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Enhancing sodium ionic conductivity in

tetragonal-Na3PS4 by halogen doping: a first
Cite this: Phys. Chem. Chem. Phys.,
2018, 20, 20525 principles investigation†
He Huang,b Hong-Hui Wu, c
Xinjiang Wang, b
Baoling Huang *b and
Tong-Yi Zhang*a
Published on 18 July 2018. Downloaded on 10/31/2023 10:13:12 AM.

Received 14th April 2018,
Accepted 17th July 2018
DOI: 10.1039/c8cp02383b
rsc.li/pccp
Tetragonal Na3PS4 (t-Na3PS4) has been demonstrated as a very promising candidate for a solid-state
sodium-ion electrolyte with high Na ionic conductivity at ambient temperature. In this paper, we
systematically investigated the Na ionic conductivity in pristine and halogen (F, Cl, Br, and I) doped
tetragonal-Na3PS4 superionic conductors using first-principles calculations. The Na ionic conductivity of
pristine t-Na3PS4 is calculated to be about 0.01 mS cm1, while much higher Na ionic conductivities
could be achieved by introducing Na ion vacancies via a halogen doping strategy. The calculated Na
ionic conductivity of t-Na3PS4 doped with 1.56% Cl is 1.07 mS cm1 at ambient temperature. Among
different halogen-doped t-Na3PS4, Br-doped t-Na3PS4 shows the lowest activation energy and the
highest Na ionic conductivity, which reaches 2.37 mS cm1 at 300 K. The low activation energy and high
Na ionic conductivity in Br-doped t-Na3PS4 are due to a relatively lower defect binding energy of the
defect pair of halogen substitution and a Na ion vacancy. Our results suggest Br-doped t-Na3PS4 may
serve as a very promising Na-ion solid-state superionic conductor.

Introduction
Na-ion batteries (NIBs) have the potential to compete with
commercially used Li-ion batteries (LIBs) for stationary energy
storage applications and innovate the landscape of electro-
chemical energy storage, due to the evenly distributed abun-
dance of the sodium resource and the cost advantages. Recent
decades have witnessed the active development of Na-ion
batteries.1–5 For both Li-ion and Na-ion batteries, the potential
hazards associated with current organic liquid electrolytes (e.g.,
leakage and flammability) are one of the major hurdles limiting
the widespread application of alkali ion batteries in large-scale
electronic devices and engines.6,7 Replacing the organic liquid
electrolytes with inorganic solid-state electrolytes (SSEs), in principle,
could eliminate the safety concerns, offering a promising way
forward to extend the application of alkali ion batteries to
industry where safety is of utmost importance.8–13
a
Shanghai University Materials Genome Institute and Shanghai Materials Genome
Institute, Shanghai University, 333 Nancheng Road, Shanghai 200444, China.
E-mail: zhangty@shu.edu.cn
b
Department of Mechanical and Aerospace Engineering, Hong Kong University of
Science and Technology, Kowloon, Clear Water Bay, Hong Kong, China.
E-mail: mebhuang@ust.hk
c
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588, USA
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8cp02383b
Up until now, there are only a few existing Na-ion solid state
electrolytes with conductivities approaching those of liquid
electrolytes (1–6 mS cm1 at room temperature).14 Currently
oxide ceramic, sulphide glass–ceramic and borate Na-ion solid
conductors are the main classes of potential Na-ion SSEs under
intensive investigation.9,12,15 NASCON-type oxides9,16,17 (such
as Na1+xZr2SixP3xO1217 with 0 r x r 3) and b00 -alumina18,19 are
well-known Na-ion SSEs exhibiting high room-temperature
ionic conductivities over 1 mS cm1. However, the harsh
synthesis conditions (such as high synthesis temperatures over
1473 K), high annealing temperatures (41273 K), and poor
room-temperature electrolyte–electrode contact make their
large-scale applications expensive and complicated. Recently,
Udovic et al.20 reported that Na2B12H12, which can be synthesized
easily, shows an ionic conductivity of the order of 0.1 S cm1
above 543 K, although its room-temperature conductivity is
relatively low. In contrast to previous Na superionic conductors,
sulphide-based Na-ion SSEs21–24 are more promising, owing to
their high ionic conductivities, low synthesis temperatures and
low grain boundary resistances. Therefore, they have been
attracting great interest.25–28 Inspired by sulphide-based Li-ion
SSEs, glass–ceramic Na3PS426 was experimentally found to have a
room-temperature conductivity of 0.2 mS cm1, which was further
increased to 1.46 mS cm1 by cation substitution of P with
As (Na3P0.62As0.38S4)29 and 1.16 mS cm1 by anion substitution
of S with Se (Na3PSe4).30 Through the aliovalent doping strategy,

