international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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An investigation of Li-decorated N-doped

penta-graphene for hydrogen storage

Jinbo Hao a, Feng Wei b, Xinhui Zhang a,**, Long Li a, Changcheng Chen a,
Ge Wu a, Liyuan Wu b,c,*, Dan Liang b, Xiaoguang Ma d, Pengfei Lu a,b,
Haizhi Song e,***
a
School of Science, Xi'an University of Architecture and Technology, Xi'an, 710055, Shaanxi, China
b
State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and
Telecommunications, Beijing, 100876, China
c
CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics,
Chinese Academy of Sciences, Beijing, 100049, China
d
School of Physics and Optoelectronic Engineering, Ludong University, Yantai, 264025, China
e
Southwest Institute of Technical Physics, Chengdu, 610041, China

highlights

The stability of two types of Li-decorated N-doped PG were studied.

Li-decorated N-doped penta-graphene is a potential material for hydrogen storage.

The hydrogen storage capacities can reach 7.88 wt%, which is higher than the values of other carbon-base materials.

article info abstract

Article history: By making use of first principles calculations, lithium-decorated (Li-decorated) and
Received 24 January 2021 nitrogen-doped (N-doped) penta-graphene (PG) was investigated as a potential material for
Received in revised form hydrogen storage. The geometric and electronic structures of two types of N-doped PG
23 April 2021 were studied, and the band gaps were 1.86 eV and 2.06 eV, respectively, depending on the
Accepted 12 May 2021 positions of the substitution. The probable adsorption sites for Li atoms on topside and
Available online xxx downside were calculated. Hydrogen molecules were added one by one to Li-decorated N-
doped PG to research the maximum hydrogen gravimetric density. It is found that up to 5
Keywords: hydrogen molecules on topside and 8 hydrogen molecules on downside can be adsorbed
Hydrogen storage around a Li atom, and the average adsorption energies are in the range of physical
Penta-graphene adsorption processes (0.1e0.4 eV). The gravimetric densities can reach 7.88 wt% for N-
Density functional theory doped PG with Li decoration. Our results suggest that Li-decorated N-doped PG is a
Physisorption significantly promising material for hydrogen storage.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and
Telecommunications, Beijing, 100876, China.
** Corresponding author. School of Science, Xi'an University of Architecture and Technology, Xi'an, 710055, Shaanxi, China.
*** Corresponding author. Southwest Institute of Technical Physics, Chengdu, 610041, China.
E-mail addresses: zhangxinhui@xauat.edu.cn (X. Zhang), wuly2018@gmail.com (L. Wu), hzsong1296@163.com (H. Song).
https://doi.org/10.1016/j.ijhydene.2021.05.089
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
Environmental pollution and energy costs have activated
research to find renewable energy sources. Hydrogen has
been considered as a promising bidder due to its attractive
natural abundance, cost-effective and environmental fuel [1].
But the efficient storage and safe transportation will be the
main problem due to its flammability and explosion hazard.
An effective and safe way is to adsorb H2 on the surface of
materials with large specific surface area at suitable condi-
tions [2].
Recently, fullerenes [3], carbon tubes [4], graphite fibers [5],
graphyne, graphene and porous carbon materials [6] have
been demonstrated as a promising hydrogen storage mate-
rials. Graphene has high specific surface area, unique me-
chanical and electronic properties, which allow it to be a
potential media. Following the discoveries of graphene, other
several two-dimensional carbon-base allotropes were
demonstrated. In 2015 a new wide-gap and intrinsic quasi-
direct semiconductor carbon allotrope with pentagonal car-
bon pattern, named penta-graphene (PG), was reported [7],
which is composed of sp2 and sp3 hybridized carbons [8].
State-of-the-art theoretical calculations confirm that penta-
graphene has energetic stability, dynamic stability, thermal
stability and mechanical stability. Although this phase is
metastable compared with graphene, it is more stable than
some nanoporous carbon phases such as 2D a-graphyne. Be-
sides, penta-graphene is energetically preferable over some
experimentally identified carbon nanostructures such as the
smallest fullerene C20, implying that penta-graphene sheet
could be synthesized [7]. PG exhibits ultrahigh ideal strength,
attractive mechanical properties, interesting negative Pois-
son's ratio and relatively higher stability. These unusual
properties make PG prospective for potential applications in
photovoltaics, electronics and optoelectronics [9]. Many of the
novel properties of materials are intimately related to the to-
pological arrangement of atoms and highlight the importance
of structure-property relationships. Penta-graphene is con-
