Journal: ChemSusChem

Manuscript number: cssc.201902943

Title: "Transition Metal Phosphorus Trisulfides and its Vacancy Defects: Emergence of a New
Class of Anode Material for Li-Ion Batteries"

Author(s): Jana, Rajkumar; Chowdhury, Chandra; Datta, Ayan

Dear Dr. Halgard Staesche,

Thank you very much for considering a revised version of the manuscript (ID: cssc.201902943).
Please find our revised manuscript titled: " Transition Metal Phosphorus Trisulfides and its
Vacancy Defects: Emergence of a New Class of Anode Material for Li-Ion Batteries ". We have
read the reviewer’s comments very carefully and have responded by making revisions and
providing further explanation and clarification. Our responses are given below. We have copied
verbatim the reviewers’ comment and followed with our response (in bold italics). We thank all
reviewers very much for their useful and helpful comments and valuable suggestions to improve
the quality of the paper and enrich our knowledge on the work to a large extent.

REVIEWER’S COMMENTS:
Reviewer 1: The manuscript titled Transition Metal Phosphorus Trisulfides and its Vacancy
Defects: Emergence of a New Class of Anode Material for Li-Ion Batteries by Rajkumar Jana et
al. demonstrated that the limitations of commercial anode materials (i.e. low specific capacity,
large volume change and high lithium diffusion barrier as well as nucleation) can be
circumvented using TMPS3 monolayer surfaces. The study reveals that lithium (Li) binds
strongly to TMPS3 monolayers (-2.31 eV) (without any distortion of surface), with Li@TMPS3
exhibiting enhanced stability compared to other 2D analogues (graphene, phosphorene, MXenes,
transition metal sulfides and phosphides). The binding energy of lithium is overwhelmingly
enhanced with vacancy defect. The vacancy mediated TMPS3 surfaces show further
amplification of Li binding energy and theoretical specific capacity from -2.03 eV to -2.32 eV
and 441.65 to 484.34 mA h g-1 for MnPS3 surface. Most importantly, minimal change in volume
(less than 2%) after lithiation makes TMPS3 monolayers more effective candidate in LIBs. The
ultralow lithium diffusion barrier (0.08 eV) compared to other existing commercial anode
material proves the superiority of TMPS3. In general, this work seems to be very interesting and
can be considered for acceptance provided that authors can well address the following questions.

Response: First of all, we are thankful to the reviewer for his/her valuable comments and
considering the manuscript in the top 20% importance list in the field and recommending it
for the publication in ChemSusChem. We highly appreciate his/her suggestion to improve the
quality of the manuscript.

Comment 1. Please comment on the long term stability of Transition Metal Phosphorus
Trisulfide as Anode Material for Li-Ion Batteries. More characterizations need to provide.

Response: We are grateful to the reviewer for his/her valuable comment on the long-term
stability of the Transition Metal Phosphorus Trisulfide as anode materials for LIBs. We have
already discussed about the stability of the Transition Metal Phosphorous Trisulfide as anode
material for LIBs in terms of negligibly small volume expansion as well as P-S and TM-S
bond expansion (please see Figure 4a-b in the revised manuscript and in “Results and
Discussion” section “ Practical application of several new electrode materials is hindered to a
large extent by enormous volume fluctuation upon lithiation. ………………… Certainly, such
a negligibly small volume change (0.6%) ensures the practical usability of MnPS 3 as an anode
material. More importantly, change of average P-S and TM-S (TM = Mn, Fe, Co, Ni) bond
lengths are also considered as vital parameters to account for the structural stability of the
electrode material. ……………….. Hence, even though all the TMPS 3 surfaces are quite
promising in terms of structural stability, MnPS 3 turns out to be a superior electrode material
for LIB application.”).
However, according to your valuable suggestion, we have performed ab initio
molecular dynamics (AIMD) simulation using VASP simulation package, of pristine and
vacancy mediated TMPS3 surfaces as well as lithiated MnPS3 surfaces at 300 K for the time
period of as long as 25 ps and from the root mean square deviation plot, it is evident that the
average positional fluctuation of each atom equilibrate within a few fraction of picoseconds
which vividly suggests the exceptionally high dynamic stability of the materials with no
structural degradation under experimental condition (please see Figure 4c-d and Figure S7 in
the revised manuscript and supporting information). Besides, we have also calculated the
radial distribution function {g(r)} between P-S and TM-S pairs for these surfaces as well as
between P-S, Mn-S and S-Li pairs for lithiated MnPS 3 surfaces (where TM = Mn, Fe, Co, Ni)
(please see Figure S9-S10 in the revised supporting information). The radial distribution
function {g(r)} between TM-S, P-S and S-Li pairs maximize at the distances which are very
close to the DFT calculated bond lengths (please see Table S1). Hence, based on the good
agreement between DFT optimized and AIMD equilibrated structures of pristine as well as
lithiated TMPS3 surfaces, it can be concluded that the modeled lithiated and non-lithiated
surfaces are highly stable during Li insertion and deinsertion indicating their long-term
stability during charge-discharge. Please see Figure 4c-d, Figure S7-9, S16 and Table S1 as
well as in Results and Discussion” section in the revised manuscript. “To check dynamic as
well as thermal stability of the TMPS 3 surfaces, we have performed ab initio molecular
dynamics (AIMD) simulation (using VASP simulation package) of TMPS 3 surfaces as well as
lithiated MnPS3 surface at 300 K for the time period of as long as 25 ps with a time step of 0.5
fs and from the root mean square deviation plot, it is evident that the average positional
fluctuation of each atom equilibrate within a few fraction of picoseconds which vividly
suggests the exceptionally high dynamic stability of the materials with no structural
degradation under experimental condition (Figure 4c-d and Figure S7). Besides, we have also
calculated the radial distribution function {g(r)} between P-S and TM-S pairs for these
surfaces as well as between P-S, Mn-S and S-Li pairs for lithiated MnPS3 surface (where TM
= Mn, Fe, Co, Ni) (Figure S8 and S9). The radial distribution function {g(r)} between TM-S,
P-S and S-Li pairs maximize at the distances which are very close to the DFT calculated bond
lengths (Table S1). Hence, based on the good agreement between DFT optimized and AIMD
equilibrated structures of pristine as well as lithiated TMPS 3 surfaces, it can be concluded that
the modeled lithiated and non-lithiated surfaces are highly stable during Li insertion and
deinsertion indicating their long-term stability during charge-discharge.” and “ Moreover,
AIMD tests of vacancy defect MnPS3 surface (with average positional fluctuations of each
atom within a few fraction of picoseconds) also overwhelmingly exhibit the dynamic as well as
thermal stability of these surfaces (Figure S16).”
Figure 4: Variation of volume change (in percentage) as a function of adsorbed Li content, x,
in (TMPS3)Lix, (b) change of TM-S (TM = Mn, Fe, Co, Ni) and P-S bond lengths (in
percentage) before and after Li adsorption, (c) plot of RMSD with time at 300 K for MnPS 3
monolayer surface, (d) plot of RMSD with time at 300 K for lithiated MnPS 3 monolayer
surface, (e) voltage profile with respect to adsorbed Li content, (f) average OCV and OCV at
fully lithiated TMPS3 surfaces.