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the introduction of Na ion defects (interstitial or vacancies) would
greatly improve the ionic conductivities of Na-ion SSEs. In previous
studies, high ionic conductivities induced by the excess of Na
ions via the substitution of P5+ with Si4+, Ge4+ and Sn4+ have been
theoretically investigated.27 Meanwhile, outstanding performance
was achieved by creating Na ion vacancies via halogen anion
doping for S2. Klerk et al.28 have performed an ab initio MD
simulation of c-Na3PS4 doped with 3.2% halogen at 525 K. An ionic
conductivity higher than 1 mS cm1 has been experimentally
reported by Chu et al.31 for the t-Na3PS4 superionic conductor
doped with 1.6% Cl. This makes halogen doped sulphide-based
Na-ion SSEs good candidates for the design of promising Na-ion
all-solid-state batteries. Some other halogen doped superionic
conductors (lithium superionic argyrodites and lithium-rich anti-
perovskites)32–36 have been investigated to achieve better cation
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ionic conductivities, which are attributed to the optimal anion
polarizability and concerted cation motions. Although chlorine-
doped Na3PS4 has been characterized previously, to the best of our
knowledge, the influences from different halogen dopants on Na
ion transport in t-Na3PS4 and the corresponding Na ion diffusion
mechanisms have not yet been systematically explored.
Herein, we performed a first principles based molecular
dynamics calculation of the Na ionic conductivity in pristine
and halogen (F, Cl, Br, and I) doped tetragonal-Na3PS4 super-
ionic conductors. We found that at room temperature, the Na
ionic conductivity of pristine t-Na3PS4 is only about 0.01 mS cm1,
while much higher Na ionic conductivities could be achieved with
the introduction of Na ion vacancies by halogen doping. Our
results show that the Na ionic conductivity of t-Na3PS4 doped with
1.56% Cl could reach 1.07 mS cm1, which is consistent with the
experimental observation.28 Further, a Na ionic conductivity as
high as 2.37 mS cm1 is predicted for Br-doped t-Na3PS4. Through
structural optimization and topology analysis, it is shown that the
halogen dopants would not affect the overall structure of pristine
t-Na3PS4, all of which display a 3D Na ion diffusion network. The
binding energy between the halogen substitution and Na ion
vacancy defect pair in the halogen doped structure reveals the
mechanism of the much lower activation energy and the higher Na
ionic conductivity in Br-doped t-Na3PS4. A further higher Na ionic
conductivity and lower activation energy could be achieved by
introducing a higher halogen atom substitution concentration.
Calculation methods
Fig. 1 shows the two crystal phases of Na3PS4, i.e., the cubic
phase (c-Na3PS4) and the tetragonal phase (t-Na3PS4).27,28
c-Na3PS4 is crystalized in the space group I43% m with the lattice
parameters a = b = c = 7.02 Å, while t-Na3PS4 is in the space
group P42% 1c with the lattice parameters a = b = 7.01 Å, and
c = 7.16 Å.27,28,31 In the tetragonal phase, the Na (6b)-site in the
c-Na3PS4 structure will split into two Na ion sites, i.e., the Na I
(2a) site and the Na II (4d) site, as shown in Fig. 1(c). Although
the two different phases of Na3PS4 are both in stable existence
with less than 2% difference of lattice parameters and similar
Na+ and PS43 polyhedral ion configurations, it is calculated
20526 | Phys. Chem. Chem. Phys., 2018, 20, 20525--20533
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Fig. 1 (a) Unit cell of cubic-Na3PS4. (b) Unit cell of tetragonal-Na3PS4.
(c) Lowest energy structure of t-Na47P16S63Br determined from DFT
calculations by replacing one S2 with Br and introducing one Na+
vacancy in the pristine 2  2  2 t-Na3PS4 supercell. Na I in gray, Na II
in blue, S in yellow, Br in green and P in purple.
that the static energy of t-Na3PS4 is 5.51 meV per atom lower
than that of c-Na3PS4, which is in close agreement with the
value of 5 meV per atom reported by Ong et al.27 Furthermore,
it has been experimentally demonstrated that t-Na3PS4 is easier
to synthesize compared with c-Na3PS4, which could only be
successfully synthesized with less than 0.1 g of precursors
inside either an Al or quartz tube at 50.37 Therefore, we choose
tetragonal-Na3PS4 as our pristine study object in this paper.
All DFT calculations in this work were performed using
the Vienna Ab initio Simulation Package (VASP)38 with the
projected augmented wave approach.39 Generalized gradient
approximation (GGA) Perdew–Burke–Ernzerhof (PBE) was
adopted for the exchange–correlation functional. For sodium,
phosphorus, sulfur, and halogen atoms, we used pseudo-
potentials with the valence configurations p6s1, s2p3, s2p4,
and s2p5, respectively. The structural relaxations for pristine
and halogen doped t-Na3PS4 (the doping level is 1.56%) were
performed based on 2  2  2 supercells containing 128 atoms
for the pristine structure and 127 atoms for the doped structures.
The Brillouin zone was sampled by a 3  3  3 Monkhorst–Pack
grid and the energy cutoff was set at 520 eV. All geometry
structures were fully relaxed until convergence criteria of forces
and energy of 0.01 eV Å1 and 105 eV were reached, respectively.
All energy cutoff and k-points have been tested until the energy
reaches its convergence. The fully optimized structures were used
as the initial configurations for the subsequent calculations.
Due to the high cost of ab initio molecular dynamics (AIMD)
methods,40 gamma-point-only sampling of k-space and a plane-
wave energy cutoff of 280 eV were used in the AIMD simulations
for both the pristine and halogen doped t-Na3PS4 structures,
except for fluorine doped cases with a higher energy cutoff
of 400 eV. All energy cutoff values were carefully tested and
selected to ensure the computation accuracy and convergence
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during the AIMD simulations. The simulation domain was a doped t-Na3PS4 via AIMD simulations. Through the AIMD
supercell of 2  2  2 optimized t-Na3PS4 lattice cells. To simulate simulations, the mean square displacements (MSDs) of Na
the Na ion vacancy effect induced by halogen dopants, one ion diffusion were extracted. According to the calculated MSDs
halogen atom X (X represents F, Cl, Br, or I) was introduced into of Na ions, the tracer diffusivity or self-diffusivity can be
the supercell by replacing one of the 48 S atoms with X while calculated using the Einstein equation:43
introducing one Na ion vacancy inside t-Na47P16S63X, corres- 1 D E
ponding to 2.08% Na ion vacancies via 1.56% halogen doping. D¼ ½rðtÞ2 ; (1)
2dt
Structure optimizations were performed for different configura-
tions containing both halogen substitution and Na ion vacancies. where t is the total simulation time, d the dimensionality of the
The AIMD simulations were performed in NVT ensembles diffusion pathway (3 in this case), and h[r(t)]2i the mean square
with Nosé–Hoover thermostats and the time steps were set to displacement of the diffusion species. By using the Nernst–
2 fs. Target temperatures ranged from 600 K to 1400 K. In each Einstein equation, the ionic conductivity s can be related to the
case, an equilibrium time of 2 ps was applied and the total tracer diffusivity44 through
simulation time was 100 ps. The Na ion trajectories at the ne2 z2 D
equilibrium state were dumped and then were used to calculate s¼ ; (2)
kT
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the Na ionic conductivities and to determine the activation