sisted entirely of pentagons, asymmetric structure and an
intrinsic quasi-direct band gap. We wonder if PG is an ideal
material for hydrogen storage. It is already found low capacity
makes the pristine PG unsuitable for hydrogen storage. In
addition to the pristine PG, doped PG also exhibits fascinating
electronic properties [10].
Doping hetero-atoms (B, S, N, P) into carbon-base media
could adjust electronic and catalytic properties, which makes
carbon-base media a prospective catalyst for the practical
applications [11e17]. Nitrogen (N) and boron (B) are the most
usual dopants to carbon-base materials because they have
similar electronic structure and size to carbon, which allow
the carbon substrate to maintain the overall carbon-base
materials with minimal strain. A comprehensive research
based on DFT theory get an insight into the hydrogen mole-
cule dissociation mechanism on pristine PG, N-doped and B-
doped PG. It is found that the average adsorption energy of
hydrogen molecules and atoms on the carbon substrate can be
substantially improved by doping N or B into PG [16].
On the carbon-base materials theoretical and experimental
researches have revealed that decorating metal on substrate is
Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
an effective way to enhance the hydrogen gravimetric density
because it can substantially increase adsorption energies of H2
[18e27]. The decorated metal atom would tune the surface
states of substrate and the unoccupied orbitals of the intro-
duced metal atoms let them show high affinities to hydrogen
molecules. Decorating metal is an effective factor for the
hydrogen storage of the carbon nanomaterials [10]. Mean-
while, the binding energies of metal on carbon-based mate-
rials should be lower than the cohesive energy of bulk metal,
indicating the metal atoms are strongly absorbed on the
carbon-based materials, which rules out the clustering of
metal atoms [28]. It is well known that the lighter metals help
to achieve higher hydrogen storage capacities. Lithium (Li)
atom is the most lightweight metal, and the binding energy of
Li atoms on PG substrate is lower than the cohesive energy
(1.63eV). Stronger binding energies would rule out the clus-
tering of Li atoms on substrate. However, so far, Li-decorated
N-doped PG or Li-decorated B-doped PG has not been dis-
cussed for hydrogen storage.
Strict requirements are proposed for H2 storage practical
applications in prospective media. Scientists were challenged
by the United States Department of Energy (DOE) to improve
hydrogen storage capacity, which is 4.5 wt% (in 2020) and 5.5 wt
% (in 2025) for board vehicle H2 storage systems. Achievable
targets is 6.5 wt% for on board hydrogen storage equipment in
light-duty vehicles [24]. To reach the target volumetric or
gravimetric densities of hydrogen storage at ambient condi-
tions, H2 adsorption energy calculated should be between
(0.1e0.4 eV) per H2 [29]. Ref. [30] estimated H2 absorption en-
ergy of 15.1 kJ/mol (0.157 eV) is needed to store efficient H2 at
30 bar [30]. According to our calculation, it is found that Li-
decorated B-doped PG cannot meet the requirements for H2
storage, which is an undesirable material for H2 storage.
In this study, we focus on the Li-decorated N-doped systems
for hydrogen storage by the first principles calculations. The
next section presents computational details, methods and
models applied to optimize the geometry structures. In the
third section, the results and discussions associated with the
properties of the pristine PG and N-doped PG have been
revealed. At last, we summarized the article and drew the main
conclusions. The study will exhibit significantly theoretical
basis for developing a new pentagonal carbon-base materials
for hydrogen storage with fascinating performances, mean-
while which would enlarge the application range of PG.
Computational details
All the calculations in the present work were carried out by
using the Vienna ab-initio Simulation Package (VASP) [31,32].
The projected augmented wave (PAW) potentials were used to
analyze the interactions between valence electrons and core
electrons [33e35]. The electron exchange-correlation in-
teractions were described by using the Perdewe
BurkeeErnzerhof (PBE) functional within the generalized
gradient approximation (GGA) [33e35], and the cut-off energy
was set to 500 eV. The DFTDF2 exchangeecorrelation func-
tional was introduced in structural optimization to take the
van der Waals (vdW) interaction into account [36].
MonkhorstePack special kpoint method [4] was used with a 5
 international journal of hydrogen energy xxx (xxxx) xxx 3

 5  1 grid for reciprocal-space integration. A vacuum region
of 15

A was applied to eliminate the interaction between two
adjacent images. The convergence criterion were set as 105 eV
for a total energy. All the atomic positions and lattice struc-
tures were fully relaxed with the threshold of a maximum
force of 0.02 eV

