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org/JPCC Article

Acepentalene Membrane Sheet: A Metallic Two-Dimensional

Carbon Allotrope with High Carrier Mobility for Lithium Ion Battery
Anodes
Tiantian Zeng, Hao Yang, Hongbo Wang,* and Gang Chen*
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ABSTRACT: The assembly paths of a 2D porous carbon

allotrope designed with acepentalene organic molecules are
rationally proposed in theory. The polymerized acepentalene
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membrane sheet with hexagonal conjunction (h-PAMS) shows

high stability. Its π-bands hold Dirac fermion-like characteristics,
with the Dirac point located below the Fermi level at the Γ point,
crossing the Fermi surface to enable high mobility charge carriers.
In addition, it has anisotropic in-plane mechanical properties and
can withstand strain loading as large as 0.9 eV/atom energy cost
against structural collapse. The synergistic effects of Li adsorption
and Li surface clustering result in 676 mAh/g capacity with a low average open-circuit voltage, making h-PAMS a promising lithium
ion battery anode material. Furthermore, the barriers for Li diffusion on the h-PAMS and penetration through the porous hole are
only 0.35 and 0.61 eV, respectively. The space expansion during the charge−discharge process is only about 10% of the stacked
multilayer. Our studies show the possibility of bottom-up fabrication of the h-PAMS and its fascinating properties for high-
performance nanoelectronics and Li ion battery anodes, calling for further investigations in both theory and experiment.

1. INTRODUCTION graphite composite has a capacity of 2596 mAh/g. Kwon et

As a typical carbon-based energy carrier material, graphite is al.13 reported a 4200 mAh/g capacity in their experimental
widely used in commercial rechargeable lithium ion batteries studies of Si-based frameworks. However, there are still some
crucial issues that remain unsolved for practical use, such as the
(LIBs) and has superior properties for use as anode materials
slow rate capability due to the low electronic conductivity and
in LIBs,1,2 including low cost, high Coulombic efficiency, good
the poor reversibility induced by the large volume expansion
cyclability, low volume change rate during charge−discharge
during Li charge−discharge processes. As a single layer of
processes, and good conducting properties. For practical
graphite, graphene has been investigated as the LIB anode
applications, graphite could gain a specific capacity of 372
material candidate, which is however limited by its weak
mAh/g,3 corresponding to the storage of one Li per six C
interaction with Li due to the inertness of the conjugated π-
atoms in the chemical formula LiC6. Graphene, a two-
electrons on both sides.14−16 Several studies have shown that
dimensional (2D) material first obtained experimentally by
defective graphene could enhance the Li adsorption for LIB
isolating a layer from graphite, is however unfavorable for LIB
anode use.17−19 The perturbation of the ideal sp2 hybridization
anodes due to its weak attraction force for holding Li ions.
integrity could help enhance the reactivity of graphene.20
Interestingly, the ideal sp2 hybridization network of graphene
Therefore, the porous 2D carbon nanostructures have gained
entirely composed of C6 hexagons shows attractive unique much research attention in the field of LIB anode materials,
properties, such as high mobility massless fermions,4,5 which could permit Li intercalation into the interlayer space of
superconductivity,6 high Young’s modulus,7 and quantum the corresponding multilayers. Furthermore, the porous holes
Hall effects.8,9 Moreover, the successful synthesis of graphene could offer active sites in which Li could reside to increase the
in experiment10 has triggered extraordinary extensive research storage capacity with an acceptable volume change during the
for new 2D nanostructures and corresponding unique
fundamental and application properties.
Limited by the low Li storage capacity at the theoretical Received: January 15, 2020
value of 372 mAh/g, the graphite anode could not meet the Revised: February 24, 2020
increasing application demand for high-performance energy Published: February 26, 2020
carriers.11 Thus, many efforts have been devoted to searching
for novel high-capacity materials; for example, Sun et al.12
found by experiment that the black phosphorus nanoparticle−

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c00376

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charge−discharge process. However, the structural defects and
the disordered porous pores would greatly reduce the
conducting properties of the defective carbon nanostructures
to significantly reduce the rate capacity.21,22 Also, in the
disordered defective carbon nanostructures, the performance
of the LIB anode may also be harmed by the irreversible side
reactions between the exposed defects and the electrolyte
solution to create poor Coulombic efficiency.23 Due to these
issues, Sander et al. have shown in experiment that the well-
aligned porous structural fragments could contribute to the
performance of battery electrodes, which facilitates fast charge
conduction on one hand and helps enlarge the area capacity
compared to the conventional LIB anode24 on the other hand.
This sheds light on designing the porous material with
uniformly arranged structural pores in an ordered pattern for
LIB anodes, which however would challenge the experimental
fabrication for controlling the distribution and the size of the
pores. The 2D porous carbon materials formed by regularly
arranging carbon polygons provide a rational route for
designing high-performance carbon-based LIB anode materials.
Notably, the non-natural 2D graphdiyne successfully synthe-
sized in 201025 has been confirmed to be a superior LIB anode
material.26−28 Composed of sp- and sp2-bonded carbons, the
porous structure was theoretically predicted by Sun et al.27 to
reach a capacity of 744 mAh/g with an excellent Li diffusion
rate among the interlayer space to perpendicularly penetrate
the sheet. Huang et al.28 confirmed it as a superior LIB anode
material and achieved reversible capacities of up to 520 and
420 mAh/g after 400 and 1000 charge−discharge cycles,
respectively. The porous 2D Ψ-graphene (372 mAh/g),29
biphenylene (774 mAh/g),30,31 phagraphene (558 mAh/
g),30,32 Θ-graphene (877 mAh/g),33 popgraphene (1487
mAh/g),34 xgraphene (930 mAh/g),35 graphenylene (1116
mAh/g),36 and haeckelite h567 (697 mAh/g)37 were also
predicted in theory to be promising LIB anode materials. In
addition, a wealth of 2D carbon allotropes composed of various
carbon polygons such as net W,38 penta-graphene,39 ph-
graphene,40 graphyne,41,42 and α-popgraphene43 stimulate
scientists to explore their use for energy storage and to design
new novel carbon nanomaterials, contributing to worldwide
carbon-based energy storage material research.