energies. Migration barriers for Na ion diffusion in the pristine
t-Na3PS4 structure were calculated using the climbing nudged
elastic band method (CI-NEB)41 through the VTST code42 linked
with VASP. A 2  2  2 k-point grid and plane wave energy
cutoff of 520 eV were used.
Results and discussion
The first principles calculations found that the halogen atom
prefers to be distributed close to the nearest Na ion vacancy in
the 2  2  2 supercell to form a defect pair of halogen
substitution and a Na ion vacancy XS VNa 0
. Fig. 1(c) typically
shows the lowest energy structure of t-Na47P16S63Br with one
distinct XS VNa
0
defect pair inside.
Table 1 shows the structural parameters of the relaxed
t-Na3PS4 supercell and the halogen doped structures. It is found
that the initial orthorhombic tetragonal crystal becomes slightly
distorted as the XS VNa0
defect pair exists non-symmetrically
inside the lattice. The volume of the pristine 2  2  2 Na3PS4
supercell is only around 0.1–0.8% smaller than those of the
corresponding t-Na47P16S63X structures, indicating that the
halogen doped structures could maintain the original tetra-
gonal lattice even with the existence of the XS VNa
0
defect pair.
The small variation in the lattice parameters of t-Na47P16S63X is
mainly due to the different anionic radii. The effective ionic
radii for S2, F, Cl, Br and I are 184, 133, 181, 196 and
220 pm, respectively, which give a smaller unit cell for the
F-doped structure and larger ones for Br- and I-doped ones.
To investigate the Na ionic conduction, we evaluated the Na
ion diffusion properties by calculating the self-diffusion coeffi-
cient of Na ions in the pristine t-Na3PS4 supercell and halogen
where n is the Na ion number density, e is the elementary
charge, z is the ionic charge, D is the tracer diffusivity, k is
Boltzmann’s constant, and T is the temperature in Kelvin. It is
known that the temperature dependency of ionic conductivity
could be represented by the conventional Arrhenius relationship:45
 
