 3 × 3 and 3 × 3 × 1 grids for
1.1, and 1.8 V for Li, Na, Mg, and Ca, respectively.14 The electronic
the TiSe2 bulk and ML models, respectively, on the Monkhorst-Pack
band structure has been measured (bandgap of 100 meV) using the
scheme.41 The Broyden-Fletcher-Goldfarb-Shanno (BFGS) minimi-
ARPES technique.18 Furthermore, it has been reported that TiSe2 has
zation scheme was implemented for geometry optimization.42 All
theoretical capacity of 260 mAh g−1 and voltage of 1.14–2.09 V.19
the systems were fully relaxed until the maximum force, displace-
Besides, this compound has a lower tendency to form intrinsic
ment between atoms and stress were converged to 0.005 eV/Å, 2 ×
defects, which is why it has been used for intercalation in MTiSe2
10–4 Å and 0.02 GPa, respectively.
(where M = V, Fe, Cu, and Ni).15,20–22
The TiSe2 bulk material was modelled with trigonal symmetry
The layers’ stack along [001] is very weakly bonded and
(1T-type), P-3m1 space group (No. 164), with fractional positions:
determined by van der Waals forces.23 On the other hand, charge
Ti (0, 0, 0), Se1 (1/3, 2/3, 1/4) and Se2 (2/3, 1/3, 3/4). Likewise, the
density waves (CDWs) usually are observed at low symmetry
initial cell parameters for calculations were a = b = 3.533 Å and c =
5.595 Å43 (Figs. 1a and 1b). The optimized lattice constant value is a
z
E-mail: [email protected] = 3.533 Å, in agreement with previously reported experimental data:
 Journal of The Electrochemical Society, 2021 168 030531

Figure 1. (a) Lateral and (b) top views for the TiSe2 bulk phase. Lateral views for the TiSe2 (001)−1 × 1 layer models with 1, 2 and 3 Mls thickness (c), (d) and
(e), respectively). (f) Top view for the TiSe2 (001)−4 × 4 Ml system. (g) Different adsorption sites where Li atoms could be adsorbed on the TiSe2 (001)−4 × 4
Ml surface. (h) Side view of Top-site. The orange, grey and green spheres represent Se, Ti and Li atoms, respectively.

a = 3.538 Å.26 The obtained electronic-bands structure was com- of 3.1 Å between MLs was considered, using as a reference the
pared (Fig. 2) to that reported by Fang et al.23; TiSe2 shows a distance between crystallographic planes in the TiSe2 bulk material
metallic behaviour. (Figs. 1d and 1e). For each TiSe2-MLs model (mono-, bi-, or tri-
Once the methodology was tested to reproduce the bulk material layered), a vacuum space of 10 Å was left along the z-axis to avoid
characteristics, MLs were modeled. A TiSe2 (001)−1 × 1 Ml was interaction between periodic images.
built by making a cut at the optimized TiSe2 bulk structure, leaving Using the supercell method, a pristine TiSe2 (001)−4 × 4 Ml was
exposed the (001) crystallographic planes (mono-layered system, constructed (Fig. 1f) from a mono-layered system, which exposes a
Fig. 1c). Then, to study quantum confinement’s effects on the larger surface area than that for the TiSe2 (001)−1 × 1 Ml, to
electronic and mechanical properties of TiSe2 (001)−1 × 1 systems, identify the non-equivalent adsorption sites on this surface. Then, the
two new system models were created by stacking two and three Li effect on the physical properties of the TiSe2 systems was studied;
TiSe2 (001)−1 × 1 Mls (bi- and tri-layered systems). A separation by Li atoms deposition at different adsorption sites on the (001)
 Journal of The Electrochemical Society, 2021 168 030531

Etot - nA Eatom
A
- nB Eatom
B
- n C Eatom
C
Ecoh = [2]
nA + nB + n C
A B C
Etot is the compound’s total energy; and Eatom , Eatom and Eatom are
the energies corresponding to the isolated atoms A, B, and C.
Besides, nA, nB and nC are the number of A, B, and C atoms in the
compound.
The mechanical properties were calculated for these systems
because they could change with the multilayers thickness variation
and the lithium interaction, with a single layer, at different
adsorption-sites. Among the most important mechanical properties,
Young’s module indicates the materials’ resistance along with the
crystallographic directions, and it is defined as54–58:

1 ¶ 2U
Eij = Cij = [3]
Figure 2. Electronic bands structure for the TiSe2 (bulk), obtained by DFT V ¶ i ¶ j
calculations with GGA (black line, this work), compared with results
obtained with the LSW (red line).23 The dashed line indicates the Fermi where Eij = Cij is Young’s modulus, V the volume, U is the
energy.
variation of the system’s energy due to mechanical work and i and
 j are the deformation along the corresponding direction. For the 2D
surface TiSe2 (001)−4 × 4 Ml. Four different adsorption sites were
considered: above the center of the hexagonal Se rings (Hollow- hexagonal systems, there are four nonzero elastic constants C11, C22,
1
site), at the top of the upper Se atoms (Top-site), at the top of the C12 and C66, with C66 = (C11 - C12 ). The 2D Young’s modulus
lower Ti atoms (Down-site), and at the top of the Se–Ti bond 2
(Bridge-site)31,44,45 (Fig. 1g). It is worth to mention that the Li atoms (in-plane stiffness) for the strains along the [100] and [010]
58–60
were deposed at just one side of the monolayer model (Fig. 1h). directions are :
When Li atoms are placed at different sites at the surface, the
C11C 22 - C12
2
100] =
E[2D
adsorption energy (EA) changes; these energies were calculated for [4]
Li at the different adsorption sites on TiSe2 (001)−4 × 4 Ml, using C 22
the following equation46–50:
And
EA = EMol + EX (DB) - EX (DB) + Mol [ 1]
C11C 22 - C12
2

where EX (DB)+ Mol is the final energy of the optimized TiSe2 (001)−4 010] =
E[2D [5]
C11
× 4 Ml structure, which has a Li atom at the X dangling bond (DB) ;
and the energies for the isolated atom and the nanostructure with an The Pugh relation (G/B) and Poisson’s ratio (v) were calculated
X dangling bond are denoted by EMol and EX (DB), respectively. from the Bulk (B) and Shear (G) modulus and elastic constants (Cij).
To evaluate the stability of the TiSe2 (001)−1 × 1 layers (1, 2, The Poisson’s ratio and the Vickers hardness (Hv ) can be obtained
and 3 Mls thickness), as well as that for the TiSe2 (001)−4 × 4 Ml using the formula55,61–63:
systems, when a Li atom is placed at different adsorption sites, the
cohesive energy was calculated. This cohesive energy (Ecoh ) is 3B - 2G
v= [ 6]
useful to know how changes the bonds’ strength when the thickness 2 (3B + G)
changes (for the TiSe2 (001)−1 × 1 layers) or when Li atoms are
placed at different adsorption-sites on the TiSe2 (001)−4 × 4 Ml G
surface; it was calculated using48,51–53: Hv = 0.92K1.137G0.708, K = . [7]
B

Figure 3. Electronic bands structure for (a) 1, (b) 2 and (c) 3 TiSe2 (001)−1 × 1 Mls. Also, the cohesive energy is shown (d).
 Journal of The Electrochemical Society, 2021 168 030531