Figure S7: Plot of RMSD with time at 300 K for TMPS3 monolayer surfaces (a) FePS3, (b)
CoPS3, (c) NiPS3.
Figure S8: Plots of radial distribution function {g(r)} between P-S and TM-S pairs for TMPS 3
monolayer surfaces at 300 K (a) MnPS3, (b) FePS3, (c) CoPS3, (d) NiPS3.

Figure S9: Plot of radial distribution function {g(r)} between P-S, Mn-S and S-Li pairs for
lithiated MnPS3 surface at 300 K.
Figure S16: Plot of RMSD with time at 300 K for vacancy defect MnPS 3 surfaces (a) Single
vacancy, (b) dual vacancy; plots of radial distribution function {g(r)} between P-S and Mn-S
pairs for vacancy defect MnPS3 surfaces at 300 K (c) single and (d) dual vacancy.

Table S1: Comparison of bond distances between DFT optimized and AIMD equilibrated
structures of lithiated and non-lithiated pristine and vacancy mediated TMPS3 surfaces.
Surface P-S pairs (Å) TM-S pairs (Å) S-Li pairs (Å)
DFT AIMD DFT AIMD DFT AIMD
MnPS3 2.04 2.05 2.61 2.55 - -
FePS3 2.04 2.04 2.52 2.44 - -
CoPS3 2.09 2.05 2.31 2.24 - -
NiPS3 2.06 2.06 2.44 2.44 - -
Single vacancy MnPS3 2.04 2.06 2.57 2.52 - -
Dual Vacancy MnPS3 2.10 2.05 2.51 2.45 - -
Lithiated MnPS3 2.05 2.05 2.59 2.55 2.44 2.45

We thank the reviewer for his/her valuable comment on providing more

characterizations of the TMPS3 monolayers. Though from the perspective of experimental
synthesis of these monolayer 2D surfaces, one should provide Raman, TEM (HRTEM,
SAED), SEM, PXRD characterizations as these are the basic characterizations required to
prove different modes of vibrations and hence nature of bonding connectivity between present
elements of the surface, morphology, surface exposed plane as well as nature of crystallinity
(i.e. single or poly crystal nature), crystal system and phase of the synthesized material . But
here we have investigated the applicability of Transition Metal Phosphorous Trisulfides as
anode material for LIB application using density functional theory (DFT) based on first
principle calculations. We do agree with the importance of synthesizing the compounds by
ourselves and characterize it. But, being a purely computational group, it is quite
unconventional for us to synthesize those surfaces and do the characterizations. However,
monolayer of a few of these surfaces (FePS3, NiPS3) have already been synthesized and
characterized through Raman, SEM and TEM ((a) Lee et al., Nano Lett. 2016, 16, 7433-7438;
(b) Cheng et al., Adv. Mater. 2018, 30, 1707433; (c) Kuo et al. Sci. Rep. 2016, 6, 20904). On
the otherhand, CoPS3 and MnPS3 have been previously synthesized both in its bulk as well as
a few-layered surfaces and characterized using raman spectroscopy, TEM and SEM ((a)
Mayorga-Martinez et al., ACS Appl. Mater. Interfaces 2017, 9, 12563−12573; (b) Long et al.,
ACS Nano 2017, 11, 11, 11330-11336; (c) Kumar et al., Journal of Materials Chemistry C
2019, 7, 324-329, (d) ACS Sens. 2020, 5, 2, 404-411, (e) Latiff et al., FlatChem 2018, 12, 1-9,
(f) Cheng-Feng et al., Nano-micro letters 2018, 10, 67). Therefore, all the TMPS 3 surfaces
(which are discussed in the current manuscript) and their characterizations (i.e. Raman, TEM
and SEM) are well explored in the literature. Above all, this article is based on purely
computational DFT study. All of our predictions are also based on DFT study to rationalize
the importance of this class of materials as next generation anode material for LIB
applications. This DFT study with high-level theory overwhelmingly supports our prediction
and conclusion completely. Apart from that, these predictions are on par with experimental
evidences in the literature as one of these surfaces, FePS3, has already shown high
performance for LIB application as an anode material (Fan et al., J. Mater. Chem. A, 2019, 7,
1529–1538) and hence these predictions are not completely supportless from experiments.
Therefore, we do believe that our high-level theoretical study is strongly supported by
experiment from literature and most importantly self-supportive and conclusive from the
viewpoint of theoretical prediction.

Comment 2. More characterizations on TMPS3 monolayer need to provide. For example, Raman,
SEM, TEM etc.