However, most of the newly designed 2D carbon allotropes
have not yet been realized in experiments, seriously hindering
their further development and applications. Therefore,
exploring 2D carbon allotropes that are easier to synthesize
is highly desired. In this regard, a rational route of assembling
molecular precursors can help to synthesize 2D carbon
nanostructures with atomic-scale precision.29,31,44,45 Following
this idea, we carefully studied the synthesis for the possibility
that acepentalene organic molecules could form 2D porous
carbon allotropes. The obtained lowest-energy 2D allotrope is
found to be metallic with high carrier mobility and strong in-
plane anisotropic mechanical properties. Furthermore, the
presence of C5 and C9 polygons enables high Li ion storage
capacity, low barriers for diffusing on the 2D nanostructure
and penetrating through the sheet, and low volume expansion
of its stacked multilayer during the charge−discharge process,
showing attractive applications for LIB anodes, which calls for
further theoretical and experimental investigations.
2. COMPUTATIONAL DETAILS
Our first-principles calculations were performed using the spin-
polarized density functional theory as implemented in the
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Vienna ab initio simulation package (VASP).46 The wave
function was constructed with the plane wave basis set with the
cutoff energy of 400 eV. The valence−core interactions were
described with the projector-augmented wave method,47 and
the exchange-correlation energy was determined by the
generalized gradient approximation (GGA) with the Perdew,
Burke, and Ernzerhof (PBE) formalism.48 The conducting
properties were also confirmed with calculations employing the
Heyd−Scuseria−Ernzerhof (HSE) hybrid functional49 with the
empirical parameter α = 0.25 to include the screened short-
range Hartree−Fock (HF) exchange term. The planar
nanostructure was studied using a supercell with the sheet
material in the xy plane. A vacuum of 20 Å along lattice z was
adopted to eliminate the interactions between the sheet and its
periodic images. The in-plane lattice constants of our studied
planar structures are >5.7 Å. Therefore, the Γ-centered
Monkhorst−Pack k-mesh50 of 13 × 13 × 1 was applied to
sample k points in the first Brillouin zone to integrate the
electronic properties. All of the atoms were fully relaxed until
the maximum force acting on each atom converges to 0.01 eV/
Å. The electronic properties were converged to 10−6 eV. Due
to the failure in describing the van der Waals interactions of
the semilocal PBE functional, Grimme’s dispersion correction
scheme was adopted to enhance the nonlocal effects, which
were previously found to even matter for metal materials.51−53
We optimized the structural constants of graphite using
Grimme’s D2 and D3 schemes.54,55 The 3.49 Å interlayer space
of graphite calculated with the D3 scheme agrees with the
experimental data of 3.51 Å. The D2 calculations give the 3.22
Å interlayer space, hinting at overestimated weak interactions
between carbon layers. Therefore, the D3 dispersion energy
correction scheme was adopted in our studies. In addition, the
dynamic stability of the carbon allotrope was examined by
calculating the phonon spectrum with the density functional
perturbation theory. The Phonopy code56 as interfaced with
VASP was used. In order to increase the accuracy of the
calculated Hellmann−Feynman force, we adopted the 10−7 eV
and 1 meV/Å convergence criteria for electronic properties
and atomic relaxation, respectively. First-principles molecular
dynamics (FPMD) simulations were also carried out to
estimate the thermal stability. The temperature was controlled
using the Nosé−Hoover method.57
3. RESULTS AND DISCUSSION
3.1. Structural Growth and Stability. 3.1.1. Structural
Configurations of Acepentalene Membrane Sheets. Using
different precursor molecules and experimental procedures,
one could fabricate different 2D carbon allotropes, for example,
the fabrication of γ-graphyne through the mechanochemical
technique by ball milling the mixture of PhBr6 and CaC2.58 As
proposed previously,27,59−61 the 2D carbon allotropes could
also be expected to be fabricated by polymerizing small organic
molecules. Considering hydrogenation and dehydrogenation as
commonly used techniques in industry, the dehydrated organic
molecules transferred to substrates could self-assemble to form
2D sheets. In our studies, we use the acepentalene, as shown in
Figure 1a, as the precursor molecule. After removing the
hydrogen atoms, we first evaluated its stability by carrying out
first-principles molecular dynamics simulations at 600 K. The
simulation results shown in Figure 1b support its stability.
Based on the dehydrogenated acepentalene precursor motifs,
three different 2D crystal configurations could be expected to
form. Keeping the structural skeletons of the neighboring
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Figure 1. (a) Acepentalene molecule, (b) potential energy versus time
of the simulation performed at 600 K of the dehydrogenated
acepentalene and the corresponding structures obtained at the
beginning and the end of the simulation, (c) h-PAMS, (d) FAMS,
(e) r-PAMS, and (f) cohesive energies of the selected 2D carbon
allotropes. The white balls are for hydrogen atoms. The green, red,
and blue balls represent the CC carbon atoms at the center of
acepentalene shared by three pentagons, the EC atoms at the edge
shared by two pentagons, and the AC atoms at the apex sites,
respectively.
dehydrogenated precursor motifs, both h- and r-PAMSs
(polymerized acepentalene membrane sheets) could be
obtained with the conjunction configurations as hexagonal
and rectangular rings, as illustrated in Figure 1c,e, respectively.