Results and Discussion TiSe2 (001)−4 × 4 Ml; then, the chemical bond’s nature only is
modified locally on those atoms of the TiSe2 (001)−4 × 4 Ml which
Electronic properties.—The TiSe2 models were optimized (bulk
are in contact with the adsorbed lithiums.
and monolayers) referred to the internal parameters, energy, force,
Furthermore, those systems with the adsorption sites labeled as
stress, and displacement. The electronic bands structure for each
Hollow and Top have associated the more significant adsorption
TiSe2 (001)−1 × 1 Ml was calculated for the trajectory Γ to K, K to
energy values (Fig. 5f) and the smaller cohesive energies. It is worth
M, and M to Γ (Fig. 3, for (a) 1, (b) 2 and (c) 3 Mls), as well as the
mentioning that Li is chemisorbed (greater than 0.3 eV) for all the
associated Ecoh. These systems are metallic (bands pass-through the
modeled systems.
Fermi energy at M and Γ points) and, from the cohesive energy plot,
Likewise, for the systems with Li atoms at the Top-, Down-, and
it is possible to see how the systems turn more stable when layers are
Bridge-sites, the Li moves to the Hollow-site as a result of the
added, leading the systems to the bulk material behaviour (Fig. 3
optimization process; due to that, the Ecoh difference is negligible for
(d)).
all systems. The Ti and Se atoms’ charge remain invariant (0.14 e
Partial density of states (PDOS), it can be seen the ionic character
and −0.07 e, respectively); however, the Se charge interacts with Li
of the Se–Ti bonds, because there is a great contribution from the Ti
charges (Fig. 6). For Li’s system at the Top-site, Se atoms interact
3-d orbitals at the conduction band ([0.3, 1] eV); while Se 4-p
with it, their charge values are −0.11 e and −0.12 e, while the Li
orbitals dominate the valence band ([−1, −0.4] eV) (Fig. 4a).
charge is 0.29 e (Fig. 6a). For Li’s system at the Down-site, the Se
However, at the energy interval [−0.4, 0] eV the contributions of
and Li charges are −0.12 e and 0.30 e, respectively (Fig. 6b). When
both atomic species (Se and Ti) are identical; even from −0.6 to
Li was placed at the Hollow-site, the Se charges are −0.11 e and
−0.4 eV, the Ti 3-d peak at the PDOS is almost half that for the Se
−0.12 e, while that for the Li is 0.31 e (Fig. 6c). If Li is placed at the
4-p, which could indicate Se-Ti covalent-ionic antibonding interac-
Bridge-site, the Se and Li charges are −0.12 e and 0.27 e,
tions.
respectively. Finally, atomic species are which interact with the Li
For the TiSe2 (001)−4 × 4 Ml (pristine system) was obtained a
atom at the surface behave in an ionic way (red circles, Figs. 6a–6d),
direct band gap of 0.152eV (Γ→ Γ, Fig. 5a). Once Li is added on the
because the Li transfers its charge to the Se atoms; however, the
TiSe2 (001)−4 × 4 Ml’s surface different sites, the metallic
remaining Se and Ti atoms behave covalently, as predominate in the
behaviour turns evident. This is because the bands associated to
system. The Li atom stabilizes the system through the interaction
the conduction states of Se 4-p (pristine system) were displaced at
with the equidistant Se atoms, which need six electrons.
the Fermi level when Li was adsorbed at the surface of the TiSe2
From these results, the electronic properties of the TiSe2
(001)−4 × 4 Ml (Fig. 5, from (a) to (e)). Thus, for the systems with
monolayers can be better understood by the lithium atoms role
adsorbed lithium, it is observed that the Ti 3-d orbitals have a greater
played at the different adsorption sites. First, the lithiated mono-
contribution from −0.2 to 0.8 eV, while the Se 4-p from −0.8 to −1
layers’ metallic behavior is due to the charge transfer between Li and
eV, following that reported by Zhao et al..19 For Li 2-s orbitals, it is
Se, since the unoccupied states of the pristine system were filled
not possible to appreciate the orbital contribution due to the system’s
when lithium was adsorbed on the TiSe2 (001)−4 × 4 Ml, reducing
size (Fig. 4, from (b) to (e)). Although, at the PDOS, there was a
the Se atoms and increasing its negative charge. Second, the
displacement of the electronic states of the lithiated monolayers
adsorption energy strongly depends on the adsorption site (i.e., at
concerning the pristine system (Fig. 4), the relative peaks’ position
the Hollow-site the Li was equidistant from the neighboring Se
for Se and Ti atoms is qualitatively similar to that of the pristine

Figure 4. PDOS for the TiSe2 (001)−4 × 4 Mls. (a) Pristine ML and MLs with Li at the different adsorption-sites: (b) Top, (c) Down, (d) Hollow and (e)
Bridge.
 Journal of The Electrochemical Society, 2021 168 030531

Figure 5. Electronic bands structure for the modelled TiSe2 (001)−4 × 4 Mls: (a) Pristine and with Li at the different adsorption sites (b) Top, (c) Down, (d)
Hollow and (e) Bridge. For the lithiated cases, the (e) Adsorption and (e) Cohesive energies are plotted.

Figure 6. Charges of TiSe2 systems (001)−4 × 4 Mls with Li: (a) Top, (b) Down, (c) Hollow and (d) Bridge. Roman numerals show systems before they are
optimized; numbers I, II, III and IV correspond to the Li atom systems at the Top, Down, Hollow and Bridge sites, respectively. The red circles show the atoms
that changed their charge due to the Li atom. The units of charge are e.