Ea
sT ¼ s0 exp  ; (3)
kT
where s0 denotes the pre-exponential factor, which depends on
temperature in a much weaker manner than the exponential
function in the Arrhenius equation, k the Boltzmann constant,
T the absolute temperature, and Ea the activation energy of
Na-ion diffusion. It implies that a lower Ea leads to a higher
ionic conductivity at a given temperature. By fitting the MSD of
Na ions at different elevated temperatures during the simula-
tion period, the diffusivity and conductivity of Na ions in
pristine and halogen doped Na3PS4 were computed. As shown
in Fig. 2(a), the introduction of Na ion vacancies could signifi-
cantly increase the Na ion diffusivity and lower the activation
energy. Pristine t-Na3PS4 exhibits a very low Na ionic conduc-
tivity of 0.01 mS cm1 at 300 K with a relatively high activation
energy of 366.1 meV, consistent with the experiment results
from Chu et al.,31 while a 2% Na ion vacancy concentration
introduced by halogen doping results in nearly 2 orders of
magnitude larger Na ionic conductivities, especially for Cl
doping (1.07 mS cm1) and Br doping (2.39 mS cm1). The
extracted activation energies in the doped structures are also
much lower compared with that of the pristine structure,
especially for the Br-doped case (only about 216 meV). The
calculated Na ionic conductivity and energy barrier for
Cl-doped Na3PS4 agree quite well with the experimental values
reported by Chu et al.31

Table 1 Structural parameters for the optimized pristine Na3PS4 supercell and halogen doped structures

Structure Halogen site Na+ vacancy site a (Å) b (Å) c (Å) a (1) b (1) g (1) Volume (Å3)
t-Na48P16S64 — — 14.018 14.018 14.310 90.00 90.00 90.00 2812
t-Na47P16S63F (8e) (2a) 13.992 14.010 14.383 90.31 90.02 90.11 2819
t-Na47P16S63Cl (8e) (2a) 14.010 14.009 14.392 90.12 89.95 89.98 2825
t-Na47P16S63Br (8e) (2a) 14.023 14.022 14.397 90.03 89.94 89.98 2831
t-Na47P16S63I (8e) (2a) 14.043 14.050 14.399 89.93 89.87 89.91 2841

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Fig. 2 (a) Arrhenius plot for pristine Na48P16S64 and halogen doped t-Na47P16S63X from AIMD simulations. The inset expanded the left corner panel for a
clearer version. (b) Isosurface of the Na ion probability distribution network with an isovalue of Pmax/ in t-Na47P16S63Br at 1000 K plotted by the pymatgen
diffusion analysis code.1
Published on 18 July 2018. Downloaded on 10/31/2023 10:13:12 AM.

We used the open source Zeo++ software46,47 to perform a
topological analysis of the free volume inside which Na ions
could normally flow. Na ions were removed from each structure
to study the largest radius of a free sphere that Na ions could
successfully pass through in the remaining PS43 skeleton,
shown as the channel size in Table 2. All the channel sizes of
the studied systems are very similar with a difference less than
0.01 Å. That means the introduction of halogen atoms and Na
ion vacancies would not lead to considerable influence on the
diffusion channel. Additional insights may be obtained by
analyzing the trajectories from the AIMD simulations. A plot
of the probability density function P(r) can provide useful
information on the low energy (high probability) sites in
crystals, as well as the migration pathways between them. P is
often defined in a spatial 3D uniform grid and can be computed
by averaging the number of alkali ions at each grid point within
Ð
a given time scale. P is normalized such that Pdr ¼ 1. Fig. 2(b)
typically shows the isosurface of the Na ion probability distribu-
tion network in Br-doped t-Na3PS4 at 1000 K plotted by the
pymatgen diffusion code.1 It demonstrates that halogen doped
t-Na3PS4 keeps a 3D diffusion pathway composed of the equili-
brium Na sites interacting with each other, which forms a body-
centered cubic diffusion network, consistent with the diffusion
network of t-Na3PS4.27 Meanwhile, we also calculated the channel
volume of all the systems by using the whole unit cell volume to
subtract the volume of the polyhedrons skeleton (PS43 or PXS33),
which is listed as the channel volume in Table 2. It shows that
I-doped t-Na3PS4 has the largest channel volume for the Na ion to
diffuse, which seems like the Na ion diffusivity should be the
highest in the I-doped structure. However, it is not the fact in our
AIMD simulations.
In this case, if we consider the Na ion vacancy as a kind of
ion of zero mass, the diffusion of Na ions could be regarded as
the diffusion of Na ion vacancies in the opposite direction
inside pristine and halogen doped t-Na3PS4. Owing to the
existence of halogen substitution and the nearest Na ion
vacancy in the most stable halogen doped t-Na3PS4, it would
be reasonable to assume that Na ion vacancies induced by
halogen doping are not free but bound to the halogen dopants
to form defect pairs at 0 K. As the thermal dissociation of defect
pairs requires supplementary energy in addition to the energy
for migration of free ion vacancies,48,49 we estimated the
activation energy of Na ion diffusion by dividing it into the
binding energy of the XS VNa 0
defect pair and the migration
energy of the Na ion in the structure containing charged
vacancies in the absence of halogen substitution, i.e.,50
Eactivation = Ebinding + Emigration, (4)
where Ebinding and Emigration are the binding energy of the
XS VNa
0
defect pair in halogen doped t-Na3PS4 and the migra-
tion energy of the Na ion in pristine t-Na3PS4, respectively.
As the result in Fig. S1 (ESI†) shows little difference between
the migration energy of the Na ion in t-Na3PS4 and that in the
Br-doped pristine structure, it is convenient to study Na vacancy
migration by omitting the effect of different kinds of halogen
elements when the Na ions are remote from those halogen atoms.

