www.acsaem.

org Article

The Abnormally Excellent Figure of Merit of 14,14,18-Graphyne at

Room Temperature: A Study on the Thermoelectric Characteristic of
Graphyne
Pengfei Qi, Ke Liu, Shipeng Bi, Zheng Chang, Kunpeng Yuan, Yufei Gao,* Xiaoliang Zhang,*
Yuhang Jing, and Dawei Tang*
Cite This: ACS Appl. Energy Mater. 2022, 5, 6363−6372 Read Online
Downloaded via INDIAN ASSOCIATION CULTIVATION SCI on September 2, 2022 at 11:49:43 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: The application of carbon-based nanomaterials in the field of

thermoelectric is enormously restricted for its high thermal conductivity. Graphyne,
as the allotrope of graphene, expresses low thermal conductivity; therefore, it can be
expected to break the limitation of carbon-based materials in thermoelectric field.
By using the first-principles calculation combined with the Boltzmann theory, the
thermoelectric properties of types of graphynes, i.e., 6,6,6-, 6,6,12-, 14,14,18-, and
18,18,18-graphyne, are systematically investigated. It is interesting to find that
14,14,18-graphyne presents excellent thermoelectric properties, whose maximum
value of ZT can reach 1.6 at room temperature; therefore, it can be seen as an
excellent carbon-based thermoelectric material. More importantly, its ZT at low
temperature is abnormally higher than that at high temperature, which breaks the
traditional view that the higher ZT exists in a high temperature range. Furthermore,
it can also be noticed that the other three types of graphynes exhibit unexpected
special thermoelectric properties: (1) 6,6,6-graphyne shows the highest Seebeck coefficient; however, its ZT value is the lowest.
Moreover, its ZT value for n-type doping is twice as that for p-type doping. (2) The ZT of 6,6,12-graphyne expresses enormous
anisotropy, whose value along the zigzag direction is even 1−2 orders of magnitude higher than that along the armchair direction.
(3) The ZT of 18,18,18-graphyne shows completely opposite anisotropy compared with the other three types of graphynes, and its
ZT value along the armchair direction is higher. Our research provides some meaningful results for enhancing the thermoelectric
performance of carbon-based nanomaterials, especially for the development of high-performance thermoelectric materials at room
temperature.
KEYWORDS: graphyne, thermal conductivity, electronic transport properties, thermoelectric characteristic, phonon characteristic,
first-principles calculations

1. INTRODUCTION materials, carbon-based materials have always been seen as a

Nowadays, the global energy crisis has arrived due to the
massive use of fossil fuels. Thermoelectric materials can
convert waste heat surplus thermal energy into electric energy;
therefore, this method shows great potential in the field of
sustainable energy.1,2 Generally, the performance of thermo-
electric materials can be characterized by the figure of merit
ZT: ZT = S2σT/κ, where S, σ, T, and κ, are the Seebeck
coefficient, electrical conductivity (EC), absolute temperature,
and thermal conductivity (TC), respectively. From this
equation, it can be noted that excellent thermoelectric
materials require a high power factor (S2σ, high Seebeck
coefficient and EC) and low TC.3 However, S, σ, and κ are
mutually coupled in most thermoelectric materials, and it is
difficult to satisfy the above requirements4 at the same time. In
recent years, some investigations showed that the quantum
confinement effect of low dimensional materials can effectively
enhance the ZT value.5−12 Among various low dimensional
hot research subject for their friendly environmental character-
istics. Since the advent of graphene in 2004, its performance
has attracted widespread attention;13 e.g., graphene has an
electron mobility as high as (15000 cm2 V−1 s−1)14 and a
unique energy band structure-Dirac cones,15 which makes
graphene has great application in the field of electronic
transport. Nevertheless, since the TC of graphene nearly
reaches 5000 W/mK,16 it cannot be directly used as a
distinguished thermoelectric material.
Received: March 9, 2022
Accepted: April 11, 2022
Published: April 25, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsaem.2c00742

6363 ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
Figure 1. Structures of (a) 6,6,6-, (b) 6,6,12-, (c) 14,14,18-, and (d) 18,18,18-graphyne.
Graphyne (GY), the new allotrope of graphene, is composed
of sp, sp2 and sp3 hybridized carbon atoms. The sp2 hybridized
carbon atoms are formed as a hexagon, and the different
hexagon structures are connected with acetylene bond (−C
C−).17,18 GY usually has excellent properties like graphene,
e.g., good chemical and thermal stabilities, high carrier
mobility,19 etc. Meanwhile, it also shows some properties
different from graphene; e.g., it is a semiconductor with band
gap,20 it can be used as a material to store lithium and
hydrogen,21 and so on. These excellent physical properties let
GY have great application prospects in energy storage and
nanophotoelectric devices. Besides this, GY also shows much a
lower TC than graphene,22,23 which let it to be an excellent
thermal management material and play an important role in
improving the thermoelectric efficiency. Up to now, the
researches of GY have not only been limited at the theoretical
level, large area graphdiyne films with 3.61 cm2 was
successfully generated on the surface of copper combining
with the chemical growth of hexaethynylbenzene, which
realized the leap from theoretical prediction to experimental
testing.24,25
In this paper, combining with the first-principles calculation
with the Boltzmann transport equation and relaxation time
approximation, the thermoelectric transport properties of four
types of GYs are obtained. First, we calculate the TCs of the
four GYs and analyze the phonon mechanisms; furthermore,
the electronic band structures and electronic transport
properties of different GYs are predicted. Finally, by analyzing
6364
www.acsaem.org Article
their thermoelectric properties based on the above results, it
can be noticed that all of the four GYs show unique
thermoelectric properties, and more importantly, 14,14,18-
GY can be regarded as an excellent thermoelectric material.
