Journal Pre-proof

Stable performance of Li-S battery: engineering of

Li2S smart cathode by reduction of multilayer
graphene-embedded 2D-MoS2

Joonghee Han, Hyungil Jang, Hoa Thi Bui, Marcus

Jahn, Doyoung Ahn, Keumnam Cho, Byeongsun
Jun, Sang Uck Lee, Schwarz Sabine, Michael
Stöger-Pollach, Karin Whitmore, Myung-Mo Sung,
Vishnu Kutwade, Ramphal Sharma, Sung-Hwan
Han

PII: S0925-8388(20)34395-4
DOI: https://doi.org/10.1016/j.jallcom.2020.158031
Reference: JALCOM158031

To appear in: Journal of Alloys and Compounds

Received date: 4 September 2020
Revised date: 17 November 2020
Accepted date: 18 November 2020
Please cite this article as: Joonghee Han, Hyungil Jang, Hoa Thi Bui, Marcus
Jahn, Doyoung Ahn, Keumnam Cho, Byeongsun Jun, Sang Uck Lee, Schwarz
Sabine, Michael Stöger-Pollach, Karin Whitmore, Myung-Mo Sung, Vishnu
Kutwade, Ramphal Sharma and Sung-Hwan Han, Stable performance of Li-S
battery: engineering of Li2S smart cathode by reduction of multilayer graphene-
embedded 2D-MoS2, Journal of Alloys and Compounds, (2020)
doi:https://doi.org/10.1016/j.jallcom.2020.158031
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© 2020 Published by Elsevier.
Stable performance of Li-S battery: engineering of Li2S smart cathode by
reduction of multilayer graphene-embedded 2D-MoS2

Joonghee Hana*†, Hyungil Jangb†, Hoa Thi Buib,f †, Marcus Jahna, Doyoung Ahnb, Keumnam
Chob, Byeongsun Junc, Sang Uck Leec, Schwarz Sabined, Michael Stöger-Pollachd, Karin
Whitmored, Myung-Mo Sungb, Vishnu Kutwade e, Ramphal Sharmab,e,*, Sung-Hwan Hanb,*

a
Electric drive technologies center for low-emission transport, Austrian Institute of
Technology, Giefinggasse, 1210, Vienna, Austria. *E-mail: Joong-Hee.Han@ait.ac.at.

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b
Department of Chemistry, Hanyang University, 222, Wangsimni-ro, Seongdong-gu, Seoul

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04763, Republic of Korea. *E-mail: shhan@hanyang.ac.kr

c
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Department of Bionano Technology and Department of Applied Chemistry, Hanyang
University, Ansan 15588, Republic of Korea.
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d
USTEM, Technical University Vienna, Wiedner Hauptstrasse 8-10/057-02, A-1040 Vienna,
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Austria.

e
Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-
a

431004, India. *Email: rps.phy@gmail.com

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f
Institute of Materials Science, Vietnam Acedamy of Science and Technology, 18 Hoang
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Quoc Viet, Cau Giay, Ha Noi,Viet Nam.

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†These authors contributed equally to this work.

Highlights:

 Transition metal chalcogenides (MoS2) were synthesized by applying a closed reflux

system.
 Multilayered graphene was formed from Carbon (C) precursor through the heat treatment
process and the calculated graphene theoretical capacity is 2231.4 mAh/g.
 Liquid-solid interfaces facilitate rapid ion transport and low interfacial impedance
 Polysulfide shuttle effects were prevented through a multilayered graphene structure as an
efficient platform for the cathode of the Li-S battery.
 Reporting here also a new class of other cathodes of Li2S, there is no conductive additive
of carbon black to the active material.

Keywords: Li-S batteries, Multilayered graphene, 2D-MoS2 cathode, Sulfur shuttle effects,
Li2S cathode

ABSTRACT:

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Lithium-sulfur (Li–S) batteries are considered promising candidates for next-generation
energy storage devices due to their ultrahigh theoretical gravimetric energy density, cost-

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effectiveness, and environmental friendliness. However, the application of Li–S batteries

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remains challenging; mainly due to a lack of understanding of the complex chemical
reactions and associated equilibria that occur in a working Li–S system. A new approach
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preparing graphene-based active cathode materials of Li-S battery with spatially confined
lithium sulfides is reported. The starting graphene-embedded 2D-MoS2 was synthesized by a
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solvothermal method in organic solvents followed by the calcination of trapped organic

solvent molecules at 800 oC to give graphene single sheets inside the 2D-MoS2 layers with
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7Å distance (MoS2-Gr-32.51). Then, it was electrochemically reduced/lithiated at potential

0.01 V vs Li+/Li generating metallic molybdenum and lithium sulfides. As a result, the
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structure of MoS2 multi-layers collapsed. The graphene multi-layer (ML-Graphene) was left
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behind and shut the lithium sulfides between the layers. The sizes of Li2Sn (n=4-6) are bigger
than the inter-layer distance of ML-Graphene, and the escape of sulfur/sulfides from the
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cathode into the electrolyte is physically blocked alleviating shuttle effects. The specific
capacity of ML-Graphene/lithium sulfides cathode was high of 1209 mAh/gMoS2-Gr at 0.1 C (1
C = 670 mA/g). The ML-Graphene exhibited the remarkable lithium intercalation capability,
and the theoretical calculation has been carried out to give 2231.4 mAh/g. Such high capacity
was hybridized with the theoretical capacity of sulfur (1675 mAh/g), and the ML-Graphene
composite with dichalcogenides (2D-MoS2) became a promising platform for the cathode of
Li-S batteries.
1. Introduction