Table 2 Channel size, channel volume, extrapolated Na+ diffusivity, conductivity at 300 K, and activation energy extracted from calculations,
in comparison with available experiment results

Our calculation Experiment

Halogen doping Channel Channel D300K
Structures concentration (%) size (Å) volume (Å3) (cm2 s1) s300K (mS cm1) Ea (meV) s303K (mS cm1) Ea (meV)
7
t-Na48P16S64 — 2.11 2739 9.46  10 0.01 366.1 0.05 317
t-Na47P16S63F 1.56 2.22 2748 6.15  105 0.64 260.9 — —
t-Na47P16S63Cl 1.56 2.21 2752 1.04  104 1.07 248.7 1.14 249
t-Na47P16S63Br 1.56 2.22 2757 2.32  104 2.39 215.6 — —
t-Na47P16S63I 1.56 2.21 2767 3.53  105 0.36 287.3 — —

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The migration energy of the Na ion in the vacancy-containing
t-Na3PS4 structure was estimated by calculating the diffusion
path and diffusion barrier of Na–Na hopping by using the
climbing nudged elastic band (CI-NEB) method. By checking
the most stable Na site in the 2  2  2 t-Na3PS4 supercell with
one Na vacancy, it is found that Na ion diffusion between Na I
sites is blocked by P atoms, while Na ions at the Na II site could
diffuse to the Na I site through the ab-axis plane or to the next
Na II site along the c axis. Therefore, we calculated the diffusion
pathway of the Na ion from the Na II site to the Na I site (path 1)
and from the Na II site to the Na II site (path 2). The illustration
of the two diffusion pathways is shown in Fig. 3. Path 1
represents the routine of Na I site hopping to the Na II site,
corresponding to Na ion diffusion along the a- or b-axis, while
path 2 represents the routine of Na II site hopping to the next
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Na II site, corresponding to Na ion diffusion along the c-axis.
Apart from path 1 and path 2, no other pathway is observed as
the body centered cubic rigid PS43 frame is found to block the
hopping of Na ions through a diagonal like pathway or other
distorted pathways. In each diffusion path, 6 transition images
were chosen for the NEB calculations and the charged state of
the system was taken into consideration. Depicted in Fig. 3, the
Na ion diffusion energy barrier along the Na II site to the Na I
site is more than 50 meV lower than that between Na II sites.
To demonstrate the preferred pathway, the partial mean square
displacements (PMSD) of Na ions along the a-axis or b-axis
(path 1) and c-axis (path 2) are plotted in Fig. S4 (ESI†). It is
found that the diffusion rate of Na ions along the a-axis or the
b-axis is larger than that along the c-axis, which means the
diffusion preferentially occurs along path 1 (Na II - Na I -
Na II), which is consistent with the lower barrier from the NEB
calculation in Fig. 3. This means the diffusion path of Na ions
between the Na I site and the Na II site along the a-axis and b-axis
directions are dominant in t-Na3PS4. At elevated temperatures
such as 1000 K, the thermodynamic contribution would promote
Fig. 3 Diffusion energy landscape of Na ions in the vacancy containing
t-Na3PS4 supercell along the a- or b-axis direction and along the c-axis
direction. The inset shows diffusion pathways of the Na ions in vacancy
containing Na47P16S64. The orange ribbons represent the migration path 1
(Na II - Na I - Na II), which is corresponding to Na ion diffusion along the
a-axis or the b-axis. The light green ribbons represent the migration path 2
(Na II - Na II), which is corresponding to Na ion diffusion along the c-axis.
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the Na ion hopping possibility along path 2, as the energy barrier
along path 2 is low and only 50 meV larger than that along path
1. So it is reasonable to observe the 3D cubic diffusion network