2. COMPUTATIONAL DETAILS
2.1. Structure of Graphyne. Figure 1 shows the crystal
structures of 6,6,6-, 6,6,12-, 14,14,18-, and 18,18,18-GY,
respectively. The blue parallelograms in Figure 1a−d represent
the unit cells with 24, 18, 14, and 16 atoms, respectively. It can
be seen from the structural diagram that GY is composed of
carbon rings and chains. Therefore, according to the
distribution of carbon rings and chains, GY can be divided
into many types. The structures of the four types of GYs in this
paper were proposed by Baughman.17 These four GYs are
chosen under the comprehensive consideration of the
calculation efficiency and excellent thermoelectric character-
istics. Besides the advantage that the atom numbers in unit cell
are suitable for DFT calculation, all of the chosen four GYs
express some unique thermoelectric characteristics (detailed
content can be seen in section 3.3). The detailed bonding and
coordinate information on the four GYs can be seen in Figure
S1 and Tables S1−S3 in the Supporting Information.
2.2. First-Principles Calculations. All the first-principles
calculations are performed by the Vienna ab initio simulation
package (VASP),26 based on density-functional theory. The
electron−ion interaction is described by projected augmented
wave (PAW)27,28 method, and the Perdew−Burke−Ernzerhof
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
Figure 2. Thermal conductivities along the X and Y direction of (a) 6,6,12-, 14,14,18-, 18,18,18-, and (b) 6,6,6-graphyne as a function of
temperature.
Figure 3. (a) Squared phonon group velocities, (b) phonon lifetimes, (c) Grüneisen parameters, and (d) three-phonon scattering phase space of
four graphynes as a function of frequency.
(PBE)29 is chosen to be exchange-correlation functional.
During the process of structure optimization, the truncated
kinetic energy is set to be 550 eV, and the shape and volume of
unit cell are fully optimized until the maximal Hellmann−
Feynman force acting on each atom is no larger than 1 × 10−6
eV/Å. The Monkhorst−Pack k-point grid is chosen to be 21 ×
21 × 1. Besides, to avoid the effect of layer−layer interactions,
sufficiently large vacuum region (20 Å) along the out-of-plane
direction of unit cell is constructed in each calculated structure.
The specific information on calculated method to obtain
thermal transport properties, electronic transport properties,
and thermoelectric properties is listed in the Supporting
Information.
6365
www.acsaem.org Article
3. RESULTS AND DISCUSSION
3.1. Thermal Transport Properties. Figure 2 shows that
the TCs along X and Y directions of the four GYs as a function
of temperature. It can be noticed from this figure that (1) the
TC of GY is much lower than that of graphene (1−2 orders of
magnitude lower), whose value is in the range of 3000−5000
W/mK;30,31 (2) the order of TCs of the four materials is
κ6,6,6‑GY > κ6,6,12‑GY > κ18,18,18‑GY > κ14,14,18‑GY, and the TC of
6,6,6-GY is obviously higher than the other three ones; (3) the
TCs of 14,14,18- and 18,18,18-GY present strong anisotropy,
while 6,6,6- and 6,6,12-GY are almost isotropic; (4) all of the
TCs decrease with the increase of temperature, which is mainly
attributed to the anharmonicity of phonon at high temper-
atures.
Combining with the formula of lattice TC,32
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
Figure 4. Electrical conductivities of (a, b) 6,6,6-, (c, d) 6,6,12-, (e, f) 14,14,18-, and (g, h) 18,18,18-graphyne with p-type and n-type doping versus
carrier concentration at 300 and 500 K.
κα = ∑ ∑ cphvg ,α 2(k ⃗ , ν)τ(k ⃗ , ν)
k ⃗
ν (1)
where k⃗ is the wave vector in the first Brillouin zone, ν is the
phonon branch, κα denotes the thermal conductivity in the α-
direction, cph is the phonon volumetric specific heat, vg,α is the
α-component of the phonon group velocity, and τ is the
phonon lifetime, the lattice TC expresses a close relationship
with phonon group velocity and phonon lifetime. Therefore, in
order to investigate the heat transport mechanism of GY in
details, the above phonon information on the four GYs is
calculated and shown in parts a and b of Figure 3, respectively.
6366
www.acsaem.org Article
According to the phonon theory, the group velocity reflects
the phonon harmonicity, meanwhile, the phonon anharmo-
nicity can be measured by the phonon lifetime. Combining
with Figure 3a, it can be clearly seen that the phonon group
velocities of 6,6,6- and 6,6,12-GY are higher than those of
14,14,18- and 18,18,18-GY in the whole frequency range. More
deeply, the difference between 6,6,6- and 6,6,12-GY is mainly
concentrated in the low frequency range (10−30 THz).