Response: We are thankful to the reviewer for his/her valuable comment on the
characterizations (i.e. Raman, SEM, TEM) of the TMPS 3 monolayers. Though from the
perspective of experimental synthesis of these monolayer 2D surfaces, one should provide
Raman, TEM (HRTEM, SAED), SEM characterizations as these are the basic
characterizations required to prove different modes of vibrations and hence nature of bonding
connectivity between present elements of the surface, morphology, surface exposed plane as
well as nature of crystallinity (i.e. single or poly crystal nature). But here we have investigated
the applicability of Transition Metal Phosphorous Trisulfides as anode material for LIB
application using density functional theory (DFT) based on first principle calculations. We do
agree with the importance of synthesizing the compounds by ourselves and characterize it.
But, being a purely computational group, it is quite unconventional for us to synthesize those
surfaces and do the characterizations. However, monolayer of a few of these surfaces (FePS 3,
NiPS3) have already been synthesized and characterized through Raman, SEM and TEM ((a)
Lee et al., Nano Lett. 2016, 16, 7433-7438; (b) Cheng et al., Adv. Mater. 2018, 30, 1707433; (c)
Kuo et al. Sci. Rep. 2016, 6, 20904). On the otherhand, CoPS3 and MnPS3 have been
previously synthesized both in its bulk as well as a few-layered surfaces and characterized by
using Raman spectroscopy, TEM and SEM ((a) Mayorga-Martinez et al., ACS Appl. Mater.
Interfaces 2017, 9, 12563−12573; (b) Long et al., ACS Nano 2017, 11, 11, 11330-11336; (c)
Kumar et al., Journal of Materials Chemistry C 2019, 7, 324-329, (d) ACS Sens. 2020, 5, 2,
404-411, (e) Latiff et al., FlatChem 2018, 12, 1-9, (f) Cheng-Feng et al., Nano-micro letters
2018, 10, 67). Therefore, all the TMPS3 surfaces (which are discussed in the current
manuscript) and their characterizations (i.e. Raman, TEM and SEM) are well explored in the
literature. Above all, this article is based on purely computational DFT study. All of our
predictions are also based on DFT study to rationalize the importance of this class of materials
as next generation anode material for LIB applications. This DFT study with high-level theory
overwhelmingly supports our prediction and conclusion completely. Apart from that, these
predictions are on par with experimental evidences in the literature as one of these surfaces,
FePS3, has already shown high performance for LIB application as an anode material (Fan
et al., J. Mater. Chem. A, 2019, 7, 1529–1538) and hence these predictions are not completely
supportless from experiments. Therefore, we do believe that our high-level theoretical study is
strongly supported by experiment from literature and most importantly self-supportive and
conclusive from the viewpoint of theoretical prediction. We have included a few sentences in
the revised manuscript. Please see “For example, NiPS 3 and FePS3 have been successfully
exfoliated to monolayers and characterized through Raman, SEM, TEM, XRD and AFM” and
“Besides, layered CoPS3 and MnPS3 have also been successfully synthesized and characterized
using various spectroscopic and microscopic techniques (i.e. Raman, XRD, SEM, TEM,
AFM).” in “Introduction Section” section in revised manuscript.

Comment 3. Whether Vacancy Defects can be deliberately controlled? If yes, how to control the
concentration of Vacancy Defects? The dependence of Battery performance on the Vacancy
Defects need to discuss as well.

Response: We thank the reviewer for his/her valuable comment on Vacancy Defects. It is quite
difficult to control vacancy defects deliberately. However, depending on synthetic procedures,
type and concentration of vacancy defects can be controlled to a larger extent. However, there
are a few synthetic procedures (under fluctuating growth conditions such as Chemical Vapor
Transport (CVT), Chemical Vapor deposition (CVD)) which will inevitably lead to vacancy
defects formation. On the contrary, concentration of vacancy defects can also be deliberately
introduced and controlled by various post-synthesis approaches i.e. ion and /or electron
irradiation, plasma treatments, high temperature annealing of the synthesized Transition
metal chalcogenides in presence of different gasses. However, both theoretically and
experimentally it has been demonstrated that precise control over these techniques can lead to
achieve complete control over the concentration of Vacancy Defects in the Transition metal
chalcogenides (i.e. Transition metal sulfides, disulfides, phosphides, phosphosulfides) [ (a) Lin
et al., 2D Mater. 2016, 3, 022002; (b) Komsa et al., Phys. Rev. Lett. 2012, 109, 035503; (c)
Komsa et al., Phys. Rev. B 2013, 88, 035301; (d) Zan et al., ACS Nano 2013, 7, 10167; (d)
Chow et al., ACS Nano 2015, 9, 1520; (e) Tongay et al., Sci. Rep. 2013, 3, 2657; (f) Mignuzzi
et al., Phys. Rev. B 2015, 91, 195411; (g) Nan et al., ACS Nano 2014, 8, 5738; (h) Wei et al.,
AIP Adv. 2014, 4, 123004; (i) Kim et al., ACS Nano 2014, 8, 2774; (j) Yamamoto et al., Nano
Lett. 2015, 15, 2067; (k) Castellanos-Gomez et al., Nano Lett. 2012, 12, 3187]. Please see
“Usually, under most commonly used fluctuating growth conditions such as Chemical Vapor
Transport (CVT), Chemical Vapor deposition (CVD), the types and concentration of vacancy
defects cannot be precisely controlled. However, very accurate and precise control over
various types of vacancy defect formation can be achieved by following different post-synthesis
approaches i.e. ion and /or electron irradiation, plasma treatments, high temperature
annealing of the synthesized Transition metal chalcogenides in presence of different gasses”
in “Results and Discussion” Section in the revised manuscript.