Compared to the r-PAMS, one of the parallel C−C bonds in
the rectangle conjunction ring is removed to leave the other
one to be shared by adjacent dehydrogenated precursor motifs
in the fused acepentalene membrane sheet (FAMS), as shown
in Figure 1d. By calculating the cohesive energies (Ecoh), we
estimated their thermodynamic stabilities, which is defined as
(Et − nEC)
Ecoh =
n (1)
where Et and EC are the total energy of a unit cell and the
energy of a free-standing C atom. The n is the number of C
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atoms contained in the unit cell. The calculated cohesive
energies of h-PAMS, r-PAMS, and FAMS as well as the
previously proposed 2D carbon allotropes are provided in
Figure 1f. Among the sp2-based 2D carbon networks, the h-
PAMS is lower in cohesive energy than the r-PAMS, FAMS,
penta-graphene,39 and ph-graphene,40 whereas it is higher in
energy than the phographenes,43,62,63 popgraphene,34 Ψ-
graphene,29 phagraphene,32 and graphene. The experimentally
fabricated graphynes25,41,64 consisting of both sp- and sp2-
hybridized C atoms have cohesive energy that is higher than
that of h-PAMS. Compared to the experimentally fabricated
graphene and graphyne, the h-PAMS having good thermody-
namic stability may become a possibility for fabrication, which
is better than r-PAMS and FAMS.
3.1.2. Conjunctions Connecting Acepentalene-Based
Motifs. In addition to the thermostabilities indicated by the
cohesive energy analysis, we also estimated the possibilities of
forming the conjunctions connecting the acepentablene-based
structural motifs. In Figure 2, the hexagonal, rectangular, and
fused conjunction configurations are illustrated. The dangling
bonds on the edges of structural fragments are saturated by
hydrogen atoms. In order to evaluate their formation, we
defined the conjunction formation energy, Ecf, as shown below:
Ecf = Efragment − nμCacepentalene − mECacepentalene
−H − mE H
(2)
ECacepentalene
−H = Eacepentalene − E Hacepentalene
‐vacancy − E H (3)
Eacepentalene − 6ECacepentalene
−H − 6E H
μCacepentalene =
10 (4)
where Efragment, Eacepentalene, Eacepentalene
and EH are energies of
H‑vacancy ,
the conjunction fragments shown in Figure 2, the acepentalene
molecule, the optimized acepentalene with a H-vacancy, and a
free-standing H atom. The μacepentalene
C and Eacepentalene
C−H are the
chemical potential of the C atom in acepentalene and the
average bonding energy of the C−H bond. The n and m are
the numbers of C atoms and C−H bonds in the conjunction
fragment, respectively. A negative value of Ecf indicates an
exothermic process. The conjunction formation energies are
calculated to be 18.02, 9.26, and 8.13 eV for the hexagonal,
rectangular, and fused conjunction configurations, respectively.
Considering the highest Ecf and the energy cost to remove one
C−C bond, the fused conjunction would probably challenge
the experimental fabrication. In the hexagonal and rectangular
conjunctions, three and two C−C bonds formed among
neighboring acepentalene-based structural motifs, respectively.
On average, they have −6.01 and −4.63 eV/bond formation
energies. The severe distortion of the sp2 hybridization in the
rectangular conjunction results in higher formation energy. In
comparison, the hexagonal conjunction has the lowest
formation energy, suggesting the priority for its formation as
the dominate conjunction species.
3.1.3. Self-Assembly of Acepentalene-Based Motifs. In
Figure 3, we show the self-assembly paths of the acepentalene-
based motifs. Making two adjacent AC atoms (see the labels of
C atoms in Figure 1a) in a pentagon ring of acepentalene to be
unsaturated by removing the corresponding H atoms, the
formation of a single C−C bond connection between
neighboring motifs (see the illustration in Figure 3a) was
investigated by a 16-image nudged elastic band (NEB)
study.65,66 The reaction would happen without activation
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Figure 2. Illustration of the conjunctions connecting neighboring acepentalene-based motifs. Conjuctions of the (a) h-PAMS, (b) r-PAMS, and (c)
FAMS sheets. The depiction of the colored balls is the same as that in Figure 1.

Figure 3. (a) Self-assembly paths of acepentalene-based motifs forming a single connection bond, (b) hexagonal conjunction with three well
separated motifs, (c) rectangular conjunction with two separated motifs, (d) hexagonal conjunction with the single-bond-connected motifs and an
isolated one, (e) rectangular conjunction by rotating one of the fragments of the single-bond-connected motifs, and (f) hexagonal conjunction by
pushing an isolated motif to the rectangular conjunction. The depiction of the colored balls is the same as that in Figure 1.

energy to release 5.40 eV energy, supporting the formation of
the C−C connecting bond. Starting from the single C−C bond
connection configuration shown in Figure 3a, two reaction
processes could be expected. One is that shown in Figure 3d to
form a hexagonal conjunction with an approaching acepenta-
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lene-based motif, which is found to be barrierless in our 16-
image NEB calculation. The other one is shown in Figure 3e.
One of the motifs can rotate under 0.05 eV activation energy
to form a rectangular conjunction configuration with the other
one. In addition, the rectangular conjunction shown in Figure
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Figure 4. (a) Orbital-resolved band structure of the h-PAMS with the π-bands marked by roman numbers and (b) Dirac cone formed with II−VI
π-bands. The contributions to the band structure from the AC, EC, and CC atoms are shown in (c−e), respectively. Iso-surfaces of the charge
densities of the I, II, and III bands at 0.012 e/Å3 in (f−h) and those of the IV, V, and VI bands at 0.008 e/Å3 in (i−k).