Furthermore, combining with the phonon lifetime in Figure
3b, it can be noticed that 6,6,6-GY has the highest phonon
lifetime, the second is 6,6,12-GY, and the lowest are 14,14,18-
and 18,18,18-GY. Overall, we can find that the trends of group
velocity and phonon lifetime are basically consistent with that
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
Figure 5. Electronic band structures of (a) 6,6,6-, (b) 6,6,12-, (c) 14,14,18-, and (d) 18,18,18-graphyne. The blue dashed line and the red solid line
present the results calculated by PBE and HSE06 hybrid functionals, respectively.
of TC in Figure 2, which can prove the accuracy of our TC
results.
In order to further understand the scattering mechanisms
(corresponding to phonon lifetime) of four GYs, Grüneisen
parameter (Figure 3c) and three-phonon scattering phase
space (Figure 3d) closely related to phonon scattering are
calculated. Physically, the Grüneisen parameter expresses a
strict relationship with the phonon scattering intensity. During
the process of anharmonic vibration of lattice, the thermal
expansion phenomenon is accompanied by the increasing
repulsion between atoms. On the contrary, when the lattice
takes on harmonic vibration, the object will not undergo
thermal expansion. According to the related theory, the
Grüneisen parameter is proportional to the thermal expansion
coefficient; therefore, it can measure the anharmonic effect of
lattice quantitatively. Considering that the anharmonic
characteristic of materials is mainly determined by phonon
scattering, the larger Grüneisen parameter, which means
stronger anharmonic characteristic, is equal to the intense
phonon scattering, and further leads to a lower lattice TC.33,34
And the three-phonon scattering phase space can characterize
the number of phonon scattering channels, more scattering
channels also leads to a reduction of TC. In combination with
Figure 3c, we can find that there is little difference among the
Grüneisen parameters of the four GYs, which means the
phonon scattering intensities of the four GYs are nearly the
same. Therefore, the differences of phonon scattering of the
four models are mainly caused by the scattering phase space,
and this inference can be proved by the results in Figure 3d;
i.e., the order of the scattering channels’ number is 6,6,6-
graphyne < 6,6,12-graphyne < 18,18,18-graphyne < 14,14,18-
graphyne. In summary, it can be concluded that the TC
relationship of the four GYs is mainly determined by phonon
group velocity and phonon scattering channel number.
6367
www.acsaem.org Article
3.2. Electronic Transport Properties. Figure 4 shows the
trends of EC calculated by the electron relaxation time. It can
be noticed that the relationship of four GYs’ EC is σ14,14,18‑GY >
σ18,18,18‑GY > σ6,6,12‑GY > σ6,6,6‑GY, which shows the opposite
trend to that of TC. Furthermore, the ECs of four GYs present
significantly different anisotropy: the ECs of 6,6,6- and
18,18,18-GY express weak anisotropy while those of 6,6,12-
and 14,14,18-GY show strong anisotropy; i.e., the ECs along
the zigzag direction of 6,6,12- and 14,14,18-graphyne are
nearly 2 orders of magnitude higher than those along the
armchair direction.
To analyze the above phenomenon, the electronic band
structures of four GYs calculated by PBE and HSE06 hybrid
functionals are shown in Figure 5. As observed from Figure 5,
the electronic band structures calculated by the two functional
calculations are consistent in trend, however, there are obvious
differences in the band gap. According to the description in
previous studies,29,30 the calculation based on hybrid func-
tionals (such as HSE06) can achieve better agreement with the
band gap obtained by experiments. Therefore, our analysis is
based on the electronic band structure calculated by HSE06.
As observed from the Figure 5, there are obvious differences
in the energy bands of four GYs. 6,6,12-, 14,14,18-, and
18,18,18-GY express Dirac-cone-like energy band, which are
similar to that of graphene,35 while 6,6,6-GY exhibits a
different considerable direct band gap. The band gaps of four
GYs are 0.938, 0.037, 0.102, and 0.162 eV, respectively. This
indicates that the 6,6,6-GY exhibits completely different
electric transport characteristics from graphene, and its
electrical transport performance will be rather weak for the
existence of the band gap, which is consistent with the results
in the EC diagram.