The demand for high-performance electric vehicles and smart grid storages has stimulated
extensive research for advanced energy storage systems. Lithium-sulfur battery (Li-S battery)
is a well-known candidate beyond the lithium-ion battery with its high theoretical capacity
and several recent reports on the progress of lithium-sulfur batteries [1-6]. However, several
technological obstacles have greatly impeded the practical commercial application of Li–S
batteries; still, there are some recent reports on to catch a great practical performance of
lithium-sulfur batteries [7-9]. The poor electronic conductivities of elemental sulfur and

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lithium sulfides lead to the limited utilization of the active material sulfur and the poor-rate
capabilities. Another key huddle is the so-called ‘‘shuttle effects’’, caused by the dissolution

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of the lithium polysulfides (Li2Sn, n = 4~8) into the electrolytes during the charge/discharge
cycling processes, resulting in the rapid capacity fading and the low coulombic efficiency of
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Li–S batteries. To unravel the above drawbacks, considerable efforts have been made to
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increase conductivity as well as to prevent the dissolution of Li2Sn by capturing sulfur/sulfide
species within conductive anchoring materials [10-14]. Although several types of carbon
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materials were investigated with the electrical conductivity, the relatively weak interaction
between nonpolar carbons and polar sulfides limits their applications as ideal anchoring
materials for Li–S batteries. On the other hand, the polar materials with the structure to trap
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the soluble Li2Sn intermediates on their hydrophilic surfaces via polar–polar interactions have
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shown to be partly effective to mitigate the Li2Sn shuttle effects. Graphene, a typical two-
dimensional (2D) material, has been a highly effective anchoring material of superior
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electrical properties (2 x 105 cm2 V-1s-1 and 106 Scm-1 at 300 K) to enhance the performance
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of Li-sulfur batteries as well as lithium-ion batteries [15-20]. However, graphene has its
limitations to be a structural platform for the cathode of the Li-S battery due to its structural
irregularity. In most cases, to fabricate electrode, the active redox material sulfur is externally
added into the cathode heterostructure by thermal evaporation or physical mixing method and
loosely coupled with carbon matrix or graphene [21-23]. But, because the sulfur is freely
introduced into the cathode system, the sulfur/sulfides can be easily escaped from the
electrodes into electrolytes, and the shuttle effects could not be solved. In recent years, the
multi-layered structures have attracted extensive attention due to their fascinating properties
and wide applications in energy storage, photocatalysis, sensors, etc. [24-26]. Especially, the
internal electric field at multilayer interfaces facilitates the charge transport and enhances the
reaction kinetics on the surface of heterostructure or multilayers [27-32]. Compared with the
theoretical and experimental advances [33-38], however, to the best of our knowledge, there
is no previous study on the experimental preparation of the multi-layered graphene structures
and trapping sulfur/sulfide active cathode materials inside for reducing the shuttle effects of
Li–S batteries.

In this work, we suggest a strategy to fabricate multi-layered graphene (ML-

Graphene) structure embedding the in-situ generated lithium sulfide active redox materials.
By exploiting the graphene-embedded 2D-MoS2 (MoS2-Gr) structure, the lithium

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intercalation capacity of ML-graphene with sulfur compounds was hybridized to construct
the highly efficient cathode materials for the high-power Li-S batteries. First, the starting 2D-

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MoS2 was synthesized by a solvothermal method in organic solvents, and organic solvent
molecules were trapped between the multi-layers of 2D-MoS2. It was calcined at 800 oC
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under the inert atmospheric conditions and carbonized to graphene single layer between 2D-
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MoS2 layers with ~7 Å distance (confirmed by theoretically as well as experimentally by
TEM). Then, the MoS2-Gr was electrochemically reduced (lithiated at potential 0.01 V vs
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Li+/Li) generating the metallic molybdenum and lithium sulfides. As a result, the structure of
2D-MoS2 multi-layers collapsed, and the graphene layered with captured Li2S and other
polysulfide structures were left behind. During the lithiation/delithiation process, the active
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cathode materials (lithium-sulfides) have been generated in-situ and trapped inside the ML-
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Graphene. The ML-Graphene with captured Li2S and other polysulfide structures became an
ideal cathode platform for the high-power Li-S batteries with long life cycles: i) by in-situ
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generated lithium sulfides are spatially confined inside the ML-Graphene, and the shuttle
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effects are physically blocked, ii) the high electrical properties of the graphene reduce the
internal resistance of the cathode system and improve the rate capabilities of Li-S batteries,
and iii) the stability and the rate capability of materials in Li-S batteries depend on the
graphene contents in it. The composite of ML-Graphene with sulfur compounds is not only
the outstanding cathode platform for Li-S battery but also the active material with the
exceedingly large lithium intercalation theoretical capacity of 2232.4 mAh/g.
2. Material and methods

2.1. Materials

Sodium molybdenum oxide hydrate (Na2MoO4•2H2O, Alfa Aesar), thiourea (SC(NH2)2,

Junsei), ethylene glycol (EG, DAEJUNG), diethylene glycol (DEG, DAEJUNG), carbon
black (CB, Timcal C65 carbon black), polyvinylidene fluoride (PVDF, average Mw~ 180,000,
Sigma Aldrich), N-Methyl-2-pyrrolidionon (NMP, 99%, Acros), and commercial battery
electrolyte (1 M LiPF6 in ethylene carbonate (EC) : dimethyl carbonate (DMC) = 1:1 (v/v),
PuriEL) were used without further purification.