3e could also be obtained by directly assembling two structural
motifs (see the illustration shown in Figure 3c), which is found
to also be barrierless. For the rectangular conjunction structure
shown in Figure 3e, we carefully carried out a 16-image NEB
calculation to evaluate the possibility to transfer it to a
hexagonal conjunction (see Figure 3f). An energy of ∼0.21 eV
could activate the reaction, which would probably occur by
thermal perturbation at room temperature. In addition to the
reactions shown in Figure 3d,f to form hexagonal conjunction
configurations, another situation should also be considered. In
Figure 3b, we also estimated whether three neighboring motifs
could self-assemble together, which is supported by our 16-
image NEB calculation. No energy barrier is found favoring the
formation of the hexagonal conjunction. To conclude, the self-
assembly process would prefer to form the hexagonal
conjunction rather than the rectangular one.
3.1.4. Stabilities of h-PAMS. Both the conjunction
formation energy and the corresponding self-assembly
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formation paths suggest the hexagonal conjunction to be the
dominate connecting structural configuration to favor the
growth of h-PAMS like structural fragments. Such a structural
fragment could be expected to act as the growth seed for
fabricating the h-PAMS sheet. For the h-PAMS sheet, we
analyzed the dynamic, thermal, and mechanical stabilities. The
corresponding data are provided in Supporting Information
Figure S1. No imaginary frequency mode is found in our
phonon spectrum analysis to show dynamic stability. Using a 4
× 4 supercell with the in-plane size of 22.92 Å × 22.92 Å, we
carried out first-principles molecular dynamics simulation at
1000 K for 10 ps. The structural configuration is well-
maintained, supporting good thermal stability. The landscape
of energy versus strain (see Supporting Information Figure
S1d) does not show structural transition, showing good
mechanical stability. In addition, applying uniaxial or
equibiaxial strains, we found the structural stability to
withstand the strain as large as 15%. All of these data of
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Figure 5. (a) Smallest rectangular unit and the directions of the applied tensile strains, (b) calculated Young’s modulus C and Poisson’s ratio υ, (c)
stress (c) and (d) energy cost versus the strain. The insets in (c) are for the structures under the maximum strains. The depiction of the colored
balls is the same as that in Figure 1.
stability analyses support the possibility of its fabrication,
calling for experimental realization.
3.2. Electronic and Mechanical Properties. After
structural optimization, we investigated the electronic proper-
ties of the h-PAMS sheet. The orbital-resolved band structures
are provided in Figure 4a. The contributions from the AC, EC,
and CC non-equivalent C atoms (see Figure 1a for the labels)
to the pz electrons are shown in Figure 4c−e, respectively. The
AC atoms consisting of the hexagonal conjunction contribute
to the pz bands the most, whereas the CC atoms contribute the
least. In Figure 4a, we marked the pz energy bands. There are
10 carbon atoms in the primitive unit cell having 10π electrons
in total. Starting from the deepest pz band, 8π electrons would
completely fill the first 4 pz bands while the other electrons
partially occupy bands V and VI to make the h-PAMS a good
metallic material. In addition, our 3D band structures of the pz
orbital show interesting properties. Bands II, III, V, and VI
show Dirac characteristics with nearly linear dispersion
relationship with k around the Γ point. In Figure 4b, we
illustrate the Dirac cone characteristics of bands II and VI.
Compared to the Dirac cone in graphene, the cones in h-
PAMS are shifted downward obviously at the Fermi level. As
shown in Figure 4b, an energy interval of ∼0.26 eV is opened
due to the inversion symmetry breaking.64−70 Using the
pseudo-charging method, as shown by Shao et al.,71 such an
energy gap could be shifted to the Fermi level to make it a
potential material for high-speed field emission transistors with
a practical on/off ratio. The V and VI bands show nearly linear
dispersion characteristics in the vicinity of thye crossing region
between the π-bands and the Fermi surface. As a result, the
charge carriers are calculated to have as large as 8.6 × 105 m/s
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velocity, agreeing with that of graphene.72,73 Furthermore, we
also evaluated the transport properties of h-PAMS under both
uniaxial and biaxial tensile strains. The strain loading does not
change the metallic conducting nature. Although the uniaxial
strain does not change the carrier velocity much, the biaxial
strain is found to have obvious effects. Under 5, 10, and 15%
biaxial strains, the velocities are found to be reduced by 12, 23,
and 40%, respectively. Remember that the maximum tensile
strain is 15% to keep the structural configuration, and the
carrier velocity could still be expected to remain at the 105 m/s
high-speed level to make the h-PAMS a potential material for
next-generation high-performance electronics.
With the purpose to have a comprehensive understanding of
the electronic properties of the h-PAMS, we also studied the
band decomposed charge densities for the pz orbital bands. As
shown in Figure 4f−k, the charge densities for bands I, II, and
III have some difference with those of bands IV, V, and VI. In
the former ones, the pz orbital electrons are, in some sense,
more localized, agreeing with their lower electron binding
energies. As seen from the side views of the density
distributions, especially the cross sections, the pz electron
characteristics agree with the orbital-resolved band structure
studies. The overlap between the neighboring pz orbitals forms
a π-like bond. The electrons are mainly distributed in the
vicinities above and below the corresponding C−C bonds. In
comparison, the charge distributions of bands IV, V, and VI
show characteristics similar to those of the conjugated π-bands
of graphene, forming well-delocalized π-bonding. The bond
length and bond angle of graphene are 1.42 Å and 120°,
respectively, in accordance with the ideal sp2 hybridization.