of Na ions in Fig. 2(b). Table 3 shows that our calculation results
for Na3PS4 are in accordance with Yu et al.’s work.29
The binding energy of a defect pair can be calculated using
the separated defect approach50
P
Ebinding = Eisolate defects  Edefect pair (5)
where Eisolate defects and Edefect pair are the formation energy of
separated defects, and the formation energy of the defect pair
in the studied system, respectively. In this calculation, the
binding energy of the XS VNa 0
defect pair can be specifically
expressed by
Ebinding = E(Na47P16S64, +|e|) + E(Na48P16S63X, |e|)
 E(Na47P16S63X)  E(Na48P16S64), (6)
where E(Na47P16S64, + |e|), E(Na48P16S63,  |e|), E(Na47P16S63)
and E(Na48P16S64) represent the energy of the 2  2  2 t-Na3PS4
supercell with one V0Na , the energy of the 2  2  2 t-Na3PS4
supercell with one XS , the energy of the 2  2  2 t-Na3PS4
supercell with one XS VNa 0
defect pair and the energy of the
pristine 2  2  2 t-Na3PS4 supercell. For all calculations,
we chose the optimized structure with the lowest energy and
assumed the same chemical potential of the electron reservoir
when the individual charged defects exist.50
Table 4 shows the binding energy Ebinding of the XS VNa 0
defect pair, and migration energy Emigration and fitted activation
energy Eactivation of Na ions in different halogen doped t-Na3PS4.
It reveals that the activation energy of Na ion diffusion in
halogen doped t-Na3PS4 obeys eqn (3), roughly comprising
the binding energy of the XS VNa 0
defect pair and the migration
energy of Na ions in the pristine structure. As for the binding
energy of Na vacancies to the halogen atoms compared with
that to sulfur, the calculated binding energies of Na vacancies
and halogen atoms for the F, Cl, Br and I doped cases,
respectively, are 215.1, 184.3, 163.8 and 246.2 meV larger than
that of Na vacancies and sulfur. That means Na vacancies prefer
to site at the equilibrium position nearest to the halogen
substitution initially. This is demonstrated by the Na vacancy
and halogen substitution sites with the nearest XS VNa 0
defect
pair in t-Na47P16S63X by structure optimization. Furthermore,
the energies of the structures with the second nearest Na
vacancy to the halogen atom are calculated 206.6, 173.4,
152.1 and 226.3 meV higher than those of the structures with
the nearest Na vacancy to the halogen atom, for the F, Cl, Br
and I doped cases, respectively. This relatively high energy
difference means a strong binding interaction between the
nearest Na vacancy and the halogen atom, which means the
Table 3 Migration energy of Na ion diffusion in t-Na47P16S63
Diffusion path Path 1 (Na II to Na I) Path 2 (Na II to Na II)
This work B68 meV 118.8 meV
Yu et al.29 70 (76) meV 123 meV
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Table 4 Binding energy of the defect pairs, migration energy, calculated Our results demonstrate the Na vacancy would circularly escape
activation energy according to eqn (4) and simulated activation energy from the Br substitution and get trapped by durative XS VNa 0
from AIMD calculations
dissociation and association during the whole MD simulation at
Binding Migration Activation Activation energy elevated temperatures, which implies the feasibility of eqn (4).
energy energy energy from MD simulation To explore the influence of halogen atoms on Na ion
Structure (meV) (meV) (meV) (meV)
diffusion in halogen doped t-Na3PS4 structures, we constructed
t-Na47P16S63F 221.6 B68 B289.6 260.9 the charge difference plot by using Bader charge analysis codes.51
t-Na47P16S63Cl 190.7 B68 B258.7 248.7
t-Na47P16S63Br 172.7 B68 B240.7 215.6 The atomic charge difference is calculated by the following:
t-Na47P16S63I 244.1 B68 B312.1 287.3
Dr = rtotal  ratom, (7)