The dependence of battery performance on the vacancy defects has already been
discussed in the manuscript to some extent (please see “Unlike graphene, here introduction of
vacancy defect substantially enhances the Li binding ability……………………… Single
vacancy defect MnPS3 preserves the low OCV of the pristine surface whereas dual vacancy
shows a slight increase.” in “Results and Discussion” section. However, according to your
valuable suggestion, we have other factors which govern the battery performance. The battery
performance of an anode material mainly depends on following factors a) stronger Li binding
ability (more than Li cohesive energy), (b) specific capacity and Open Circuit Voltage (OCV),
(c) charge-discharge rate, (d) structural stability during charge-discharge (i.e. Li insertion and
deinsertion). Among these governing factors, we have already discussed in the manuscript
regarding (a) Li binding ability of different vacancy defect MnPS 3 surfaces (please see Figure
6b and d and “Results and Discussion” part “Unlike graphene, here introduction of vacancy
defect substantially enhances the Li binding ability (binding energy increases from -2.03 to -
2.32 eV) ……………. Li binding energy is still much higher than its bulk cohesive energy (-
1.63 eV) indicating positive effect of vacancy defects on the surface. Therefore, in terms of Li
binding ability MnPS3 with single vacancy defect proves to be superior than the dual one.”).
We have also discussed about the second part i.e. specific capacity and OCV of vacancy defect
MnPS3 surfaces (please see Figure 6e-f and “Results and Discussion” part “Besides, both the
single and dual vacancy defect MnPS3 surfaces can accommodate 24 atoms of Li similar to the
pristine surface……… The average OCV for MnPS 3 surfaces are 0.97 V and 1.01 V
respectively for single and dual vacancy whereas that for OCVs at fully lithiated condition are
0.53 V and 0.8 V….…………… A specific capacity of 462.04 and 484.34 mA h g -1 was
observed for single and dual vacancy respectively. Therefore, vacancy defects in TMPS 3
monolayers turns out to be quite beneficial towards application in LIBs as an anode
material.”).
But according to your valuable suggestion we have now discussed the other two battery
performance governing criteria (i.e. charge-discharge rate and structural stability during
charge-discharge) of vacancy defect MnPS3 surfaces in details in revised manuscript (please
see Figure 6g-i and Results and Discussion part “ The charge-discharge rate of vacancy
defects MnPS3 surfaces have been investigated by calculating Li diffusion barriers on the
surfaces. As adsorption of Li is more favorable on vacancy site (A site) compared to tri
coordinated B site, the diffusion of Li has been considered between two adjacent equivalent
vacancy sites (Figure S13, S15 and Table S2). Single and dual vacancy defect MnPS 3 exhibit
relatively low diffusion barriers of 0.24 and 0.21 eV respectively (Figure 6g). These very low Li
diffusion barriers of vacancy defect MnPS3 surfaces prove their suitability towards LIB
application. To check the structural stability of the vacancy defect MnPS 3 monolayer surfaces
we have studied the percentage of volume change as a function of lithiation (Figure 6h). As
depicted from Figure 6h there is negligibly small expansion of volume (less than 2%) of
vacancy defect MnPS3 surfaces upon gradual insertion of Li atoms on the surfaces. The
maximum volume expansion for single vacancy defect is 0.88% while that for dual vacancy it
is 1.7% upon full lithiation. Besides, the average expansion of P-S and TM-S bond lengths are
only 0.88%, 0.08% and 0.66%, 0.64% respectively for single and dual vacancy MnPS 3 surface
(Figure 6i). Evidently, such as negligibly small change of volume and bond lengths
demonstrates the exceptional stability of these vacancy defect surfaces upon lithiation (i.e.
during charge-discharge process). Moreover, AIMD tests of vacancy defect MnPS 3 surface
(with average positional fluctuations of each atom within a few fraction of picoseconds) also
overwhelmingly exhibit the dynamic as well as thermal stability of these surfaces (Figure
S16)”.

Figure 6: Vacancy defect structures of MnPS3 surface and corresponding more stable Li
adsorption sites (A site) (a) single vacancy, (b) Li adsorbed single vacancy defect surface, (c)
dual vacancy, (d) Li adsorbed dual vacancy surface (dotted encircles indicate the vacancy
positions); (e) voltage profile with respect to Li content (y = 0.25 and 0.50 respectively for
single and dual vacancy), (f) average OCV and OCV at fully lithiated vacancy defect MnPS 3
surface, (g) the migration paths as well as diffusion barriers for Li motion over vacancy defcet
MnPS3 surfaces, (h) Variation of volume change (in percentage) as a function of adsorbed Li
content (y = 0.25 and 0.50 respectively for single and dual vacancy), (i) change of Mn-S and
P-S bond lengths (in percentage) before and after Li adsorption for vacancy defect MnPS 3
surfaces.

Figure S13: Less stable Li adsorption sites (B site) on vacancy defect MnPS 3 surfaces (a)
single vacancy, (b) dual vacancy.
Figure S15: Schematic presentation of different diffusion paths of Li over (c) single and (d)
dual vacancy defect MnPS3 surfaces.

Figure S16: Plot of RMSD with time at 300 K for vacancy defect MnPS 3 surfaces (a) Single
vacancy, (b) dual vacancy; plots of radial distribution function {g(r)} between P-S and Mn-S
pairs for vacancy defect MnPS3 surfaces at 300 K (c) single and (d) dual vacancy.

Table S2: Binding energies of Li on different sites of vacancy defect MnPS3 surfaces.
Vacancy Defect Surface Li adsorption site Binding Energy (eV)
Single Vacancy A site -2.32
B site -0.89
Dual Vacancy A site -1.95
B site -1.56
Comment 4. Related work on other 2D materials based energy applications, such as, SnO2−x,
Angewandte Chemie International Edition 57 (29), 8901-8905; graphite/electrolyte interface in
lithium-ion batteries, Nano Energy 34, 131-140; A black/red phosphorus hybrid, Journal of
Materials Chemistry A 5 (14), 6581-6588; and black phosphorus materials, Nanoscale 9 (36),
13384-13403; could be compared and cited in the revision. Advantage and disadvantage between
TMPS3 and those 2D materials need to discuss.