However, The C−C bonds of h-PAMS are 1.39, 1.44, and 1.51
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Figure 6. (a) Lowest-energy stacking configuration, (b) band structure of the bulk h-PAMS, and (c) corresponding Young’s modulus C and
Poisson’s ratio υ. In (a), the yellow and gray balls represent C atoms of the lower and upper h-PAMS layers, respectively.
Å in length, and the bond angles are 102, 108, 120, 132, and
156°, showing the mixing nature of sp2 and sp hybridizations.
Compared to the ideal sp2 hybridization of graphene, bands I,
II, and III bear the effects of sp hybridization, much to lower
the binding energies correspondingly. In our studies, we
compared the sp-hybridized HCCH and sp2-hybridized
H2CCH2 bonds. The former has a Fermi energy 0.45 eV
lower than that of the latter. The experimentally fabricated γ-
graphyne58 containing both ideal sp and sp2 hybridization
configurations is calculated to have a Fermi level 1.30 eV lower
than that of graphene. For the h-PAMS, its Fermi energy is
found to be 0.85 eV lower than that of graphene due to the
mixing of sp with sp2 hybridizations.
To facilitate the mechanical property study, we used the
smallest rectangular unit cell, as shown in Figure 5a, instead of
the primitive cell. By applying strains along lattice A and its
perpendicular lattice B, we calculated the in-plane Young’s
modulus C and Poisson’s ratio υ. As shown in Figure 5b, the h-
PAMS shows strong anisotropic mechanical properties. The
biggest Young’s modulus is obtained along the lattices, which is
calculated to be 259 N/m, which is close to the 271 N/m for a
hexagonal boron nitride sheet.74 However, it becomes quite
small along the diagonal line of the unit cell, which is only 25
N/m. Different from the Young’s modulus, Poisson’s ratio
gains the maximum value of 0.93 along the diagonal direction,
whereas it decreases to 0.27 along the lattice direction.
Therefore, the h-PAMS would act as a hard material along the
lattice direction while it becomes a soft material in the diagonal
direction. With such strong anisotropic mechanical properties,
we applied the strain along the diagonal line and let the unit
cell be reshaped while keeping the lattice length unchanged
until reaching the strain-tuned metastable state. As shown in
Figure 5c, the strain applied along the diagonal direction can
be increased to 32%. The corresponding unit cell would
reshape to reduce the lattice angle from 90 to 72°. A slightly
bigger strain would make a structural transition to a new 2D
carbon allotrope (see the Supporting Information Figure S2).
We need to mention that this transition would be difficult to
occur. The 32% tensile strain loading would be as high as 0.9
eV/atom energy, which would probably be inaccessible for
practical use of h-PAMS. In addition, the energy costs of
applying diagonal and biaxial strains are studied in Figure 5d.
The h-PAMS could remain against structural collapse under
biaxial strain as large as 15%. The energy cost increases quickly
along with the biaxial strain loading. In comparison, it increases
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slowly with the diagonal strain loading, agreeing with the
strong anisotropic mechanical properties. In our studies, its
conducting properties under diagonal strains are also
examined. Under the 10, 20, and 30% diagonal strains, the
conducting properties remain, whereas the charge carrier’s
velocities are reduced by 17, 21, and 37%, respectively,
supporting its potential use as good conducting materials for
high-performance nanoelectrics.
Because the stacked multilayer h-PAMS instead of the
monolayer would be most likely to be used, we also studied the
bulk materials composed of the stacked h-PAMS layers.
According to the geometrical characteristics of the h-PAMS,
we carried out an extensive search of the stacking
configurations and presented the low-lying isomers in the
Supporting Information Figure S3. The ground-state config-
uration of the bulk h-PAMS is illustrated in Figure 6a, which
consists of a monolayer with its in-plane inversion counterpart
being 3.38 Å lifted up. In reference to the free-standing
monolayer, the bulk h-PAMS gains 47 meV/atom as the
stacking energy, which is almost equal to that of graphite (48
meV/atom). Figure 6b shows the calculated energy band
structure of the bulk h-PAMS. Compared to the monolayer,
the stacking does not alter the good conducting properties.
Also, the bulk h-PAMS is confirmed in theory to have
anisotropic mechanical properties. The studied Young’s
modulus and Poisson’s ratio in Figure 6c show characteristics
similar to those of the monolayer.
3.3. Potential Use for LIB Anodes. Attributed to the
metallic properties with high carrier mobility and the porous
holes to attract Li ions, the h-PAMS could be a good potential
LIB anode material. In our studies, we optimized the Li
adsorption on the h-PAMS monolayer. As marked in Figure 7a,
four non-equivalent sites are found for Li adsorptions, which
are the hollow center sites of the C9 nonagon (H9), the C6
hexagon (H6), the C5 pentagon (H5), and the top site (T) on
top of the C atom surrounded by three C5 pentagons. The
adsorption energy (E a ) as defined below is calcu-
lated.24,29,34,36,75
Ea = E Li/PAMS − E PAMS − E Li (5)
where ELi/PAMS and EPAMS are the calculated total energies of
the h-PAMS sheet with and without Li adsorption and ELi is
the energy of a free-standing Li atom. The Ea values are found
to be −2.63, −2.61, −2.60, and −2.47 eV for the adsorptions
on H9, H6, H5, and T sites, respectively. Bader charge analysis
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Figure 7. (a) Non-equivalent sites for Li adsorptions. (b,c)
Geometrical configurations with 1, 2, and 3 Li atoms per unit cell
adsorbed on the h-PAMS monolayer. The gray and blue balls
represent C and Li, respectively.
shows charge transfer from Li to h-PAMS. The resulting Li+ is
attracted through Coulomb interaction by its nearby negative
charge, favoring the multiple coordination adsorption site.