Next, we predict the electron effective mass (m*), two-
dimensional in-plane elastic modulus (C2D), deformation
potential energy (EDP), carrier mobility (μ2D), and electron
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials www.acsaem.org Article

Table 1. Calculated Values of the Carrier Effective Mass (m*), Two-Dimensional In-Plane Elastic Modulus (C2D), Deformation
Potential Energy (EDP), Carrier Mobility (μ2D), and Electron Relaxation Time (τ) of Four GYs with Different Types of Doping
(n-Type and p-Type) along the Zigzag and Armchair Directions at 300 Ka
carrier type m*/m0 C2D (J/m2) EDP (eV) μ2D (cm2/(V s)) τ (fs)
6,6,6-GY electron (armchair) 1.05 200.07 5.23 93.57 56.21
electron (zigzag) 0.64 164.90 3.74 409.57 149.09
hole (armchair) 1.16 200.07 6.04 57.96 38.30
hole (zigzag) 0.59 164.90 5.52 221.06 74.28
6,6,12-GY electron (armchair) 1.94 150.17 5.44 19.20 21.21
electron (zigzag) 0.61 142.65 2.66 765.78 266.40
hole (armchair) 2.28 150.17 6.90 8.64 11.21
hole (zigzag) 0.70 142.65 1.67 1481.50 592.16
14,14,18-GY electron (armchair) 0.03 88.38 4.93 45779 875.79
electron (zigzag) 0.03 30.45 0.80 637651 11858
hole (armchair) 0.02 88.38 5.17 100600 1237.20
hole (zigzag) 0.04 30.45 0.23 3551616 96258
18,18,18-GY electron (armchair) 0.02 96.19 5.30 119180 1372.80
electron (zigzag) 0.05 140.79 4.34 37508 1137.20
hole (armchair) 0.02 96.19 5.43 89377 1159.30
hole (zigzag) 0.05 140.79 6.45 14855 481.18
a
The boldface emphasize the unique performance of 14,14,18-GY.

Figure 6. Seebeck coefficients (S) of (a) 6,6,6-, (b) 6,6,12-, (c) 14,14,18-, and (d) 18,18,18-graphyne with n-type and p-type doping versus carrier
concentration at 300 and 500 K.

relaxation time (τ) of different GYs at room temperature by
performing the deformation potential theory, the results are
shown in Table 1. To promote the accuracy of the effective
mass, we also calculated the “average effective mass” (m̅ *),36
which is different from the conventional effective mass (m*)
and still valid for the material with a Dirac cone-like electronic
energy bands. The recalculated effective masses are shown in
Table S4 in Supporting Information. We found that the values
of average effective mass are basically consistent with those of
conventional effective mass, which can prove that our
calculation is effective. Combining with the information in
6368
Table 1, it can be noticed that the electron effective masses of
14,14,18- and 18,18,18-GY is 2 orders of magnitude smaller
than other GYs, which will lead to greater carrier mobility and
electron relaxation time, the related values of 14,14,18-GY
even reach 63765 cm2/(V s), 11858 fs (electron along the
zigzag direction) and 3551616 cm2/(V s), 96258 fs (hole along
the zigzag direction). Furthermore, 14,14,18-GY has a smaller
deformation potential energy compared with that of 18,18,18-
GY; therefore, its electron relaxation time is longer, which can
prove the results of EC in Figure 4.
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
Figure 7. Thermoelectric figure of merit (ZT) of (a, b) 6,6,6-, (c, d) 6,6,12-, (e, f) 14,14,18-, and (g, h) 18,18,18-graphyne with p-type and n-type
doping versus carrier concentration at 300 and 500 K.
3.3. Thermoelectric Properties. Figure 6 shows the
Seebeck coefficients of p- and n-type doping GYs as a function
of carrier concentration at 300 and 500 K. It can be observed
from Figure 6 that the maximum value of the Seebeck
coefficient of 6,6,6-GY can reach 500 μV/K at 1 × 1011cm−2,
which is obviously higher than those of the other three GYs.
The corresponding values of 6,6,12-, 14,14,18-, and 18,18,18-
GY are only 130, 200, and 170 μV/K, which are lower than the
standard of excellent thermoelectric materials (200−300 μV/
K).1,37 According to the related theories, the high Seebeck
coefficient of 6,6,6-GY could be attributed to its unique band
structure comparing with other three GYs. As shown in Figure
5a, there are multiple energy valleys around the bottom of the
6369
www.acsaem.org Article
conduction band and the top of valence band, which will lead
to a significant increase of the density of states around the
Fermi level and further play a positive role in Seebeck
coefficient. Moreover, it is worth to notice that the peak
positions of the Seebeck coefficient of the latter three GYs
show a left-shift trend following along with the increase of
temperature, which results in the abnormal phenomenon that
the low temperature models have higher Seebeck coefficients
in the low carrier concentration range.
On the basis of electronic and thermal transport coefficients,
the ZT values of four GYs can be estimated. The calculated ZT
as a function of carrier concentration at 300 and 500 K are
shown in Figure 7. It can be noticed that the maximum ZT of
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
four GYs have a relationship as 14,14,18-GY > 18,18,18-GY >
6,6,12-GY > 6,6,6-GY. In particular, the maximum ZT of
14,14,18-GY even reaches a really high value of 1.6, which is
much higher than that of graphene. Generally, the ZT value is
directly proportional to the Seebeck coefficient and EC and
inversely proportional to the TC. Therefore, the trend of
Seebeck coefficient (S14,14,18‑GY > S18,18,18‑GY > S6,6,12‑GY, Figure
6), EC (σ14,14,18‑GY > σ18,18,18‑GY > σ6,6,12‑GY, Figure 4) and TC
(κ6,6,12‑GY > κ18,18,18‑GY > κ14,14,18‑GY, Figure 2) of the three GYs
can explain the ranking of ZT of 6,6,12-, 14,14,18-, and
18,18,18-GY. Quite specially, 6,6,6-GY expresses the highest
Seebeck coefficient; however, its maximum ZT is the lowest
one among the four GYs. According to the results in Figure 2
and 4, it can be noticed that this phenomenon is mainly due to
its low EC and high TC. Furthermore, there are obvious
differences between the ZT values of p- and n-type doping
6,6,6-GY, the ZT value of n-type doping is about twice as that
of p-type. Meanwhile, the same phenomenon is not appeared
in the other three GYs. Combining with the results in Figure 2,
4, and 6, it can be confirmed that this phenomenon is mainly
due to the large difference between the EC of p- and n-type
doping 6,6,6-GY.