A1.
The average adsorption energies of H2 molecules on the
substrate were computed as

thickness of 1.2
A.
Etot  Esub þmEH2
Eads ¼
m namely, C1 site and C2 site, as shown in Fig. 1 (b) and Fig. 1 (c).
where Etot is the total energy of H2 adsorbed on the sub-
strate, Esub is the energy of the substrate, EH2 is the energy of a
H2 molecule. Accordingly, a more negative adsorption energy
means stronger binding.
The charge density differences were calculated as
Dr ¼ rtot  ðrsub þ rLi Þ

To study the stability of N-doped PG, we calculated the
Dr ¼ rtot  rsub þ rLi þ rH2
where rtot is the total charge density of Li-decorated N-doped
PG, rsub , rLi and rH2 denote the charge density of N-doped PG,
the single Li atom and the H2 molecule, respectively.
For the molecules adsorbed on metal surfaces, the vdW-
DF2 function has provided the most reliable results [24],
especially H2 molecules on Cu surfaces [37]. In the present
work, vdW-DF2 method was used to correct the energy of H2
molecules adsorbed on Li-decorated N-doped PG. The
exchange-correlation energy in vdW-DF2 method is written
by
XC ¼ EX
EvdW þ ELDA þ Enl
GGA
C C
where EGGA is the GGA exchange energy, ELDA is the LDA short-
X C
range correlation energy, and Enl
C describes the long-range
exchange contribution.
which composes of 4 sp2 hybridized C atoms on Cl sites and 2
sp3 hybridized C atoms on C2 sites. The fully relaxed lattice
parameters are a ¼ b ¼ 3.64
A, which are consistent with
previous work with the value of 3.64
A [8,24,38,39]. There exist
two types of CeC bond. The longer bond C1eC2 is 1.55
A and
the shorter bond C1eC1 is 1.34
A, which accord well with the
previous values (1.55
A and 1.34
A) [8]. From the side view a


buckling (0.6 A) is observed, leading to a 2D sheet with a total
There are two optional sites to dope N atom into PG,
(1)
The fully relaxed lattice parameters are 3.62
A and 3.63
A,
respectively. They have the similar lattice parameter of 3.64
A
to the pristine PG, indicating that doped N atom causes a mild
distortion, which results from the similar covalent radius of
carbon (73pm) and nitrogen atom (71pm) [17]. Therefore, N-
doped PG has the similar bond distance of 1.36
A and 1.56

A on
(2)
C1 site, 1.35

A and 1.56

A on C2 site.
(3) formation energy by the formula
Ef ¼ ENdoped  EPG þ nEC  nEN (5)
where ENdoped , EPG , nEC and nEN represent the total energy of N-
doped PG, the pristine PG, carbon atoms substituted by ni-
trogen dopant and the total energy of N dopant, respectively. n
represents the number of dopant. The formation energies of
two types N-doped PG are 2.52 eV and 2.78 eV, respectively,
which accord well with others [24]. The predicted formation
energies are positive, indicating N-doped PG can be synthe-
sized by the experimental methods, e.g., laser ablation [11].
Structural and energetic parameters of the fully relaxed PG, N-
(4) doped PG on C1 and C2 sites are shown in Table 1, including
bond types, bond length, lattice constants and formation
energies.
Electronic properties of N-doped PG

In order to understand the electronic properties and the nature

Results and discussions
of bonding in PG and N-doped PG systems, the band structure
and the projected density of states (PDOS) of the pristine PG
Structure and stability of N-doped PG
and two types of N-doped PG based on GGA-PBE are presented
in Fig. 2. The energy gap is the distance from the bottom of the
The optimized geometric structure of PG was shown in
conduction band to the top of the valence band. Obviously,
Fig. 1(a). There are 6 carbon atoms per primitive cell of PG,

Fig. 1 e Schematic of fully relaxed penta-graphene (PG) and N-doped PG structures. (a) Top and side views of the pristine PG.
(b) Top and side views of N-doped PG on C1 site. (c)Top and side views of N-doped PG on C2 site.