Therefore, the H9 site is the best adsorption site for the Li+ ion
to develop 2.26 Å long ionic bonds with its neighboring EC
atoms and 2.50 Å long bonds with AC atoms. The 2.26 Å Li−
EC bond length is only slightly longer than the sum of the
atomic radii of Li and C. Also, the corresponding EC atoms are
found to gain ∼0.97 e charge in total accordance with our
Bader analysis, which should account for the main contribution
to the Coulomb attraction to the Li+ ion.
Using the primitive unit cell containing 10 C atoms, we
examined the Li ion storage capacity. Introducing 1, 2, and 3
ions one by one into the unit cell, the optimized storage
configurations are provided in Figure 7b−d. For the case of
LiC10, the Li ion would stay at the H9 hollow site. The
succeeding Li adsorption would be upon the H6 multi-
coordinate site, which would connect with its three
neighboring Li at H9 sites to form the hexagonal adsorption
network (see Figure 7c for Li2C10). Different from the Li2C10
adsorption configuration, the Li3C10 only consists of the
adsorptions at H9- and H5-like sites. Upon the Li2C10
configuration, the third Li could be first adsorbed at the T
site in a metastable adsorption configuration, which would
easily transit to the ground-state adsorption configuration (see
Figure 7d) under 0.05 activation energy. Then, the adsorbed Li
ions form the kagome lattice geometry. Considering the one by
one adsorption process, the energy gain (Eg) as defined below
could be used to evaluate whether the succeeding adsorption
of a newly introduced Li is exothermic.
Eg = En + 1 − En − Eparticle
(6)
where En and En+1 are the total energies of the configurations
with n and n+1 Li ions. Eparticle is the energy per atom of the
magic cluster Li20 containing 20 valence electrons to
completely fill the electronic shell of the Jellium model to
gain superior stability. The negative energy indicates an
exothermic process. The energy gains are −1.07, −0.36, and
−0.54 eV/Li for the LiC10, Li2C10, and Li3C10, respectively, to
support the Li charging process. For the Li3C10, the
interatomic distance between the nearest Li is ∼2.92 Å,
slightly shorter than the 3.02 Å bond in the bulk Li, for which
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the repulsion among Li ions would prevent storage of much
more Li. In our studies, we compared the cases of the Li
clustering upon the preadsorbed Li (we refer to this situation
as surface clustering hereafter to facilitate discussion) and the
direct adsorption on the h-PAMS sheet. For the Li2C10
adsorption configuration shown in Figure 7c, the discretely
distributed Li ions do not favor the surface clustering.
However, on the kagome configuration of Li in Li3C10
configuration, the clustering of excess Li upon the preadsorbed
Li ions would gain slightly lower total energy than the
adsorption at a hexagonally hollow center of the kagome
configuration (see the Supporting Information Figure S4). As a
result, this would challenge the Li storage capacity of the h-
PAMS beyond Li/C = 3:10, where the surface clustering would
start to be preferable. So, we would like to adopt Li3C10 as the
maximum storage capacity of Li on the h-PAMS monolayer.
Correspondingly, the LiC10, Li2C10, and Li3C10 gain capacities
of 223.24, 446.48, and 676.49 mAh/g. For the LIB, the open-
circuit voltage (OCV) for Li intercalation is also a crucial
property. It could be estimated as shown below when both
volume and entropy effects are neglected.24,76
E Lix1/PAMS − E Lix2 /PAMS + (x 2 − x1)μLi
OCV ≈
(x 2 − x1)e (7)
where ELix1/PAMS and ELix2/PAMS are the total energies of the Lix1
and Lix2 adsorbed h-PAMS sheets, respectively. μLi is the
chemical potential calculated as the energy per atom of bulk Li.
The LiC10, Li2C10, and Li3C10 are found to have 0.548, 0.194,
and 0.137 V OCVs. The h-PAMS monolayer has a specific
capacity (Li3C10) higher than that of the commonly used
graphite anode (LiC6). The average OCV calculated by
averaging the voltage profile versus Li concentration16 is found
to be 0.293 V for the h-PAMS, which is slightly higher than
that of graphite (0.11 V)77 and bco-C16 (0.23 V)22 but much
lower than that of 2D VS2 (0.93 V),77 Mo2C (0.68 V),78
popgraphene (0.45 V),34 and ψ-graphene (0.64 V).29 The
lower OCV enables it to supply a higher operating voltage with
larger energy capacity.
In addition, the average adsorption energy of Li, as referred
to the chemical potential of Li in body-centered cubic bulk is
widely used in theoretical studies to measure whether the Li
could be stored or not, which we would like to consider as Ea*,
as defined below:
(EnLi/PAMS − E PAMS − nμLi )
Ea* =
n (8)
where EPAMS and EnLi/PAMS are the total energies of the pristine
h-PAMS sheet and the n Li ion adsorbed h-PAMS.
Accordingly, a negative value indicates an exothermic process
favoring Li storage. For the above-discussed LiC10, Li2C10, and
Li3C10, the E*a values are −0.55, −0.19, and −0.14 eV/Li,
favoring the Li lithiation correspondingly. Referring to the
kagome lattice of Li in Li3C10 configuration, we could optimize
the structure of Li4C10 by putting a Li ion at the center of each
hexagon of the kagome lattice. The corresponding E*a of the
optimized structure is −0.09 eV/Li, also favoring Li lithiation.