It is interesting to notice that the ZT values of 6,6,12-,
14,14,18-, and 18,18,18-GY at low temperature are higher than
those at high temperature in low carrier concentration range.
Combining with the trends of EC and Seebeck coefficient, we
can notice that this unusual phenomenon is mainly caused by
the abnormal left-shift of the peak of Seebeck coefficient with
the reduction of temperature. More importantly, it is worth
mentioning that the peak of ZT of 14,14,18-GY along the
zigzag direction has a more significant left-shift trend as the
temperature decreased, which results in the phenomenon that
ZT peak of this model at 300 K appears in the carrier
concentration range mentioned above, where the ZT of low-
temperature model is even higher. The anomalous phenom-
enon of Seebeck coefficient may originate from bipolar effect.38
The bipolar effect is caused by the excitation of electrons from
valence bands to conduction bands at a finite T which leaves
holes in the valence band, therefore, it usually appears in the
semiconductors with a narrow band gap Δ (Δ < 0.5 eV) and
geometrically similar conduction and valence bands.39 Since
the excited carriers in lower carrier concentration range will
have a high proportion, the bipolar effect will be more seriously
manifested in lower carrier concentration range. Considering
the significant negative impact of bipolar effect on Seebeck
coefficient at high temperature, i.e., the Seebeck coefficient
shows a decaying trend with the increase of temperature,38 the
abnormal enhancement of Seebeck coefficient in the low
carrier concentration range with the reduction of temperature
can be understood. At same time, the same phenomenon can
also be found in these two references.39,40 Moreover, we have
calculated the energy band structures of four GYs. From the
Figure 5, we can see that the band gaps of 6,6,6-, 6,6,12-,
14,14,18-, and 18,18,18-GY are 0.938, 0.037, 0.102, and 0.162
eV, respectively, and the conduction and valence bands of the
last three GYs also have similar geometries. These two
phenomena obey the influence conditions of bipolar effect
mentioned above; therefore, it can prove the conclusion that
the higher ZT values of 6,6,12-, 14,14,18-, and 18,18,18-GY at
low temperature originate from the bipolar effect. This can be
seen as the reason for the unusual phenomenon that maximum
ZT value (1.6) of this model appears at room temperature.
Considering that the ZT of most materials shows an increasing
6370
www.acsaem.org Article
trend following with the increasing temperature,2,11,37,41 the
abnormal ZT trend of GY provides a new idea for the
development of thermoelectric materials at room temperature.
Moreover, it should be noted that GY is not the only example
of ZT decreasing with increasing temperature; e.g., in ref 40,
the function S2σ/τ (an indicator of the behavior of ZT) of
Mg2Sn reduces with the increase of temperature in the low
carrier-concentration bipolar regime (1× 1019 ∼ 5× 1019
cm−3). In ref 39, the ZT values of CaMg2Bi2 are nearly the
same at 300, 600, and 900 K in the low carrier concentration
range.
Furthermore, it can be also found from Figure 7 that the ZT
of the four GYs present obvious anisotropy. The phenomenon
of the first three GYs is ZTzigzag > ZTarmchair, and that of
18,18,18-GY is completely the opposite. There are two reasons
for this phenomenon: (1) the EC of 18,18,18-GY along the
armchair direction is higher than that along the zigzag
direction; however, for the other GYs, the ECs along the
zigzag direction are much higher; (2) the TC of 18,18,18-GY
along the zigzag direction is larger than that along the armchair
direction, which further enhances its opposite anisotropy
(ZTzigzag < ZTarmchair). Besides, we can also find that the ZT
value of 6,6,12-GY shows extremely strong anisotropy, whose
difference is nearly 2 orders of magnitude. Comparing with the
results of TC, EC, and Seebeck coefficient, it can be noticed
6,6,12- and 14,14,18-GY possess more obvious anisotropy
(zigzag > armchair), which determines the significant
anisotropy of ZT of these two GYs. However, the TC of
14,14,18-GY expresses the same anisotropy of EC (zigzag >
armchair), this will offset the anisotropy of ZT caused by EC.
Meanwhile, 6,6,12-GY has isotropic TC; therefore, the more
notable anisotropy of ZT of 6,6,12-GY can be understood.
At last, the thermoelectric properties of four GYs are
summarized as follows: (1) 6,6,6-GY has the largest Seebeck
coefficient, which means the stronger conversion ability of
thermal energy; however, its ZT value is the lowest for its low
EC and high TC. Furthermore, its ZT value for n-type doping
is around twice as that of p-type doping. (2) The ZT of 6,6,12-
GY expresses extremely significant anisotropy, as the ZT along
the zigzag direction is 1−2 orders of magnitude higher than
that along the armchair direction. (3) Compared with the ZT
at high temperature range, 14,14,18-GY exhibits an abnormally
higher ZT at low temperature, whose maximum value
approaches to 1.6. This value means the carbon-based
materials can be also used as excellent thermoelectric material
and will play important role in the applications of thermo-
electric material at room temperature. (4) Although the ZT
value of 18,18,18-GY also shows anisotropy, its ZT value along
the armchair direction is higher, which is opposite to the cases
of the other three GYs.