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
4 international journal of hydrogen energy xxx (xxxx) xxx

single Li atom adsorption, there are seven possible adsorption

Table 1 e Structural and energetic parameters of the
sites: one hollow (H) site above the center of a pentagon, three
relaxed pristine PG and N-doped PG, including lattice
constants, bond types, bond length and formation energy top (T1, T2 and T3) sites on the top of C and N atoms, and three
(Ef). bridge (B1, B2 and B3) sites between atoms, as shown in Fig. 3.
The adsorption sites on both sides are considered, i.e. topside
Structure Lattice Bond Bond Ef
parameters (

A) types length(

A) (eV) and downside. The average Li adsorption energy is written by

Pristine 3.64 C1eC1 1.34 _

C1eC2 1.55
N-doped on 3.62 C1eN 1.36 2.52
C1 C2eN 1.56
N-doped on 3.63 C1eC1 1.35 2.78
C2 C2eN 1.56
doping N atoms onto C1 site or C2 site will induce different
change of band structure. The conduction band minimum
(CBM) determined by impurity states shifts to low energy range
substantially, reducing the band gaps. With the doping of im-
purity atoms, the band gap of N-doped PG on C1 and C2 is
1.86 eV and 2.06 eV, respectively. It can be seen that doping N
atoms on C2 site reduces the band gap, which accords well with
previous work [40]. Still, these two types of N-doped PG sys-
tems are intrinsic quasi-direct band gap semiconductor.
The PDOS of N doping on C1 site and on C2 site have
obvious resonation peaks, indicating the hybridization inter-
action between doped nitrogen atoms and substrates carbon
atoms. N dopants hybridize with the 2p states of the neigh-
boring carbon atoms, resulting in the strong bonding of the N
atom with substrate. To understand the difference of doped
sites, the bader charge analysis of the two types of system has
been studied in detail, which shows that N atom donates
0.871e on C1 site, and 0.937e on C2 site. N doping on C2 site
contributes more electrons than that on C1 site. This finding is
similar to that of other studies [24].
Adsorption of Li on N-doped PG
Decorating metal is an effective factor for the hydrogen stor-
age of the carbon nanomaterials. In the N-doped PG, even for a


Etot  Esub þmELi
Eads ¼ (6)
m
where Etot is the total energy of Li adsorbed on the substrate,
Esub is the energy of the substrate, ELi is the energy of a Li atoms,
m is the number of Li atom. These sites are concluded in Table 2
for two types of N-doped PG sites C1 and C2, respectively. Li
atom tends to adsorb on the site with a larger binding energy
resulting in a stronger bonding interaction. The strength of the
bonding interaction and its nature were researched by quan-
tum chemical topological approach [43]. For the N-doped PG C1
site and topside T2 site have maximum binding energy
1.848 eV, and on downside B1 site has maximum binding
energy 2.561 eV, indicating that T2 site topside and B1 site
downside are the most likely ones to absorb Li atom. Mean-
while we found that Li atoms binding energies on N-doped PG
are lower than the cohesive energy (1.63 eV) of the bulk metal,
indicating that lithium atom is strongly bonded with the N-
doped PG, which prevents the metal agglomeration. When Li is
absorbed on T2 site topside, the bonding distance between Li
atom and the nearest C atom is 2.326
A, and on B1 site down-
side, the bonding distance with the nearest C atom is 2.029
A.
In the case of N-doped PG on C2 site, there is no stable
adsorption sites after fully relaxed for B1, H, T1 and T3 sites.
The binding energies are positive for B2 and B3 sites, indicating
they are also not stable. The binding energies of T2 site is
higher than cohesive energy, which can result in the Li metal
clustering issue. It can be seen that Li-decorated N-doped on
C2 site doesn't fit for hydrogen storage due to the unfavorable
stability. Therefore, we focus on the C1 site for further
discussion.

Fig. 2 e Band structure based on GGA-PBE and the projected density of states (a) The pristine PG (b) N-doped on C1 site. (c) N-
doped on C2 site.

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
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 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3 e Adsorption situation of Lithium at topside and downside. (a) Top view and side view of N-doped PG on C1 site. (b)
Top view and side view of N-doped PG on C2 site.