Provided that this could be obtained in experiment, the h-
PAMS would gain a 893.97 mAh/g capacity. However, as
discussed above, if the Li surface clustering occurs, the uniform
coverage configuration of Li on h-PAMS for Li4C10 will be
difficult to form, which is worthy of detailed experimental
studies to check the effects of the surface clustering.
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Figure 8. Illustration of the Li diffusions on the h-PAMS monolayer (a) and the NEB converged paths (b).

Figure 9. (a) Diffusions in the interspace between the neighboring h-PAMS layers, (b) NEB converged diffusion paths, and (c) configurations of
bulk h-PAMS at the maximum storage capacity. The yellow and gray balls are for the C atoms of the lower and upper h-PAMS layers, respectively.
The blue and red balls represent the adsorbed Li ions upon the lower and upper h-PAMS layers, respectively.

The charge−discharge rate is also a crucial parameter for
LIBs. Therefore, we also studied the ion kinetics by
investigating the Li diffusion with the NEB method. Four
non-equivalent movement paths are studied, which are the H9
to H6, H6 to H5, H5 to H5, and H5 to H9. The converged NEB
results are provided in Figure 8. For the Li diffusions on the h-
PAMS sheet, the smallest and the largest energy barriers are
0.15 and 0.35 eV, respectively, which are comparable to those
of graphite (0.22 and 0.40 eV).79−81 Therefore, the h-PAMS
monolayer has good Li ion kinetics to facilitate a fast charge−
discharge process. In addition, the smallest vertex-center
distance of the C9 nonagon in h-PAMS is ∼1.92 Å, which is
35% longer than that of the C6 hexagon in graphene, which
may permit the Li ion to penetrate through. Compared to the
7.29 eV energy barrier for Li penetration through the C6
hexagon, the barrier is obviously reduced to 0.61 eV for the
6007
case of the C9 nonagon. For the fact that the multilayer h-
PAMS would be probably used, the preferable Li ion kinetics
for both the diffusion on the side surface of h-PAMS and the
penetration through it make the h-PAMS-based nanomaterial
superior for LIB anodes.
For the h-PAMS to be used as stacked multilayers, we also
checked the volume expansion during the charge−discharge
process and the ion kinetics in the interlayer space of the bulk
h-PAMS. The ground-state stacking configuration consists of a
layer with its in-plane inversion counterpart being vertically
displaced by ∼3.38 Å. As shown in Figure 9, only two diffusion
paths in the interlayer space need detailed studies due to the
stacking characteristics. Our NEB calculations suggest the
improved diffusion kinetics with the energy barrier as low as
0.24 eV. For the Li penetration through the C9 hole, we also
calculated the energy barrier by using a 16-image NEB
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calculation. Attributed to the attraction from the top site C in
the neighboring h-PAMS layer, the barrier for Li penetration is
increased to ∼1.0 eV. The low activation energies suggest good
ion kinetics for Li lithiation and delithiation of the h-PAMS
multilayer. Furthermore, by intercalating Li ions one by one,
we also examined the maximum storage capacity of the Li
intercalated bulk h-PAMS. The one with six Li ions
intercalated in the primitive unit cell C20 is illustrated in
Figure 9c, which consists of two C10 layers with three Li ions
adsorbed on each of them (the configurations of the other Li
storages are provided in the Supporting Information Figure
S5). Here, three Li ions on each layer are arranged in a trigonal
pattern rather than the kagome configuration shown in Figure
7d. The ground-state geometry of Li6C20 is 0.7 eV lower in
energy than the one formed by simply stacking the monolayers
with Li3 adsorbed on each layer in the kagome pattern.
Compared to the pristine bulk h-PAMS, the interlayer space is
expanded by 9.4% of the Li6C20. The corresponding energy
gain Eg (see formula 6) and the adsorption energy E*a (see
formula 8) are calculated to be −0.03 and −0.58 eV/Li, which
support the lithiation against the formations of metal clusters
and bulk, respectively. In addition, we also estimated whether
the inserted Li atoms would like to cluster together or not.
Putting a Li2 dimer with the Li−Li bond length of 2.73 Å (the
length calculated for a free-standing Li2 dimer) in the interlayer
space between two h-PAMS layers in the configuration with
the Li−Li bond being parallel to the layer, we then carefully
optimized the structure. The Li2 dimer is however found to
break during the optimization. In the final configuration, the
interatomic distance between the Li atoms is calculated to be
3.89 Å to form the configuration with two well-separated single
Li atoms adsorbed on the layer structure. Furthermore, with
the configuration at a maximum Li storage at a capacity of Li/
C = 3:10, we put one more Li atom upon a triangle composed
of three neighboring Li atoms adsorbed on the layer structure
to construct a tetrahedron-like structure. Then, the structure
was fully optimized. However, excess Li could not remain upon
the Li metal layer, which is found to be in the metal layer in the
optimized configuration, hindering the formation of a metal
particle in the interlayer space. This could be attributed to the
combination effects of the energy cost in expanding the
interlayer space to accommodate the excess Li to stay upon the
Li metal layer and the energy gain by maximizing the
coordination number of excess Li atoms with both the upper
and lower h-PAMS layers to hold it in the Li metal layer. These
results rule out the possibility of Li clustering in the interlayer
space in the configuration with maximum Li storage capacity.