4. CONCLUSIONS
In this paper, by performing the first-principles calculations
combining with the Boltzmann transport equation and
relaxation time approximation, thermal transport, electronic
transport, and thermoelectric properties of four kinds of GYs
are investigated. (1) Thermal transport properties: the order of
TCs of four GYs is κ6,6,6‑GY > κ6,6,12‑GY > κ18,18,18‑GY > κ14,14,18‑GY,
and the numerical difference is mainly determined by the
change of phonon group velocity and the number of phonon
scattering channel. (2) Electronic transport properties: EC
expresses an opposite relationship to that of TC, i.e., σ14,14,18‑GY
> σ18,18,18‑GY > σ6,6,12‑GY > σ6,6,6‑GY. In particular, the band
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
structure of 6,6,6-GY exhibits a shape of non-Dirac cone and a
large direct band gap, which is different from those of the other
three GYs and graphene. (3) Thermoelectric properties:
although 6,6,6-GY has the highest Seebeck coefficient, its ZT
is lowest due to the small EC and large TC. Moreover, there is
a large difference between the ZT values of n- and p-type
doping. For the great anisotropic EC and the isotropic TC, the
ZT value of 6,6,12-GY exhibits extremely significant
anisotropy, whose value along the zigzag direction is 1−2
orders of magnitude higher than that along the armchair
direction. 14,14,18-GY exhibits abnormally higher ZT value
(1.6) at low temperature, which is mainly caused by the
abnormal variation of the Seebeck coefficient in low carrier
concentration range. 18,18,18-GY shows opposite anisotropy
(armchair > zigzag) compared with the other three GYs, which
is mainly due to the special properties of EC. Our work
systematically investigates the thermoelectrical performance of
four GYs. The excellent ZT value of 14,14,18-GY reveals that
this material can break the limitations of carbon-based
materials and low-temperature condition in the field of
thermoelectric materials; i.e., carbon-based materials can be
also used as excellent thermoelectric materials at room
temperature.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.2c00742.
Structural information and phonon dispersions of four
GYs; computational details of thermal transport proper-
ties, electronic transport properties, and thermoelectric
properties; and relevant electrical calculation parameters,
e.g., average effective mass, fitting curves of EDP and C2D,
and electronic density of states (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Yufei Gao − Key Laboratory of Ocean Energy Utilization and
Energy Conservation of Ministry of Education, School of
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China; orcid.org/0000-
0003-3318-0987; Email: gaoyufei@dlut.edu.cn
Xiaoliang Zhang − Key Laboratory of Ocean Energy
Utilization and Energy Conservation of Ministry of
Education, School of Energy and Power Engineering, Dalian
University of Technology, Dalian 116024, China;
Email: zhangxiaoliang@dlut.edu.cn
Dawei Tang − Key Laboratory of Ocean Energy Utilization
and Energy Conservation of Ministry of Education, School of
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China; orcid.org/0000-
0002-0068-7207; Email: dwtang@dlut.edu.cn
Authors
Pengfei Qi − Key Laboratory of Ocean Energy Utilization and
Energy Conservation of Ministry of Education, School of
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China
Ke Liu − Research Office of Propulsion Technology, Expace
Technology Corporation Limited, Beijing 100176, China
Shipeng Bi − Key Laboratory of Ocean Energy Utilization and
Energy Conservation of Ministry of Education, School of
6371
www.acsaem.org Article
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China
Zheng Chang − Key Laboratory of Ocean Energy Utilization
and Energy Conservation of Ministry of Education, School of
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China
Kunpeng Yuan − Key Laboratory of Ocean Energy Utilization
and Energy Conservation of Ministry of Education, School of
Energy and Power Engineering, Dalian University of
Technology, Dalian 116024, China
Yuhang Jing − Department of Astronautical Science and
Mechanics, Harbin Institute of Technology, Harbin 150001,
China; orcid.org/0000-0001-5520-3866
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.2c00742
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Y.G. acknowledges the financial support from National Natural
Science Foundation of China under Grant Nos. 52176166 and
11602149 and the Fundamental Research Funds for the
Central Universities under Grant No. DUT19RC(3)006. X.Z.
acknowledges the support from the National Natural Science
Foundation of China under Grant No. 52076031 and the
computing resources from the Supercomputing Center of
Dalian University of Technology and National Supercomput-
ing Center in Shenzhen. Y.J. acknowledges the financial
support from National Natural Science Foundation of China
under Grant No. 12172112. D.T. acknowledges the support
from the National Natural Science Foundation of China under
Grant No.51720105007.
■
REFERENCES
(1) Sajjad, M.; Mahmood, Q.; Singh, N.; Larsson, J. A. Ultralow
lattice thermal conductivity in double perovskite Cs2PtI6: A promising
thermoelectric material. ACS Appl. Energy Mater. 2020, 3 (11),
11293−11299.