Table 2 e Lithium adsorption energy (eV) for N-doped PG distance is very close to the bond length (0.732
A) of free H2
at C1 and C2 sites. molecule, indicating that H2 adsorption is a weak interaction
with N-doped PG which is well consistent with what reported
B1 B2 B3 H T2 T3
in Ref. [42]. The HeH distance (0.742
A) is slightly superior to
1.396 1.533 1.745 1.848 1.483
the bond length (0.732

N-doped C1 Topside __
A) of free H2 molecule. The increase of
N-doped C1 Downside 2.561 1.967 2.557 __ 2.551 __
the bond length result from the partial charge transfer implied
N-doped C2 Topside __ 2.671 __ __ 1.246 __
N-doped C2 Downside __ 1.889 1.884 __ 1.478 __ by the hybridization partially, which is confirmed by making
use of quantum chemical topological approach [43e45].
By adding numbers of H2 molecules one by one to adsorb
The electron charge density differences were calculated for on the Li-decorated Nedoped PG, the average adsorption en-
Li-decorated N-doped PG to investigate the binding interaction ergies (Eads) are calculated by formula (1) and summarized in
between the Li atom and N-doped PG (see Fig. 4). The yellow Table 4. The calculated average adsorption energies of
and blue color represent charge accumulation and reduction, hydrogen molecules are in the range of 0.117 to 0.210 eV/H2
respectively. It is found that the charge decrease around Li on the topside, which is in the range of suitable adsorption
atoms and accumulate around substrate atoms, indicating energies (0.1 to 0.4 eV) for practical applications [25]. To
charges transfer from Li to PG. Bader charges analysis is per- improve hydrogen uptake capacity of N-doped PG, hydrogen
formed to confirm the charge transfer, as shown in Table 3. molecules are added one by one to downside. As showed in
Our results show that there is a significant electron transfer of Fig. 5(aem), hydrogen molecules can be adsorbed around Li
0.852 from carbon to nitrogen, 0.763 and 0.665 electrons atoms with the average adsorption energies from 0.106 eV to
transfers to N-doped PG substrate from Li atoms on T2 site 0.241 eV, which is also suitable for the practical applications.
topside and B1 site downside, respectively. These efficient Li atom on the topside can capture up to 5 hydrogen molecules
charge transfer resulting in the strong bonding energy. The with favorable adsorption energies in the range from 0.1 to
electron transfer makes Li a residual charge, inducing nearby 0.4 eV, meanwhile Li atom on downside can capture up to 8
hydrogen molecules to be polarized [41]. hydrogen molecules with suitable adsorption. Meanwhile, the
bond length of these hydrogen molecules is approximate
Hydrogen storage performances of Li-decorated N-doped PG 0.740

A, and the distance between H2 and Li is in a reasonable
range (<4
A), indicating that hydrogen molecules can be
Based on the most stable structure of Li-decorated N-doped captured by metal Li and well stored in Li-decorated N-doped
PG, we further discuss the adsorption behaviors of H2 mole- PG. Besides, to check the stability of Li atoms on the N-doped
cules. There exist two main orientations, i.e., H2 perpendicular PG substrate after the H2 adsorption, we calculated the Li-
or parallel to the Li-decorated N-doped PG sheet. After opti- atom binding energy of some configuration as shown in
mizing the structure of a single H2 molecule toward the sub- Fig. 5(a,e,m), and found the binding energy is 1.997 eV,
strate, the H2 molecule prefers to tilt towards the Li atom, 2.065 eV, and 1.971 eV, respectively. They are lower than
instead of perpendicular or parallel, as shown in Fig. 5. By the the cohesive energy (1.63 eV), which prevents the metal
addition of H2 molecules a stable configuration can be ob- agglomeration. Furthermore, Li atoms bonded to underlying
tained, where Li atom is at a distance of 2.299
A from the surfaces can be estimated by the quantum chemical topo-
substrate, H2 is at a distance of 2.052

A from the Li atom, and logical approach [43e45].
the HeH distance is 0.742
A, as shown in Fig. 5(a). The HeH

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e Top and side views of charge density difference of (a) N-doped PG and (b) Li-decorated N-doped PG. The yellow
isosurface indicates an electron gain, while the blue one represents an electron loss. The isosurface level is 0.015 e/Bohr3.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