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2.2. Material preparations

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2.2.1. Preparation of EG-MoS2 and MoS2-Gr-1.91
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Na2MoO4·2H2O (1.21 g, 5.0 mmol) and thiourea (1.52 g, 20.0 mmol) were dissolved in a
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solution of EG (20 mL) and triple-distilled H2O (10 mL) and heated at 200 oC for 24 h in
Teflon-lined stainless autoclave to obtain MoS2. After the heating, black-colored products
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were collected by centrifugation at 3000 rpm for 30 min. The products were washed with DI
water and ethanol three times and then dried at 80 oC for 24 h (EG-MoS2). Then, the
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precipitates were calcined in a tube furnace at 800 oC under N2 flow (99.9999%) for 2 h to
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form MoS2-Gr-1.91 which contains 1.91 wt% graphene content (Elemental Analysis data in
Table 1).
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2.2.2. Preparation of DEG-MoS2 and MoS2-Gr-8.86

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Na2MoO4·2H2O (8.47 g, 35 mmol), and thiourea (10.64 g, 140 mmol) were dissolved in
210mL DEG in a round flask. The solution was stirred with a magnetic bar and heated to
reflux at 200 °C for 8 h. After the system cooled down, the products were washed with DI
water and ethanol 3 times. The products were dried in an oven at 80 oC for 24 h and stored
for the next step. The received products were calcined in a tube furnace at 800 oC under N2
flow for 2 h to form MoS2-Gr-8.86 which contains 8.86 wt% graphene content (EA data
included in Table 1).
2.2.3. Preparation of PPV-MoS2 and MoS2-Gr-32.51

2.2.3.1. Preparation of polypropylviologen (PPV)

The mixture of 4,4-bipyridine (0.2 g, 1.3 mmol) and 1,3-dibromopropane (0.26 g, 1.3 mmol)
are dissolved in 50 mL of acetonitrile. Then the solution was stirred with a magnetic bar and
heated to reflux at 80 °C for 24 h, and the product was collected after washing with an
acetonitrile solution.

2.2.3.2. Preparation of PPV-MoS2 and MoS2-Gr-32.51

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Na2MoO4·2H2O (1.21 g, 5 mmol), thiourea (1.52g, 20 mmol) were dissolved in 50 mL of

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DEG in a round flask, then PPV (1.74 g, 5 mmol monomer) was added to the round flask.
The solution was stirred and heated to reflux at 200 °C for 8 h. After the system cooled down,
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the products were washed with DI water 3 times and ethanol 3 times (1.486 g of products).
The received products were calcined in a tube furnace at 800 oC under N2 flow for 2 h to give
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MoS2-Gr-32.51 which contains 32.51 wt % of graphene content (EA data in Table 1).
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2.3. Characterizations

The surface topography and multilayered structure of these materials were characterized by
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using a Field-emission-electron-microscopy (FE-SEM, HITACHI S-4200) at an accelerating

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voltage of 15 kV and a High-resolution-transmission-electron-microscopy (HRTEM, JEOL-

2100F) at the voltage 200 kV. Electron-Energy-Loss-Spectroscopy (EELS) and High-Angle
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Annular-Dark-Field (HAADF) were conducted with a HR-TEM (FEI TECNAI F20) at an

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accelerating voltage of 200 kV. The elements distribution in materials was also studied by
element mapping using a Scanning-transmission-electron-microscopy (STEM) at 200 kV.
The crystal structures of these composites were determined using an X-ray Diffractometer
(XRD, Rigaku, D/MAX 2500 V, CuKα, λ = 0.15418 nm), the data were collected in the range
o o
from 5 to 80 (2θ) and at a scan rate of 3 o/min. The surface chemical composition was
examined using an X-ray photoelectron spectroscopy (XPS) with a monochromatic Al-Kα X-
ray source (µFocus 350) and a hemispherical WAL-150 analyzer. Raman spectra were
examined by a Raman spectrometer (JASCO, NRS-3100) with an excitation wavelength of
532 nm. The number of constitutional elements (C, H, N, S) was determined by an Elemental
analyzer (FLASH EA1112) (Table 1)
2.4. Electrochemical measurements

The cathodes of the lithium-sulfur batteries were fabricated by casting the slurry containing
60 wt% of active material, 20 wt% of CB, and 20 wt% of PVDF dissolved in NMP onto a
clean Cu foil (thickness = 90 µm). After drying at 120 oC for 4 h in an oven, they were
pressed under the conditions of 100 oC in 5 mins/times and vacuum-dried at 120 oC for 12 h.
Using the standard CR2032-type coin cells (electrolyte used by 1M of Lithium
hexafluorophosphate (LiPF6) with mixing Ethylene carbonate (EC) and Dimethyl carbonate
(DMC), 1:1 in volume ration of EC and DMC; electrolyte amount 0.4ml and active material

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loading 1gcm-2), the electrodes were assembled in an Ar-filled glove box (MBraun Glovebox
System, Germany, 0.1 ppm oxygen and 0.1 ppm moisture) with Li-metal foil (0.75 mm thick)

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as a counter electrode, and separator (Freudenberg, Germany). Cyclic voltammetry (CV)
measurements were performed on an IVIUM Compact Stat analyzer between 0.01 - 3.0 V vs
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Li+/Li at a scan rate of 0.1 mVs-1 at room temperature. Electrochemical-impedance-
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spectroscopy (EIS) measurements were performed in the frequency range of 1 MHz to 0.1 Hz
with an amplitude of 5 mV RMS. Galvanostatic discharge-charge (GDC) experiments were
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carried out at different applied current densities in a voltage range from 0.01 to 3 V with a
battery cycle tester (Parametric Battery Cycler, McSciene, 102Q ProMetro). Galvanostatic-
Intermittent-Titration-Technique (GITT) was used to determine the lithium-ion diffusion
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coefficient during charging and discharging processes. The current density was 0.1C with
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operating time 20 min, holding time 40 min.