Response: We thank the reviewer for reviewing this manuscript and providing valuable
comments and suggestions. Even though all of the above-mentioned pioneering works are
related to our manuscript, most of these are purely based on experimental findings. However,
according to your valuable suggestion, we have compared these 2D materials with our work
(i.e. TMPS3 surfaces) and provided a comparative study of advantage and disadvantage
between TMPS3 and those 2D materials and cited these works in our revised manuscript
Please see “The battery performance of TMPS3 class of materials are comparable to those of
other classes of 2D materials such as SnO2-x/C, graphite with 0.5 wt% PTSI as well as black
and red phosphorous. Prof. Zhang et al. demonstrated SnO 2-x nanoparticle grafted on carbon
nanofibers with high reversible capacity, ultrahigh cyclic stability and exceptional rate
capability can be a potential candidate not only in LIB but also in sodium ion battery (SIB)
applications. In another study, they showed that mere modification in graphite/electrolyte
interface with PTSI additive remarkably enhances the specific capacity as well as cycling
stability compared to graphite. However, even though SnO 2-x/C composite exhibits higher
specific capacities for SIB application, graphite/electrolyte interface with 0.5 wt% PTSI
demonstrates much lower specific capacity compared to pristine and vacancy defect TMPS3
surfaces for LIBs. When TMPS3 class of materials are compared to another immerging class
of anode LIB material black and /or red phosphorous, it is observed that even though
monolayer black phosphorous (phosphorene) holds very high specific capacity, the Li binding
ability of single layer phosphorene is less (-1.80 eV) in comparison with TMPS 3 (average Li
binding energy = -2.10 eV) surfaces. Pristine and vacancy defect TMPS 3 monolayer surfaces
are much superior in terms of charge-discharge rate in comparison with phosphorene. The
predicted Li diffusion barrier for single layer phosphorene is 0.76 eV while that for MnPS 3
surface 0.08 eV (pathway-I). Single and dual vacancy defect MnPS 3 also exhibit superiority
(0.24 eV, 0.21 eV respectively) over phosphorene. Therefore, TMPS 3 class of materials hold
strong promise towards LIBs as anode material.” In “Results and Discussion Section” in
revised manuscript.
Please see references 35a, b, c and d in the revised manuscript as citation of the above-
mentioned work.

Comment 5. Please comment on the potential commercial applications of TMPS3 for the future
batteries?

Response: We are thankful to the reviewer for his/her valuable comments on this manuscript.
Pristine and vacancy defect TMPS3 monolayer surfaces hold great promise in commercial
application in future LIB technologies. Currently graphene (single layer graphite) is the
commercial anode material for LIB application. Interestingly, these TMPS 3 surfaces not only
have all of the advantages of graphene but also can overcome all the shortcomings of
graphene (i.e. low specific capacity, high diffusion barrier, weak Li adsorption resulting
degradation). Pristine and vacancy defect TMPS 3 surfaces exhibits stronger Li adsorption
avoiding dendrite formation and degradation, high specific capacity and ultralow diffusion
barrier of Li atom compared to graphene. Not only graphene, TMPS 3 surfaces are comparable
and / or superior to other potential class of anode material in commercial applications for
future batteries. These criteria of TMPS 3 surfaces vividly justifies its potentiality in
commercial application for future batteries.

Comment 6. Besides TMPS3 monolayer, whether authors investigate the case of TMPS3
multiple layer? Any difference between TMPS3 monolayer and multiple layer?

Response: We thank the reviewer for raising this valuable question which will not only
improve the quality of this manuscript but also enrich our knowledge to a greater extent. Even
though our initial assumption was that multiple layer of TMPS 3 will decrease the battery
performance because of aggregate formation due to overlap between various layers as well as
partial availability of interlayer interface for Li adsorption, but according to your valuable
suggestion we have investigated the case of multilayer (bilayer) for MnPS 3 surface (the best
surface among TMPS3) towards battery performance. It can be found that multilayer (bilayer)
MnPS3 (MnPS3(BL)) is inferior to single layer (monolayer) MnPS 3 (MnPS3(ML)) in terms of
battery performance. Please see Figure 5, Figures S11 and “Along with the monolayers of
TMPS3 surfaces, we have investigated the effect of multiple layers on the battery performance
because introduction of multiple layers can modulate LIB performance to a larger extent. [35d, 36]
As monolayer MnPS3 (MnPS3(ML)) is superior compared to other TMPS 3 surfaces, we have
considered bilayer MnPS3 (MnPS3(BL)) surface to study the effect of multilayer on battery
performance (Figure 5a). Unlike phosphorene, [35d, 36]
MnPS3(BL) exhibits a decrease in Li
binding energy (-1.86 eV) compared to MnPS 3(ML) (-2.03 eV) and hence relatively weaker Li
binding on multilayer surface (Figure 5b and Table 1). However, the adsorption energy of Li
is still higher than the cohesive energy (-1.63 eV) of bulk Li indicating applicability in LIBs.
MnPS3(BL) also demonstrates an amount of 0.99 |e| charge transfer form Li to surface
indicating presence of Li+ in surface adsorbed state (Figure S10 and Table 1). Besides,
MnPS3(BL) can only accommodate a maximum of 36 Li atoms upon full lithiation i.e. only
75% of active sites can be accessed by Li atoms for intercalation due to partial availability of
interlayer interface for Li adsorption. This leads to an enormous decrease in specific capacity
(from 441.65 to 331.24 mA h g-1) (Figure S11). Along with that, OCVs for MnPS 3(BL) ranges
from 1.86 to 0.82 eV as evident from the electrode potential vs intercalated Li content plot
(Figure S12). Figure 5c shows OCV at full lithiation and average OCV for MnPS 3(BL) are
0.82 and 0.95 V respectively which is relatively higher than that of MnPS 3(ML) indicating
inferiority of multiple layer MnPS3 over single layer. When the structural stability of
MnPS3(BL) is investigated, it is observed that the average volume expansion upon gradual
lithiation is 4.3% while that for full lithiation 11.6% (Figure 5d). Besides, the average
expansion of P-S and Mn-S bond lengths are as high as 8.98 and 4.77% (Figure 5e). These
findings clearly demonstrate higher structural instability in MnPS 3(BL) compared to
MnPS3(ML) during Li insertion. MnPS3(BL) displays higher diffusion barriers (0.68 and 0.33
V respectively for pathway-I and II) in comparison with MnPS 3(ML) (0.41 and 0.08 eV)
indicating hindrance in smooth Li motion on surface and hence retardation in facile charge-
discharge rate (Figure 5f and Table 2). Hence, monolayer MnPS3 proves to be much superior
to multiple layer in LIB application.” in “Results and Discussion” section in revised
manuscript.

Figure 5: (a) Bilayer MnPS3 (MnPS3(BL))surface, (b) Li adsorbed MnPS3(BL), (c)

comparison of average OCV and OCV at fully lithiated MnPS3 mono and bilayer surfaces, (d)
Variation of volume change (in percentage) as a function of adsorbed Li content, x, in
MnPS3(BL)/Lix, (e) comparison between the change of Mn-S and P-S bond lengths (in
percentage) before and after Li adsorption for mono and bilayer MnPS3, (f) the diffusion
barriers for Li over MnPS3(BL) surface corresponding to different migration paths.
Figure S10: Top view of CDD plot of Li adsorbed MnPS 3(BL) surface, isodensity value at
surfaces is ±0.001 e/ a.u.3 (Positive: red and Negative: blue) of CDD.