where MH2 and Mhost are the molecular mass of single H2

Table 3 e Bader charges (BC) obtained with VASP for Li-
molecule and N-doped PG, respectively. Using formula (4), the
decorated N-doped PG. The charge expressed as the
number of the electronic charge e is defined asDQ ¼ Q  uptake capacity of H2 for Li-decorated N-doped PG can reach
Qval , whereQ val is the valence charge. 7.88 wt%. We compared our results with previous work on
carbon-base materials for H2 storage. For instance, Li-
System Atom BC
decorated C41 allotrope (7.12 wt%) [6], Li-decorated T-gra-
N-doped PG C 0.915
phene (7.7 wt%) [46], Ti-doped graphene nanoribbon (6.0 wt%),
N 0.852
Cu-functionalized graphene (4.23 wt%), Ni-decorated defec-
Li-decorated N-doped PG C 0.693
N 0.784 tive and pristine graphene (7.02 wt% and 5.81 wt%) [47e50], Y-
Li Topside 0.763 decorated porous graphene (7.87 wt%) [51]. Additionally, the
Li Downside 0.665 gravimetric density of other nanomaterials for Hydrogen
storage including metal decorated phosphorene (3.6 wt%) and
containing single vacancies (5.30 wt%) [52,53], Cr2C (7.60 wt%)
[54] and hexagonal boron nitride (2.60 wt%) [55]. Our result can
The average binding energies are listed in Table 4. It shows fully satisfy the requirement of DOE and are higher than the
that the average binding energy decrease as the number of H2 values in previous studies on carbon-base materials [48e55].
molecules adsorbed increases from one to five on the topside, To demonstrate the mechanism of hydrogen adsorption,
indicating that the more H2 molecules are added, the weaker charge density difference (see Fig. 6) and bader charge of H2
the interaction between H2 molecules and N-doped is. molecules on Li-decorated N-doped PG were calculated. The
For the Li-decorated N-doped PG, we can see that the bader charge analysis of the two H atom has been studied,
maximum number of H2 molecules to be allowed is thirteen. which shows that one of the H atom donates 0.131 electrons,
In order to evaluate the maximum H2 storage ability, the and the other gains 0.134 electrons, which indicate that H2 is
gravimetric density is calculated by the following formula polarized to the dipole under the electric field induced by the
  Li ion. Therefore, the polarization interaction underlies the
MH2
H2 ðwt%Þ ¼  100 (7) adsorption of H2 around Li. This findings accord well with
MH2 þ Mhost
previous work [56].

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 5 e Top and side view of hydrogen storage performances. Up to 5 hydrogen molecules on topside (a)e(e) and 8 hydrogen
molecules on downside (f)e(m) can be adsorbed to Li-decorated N-doped PG one by one.

Table 4 e The average binding energy of hydrogen molecules (eV/H2) respect to adsorption of Li on topside and downside.
Adsorption sites 1H2 2H2 3H2 4H2 5H2 6H2 7H2 8H2
Li Topside 0.210 0.198 0.176 0.117 0.128
Li Downside 0.241 0.231 0.140 0.219 0.132 0.106 0.100 0.117

Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
8 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 6 e Charge density difference plots. The adsorption configurations and charge transfer are plotted. The yellow
isosurface indicates an electron gain, while the blue one represents an electron loss. The isosurface level is 0.015 e/Bohr3.
Conclusions
In summary, we perform the first-principle approach to
investigate Li-decorated N-doped penta-graphene (PG) for
hydrogen storage. Li is the most lightweight metal and the
binding strengths of Li atoms on N-doped PG are lower than
cohesive energy (1.63 eV). Stronger binding would rule out
the clustering of Li atoms on N-doped PG. The stability of
two types of Li-decorated N-doped PG are studied by first
principles calculations. It can be seen that N-doped on C2
site is not fit for hydrogen storage due to the unfavorable
stability. From our calculation results, it can be seen that Li
prefer to stay at T2 site on topside, and at the bridge site B1
on downside. Li on topside can adsorb up to 5 hydrogen
molecules with adsorption energies in the energy range
from 0.117 to 0.210 eV/H2, which are suitable adsorption
energy (0.1 to 0.4 eV). Meanwhile Li on downside can
adsorb up to 8 hydrogen molecules with suitable adsorption
energies. The hydrogen storage capacities of Li-decorated N-
doped PG can reach 7.88 wt%, which is favorable for the
requirement of DOE.
Penta-graphene is not only dynamically and mechani-
cally stable, but also has unique atomic configuration and
electronic properties. Penta-graphene is consisted entirely of
pentagons and asymmetric structure. These unique proper-
ties make Li-decorated on the topside captures to 5 hydrogen
molecules with favorable adsorption energies, and Li atom
on downside can capture up to 8 hydrogen molecules with
suitable adsorption. Our results suggest that Li-decorated N-
doped PG may be a significantly potential hydrogen storage
medium.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089
Acknowledgments
This work was supported by the Fund of State Key Laboratory
of IPOC(BUPT) (IPOC2019ZZ04 and IPOC2019A013), P. R. China.
LW thanks the support funded by China Postdoctoral Science
Foundation (No. 2019M660563).
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Please cite this article as: Hao J et al., An investigation of Li-decorated N-doped penta-graphene for hydrogen storage, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.089