atoms, and is the case with maximum adsorption energy), whereas change (Table II) if these atoms are placed at the Top-and Hollow
for the other cases, the Li-Se bonds had different lengths (weak sites.
adsorption energy). Nevertheless, if Li atoms are placed at the Bridge absorption site,
the elastic constant values’ decrease is greater: 22% for C11, 28% for
Mechanical properties.—The elastic constants for the TiSe2 bulk C22 1%, for C12 and 20% for C66. A decrement was observed for the
and (001)−1 × 1 Ml systems were calculated (Table I); all values Young’s modulus, along with the crystallographic direction [100]
decrease while the system becomes thinner: C11 decreases by around and [010], for all the systems. For the Top-, Down-, Hollow- and
58%, C22 54%, C12 38% and C66 61%. These values increase Bridge-sites the decrements are 3%, 8%, 4% and 27%, along the
gradually with the number of the layers and converge to the crystallographic direction [100]; while for [010] are 16%, 23%, 19%
respective bulk material’s values. On the other hand, Young’s and 37%, respectively. These results show that the Bridge-site is the
modulus of 1 layer system decreases by 62% and 55% in the least favourable for Li atoms storage, because the Young’s modulus
crystallographic directions [100] and [010], respectively (Fig. 7a). In values found are the lowest.
addition, to analyze de Vickers hardness (Hv ) of multilayers, the The Vickers hardness (Hv ) average (3.94 GPa) suggests that the
hardness of the 1-layer system decreases 55% compared to the bulk material maintains its hardness when the Li atom is added. From the
material; however, by adding layers, the hardness increases calculated mechanical properties for TiSe2 (001)−1 × 1 and
(Table I). Once the Li atoms were placed at different adsorption- lithiated −4 × 4 Mls, Young’s modulus values for the former
sites on the systems, the elastic constant values almost did not systems are smaller than the corresponding value for the bulk
 Journal of The Electrochemical Society, 2021 168 030531

Table I. Elastic constants Cij, Young’s modulus along with the material, for the same crystallographic directions [100] and [010];
crystallographic directions E100 and E010 , Bulk modulus ( B), Shear but those values grow with the number of the layers in the modeled
modulus (G ), G /B and Poisson’s ratio (v), Vickers hardness (Hv ) of system (Fig. 7). The calculated elastic constants values show similar
the multilayers systems. All values are in GPa units. behaviour for the multilayered systems; however, C12 exhibits a
smaller variation. On the other hand, Li’s effect on the systems’
Systems 1 layer 2 layers 3 layers Bulk mechanical properties is minimal when Li is placed at the Top and
Hollow adsorption sites.
C11 49.51 69.01 76.29 117.98
Because the G/B ratio value is a parameter to differentiate
C22 54.10 76.04 83.92 117.98
between a fragile or ductile material, the results indicate (Fig. 7c)
C12 12.83 18.25 20.41 20.69
that the TiSe2 (001)−1 × 1 Ml systems, the bulk material and the
C66 18.76 26.08 28.84 48.64
lithiated (001)−4 × 4 Ml systems are brittle (Fig. 7d).59,61 Besides,
E100 40.70 58.10 63.72 105.73
from the calculated Poisson ratio (v) which tells us if the material is
E010 47.51 66.34 72.90 105.73
metallic (0.33), ionic-covalent (between 0.2 and 0.3) or strongly
B 17.68 25.13 22.73 28.46
covalent (less than 0.15),63,64 it is possible to observe a change from
G 13.27 18.04 18.21 27.57
ionic-covalent to strongly covalent as layers are added to the TiSe2
G /B 0.75 0.71 0.80 0.96
(001)−1 × 1 system (Fig. 7c); for the lithiated (001)−4 × 4 systems
v 0.19 0.21 0.18 0.13 was found that all exhibit an ionic-covalent behaviour (Fig. 7d).
Hv 4.14 4.89 5.57 9.28

Figure 7. Young’s modulus of (a) (001)−1 × 1 Mls and (b) (001)−4 × 4 Ml with Li systems. G/B and Poisson ratio of (c) TiSe2 (001)-MLs and (d) (001)−4 ×
4 Ml with Li.

Table II. Elastic constants Cij, Young’s modulus along with the crystallographic directions E100 and E010 , Bulk modulus ( B), Shear modulus (G ),
G /B and Poisson’s ratio (v), Vickers hardness (Hv ) of the monolayers with Li. All values are in GPa units.

Systems 4 × 4 Ml Top-site Down-site Hollow-site Bridge-site

C11 49.51 48.87 43.12 48.30 38.29

C22 54.10 48.89 42.54 47.83 38.84
C12 12.83 14.64 11.78 14.65 12.89
C66 18.76 17.41 15.96 17.12 14.93
E100 40.70 39.58 37.35 39.24 29.80
E010 47.51 39.82 36.60 38.27 29.79
B 17.68 23.96 12.45 23.86 18.36
G 13.27 15.63 10.59 14.97 13.17
G /B 0.75 0.65 0.85 0.62 0.71
v 0.19 0.25 0.18 0.26 0.23
Hv 4.14 3.96 4.06 3.67 3.91
 Journal of The Electrochemical Society, 2021 168 030531

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