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2.5. ab initio calculations

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All ab initio calculations were performed with the Vienna Ab initio Simulation Package
(VASP 5.4.1) [39-42]. We used the Perdew-Burke-Ernzerhof (PBE) exchange-correlation
functional using the projector augmented wave (PAW) method [43]. The calculations for
geometric optimization were carried out in periodically repeated supercell with 5 x 5 x 3 k-
point sampling. We used (5 x 5 x 1) and (3 x 3 x 1) supercells for Type A and Type B unit
cells as shown in Figure 3. Plane-wave cutoff energy of 500 eV was used. Lattice constants
and internal atomic positions were fully optimized until the residual forces were less than
0.04 eV/ Å. We included van der Waals corrections for all calculations using the DFT-D3
method with Becke-Jonson damping [44].
Table 1 Elemental Analysis (S, C, N, H) of MoS2-Gr-1.91, MoS2-Gr-8.86, and MoS2-Gr-
32.51.

Sample name Sulfur [wt%] Carbon [wt%] Nitrogen [wt%] Hydrogen [wt%]

MoS2-Gr-1.91 37.45 1.91 0 0.04

MoS2-Gr-8.86 33.29 8.86 0.63 0.39

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MoS2-Gr-32.51 23.07 32.51 2.23 0.35

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3. Results and discussion
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3.1. Preparations and characterizations of Graphene-embedded 2D-MoS2 structures

An approach preparing the ML-Graphene and the spatially confined sulfur/sulfide active
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materials inside graphene multi-layers is proposed in Fig. 1.

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Fig. 1 Scheme for preparation of graphene-embedded 2D-MoS2 and its electrochemical
reduction process to give multi-layered graphene structures. During the reduction (lithiation)
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process down to 0.01 V vs. Li+/Li, lithium sulfides were generated inside graphene multi-
layers, in situ, and participated in sulfur redox cycles.
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The 2D-MoS2 was effectively synthesized by using organic sulfur precursors, especially
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thiourea. By choosing the proper solvent, the reaction was carried out in normal glassware
under atmospheric pressure. The reaction was easy to increase the reaction scale, and 10 g
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scale synthesis or higher were possible out without any problem. As indicated in Fig. 1,
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organic solvent molecules were trapped between the multi-layers of 2D-MoS2 during the
solvothermal process. They were calcined at 800 oC under the inert atmospheric conditions
and carbonized to graphene single sheets between the 2D-MoS2 layers (MoS2-Gr) with ~7 Å
distance. Additionally, in the SEM images of EG-MoS2 (a) and MoS2-Gr-1.91 (b), there were
not many differences in the surface morphology after calcination at 800 oC in 2 h. However,
the grain boundary of DEG-MoS2 and PPV-MoS2 materials increased after calcination of
(Supporting Information Fig. S1c-d, S1e-f), resulting in the large graphene contents. In the
lithiation process, Mo is collapsed in graphene multilayer which increases the energy density
of the material. This special structure makes the interaction forces inside the layer strong,
while the interaction between layers is relatively weak, and this makes it easy for external
substances to be embedded. The collapse of Mo inside the graphene multilayer can prevent
polysulfide groups from dissolving in Li–S batteries and reducing the shuttle effect [45].

High-Resolution-Transmission-Electron-Microscopic (HR-TEM) images demonstrate the

multi-layered fine structures of MoS2-Gr-1.91 with carbon materials between layers (Fig. 2a-
b). Electron-Energy-Loss-Spectroscopy (EELS) of the vertically crossed MoS2-Gr-1.91
showed the alternatively oscillating carbon and sulfur signals with 7 Å distance indicating the
alternative multi-layered structure of the graphene with the 2D-MoS2 (Fig. 2c), which is the
confirmation of single-layer graphene in between the two 2D-MoS2 layers crystal structure,

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not the lattice fringes. High-Angle-Annular-Dark-Field (HAADF) experiment also confirmed
the regularly repeated multi-layers of graphene and 2D-MoS2. After the calcination, with

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three different graphene contents, the typical D band and G band of graphene in Raman
spectra were observed in Fig. 2d: The D-band (1356 cm-1) associated with the vibration of
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defects and disorder of sp3-carbon, and the G-band (1592 cm-1) related to the in-plane
vibration of sp2 carbon with the two-phonon 2D band at a frequency of ~ 2750cm−1 [46, 47].
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The Raman signals increased as the carbon contents increase. Without carbonization, MoS2
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does not have the graphene Raman peaks in the range of 1100 – 1800cm-1 in Fig. S2a
included in the Supporting Information.
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High-resolution XPS spectra of MoS2-Gr-1.91 composite were investigated to identify the

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chemical states of the carbonized carbons (Fig. 2f). In XPS spectra, they have common
carbon structures with oxygen species: sp2/sp3 hybridized carbon peak at 284.7 eV, the
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epoxy/ether group (C-O-C) peak at 286.3 eV, and carbonyl group (O-C=O) peak at 288.7 eV.
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It is important to note that there is a shake-up satellite peak at 289.7 eV in the spectra of
MoS2-Gr-1.91 (inset images of Fig. 2f). This is the typical π-π* transition of aromatic carbon
moieties or graphene, logically suggesting the state of graphene [47, 48]. Furthermore, the
Surface chemical composition of MoS2-Gr-1.91, MoS2-Gr-8.86, and MoS2-Gr-32.51 was
characterized by XPS measurements (Fig. 2α).
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Fig. 2α (a) XPS surveys of MoS2-Gr-1.91 (black), MoS2-Gr-8.86 (red), and MoS2-Gr-32.51
(blue); high resolution XPS spectra of Mo3d, S2p, C1s of MoS2-Gr -1.91 (b) (c) (d), MoS2-Gr-
8.86 (e) (f) (g) and MoS2-Gr-32.51 (h) (i) (j), respectively.