Figure S11: Fully lithiated (with 36 atoms) MnPS3(BL) surface (a) side view, (b) top view.

Figure S12: Voltage profile with respect to Li content MnPS3(BL) surface.

Table 1: Binding energies (Eb), average Li-S distances (dLi-S) and charge transfer (ΔQ) for Li
binding on TMPS3 surfaces at different sites.

TMPS3 Li Eb dLi-S ΔQLi

adsorption (eV) (Å) (|e|)
Sites
MnPS3 -2.03 2.44 1.00
FePS3 -2.31 2.46 0.99
CoPS3 H-Site -1.71 2.52 0.99
NiPS3 -2.29 2.45 0.99
MnPS3(BL) -1.86 2.44 0.99
MnPS3 -1.48 2.50 0.99
FePS3 B-site -2.18 2.48 0.99
CoPS3 -1.62 2.56 0.99
NiPS3 -2.15 2.47 0.99

Table 2: Migration path dependent activation energy barriers (∆E‡) for TMPS3 surfaces.

TMPS3 Activation barrier (∆E‡) (eV)

Migration Path-I Migration Path-II
MnPS3 0.41 0.08
FePS3 0.55 0.20
CoPS3 0.64 0.36
NiPS3 0.59 0.11
MnPS3(BL) 0.68 0.33
Reviewer 2: The manuscript entitled with "Transition Metal Phosphorus Trisulfides and its
Vacancy Defects: Emergence of a New Class of Anode Material for Li-Ion Batteries" proposed a
kind of anode materials (TMPS3) for LIBs. The DFT results and discussions are basically
complete and reasonable, but lack of experimental data to confirm these theoretical predictions.
The current data are insufficient to support the conclusion. My comments are below.

Response: First of all, we are thankful to the reviewer for his/her valuable comments and
considering the manuscript important in the field of Li-ion battery application. We are
grateful to the reviewer for appreciating our DFT study. We highly appreciate his/her
suggestion to improve the quality of the manuscript. However, we beg to differ with the
reviewer regarding his/her comment that lack of experimental data cannot confirm these
theoretical predictions and the insufficiency of the current data to support the conclusion. We
do agree with the fact that we have not shown any experimental results in the manuscript. But
it needs to be rationalized that this manuscript is completely based on theoretical study and
prediction. Most importantly, we have performed the state-of-the-art level theoretical
calculation and proposed our prediction. This DFT study with high-level theory
overwhelmingly supports our prediction and conclusion completely which is already been
appreciated by the reviewer. Besides, being from purely theoretical group it is unconventional
for us to synthesize the compounds and study their LIB performance. Apart from that, these
predictions are on par with experimental evidences in the literature as one of these surfaces,
FePS3, has already shown high performance for LIB application as an anode material (Fan et
al., J. Mater. Chem. A, 2019, 7, 1529–1538) and hence these predictions are not completely
supportless from experiments. Therefore, we do believe that our high-level theoretical study is
strongly supported by experiment from literature and most importantly self-supportive and
conclusive from the viewpoint of theoretical prediction.

Comment 1. No experimental data regarding to the electrochemical performance of these

researched anode materials for LIBs have been found in the current manuscript. As authors said
in the Intro part, several layered TMPS3 materials have been successfully synthesized, the
following difficulty might be how to precisely introduce vacancy defects into these layered
materials. Authors should at least include some experimental data about CV, discharge-charge
profile, cycling stability, etc. Only DFT data may not be enough to confirm these conclusions.

Response: We thank the reviewer for reviewing this manuscript and providing valuable
comments. We do agree with the reviewer’s comment that there might be difficulty in
introducing vacancy defects precisely into these layered materials. However, depending on
synthetic procedures, type and concentration of vacancy defects can be controlled to a larger
extent. Though there are a few synthetic procedures (under fluctuating growth conditions
such as Chemical Vapor Transport (CVT), Chemical Vapor deposition (CVD)) which will
inevitably lead to vacancy defects formation, different types and concentrations of vacancy
defects can also be deliberately and precisely introduced and controlled by various post-
synthesis approaches i.e. ion and /or electron irradiation, plasma treatments, high temperature
annealing of the synthesized Transition metal chalcogenides in presence of different gasses.
However, both theoretically and experimentally it has been demonstrated that precise control
over these techniques can lead to achieve complete control over the different types and
concentrations of Vacancy Defects in the Transition metal chalcogenides (i.e. Transition
metal sulfides, disulfides, phosphides, phosphosulfides) [ (a) Lin et al., 2D Mater. 2016, 3,
022002; (b) Komsa et al., Phys. Rev. Lett. 201, 109, 035503; (c) Komsa et al., Phys. Rev. B
2013, 88, 035301; (d) Zan et al., ACS Nano 2013, 7, 10167; (d) Chow et al., ACS Nano 2015,
9, 1520; (e) Tongay et al., Sci. Rep. 2013, 3, 2657; (f) Mignuzzi et al., Phys. Rev. B 2015, 91,
195411; (g) Nan et al., ACS Nano 2014, 8, 5738; (h) Wei et al., AIP Adv. 2014, 4, 123004; (i)
Kim et al., ACS Nano 2014, 8, 2774; (j) Yamamoto et al., Nano Lett. 2015, 15, 2067; (k)
Castellanos-Gomez et al., Nano Lett. 2012, 12, 3187]. Please see “Usually, under most
commonly used fluctuating growth conditions such as Chemical Vapor Transport (CVT),
Chemical Vapor deposition (CVD), the types and concentration of vacancy defects cannot be
precisely controlled. However, very accurate and precise control over various types of vacancy
defect formation can be achieved by following different post-synthesis approaches i.e. ion
and /or electron irradiation, plasma treatments, high temperature annealing of the synthesized
Transition metal chalcogenides in presence of different gasses.” in “Results and Discussion”
section in revised manuscript.
 We beg to differ with the reviewer comment that “Only DFT data may not be enough to
confirm these conclusions” and his suggestion to include some experimental data. We do
agree with the fact that inclusion of experimental data along with theoretical study will
strengthen the study and conclusion. But it needs to be rationalized that this manuscript is
completely based on theoretical study and prediction. Most importantly, we have performed the
state-of-the-art level theoretical calculation and proposed our prediction. This DFT study with
high-level theory overwhelmingly supports our prediction and conclusion completely which is
already been appreciated by the reviewer. Besides, being from purely theoretical group it is
unconventional for us to synthesize these compounds and study their LIB performance. Apart
from that, these predictions are on par with experimental evidences in the literature as one of
these surfaces, FePS3, has already shown high performance for LIB application as an anode
material (Fan et al., J. Mater. Chem. A, 2019, 7, 1529–1538) and hence these predictions are
not completely supportless from experiments. Therefore, we do believe that our high-level
theoretical study is strongly supported by experiment from literature and most importantly
self-supportive and conclusive from the viewpoint of theoretical study.