For the Li7C20 and Li8C20, our calculations give 0.14 and 0.09
eV/Li energy gains, though their adsorption energies still
remain at negative values, which indicates the formation of a
metal cluster to hinder the Li lithiation in bulk h-PAMS. Again,
the Li surface clustering would begin to matter. As shown in
Supporting Information Figure S6, the intercalation of a Li ion
on the subsurface of the (0001) surface of Li6C20 is 0.39 eV
higher in total energy than the surface clustering that is
energetically unfavorable. Thus, the Li/C = 3:10 would
probably account for the maximum storage capacity (676.49
mAh/g) for bulk h-PAMS, agreeing with the conclusion
obtained for the free-standing h-PAMS monolayer. In addition,
we also carried out MD simulations for the h-PAMS layered
bulk with maximum Li loading. The simulation lasts for 10 ps
at the temperature of 500 K. During the simulation, no
structural breaking or Li clustering of the inserted Li atoms
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occur, supporting the structural stability. Also, the stacking
energy of h-PAMS layered bulk is almost the same as that of
graphite calculated using the Grimme’s D3 scheme corrected
density functional theory calculations. The interlayer space is
3.38 Å for h-PAMS layered bulk, whereas it is 3.49 Å for
graphite. The h-PAMS layered bulk could be expected to act
like graphite, in which it would have a similar solid−electrolyte
interphase structure. If the layer structure of the bulk h-PAMS
to be used as the interface fragment between the solid bulk and
the electrolyte, the bigger C9 hole in the h-PAMS layer may
also help Li diffuse through the interface structure. There is no
dangling bond in the h-PAMS layer to prevent strong bonding
between h-PAMS and electrolyte solution, which would in turn
greatly suppress the irreversible side reactions to maintain
good Coulombic efficiency.23 Furthermore, our calculations
show that the hollow center site of the C9 hole is the best
adsorption site of a single Li. The hybridization distortion
induced by changing the 120 °C bond angle of the ideal sp2
hybridization only slightly enhances the reactivities of the C
atoms at the hole edge, resulting in 0.19 eV/bond stronger Li−
C binding compared to the Li adsorption on graphene.
Compared to the strong σ-type C−C covalent bond, the Li
adsorption would not damage the integrity of the h-PAMS
interface layer between the bulk h-PAMS and the electrolyte.
In addition, the C9 hole is smaller by 1.5 Å in diameter than
the porous hole of the graphdiyne sheet proposed by Gong et
al.82 According to Gong et al.’s study, such a hole could
effectively hinder bigger molecules to penetrate through. So,
the interface structure as the h-PAMS layer could also help
protect the inner bulk fragment by permitting only Li ions to
go through, showing interesting properties for high-perform-
ance LIB anode applications. Here, we would also like to have
a tentative discussion on its compatibility with Cu. The
adsorption of a single Cu atom on h-PAMS would release
∼1.44 eV energy, comparable to the case of its adsorption on
the Si (111)-(7 × 7) surface.83,84 Considering that Cu is the
frequently used metallic electrode on silicon, we would like to
say that the Cu could be expected to develop, in some sense, a
strong connection with the bulk h-PAMS material. Further-
more, the calculated OCV of the h-PAMS is about 0.29 V to
meet the requirement of using Cu as a potential current
collector material.85,86 So, we think that the h-PAMS would
probably be compatible with a Cu current collector, supporting
its potential application for LIB anodes.
4. CONCLUSIONS
Using an acepentalene organic molecule as a precursor, the
acepentalene membrane sheet h-PAMS as a 2D holey carbon
allotrope has been rationally designed. Both the analysis of the
conjunction configuration and the study of the self-assembly
path support its formation to shed light on its experimental
fabrication. The cohesive energy of h-PAMS lies among those
of the experimentally obtained sp2 network of graphene and
the synthesized sp−sp2 mixed graphdiyne. Our FPMD
simulations, mechanical property analysis, and phonon
spectrum studies support its high heat stability, mechanical
stability, and dynamic stability, correspondingly. Interestingly,
its π-electrons as charge carriers show Dirac fermion-like
characteristics. The corresponding Dirac point is located below
the Fermi energy at the Γ point. A band split of 0.26 eV is
opened at the Dirac point due to the broken inversion
symmetry. The crossing of the π-bands with the Fermi surface
enables high carrier velocities, making the h-PAMS attractive
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for use in high-performance nanoelectronics. The high Li ion
storage capacity, the fast ion diffusion kinetics for both the in-
plane move and the penetration through the sheet, and the low
OCV value make the h-PAMS a promising LIB anode material
when used as the free-standing monolayer as well as the
stacked bulk. Furthermore, the space expansion of the stacked
bulk h-PAMS is only 9.4% during the charge−discharge
process, which favors its use as LIB anodes.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c00376.
Phonon spectrum, MD, stress−strain, and energy surface
(Figure S1); structure on the strain (Figure S2); stacking
configurations (Figure S3); adsorptions of Li atoms on
the monolayer and bulk h-PAMS (Figures S4−S6)
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Hongbo Wang − Laboratory of Advanced Materials Physics and
Nanodevices, School of Physics and Technology, University of
Jinan, Jinan, Shandong 250022, China; orcid.org/0000-
0003-1087-0627; Email: sps_wanghb@ujn.edu.cn
Gang Chen − School of Physics and Electronics, Shandong
Normal University, Jinan, Shandong 250358, China;
Laboratory of Advanced Materials Physics and Nanodevices,
School of Physics and Technology, University of Jinan, Jinan,
Shandong 250022, China; Email: phdgchen@hotmail.com
Authors
Tiantian Zeng − Laboratory of Advanced Materials Physics and
Nanodevices, School of Physics and Technology, University of
Jinan, Jinan, Shandong 250022, China
Hao Yang − Laboratory of Advanced Materials Physics and
Nanodevices, School of Physics and Technology, University of
Jinan, Jinan, Shandong 250022, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c00376
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (NSFC)
under Grants Nos. 11674129 and 11704153.
■
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