Fig. 2α (a) shows the full range of XPS survey spectra of those composites which confirmed
the presence of Mo, S, O, and C elements. The existence of oxygen in composites may due to
the use of precursors, solvent, and moisture during the synthesis process. Fig. 2α (b), (e), (h)
showed Mo 3d profile spectra of MoS2-Gr-1.91, MoS2-Gr-8.86 and MoS2-Gr-32.51,
respectively. High-resolution XPS of Mo3d profiles presents a peak at 226.2 eV of S2s and
characteristic peaks at 229.0 eV of Mo3d5/2 and 232.2 eV of Mo3d3/2 which indicated the Mo4+
oxidation state of MoS2, respectively. There are also two peaks at 235.93 V and 232.5 V
concerning Mo6+ of MoO3. The oxygen signal increased at the Fig. 2α h, in which the organic
molecule source for graphene was PPV, because the PPV has pyridinium salts in its backbone,
and is hygroscopic due to its ionic salt nature. The high moisture content increased the
formation of molybdenum oxides during the calcination step. The high-resolution XPS of
S2p spectra of MoS2-Gr-1.91, MoS2-Gr-8.86, and MoS2-Gr-32.51 had shown in Fig. 2α (c),
(f) & (i) respectively. All spectrums have 2 peaks at 163.0 eV of S2p5/2 and 162.0 eV of S2p3/2
which confirmed the formation of S2- in MoS2. The high-resolution XPS of C1s spectra of

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MoS2-Gr-1.91, MoS2-Gr-8.86, and MoS2-Gr-32.51 had shown in Fig. 2α (d), (g), (j),
respectively. They have common carbon structures with oxygen species: sp2/sp3-hybridized

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carbon peak at 284.7 eV, the epoxy/ether group peak (C-O-C) at 286.3 eV, and carbonyl

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group (O-C=O) peak at 288.7 eV. It is important to note that there is a shake-up satellite peak
at 289.7 eV in the spectra of MoS2-Gr-1.91 inset images of Fig. 1f. There is the typical π-π*
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transition of aromatic carbon moieties or graphene logically suggesting a state of graphene in
all composites [47, 48].
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The main peak of pristine 2D-MoS2 in the XRD spectrum is located at 2θ = ~14o, which
represents the interlayer distance of 6.15 Å (JCPDS No: 24-0515) by Bragg’s law. But the
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interlayer distance of the MoS2 prepared by the solvothermal method in organic solvents was
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expanded to 9 ~ 10 Å with the shift of the main peak to 2θ = 10 o in Fig. S2b included in the
Supporting Information. During the synthesis processes, organic molecules, such as EG,
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DEG, and PPV, were trapped inside the layer of MoS2 after the careful washing out of the
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physically adsorbed organic molecules on the external surface. After the calcination, the main
peak of MoS2-Gr-1.91 has returned to normal spacing about 6.41 Å (Fig. 2e). When DEG
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was used as a solvent, the main peak at 2θ = 10 did not completely move back to 14 o,
which indicates some portion of organic molecules were converted into multi-layers of
graphene between the MoS2 layers (Fig. 2e2).
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Fig. 2 Characterization of MoS2-Gr with different graphene contents: (a-b) HRTEM images
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of MoS2-Gr-1.91 (MS: MoS2 sheet, GR: graphene layer), (c) EELS and HAADF data of
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MoS2-Gr-1.91 (Inset image: HRTEM image for the measurement of the EELS and HAADF),
(d) Raman spectra of MoS2-Gr-1.91 (1), MoS2-Gr-8.86 (2), and MoS2-Gr-32.51 (3), (e) XRD
patterns of MoS2-Gr-1.91 (1), MoS2-Gr-8.86 (2), and MoS2-Gr-32.51 (3) and (f) High-
resolution XPS spectra of C1s of MoS2-Gr-1.91 (Dotted line indicates the raw data) (inset
image: HR-XPS of π-π* transition of graphene at 298.8 eV).

3.2. Synthesis of multi-layered graphene structure for sulfur redox system

The single-layer graphene sheets are not only difficult to synthesize but also almost
impossible to arrange in the regular form, especially 3-dimensional structures. They have
been generally investigated as one single sheet form or prepared as bulk aggregates with
amorphous carbons. In this report, we have succeeded to arrange the graphene layers in a
multi-layer structure with a distance larger than 3 Å, which is the interlayer distance in
graphite. As shown in Fig. 1, the MoS2-Gr was prepared with the regular multi-layered
graphene, but separated by the alternative MoS2 sheets with 7 Å distance. The MoS2 is an
electrochemically active material and was electrochemically lithiated at potential 0.01 V vs.
Li+/Li. After the lithiation, MoS2 was turned into metallic molybdenum and lithium sulfides,
and the structure of MoS2 multi-layers collapsed. But, the graphene is electrochemically inert
and existed intact during the lithiation. As a result, graphene layers were left behind (ML-
Graphene), and reduced metallic molybdenum and lithium sulfides supported the graphene

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sheets to maintain their inter-layer distance.