Comment 2. AIMD tests are suggested, aiming to study the stability of Li@TMPS3 at room
temperature. The possibility of electrode decomposing during cycling (charge-discharge) should
be checked.

Response: We are grateful to the reviewer for reviewing this manuscript and providing this
valuable suggestion. According to reviewer’s valuable comment, However, according to your
valuable suggestion, we have performed ab initio molecular dynamics (AIMD) simulation
using VASP simulation package, of pristine and vacancy mediated TMPS 3 surfaces as well as
lithiated MnPS3 surfaces at 300 K for the time period of as long as 25 ps and from the root
mean square deviation plot, it is evident that the average positional fluctuation of each atom
equilibrate within a few fraction of picoseconds which vividly suggests the exceptionally high
dynamic stability of the materials with no structural degradation under experimental condition
(please see Figure 4c-d and Figure S7 in the revised manuscript and supporting information).
Besides, we have also calculated the radial distribution function {g(r)} between P-S and TM-S
pairs for these surfaces as well as between P-S, Mn-S and S-Li pairs for lithiated MnPS 3
surfaces (where TM = Mn, Fe, Co, Ni) (please see Figure S9-S10 in the revised supporting
information). The radial distribution function {g(r)} between TM-S, P-S and S-Li pairs
maximize at the distances which are very close to the DFT calculated bond lengths (please see
Table S1). Hence, based on the good agreement between DFT optimized and AIMD
equilibrated structures of pristine as well as lithiated TMPS 3 surfaces, it can be concluded that
the modeled lithiated and non-lithiated surfaces are highly stable during Li insertion and
deinsertion indicating their long-term stability during charge-discharge. Please see Figure 4c-
d, Figure S7-9 and Table S1 as well as in Results and Discussion” section in the revised
manuscript. “To check dynamic as well as thermal stability of the TMPS 3 surfaces, we have
performed ab initio molecular dynamics (AIMD) simulation (using VASP simulation package)
of TMPS3 surfaces as well as lithiated MnPS3 surface at 300 K for the time period of as long
as 25 ps with a time step of 0.5 fs and from the root mean square deviation plot, it is evident
that the average positional fluctuation of each atom equilibrate within a few fraction of
picoseconds which vividly suggests the exceptionally high dynamic stability of the materials
with no structural degradation under experimental condition (Figure 4c-d and Figure S7).
Besides, we have also calculated the radial distribution function {g(r)} between P-S and TM-S
pairs for these surfaces as well as between P-S, Mn-S and S-Li pairs for lithiated MnPS3
surface (where TM = Mn, Fe, Co, Ni) (Figure S8 and S9). The radial distribution function
{g(r)} between TM-S, P-S and S-Li pairs maximize at the distances which are very close to the
DFT calculated bond lengths (Table S1). Hence, based on the good agreement between DFT
optimized and AIMD equilibrated structures of pristine as well as lithiated TMPS 3 surfaces, it
can be concluded that the modeled lithiated and non-lithiated surfaces are highly stable
during Li insertion and deinsertion indicating their long-term stability during charge-
discharge.” and “ Moreover, AIMD tests of vacancy defect MnPS 3 surface (with average
positional fluctuations of each atom within a few fraction of picoseconds) also overwhelmingly
exhibit the dynamic as well as thermal stability of these surfaces (Figure S16).”
Figure 4: Variation of volume change (in percentage) as a function of adsorbed Li content, x,
in (TMPS3)Lix, (b) change of TM-S (TM = Mn, Fe, Co, Ni) and P-S bond lengths (in
percentage) before and after Li adsorption, (c) plot of RMSD with time at 300 K for MnPS 3
monolayer surface, (d) plot of RMSD with time at 300 K for lithiated MnPS 3 monolayer
surface, (e) voltage profile with respect to adsorbed Li content, (f) average OCV and OCV at
fully lithiated TMPS3 surfaces.

Figure S7: Plot of RMSD with time at 300 K for TMPS3 monolayer surfaces (a) FePS3, (b)
CoPS3, (c) NiPS3.
Figure S8: Plots of radial distribution function {g(r)} between P-S and TM-S pairs for TMPS 3
monolayer surfaces at 300 K (a) MnPS3, (b) FePS3, (c) CoPS3, (d) NiPS3.

Figure S9: Plot of radial distribution function {g(r)} between P-S, Mn-S and S-Li pairs for
lithiated MnPS3 surface at 300 K.
Figure S16: Plot of RMSD with time at 300 K for vacancy defect MnPS 3 surfaces (a) Single
vacancy, (b) dual vacancy; plots of radial distribution function {g(r)} between P-S and Mn-S
pairs for vacancy defect MnPS3 surfaces at 300 K (c) single and (d) dual vacancy.