(2) Majumdar, A.; Chowdhury, S.; Ahuja, R. Ultralow thermal
conductivity and high thermoelectric figure of merit in two-
dimensional thallium selenide. ACS Appl. Energy Mater. 2020, 3
(9), 9315−9325.
(3) Gao, Y. F.; Ning, W. B.; Zhang, X. L.; Liu, Y. Z.; Zhou, Y. G.;
Tang, D. W. The effective regulation of nanotwinning on the
multichannel thermal transport in hybrid organic-inorganic halide
perovskite. Nano Energy 2021, 82, 105747.
(4) Snyder, G. J.; Toberer, E. S. Complex thermoelectric materials.
Nat. Mater. 2008, 7 (2), 105−114.
(5) Majumdar, A. Thermoelectricity in semiconductor nanostruc-
tures. Science 2004, 303 (5659), 777−778.
(6) Hicks, L. D.; Dresselhaus, M. S. Effect of quantum-well
structures on the thermoelectric figure of merit. Phys. Rev. B 1993, 47
(19), 12727−12731.
(7) Butler, S. Z.; Hollen, S. M.; Cao, L.; Cui, Y.; Gupta, J. A.;
Gutiérrez, H. R.; Heinz, T. F.; Hong, S. S.; Huang, J.; Ismach, A. F.;
Johnston-Halperin, E.; Kuno, M.; Plashnitsa, V. V.; Robinson, R. D.;
Ruoff, R. S.; Salahuddin, S.; Shan, J.; Shi, L.; Spencer, M. G.;
Terrones, M.; Windl, W.; Goldberger, J. E. Progress, challenges, and
opportunities in two-dimensional materials beyond graphene. ACS
Nano 2013, 7 (4), 2898−2926.
(8) Wang, N.; Gong, H.; Sun, Z.; Shen, C.; Li, B.; Xiao, H.; Zu, X.;
Tang, D.; Yin, Z.; Wu, X.; Zhang, H.; Qiao, L. Boosting
thermoelectric performance of 2D transition-metal dichalcogenides
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372
ACS Applied Energy Materials
by complex cluster substitution: The role of octahedral Au6 clusters.
ACS Appl. Energy Mater. 2021, 4 (11), 12163−12176.
(9) Sharma, S.; Singh, N.; Schwingenschlögl, U. Two-dimensional
tellurene as excellent thermoelectric material. ACS Appl. Energy Mater.
2018, 1 (5), 1950−1954.
(10) Gao, Y. F.; Zhou, Y. G.; Hu, M. Enormous suppression of
phonon transport in silicon nanowires with five-fold twin boundary. J.
Mater. Chem. A 2018, 6 (38), 18533−18542.
(11) Sajjad, M.; Singh, N.; Sattar, S.; De Wolf, S.; Schwingenschlögl,
U. Ultralow lattice thermal conductivity and thermoelectric properties
of monolayer Tl2O. ACS Appl. Energy Mater. 2019, 2 (5), 3004−3008.
(12) Zhang, Z.; Zheng, S.; Li, J.; Wang, B.; Yue, L.; Wu, Y.; Dong,
X.; Chen, L.; Gao, L.; Lu, G. Realizing high thermoelectric
performance in the ZnTe-alloyed CuGaTe2 through band engineer-
ing. ACS Appl. Energy Mater. 2020, 3 (12), 12400−12406.
(13) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.;
Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field
effect in atomically thin carbon films. Science 2004, 306 (5696), 666−
669.
(14) Morozov, S. V.; Novoselov, K. S.; Katsnelson, M. I.; Schedin,
F.; Elias, D. C.; Jaszczak, J. A.; Geim, A. K. Giant intrinsic carrier
mobilities in graphene and its bilayer. Phys. Rev. Lett. 2008, 100 (1),
016602.
(15) Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K.
S.; Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys.
2009, 81 (1), 109−162.
(16) Lindsay, L.; Broido, D. A. Enhanced thermal conductivity and
isotope effect in single-layer hexagonal boron nitride. Phys. Rev. B
2011, 84 (15), 155421.
(17) Baughman, R. H.; Eckhardt, H.; Kertesz, M. Structure-property
predictions for new planar forms of carbon: Layered phases
containing sp2 and sp atoms. J. Chem. Phys. 1987, 87 (11), 6687−
6699.
(18) Gao, Y. F.; Zhang, X. L.; Tang, D. W.; Hu, M. Unexpected
anisotropy of (14,14,14)-graphyne: A comprehensive study on the
thermal transport properties of graphyne based nanomaterials. Carbon
2019, 143, 189−199.
(19) Zhang, H.; Zhao, M.; He, X.; Wang, Z.; Zhang, X.; Liu, X. High
mobility and high storage capacity of lithium in sp−sp2 hybridized
carbon network: The case of graphyne. J. Phys. Chem. C 2011, 115,
8845−8850.
(20) Zhou, J.; Lv, K.; Wang, Q.; Chen, X. S.; Sun, Q.; Jena, P.
Electronic structures and bonding of graphyne sheet and its BN
analog. J. Chem. Phys. 2011, 134 (17), 174701.