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It is interesting to notice that the sulfur of MoS2 was converted into lithium sulfides during
the lithiation process, which was shut inside ML-Graphene. The graphene inter-layer distance
-p
is supposed to be the same dimension of MoS2-Gr (6 ~ 7 Å). This distance of ML-Graphene
re
inter-layers is especially critical because the sizes of elemental S8 and Li-Sn (n = 4~8) are
bigger than 8 Å, and Li-Sn (n = 1 ~ 3) are not soluble in electrolytes. This means that the
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redox couples of sulfur/sulfide compounds in the lithiation-delithiation process are spatially

trapped inside ML-Graphene and cannot leach out of it [49, 50]. The graphene layered
structure with the inter-layer distance shorter than 7 Å with sulfur/sulfide inside is the strong
a

candidate for Li-S battery because it can solve the problem of poor conductivity of sulfur and
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shuttle effects. The dissolution of sulfur/sulfide can be physically controlled, and the escape
of sulfur/sulfides from the cathode into the electrolyte is blocked alleviating shuttle effects.
u
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3.3. Theoretical calculation of lithium intercalation capacity and layer distance of ML-
Graphene

Lithium intercalation into graphite with 3Å layer distance is a well-understood phenomenon

and provides the basis for the anode system of current lithium-ion batteries. In this study, the
ML-Graphene, in other words, the inter-layer spaced graphene (ISG) with an interlayer
spacing of about 6 ~ 7 Å was experimentally synthesized from MoS2-Gr. Considering the
increased interlayer spacing, the inter-layer spaced graphene can be expected to sorb more Li
atoms than the pristine graphite (PG) due to repulsion between intercalated Li atoms.
Therefore, we considered two different types of graphite unit cells as shown in Fig. 3 to
describe the fully charged PG and the multi-layered graphene structures. Type A containing
six carbons in a unit cell can have a stable LiC6 composition of fully charged PG while Type
B, a conventional graphite unit cell containing two carbons, has only a Li excess LiC4
composition due to the preference of Li atoms for hollow sites. If the inter-layer distance is
bigger than 3 Å, Li atoms can have an on-top binding site above and below the graphene
sheet, and Type A can be used for Li excess structure up to Li6C6 composition.

To verify the stability of Li excess Li6C6 composition in the inter-layer spaced graphene
(ISG), we compared the formation energy (ΔEf) of Li6C6 in ISG to that of LiC6 in PG. The
ΔEf can be decomposed into reconstruction energy (ΔEr) of graphene stacking in graphite and

of
binding energy (ΔEb) of Li atoms, as shown in Fig. 3. The ΔEr from AB stacking to AA
stacking is calculated as 0.056 eV per unit cell by changing the inter-layer distance (dL) from

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3.40 Å to 3.52 Å, regardless of Type A or B. But, the ΔEb and ΔEf depend on the Li atom
binding site and Li atom layer configuration. LiC6 composition of PG has a single Li atom
-p
layer with Li atoms on the hollow sites, whereas the Li6C6 composition of ISG can have AA
re
and AB stacked Li atom bilayers with Li atoms on the on-top sites. (ISG_LiAA and ISG-
_LiAB). The ΔEb of PG, ISG_LiAA, and ISG_LiAB are calculated as -0.120, 0.807, and -
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0.172 eV per unit cell, respectively. ISG_LiAA maintains a planar graphene structure and has
a larger dL of 6.41 Å due to repulsion between Li atom bilayer. However, ISG_LiAB has a
slightly distorted graphene structure, which increases ΔEb to a negative value because the
a

distorted structure induces sp3 hybridized atomic orbital character of carbon for Li atom
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binding. Consequently, the results of negative ΔEf values calculated from ΔEr and ΔEb in
Table 2 reveal that LiC6 composition of PG are stable as already well-known, and Li excess
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Li6C6 composition can be stabilized if graphite has the increased interlayer spacing and
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alternating AB stacking of Li atom bilayers with a slightly distorted graphene structure.

Based on the computational results, the theoretical capacity of lithium intercalation of the
ML-Graphene is calculated to be the value 2231.4 mAh/g; which is the exceptionally high
value so far. Such high capacity was hybridized with the theoretical capacity of sulfur (1675
mAh/g) for the effective cathode material of Li-S battery to fulfill the gap of academic and
commercialization of Li-S battery.
 of
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-p
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a lP
u rn
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Fig. 3 Schematics of Li intercalation in pristine graphite (PG) and inter-layer spaced

graphene (ISG) via the reconstruction of graphene-stacking and Li atom binding with two
different types of the unit cell and supercell structures within the same P6/mmc space group.
ΔEr and ΔEb correspond to the energy required to reconstruct AA stacked graphite into AB
stacked graphite and Li atom binding on AA stacked graphite. ΔEf is the formation energy of
the Li intercalated system. Purple and gray colors indicate Li and C atoms. Purple and green
colors indicate different types of A and B Li atom layers, respectively.
Table 2 Calculated reconstruction energy (ΔEr), Li binding energy (ΔEb), and formation
energy of full charged Li intercalated system (ΔEf).

ΔEr ΔEb ΔEf

Full charged
dL (Å)
composition (eV/ unit cell) (eV/ unit cell) (eV/ unit cell)

LiC6 -0.120 -0.065 3.63

of
Li6C6 (AA
0.056 0.807 0.863 6.41

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stacking of Li)

Li6C6 (AB
stacking of Li)
-0.172
-p -0.116 6.07
re
a
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Inter-layer distance of graphene sheets.