dissociation energy takes an important role in the diffusion of
the Na vacancy. In this case, successful Na vacancy hopping
is achieved by Na vacancy dissociation from the nearest
halogen atoms and its migration through the PS43 skeleton,
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where rtotal and ratom are the total charge density of the system
and the superposition of atomic charge densities, respectively.
Fig. 4 displays the 3D charge difference of Br-doped t-Na3PS4
and the 2D charge difference slice along the plane passing

as described by eqn (4) in the manuscript. However, among the through the Na vacancy, the Br substitution and the nearest
halogen doped structures, the BrS VNa 0
defect pair has the P atom, showing obvious charge transfer between P atoms and
lowest binding energy of 172.7 meV, resulting in the lowest S atoms or Br atoms and little charge difference of these Na
activation energy of Na ions in all halogen doped structures, ions. The 2D charge difference slice particularly indicates a
as shown in our DFT calculations. large number of electrons accumulates between the P–S or P–Br
Considering the feasibility of eqn (4), with the existence of bonds, together maintaining the covalent states of the PS43 or
both Na ion vacancies and halogen dopant substitutions inside PS3Br3 tetrahedrons. It shows that the electron accumulation
t-Na3PS4, it is worth for us to check the dynamic statistic of the between P and Br is smaller than that between P and S in the
Na vacancy distribution. As the total activation energy of Na ion remote positions, indicating weaker interaction of P–Br bonds.
diffusion is ideally divided into two parts, described in eqn (4), Meanwhile, at lower isosurface values (i.e., 0.002 e Bohr3),
i.e., the dissociation energy that the Na vacancy need to escape obvious charge deficiency around Na ions was observed,
from the nearby halogen substitution and the migration energy meaning electron transfer from Na atoms to the PS43 skeleton,
of the Na ion in vacancy containing t-Na3PS4, it is necessary to as also demonstrated by the remaining less electron distribution
track the Na vacancy to see whether it keeps undergoing
association and dissociation processes with the halogen atom
during the whole simulation. Through checking the energy of
different XS VNa 0
orderings, it is found the energy differences
are quite small (o2 meV per atom) in all the halogen doped
cases, providing the possibility of Na vacancy hopping inside
halogen doped t-Na3PS4. This is demonstrated by the even
Na ion probability distribution network shown in Fig. 2(b).
To check whether the Na vacancy becomes re-trapped by the
halides during the simulation, we set 48 equal sized 3.5 Å cubic
regions to take the likelihood of Na vacancies in the
Na47P16S63Br structure and count the distribution of Na vacan-
cies at the central cubic region near the Br atom (B3.1 Å), the
distribution of Na vacancies at the remote cubic region remote
from the Br atom (B9.1 Å), and the distribution of Na vacancies
at the other 46 cubic regions in the AIMD simulation. The
distribution is averaged for each cubic region as the definition
of the frequency ratio of observed Na vacancies inside the cubic
region to the number of simulation steps (2000 steps). Shown
in Table S1 (ESI†), it is found the Na vacancy sites near the
halogen atom have a much larger possibility compared to those
remote from the Br atom at 600 K, while nearly the same
possibilities of Na vacancies near the Br atom and remote from Fig. 4 (a) 3D charge difference plot of the t-Na47P16S63Br structure along
the Br atom are observed at elevated temperatures, which could the (1, 1, 0) view direction. The yellow region indicates electron gain, and
the blue indicates electron loss. The isovalue is 0.01 e Bohr3. The silver
be ascribed to the higher thermal energy increasing the hopping
balls represent Na atoms, orange ones represent S atoms, brown ones
possibility of Na vacancies to overcome the large dissociation represent Br atoms, and purple ones represent P atoms. (b) The corres-
energy from Br substitution, showing even distributions of ponding 2D charge difference slice along the plane passing through the Na
Na vacancies in other cubic regions at elevated temperatures. vacancy, the Br substitution and the nearest P atom.

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 View Article Online

PCCP Paper

Table 5 The electron distribution of the PS3X3 tetrahedrons and corresponding bond lengths of P–X (X represents different halogen dopants) and P–S.
The term ‘‘neighbor’’ means the nearby positions (o3.5 Å) while ‘‘remote’’ means the relatively separated positions (46.5 Å)

Electron distribution (electrons) Bond length (Å)

X Neighbor P Remote P Neighbor S Remote S Neighbor Na Remote Na P–X P–S
F-case 7.816 3.355 3.815 6.817 6.916 0.175 0.169 1.66 2.02
Cl-case 7.564 3.696 3.811 6.809 6.915 0.177 0.169 2.23 2.01
Br-case 7.476 3.790 3.808 6.814 6.915 0.179 0.169 2.42 2.01
I-case 7.316 3.946 3.806 6.810 6.918 0.182 0.169 2.61 2.02

around Na ions in Table 5. Herein, the electron numbers in all
studied cases are calculated by integrating the electron density in
each Bader volume defined as the boundary of the surface through
which the charge density gradient has a zero flux. The large
electron loss indicates the ionic state of these Na atoms inside
Published on 18 July 2018. Downloaded on 10/31/2023 10:13:12 AM.
Chu et al.31 demonstrated the successful synthesis of a stable
Cl-doped Na3PS4 superionic conductor. Due to the large similarity
among these halogen doped t-Na3PS4 structures, it is expected that
other halogen doped samples can be synthesized under similar
synthesis conditions.