(21) Zhang, H. Y.; Zhao, M. W.; Bu, H. X.; He, X. J.; Zhang, M.;
Zhao, L. X.; Luo, Y. H. Ultra-high hydrogen storage capacity of Li-
decorated graphyne: A first-principles prediction. J. Appl. Phys. 2012,
112 (8), 084305.
(22) Yang, X. X.; Dai, Z. H.; Zhao, Y. C.; Meng, S. Phonon thermal
transport in a class of graphene allotropes from first principles. Phys.
Chem. Chem. Phys. 2018, 20 (23), 15980−15985.
(23) Jing, Y. H.; Hu, M.; Gao, Y. F.; Guo, L. C.; Sun, Y. On the
origin of abnormal phonon transport of graphyne. Int. J. Heat Mass
Transfer 2015, 85, 880−889.
(24) Li, G.; Li, Y.; Liu, H.; Guo, Y.; Li, Y.; Zhu, D. Architecture of
graphdiyne nanoscale films. Chem. Commun. 2010, 46 (19), 3256−
3258.
(25) Mishra, S. B.; V G, A.; Ramaprabhu, S.; Nanda, B. R. K.
Graphdiynea two-dimensional cathode for aluminum Dual-Ion
batteries with high specific capacity and diffusivity. ACS Appl. Energy
Mater. 2021, 4 (8), 7786−7799.
(26) Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab
initio total-energy calculations using a plane-wave basis set. Phys. Rev.
B 1996, 54 (16), 11169−11186.
(27) Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the
projector augmented-wave method. Phys. Rev. B 1999, 59 (3), 1758−
1775.
(28) Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B
1994, 50 (24), 17953−17979.
6372
www.acsaem.org Article
(29) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient
approximation made simple. Phys. Rev. Lett. 1996, 77 (18), 3865−
3868.
(30) Balandin, A. A.; Ghosh, S.; Bao, W. Z.; Calizo, I.;
Teweldebrhan, D.; Miao, F.; Lau, C. N. Superior thermal conductivity
of single-layer graphene. Nano Lett. 2008, 8 (3), 902−907.
(31) Balandin, A. A.; Ghosh, S.; Teweldebrhan, D.; Calizo, I.; Bao,
W.; Miao, F.; Lau, C. N. Extremely high thermal conductivity of
graphene: prospects for thermal management applications in silicon
nanoelectronics. 2008 IEEE Silicon Nanoelectronics Workshop 2008,
1−2.
(32) Gao, Y.; Zhang, X.; Jing, Y.; Hu, M. The unexpected non-
monotonic inter-layer bonding dependence of the thermal con-
ductivity of bilayered boron nitride. Nanoscale 2015, 7 (16), 7143−
7150.
(33) Qin, G.; Zhang, X.; Yue, S.-Y.; Qin, Z.; Wang, H.; Han, Y.; Hu,
M. Resonant bonding driven giant phonon anharmonicity and low
thermal conductivity of phosphorene. Phys. Rev. B 2016, 94 (16),
165445.
(34) Fan, H.; Wu, H.; Lindsay, L.; Hu, Y. Ab initio investigation of
single-layer high thermal conductivity boron compounds. Phys. Rev. B
2019, 100 (8), 085420.
(35) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.;
Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. Two-
dimensional gas of massless Dirac fermions in graphene. Nature 2005,
438 (7065), 197−200.
(36) Cheng, L.; Zhang, C. M.; Liu, Y. Y. The optimal electronic
structure for high-mobility 2D semiconductors: exceptionally high
hole mobility in 2D antimony. J. Am. Chem. Soc. 2019, 141 (41),
16296−16302.
(37) Sun, Z. H.; Yuan, K. P.; Chang, Z.; Bi, S. P.; Zhang, X. L.; Tang,
D. W. Ultra-low thermal conductivity and high thermoelectric
performance of two-dimensional triphosphides (InP3, GaP3, SbP3
and SnP3): A comprehensive first-principles study. Nanoscale 2020, 12
(5), 3330−3342.
(38) Gurevich, Y. G.; Titov, O. Y.; Logvinov, G. N.; Lyubimov, O. I.
Nature of the thermopower in bipolar semiconductors. Phys. Rev. B
1995, 51 (11), 6999−7004.
(39) Gong, J. J.; Hong, A. J.; Shuai, J.; Li, L.; Yan, Z. B.; Ren, Z. F.;
Liu, J. M. Investigation of the bipolar effect in the thermoelectric
material CaMg2Bi2 using a first-principles study. Phys. Chem. Chem.
Phys. 2016, 18 (24), 16566−16574.
(40) Pulikkotil, J. J.; Singh, D. J.; Auluck, S.; Saravanan, M.; Misra,
D. K.; Dhar, A.; Budhani, R. C. Doping and temperature dependence
of thermoelectric properties in Mg-2(Si,Sn). Phys. Rev. B 2012, 86
(15), 155204.
(41) Zhao, Q.; Qin, B. C.; Wang, D. Y.; Qiu, Y. T.; Zhao, L. D.
Realizing high thermoelectric performance in polycrystalline SnSe via
silver doping and germanium alloying. ACS Appl. Energy Mater. 2020,
3 (3), 2049−2054.
https://doi.org/10.1021/acsaem.2c00742
ACS Appl. Energy Mater. 2022, 5, 6363−6372