3.4 Multi-layered graphene with sulfur compounds as cathode materials of lithium-

a

sulfur batteries
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Fig. 4a1 displays the first three cyclic voltammograms (CVs) of MoS2-Gr-32.51 in a
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potential range of 0.01 – 3.0 V vs. Li+/Li (Experimental details, CVs of MoS2-Gr-1.91 and
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MoS2-Gr-8.86; Fig. S3 a & b in Supporting Information, respectively). The first reduction

peak at ca. 0.95 V is related to the insertion of Li+ ions into the interlayer space of 2D-MoS2
forming 1T LixMoS2 (x = 0 – 1) [51-53]. A broad peak with a shoulder at 0.75 ~ 0.3 V
corresponds to the complete lithiation to Li2S and Mo from the LixMoS2 [49]. At the
delithiation step, the major peak at 2.3 V is ascribed to the oxidation of lithium sulfides to
sulfur (Sn) [54, 55]. At the 2nd scan, there appeared a new lithiation peak at 1.8 V with a
shoulder at 2.2 V and coupled with the delithiation peak at 2.3 V, which is the typical sulfur
reduction and sulfide oxidation cycle (lithiation and delithiation cycle). The formation of
sulfur redox couple was fully activated by the pretreatment cycles (cell formation cycles) of
scanning up to 0.01 V. The presence of graphene between the inter-layer of MoS2 has
promoted the complete reduction of Mo and the formation of lithium sulfides inside (are
present in below reactions).

1st discharge process:

At voltage potential 0.95 V vs Li+/Li: MoS2 + xLi  LixMoS2 (x = 0-1)

At voltage potential < 0.75V vs Li+/Li: LixMoS2 + (4-x)Li+ + (4-x)e-  2Li2S + Mo

1st charge process:

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At voltage potential 2.3V vs Li+/Li: Mo + 8Li2S  S8 + Mo + (16-x)Li+

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(0 < x ≤ 16)

From 2nd cycles (reversible reaction)

-p
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At voltage potential 1.8V/2.3V vs Li+/Li: 8Li2S ↔ 16Li+ + 16e- + S8
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During the discharging process, two different reactions took place independently: the one
a

is the sulfur reduction process, and the other is the lithium intercalation process in ML-
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Graphene. The two processes were monitored by the scanning at the different voltage region:
the sulfur reduction/oxidation region at 3 - 1.5 V vs Li+/Li (Fig. 4a3) and the lithium
u

intercalation region of ML-Graphene at 1.5 - 0.01 V vs Li+/Li (Fig. 4a2). They showed the
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independent self-regulating processes and indicated the discharging capability of the system
was the additional value of the sulfur reduction and the lithium intercalation in ML-
Graphene. This strongly define that the cathode is the hydride system.

The rate capability of the ML-Graphene in Li-S battery was further investigated at various
current densities from 0.1 C to 10 C (1 C = 670 mA/g), 10 cycles each in Fig. 4b. The initial
discharge capacity of the cell at 0.1 C depended on the graphene contents: 1209 mAh/g active
material for ML-Gr-32.51; 777 mAh/g active material for ML-Gr-8.86; 749 mAh/g active
material for ML-Gr-1.91, respectively. At the high scan rates of 5 C and 10 C, the capacity of
ML-Gr-32.51 was achieved to be 663 mAh/g active material and 552 mAh/g active material,
respectively (the active material means not only sulfur contents but the total MoS2-Gr
weight). Fig. 4c shows the long cycle performance of the ML-Gr-32.51 electrode at a high
current density of 1000 mA/g up to 600 charging/discharging cycles for Li-S battery. The
coulombic efficiency was almost 100% (Fig. 4c) and there was no noticeable performance
degradation throughout the test. The specific capacities of ML-Gr-1.91 as a cathode electrode
of Li-S battery were tested with good stability at a current density of 0.1 C (1 C = 670 mA/g)
in Fig. S4a included in the Supporting Information. Fig. 4d shows voltage profiles of MoS2-
Gr-32.51 electrode in the potential range 0.01-3V vs Li+/Li at a current density of 100mA/g
(1st cycle, 2nd cycle, 10th cycle, 20th cycle). Wang et al. and Yin et al. also reported a similar
range (0.01-3V vs Li+/Li) of potential in which it shows the contribution of MoS2 and

of
Graphene when Lithium intercalation/deintercalation [56, 57]. It is worthwhile to note that

ro
the starting voltage of the discharging steps of cells was 2.4 V, lower than those of long-chain
lithium sulfide oxidation potential (Fig. 4d) [54]. The low starting potential is known to be

-p
related to the oxidation of small size lithium sulfides of S2-4, which were generated by the
size restriction of the graphene inter-layer distance (6-7 Å). Besides, the small lithium
re
sulfides (S2-4) have poor solubility in electrolytes and have a positive contribution to
minimize the shuttle effects [58]. The Nyquist plots were obtained by Electrochemical-
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impedance-spectroscopy (EIS) measurements of the ML-Graphene in the potential range of

0.01 - 3.0 V vs Li+/Li (Fig. S5). The charge transfer resistance (Rct) of active materials also
a

depends on the graphene contents from 191.8 Ω for ML-Gr-1.91 to 53.2 Ω, 51.3 Ω for ML-
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Gr-8.86 and ML-Gr-32.51, respectively. The formation of graphene by the calcination

improved the conductivity as expected. The four-point conductivity measurement showed the
u

meaningful conductivity increase after the calcination step (Fig. S4b, Supporting
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Information).
 of
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-p
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Fig. 4 (a) Cyclic voltammograms of ML-MoS2-Gr-32.51 at a scan rate of 0.1 mV/s, voltage
range 0.01-3 V vs Li+/Li (1); 0.01-1.5 V vs Li+/Li (2); 1.5 - 3 V vs Li+/Li (3), (b) Rate
a

capability performance of ML-MoS2-Gr-32.51, ML-MoS2-Gr-8.86 and ML-MoS2-Gr-1.91

rn

(10 cycles each). The capacity data is based on the coin-cell loaded as 1gcm-2 MoS2-Gr active
material. (1 C = 670 mA/g), (c) Long-term cycling performance of ML-MoS2-Gr-8.86 at
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current density of 1000 mA/g and coulombic efficiency of ML-MoS2-Gr-32.51 and (d)
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voltage profiles of MoS2-Gr-32.51 electrode in the potential range 0.01-3V vs Li+/Li at

current density of 100mA/g (1st cycle, 2nd cycle, 10th cycle and 20th cycle) [56].