Table S1: Comparison of bond distances between DFT optimized and AIMD equilibrated
structures of lithiated and non-lithiated pristine and vacancy mediated TMPS3 surfaces.
Surface P-S pairs (Å) TM-S pairs (Å) S-Li pairs (Å)
DFT AIMD DFT AIMD DFT AIMD
MnPS3 2.04 2.05 2.61 2.55 - -
FePS3 2.04 2.04 2.52 2.44 - -
CoPS3 2.09 2.05 2.31 2.24 - -
NiPS3 2.06 2.06 2.44 2.44 - -
Single vacancy MnPS3 2.04 2.06 2.57 2.52 - -
Dual Vacancy MnPS3 2.10 2.05 2.51 2.45 - -
Lithiated MnPS3 2.05 2.05 2.59 2.55 2.44 2.45

Additionally, cycling i.e. charge-discharge is theoretically simulated by following the

migration path of Li and its corresponding energy barriers. Therefore, structural instability
during the migration of Li from one site to another may also be an indicative of electrode
decomposition during cycling (charge-discharge). As shown in Figure 1, there is no structural
distortion in the surface during Li diffusion from one to another site. This study also vividly
supports high stability of electrode material during cycling without decomposition.

Figure 1: Structures of every steps during Li diffusion from one site to another on MnPS 3
monolayer surface following migration along pathway-I.

Comment 3. Whether vacancy itself could have negative effects to the stability of pure TMPS3
materials?

Response: We are thankful to the reviewer for his/her valuable comments and suggestions. We
do agree with the reviewer that vacancy may have negative effects to the stability of pure
materials. But, for TMPS3 materials vacancy does not have any negative effect to the stability
of pristine surface. This conclusion is evidenced in several studies.
Firstly, AIMD simulation tests on single and dual vacancy MnPS3 surfaces at 300 K for
the time period of as long as 25 ps and from the root mean square deviation plot, it is evident
that the average positional fluctuation of each atom equilibrate within a few fraction of
picoseconds which vividly suggests the exceptionally high dynamic stability of the materials
with no structural degradation under experimental condition (Please see Figure S16 and
“Results and Discussion” section in the revised manuscript. “Moreover, AIMD tests of
vacancy defect MnPS3 surface (with average positional fluctuations of each atom within a few
fraction of picoseconds) also overwhelmingly exhibit the dynamic as well as thermal stability
of these surfaces (Figure S16a-b).” Besides, we have also calculated the radial distribution
function {g(r)} between P-S and Mn-S pairs for both the single and dual vacancy surfaces
(please see Figure S16c-d in the revised supporting information) maximizing at the distances
which are very close to the DFT calculated bond lengths (please see Table S1). Hence, based
on the good agreements between DFT optimized and AIMD equilibrated structures of lithiated
as well as non-lithiated pristine and vacancy mediated TMPS 3 surfaces, it can be concluded
that the modeled lithiated and non-lithiated surfaces are highly stable during Li insertion and
deinsertion.
Table S1: Comparison of bond distances between DFT optimized and AIMD equilibrated
structures of lithiated and non-lithiated pristine and vacancy mediated TMPS3 surfaces.
Surface P-S pairs (Å) TM-S pairs (Å) S-Li pairs (Å)
DFT AIMD DFT AIMD DFT AIMD
MnPS3 2.04 2.05 2.61 2.55 - -
FePS3 2.04 2.04 2.52 2.44 - -
CoPS3 2.09 2.05 2.31 2.24 - -
NiPS3 2.06 2.06 2.44 2.44 - -
Single vacancy MnPS3 2.04 2.06 2.57 2.52 - -
Dual Vacancy MnPS3 2.10 2.05 2.51 2.45 - -
Lithiated MnPS3 2.05 2.05 2.59 2.55 2.44 2.45
Figure S16: Plot of RMSD with time at 300 K for vacancy defect MnPS 3 surfaces (a) Single
vacancy, (b) dual vacancy; plots of radial distribution function {g(r)} between P-S and Mn-S
pairs for vacancy defect MnPS3 surfaces at 300 K (c) single and (d) dual vacancy.
Secondly, to check the structural stability of the vacancy defect MnPS 3 monolayer
surfaces we have studied the percentage of volume change as a function of lithiation. Our
study reveals that there is negligibly small change of volume (less than 2%) of vacancy defect
MnPS3 surface upon gradual insertion of Li atoms on the surfaces. The maximum volume
expansion for single vacancy defect is 0.88% while that for dual vacancy it is 1.7% upon full
lithiation. Besides volume factor, the change of bond lengths of constituted elements is also
considered to be crucial to predict structural stability of electrode materials. The average
expansion of P-S and Mn-S bond lengths are only 0.88%, 0.08% and 0.66%, 0.64%
respectively for single and dual vacancy MnPS 3 surface. Evidently, such as negligibly small
change of volume and bond lengths proves the exceptional stability of these vacancy defect
surfaces even after lithiation and hence proves the robustness of the vacancy defect surfaces.
Please see Figure 6h-i and “Results and Discussion” section of the revised manuscript. “To
check the structural stability of the vacancy defect MnPS 3 monolayer surfaces we have studied
the percentage of volume change as a function of lithiation (Figure 6h). As depicted from
Figure 6h there is negligibly small expansion of volume (less than 2%) of vacancy defect
MnPS3 surfaces upon gradual insertion of Li atoms on the surfaces. The maximum volume
expansion for single vacancy defect is 0.88% while that for dual vacancy it is 1.7% upon full
lithiation. Besides, the average expansion of P-S and TM-S bond lengths are only 0.88%,
0.08% and 0.66%, 0.64% respectively for single and dual vacancy MnPS3 surface (Figure 6i).
Evidently, such as negligibly small change of volume and bond lengths demonstrates the
exceptional stability of these vacancy defect surfaces upon lithiation (i.e. during charge-
discharge process).”
Figure 6: Vacancy defect structures of MnPS3 surface and corresponding more stable Li
adsorption sites (A site) (a) single vacancy, (b) Li adsorbed single vacancy defect surface, (c)
dual vacancy, (d) Li adsorbed dual vacancy surface (dotted encircles indicate the vacancy
positions); (e) voltage profile with respect to Li content (y = 0.25 and 0.50 respectively for
single and dual vacancy), (f) average OCV and OCV at fully lithiated vacancy defect MnPS 3
surface, (g) the migration paths as well as diffusion barriers for Li motion over vacancy defcet
MnPS3 surfaces, (h) Variation of volume change (in percentage) as a function of adsorbed Li
content (y = 0.25 and 0.50 respectively for single and dual vacancy), (i) change of Mn-S and
P-S bond lengths (in percentage) before and after Li adsorption for vacancy defect MnPS 3
surfaces.