the structures. Furthermore, we investigated the Na ionic conduction with a

Through local charge transfer analysis for different halogen
doped cases, shown in Table 5, the charge transfer for F, Cl, Br
and I atoms becomes smaller and smaller, in accordance with
the variation of electronegativities of these halogen dopants.
A relatively smaller electronegativity property of the dopants
may benefit Na ion diffusion because of weaker Na–halogen
interaction. However, the larger bond length between P atoms
and heavier halogen atoms may cause local tetrahedron exten-
sion and lattice distortion and restrict Na ion fast transport.
We conjecture these two factors would affect Na ion diffusion
in a contrary way, eventually rendering Br substitution most
beneficial for Na ion transport with minor charge difference
of adjacent P atoms compared with the remote ones. We also
plot the electron density of states for different halogen doped
t-Na3PS4, shown in Fig. S2 (ESI†), all of which have band gaps
larger than 2 eV as the merit of good solid electrolytes in Na ion
batteries.
To examine the phase stability of halogen doped t-Na3PS4,
we constructed the corresponding compositional phase diagrams
at 0 K (see Fig. S3 (ESI†) for each halogen doped case). Apparently,
the phase diagrams for these halogen doped structures are very
similar. At 0 K, the Gibbs energy variations during the formation of
halogen doped t-Na3PS4 (E = 0.002 eV per atom for the F doped
structure, and E = 0.005 eV per atom for the Cl, Br and I doped
structures) are slightly positive, i.e., the t-Na47P16S63X (X represents
F, Cl, Br or I) material tends to decompose into P2S5, Na2S, and
NaX with the following reaction:
higher concentration of halogen atom substitution. By replacing
two of the 48 S atoms with Br atoms while introducing two Na ion
vacancies inside t-Na46P16S62Br2, it introduces 4.16% Na ion
vacancies via 3.12% Br doping in the t-Na3PS4 structure. Based
on the energy minimization criteria, it is found that two
BrS VNa0
defect pairs prefer to keep away from each other in
the supercell. When the concentration of defect pairs doubles
(i.e., t-Na46P16S62Br2), the decomposition energy is calculated to
be 0.010 eV per atom, which is still low and indicates
t-Na46P16S62Br2 could be synthesized at elevated temperatures.
We also conducted ab initio MD simulations for t-Na46P16S62Br2
at different temperatures, and the results of Na ionic conduc-
tivities are given in Fig. 5. Compared with the result of 1.56%
Br-doped t-Na3PS4, the 3.12% Br-doped case depicts a
higher Na ionic conductivity, with a value as considerable as
5.42 mS cm1 at room temperature. The certain increase of Na
ionic conductivity is attributed to the larger change in Na ion
hopping provided by more Na ion vacancies and hence
the enhancement of the pre-exponential factor s0 in eqn (3).
Meanwhile, we noted that when the Na vacancy concentration
doubles with higher Br doping, the calculated Na ionic
conductivity increases more than 100% from 2.37 mS cm1 to

Na47P16S63X - P2S5 + Na2S + NaX.

This small energy increase will be compensated for at elevated
temperature due to entropy effects, leading to stable halogen
doped structures. Actually many experimentally synthesized
sulphide solid-state electrolytes are predicted to be unstable
at 0 K by DFT calculations. For example, the fast conductors
Li10GeP2S12 and Na10SnP2S12 have decomposition energies
(energies above hull) of 0.025 eV per atom52 and 0.007 eV per
atom,53 respectively. However, considering the product of the
Boltzmann constant kT as a value of 25.7 meV per atom,
at room temperatures, entropy contributions may reduce the Fig. 5 Arrhenius plot for t-Na47P16S63Br and t-Na46P16S62Br2 from AIMD
Gibbs energy and stabilize these meta-stable solid-state electrolytes. simulations.

This journal is © the Owner Societies 2018 Phys. Chem. Chem. Phys., 2018, 20, 20525--20533 | 20531

Paper
5.42 mS cm1. This nonlinear increase may be ascribed to more
concerted and correlative diffusion events participating in the
Na ion diffusion between these two XS VNa 0
defect pairs. The
extracted activation energy for diffusion is 204.9 meV, close to
that of 1.56% Br-doped t-Na3PS4. The similar value of the
activation energy at two different Br doping concentrations
indicates that Na ions would keep their diffusion pathway at
the dilute Na ion vacancy concentration, which demonstrates
the practicability of eqn (4).
Conclusions
We calculated the Na ionic conductivity in pristine and halogen
(F, Cl, Br, and I) doped tetragonal-Na3PS4 superionic conductors
through ab initio molecular dynamic simulations. We demon-
Published on 18 July 2018. Downloaded on 10/31/2023 10:13:12 AM.
strated that the Na ionic conductivity of pristine t-Na3PS4 is only
about 0.01 mS cm1, while a much higher Na ionic conductivity
could be achieved with the introduction of Na ion vacancies by
a halogen doping strategy. A Na ionic conductivity as high as
2.37 mS cm1 is predicted for Br-doped t-Na3PS4. It was found
that the introduction of halogen substitution and Na ion vacan-
cies has little effect on the overall structure of pristine t-Na3PS4,
which shows a 3D Na ion diffusion path. The lowest defect
binding energy is in the Br-doped t-Na3PS4 structure because of
the relatively weak bond strength of Na–S or Na–Br bonds, which
leads to the lowest activation energy of Na ions and the highest Na
ionic diffusivity/conductivity in all halogen doped cases. A further
higher Na ionic conductivity and lower activation energy could
be reached by introducing higher halogen atom substitution
concentrations. The AIMD calculations suggest Br-doped t-Na3PS4
as a very promising Na-ion solid-state superionic conductor near
ambient temperature.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Mr He Huang acknowledges the financial supports from the
Joint School of XJTU and HKUST. The project is supported by
the 111 project (no. D16002) from the State Administration of
Foreign Experts Affairs and the Ministry of Education, PRC.
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Phys. Chem. Chem. Phys., 2018, 20, 20525--20533 | 20533