The formation of metallic Mo and lithium sulfides by the lithiation step, and
elemental sulfur by the delithiation step, were further monitored by an XRD after the 5 pre-
cycles of MoS2-Gr-32.51 (Fig. 5a). After the full lithiation step at 0.01 V, a characteristic
MoS2 signal at 2θ = 14o was completely disappeared with the destruction of the 2D-MoS2
layered structure, and Li2S peaks at 2θ = 26o and 29o appeared as well as that of metallic Mo
peak. At the full delithiation at 3.0 V, a strong, broad peak at 2θ = 22o increased indicating the
formation of elemental sulfurs from the lithium sulfides without regenerating the starting
MoS2. At subsequent cycles, characteristic MoS2 peaks were not recovered, and the reversible
sulfur redox peaks became dominant in the potential range of 0.01 – 3.0 V vs Li+/Li as shown
in Fig. 4a1 [40, 43, 44]. This also supports that MoS2 in MoS2-Gr nanostructure lost their
layered 2D-structures by pre-cycles and generated a new redox couple of Li2S/Sn active
materials in the ML-Graphene. The lithium diffusion coefficient of the ML-Graphene was
measured by a Galvanostatic-intermittent-titration-technique (GITT). Lithium-ion diffusion
coefficients are in the order of 10-16 cm2 S-1 (Fig. 5b). It is interesting to see the diffusion
constant jump in the lithiation step at around 1.9 V, at which elemental sulfur accepts
electrons to sulfides. The reduction of sulfur facilitated the diffusion of lithium-ion at 1.9 V.
At the voltage below 0.4 V, the formation of Li2Sn (n = 1 ~ 3) is predominant and provides

of
the thermodynamic stability of the system.

ro
-p
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a lP
u rn

Fig. 5 (a) X-ray diffraction patterns: a, MoS2-Gr-32.51; b, after lithiation at 0.01 V; c, after
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delithiation at 3.0 V. MoS2-Gr electrode was pre-cycled 5 times in 0.01 – 3.0 V vs. Li+/Li. (b)
Lithium diffusion coefficients by Galvanostatic-Intermittent-Titration-Technique (GITT) of
ML-Graphene at 2nd cycle.

3.5 State-of-the-art design

Table S1. Design the state-of-the-art of the Li2S-multilayers graphene cathode with an
indirect comparison of the micro-porous sulfur cathode for the Li-S battery. For the first time,
we have done experimental and theoretical correlation of multilayered graphene and
electrochemical performance for alleviating sulfur shuttle effects in the Li-S batteries via
initial graphene-embedded 2D-MoS2 cathode. As per our knowledge from the available
literature, there is no direct comparison available with our work. However, porous carbon
cathode battery work has similar electrolyte LiPF6, EC: DMC used for the battery
performance as presented in Table S1 [59, 60].

Porous carbon materials with high specific areas and large pore volumes have received
significant attention due to their economic value, large-scale reliability, ability to shorten
ion/electron transport pathways and availability of active sites. However, a problem
associated with many porous carbon materials is that they are difficult to be anchored on the
current collector, leading to delamination and loss of active materials. It is interesting to
notice in the present work that the sulfur of MoS2 was converted into stable lithium sulfides

of
during the reduction/lithiation process, which was shut inside ML-Graphene. The graphene
inter-layer distance is supposed to be the same dimension of MoS2-Gr (6 ~ 7 Å). This

ro
distance of ML-Graphene inter-layers is especially critical because the sizes of elemental S8
and Li-Sn (n = 4~8) are bigger than 8 Å and Li-Sn (n = 1 ~ 3) are not soluble in electrolytes
-p
(LiPF6, EC: DMC). The multi-layered graphene layered structure with the inter-layer distance
re
shorter than 7 Å with sulfur/sulfide inside is the strong candidate for Li-S battery because it
can solve the problem of poor conductivity of sulfur and alleviating shuttle effects. In other
lP

words, solving these problems, or at least reducing their effect, is critical to paving the way
for large-scale engineering of Li–S batteries. For achieving high-loading, high capacity
output, and long cycling life Li–S cathodes, novel conductive hosts need have been designed
a

with high electrical conductivity, fast Li+ transport channels, and the capability to confine the
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lithium, therefore electrochemical energy to solve the problem polysulfides shuttling effect.
For the thick cathode, the top-down design of a conductive network with unrestricted Li+
u

transport channels during long-term cycling has been confirmed for scale-up of readily
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available and low-cost cathode fabrication strategies may also be explored.

4. Conclusions

In conclusion, the multi-layered graphene structures (ML-Graphene) were in-situ generated

with lithium sulfides between the layers. It was prepared by the calcination and the reduction
(lithiation) of 2D-MoS2 with trapped organic molecules. The ML-Graphene provided a
significant methodology to alleviate the shuttle effects of lithium-sulfur batteries and was
applied to the cathode of lithium-sulfur batteries. In this system, the active sulfur/sulfide
compounds were not externally introduced but generated in situ internally between the
graphene layers. The graphene inter-layer distance is supposed to be the same dimension of
MoS2-Gr (6 ~ 7 Å). The sizes of Li2Sn (n = 4 ~ 8) are bigger than 8 Å (n = 1 ~ 3 are not
soluble in electrolytes), and the redox couple of sulfur/sulfide compounds in the lithiation-
delithiation process are spatially trapped inside the ML-Graphene. The initial discharge
capacity of the cell at 0.1 C depended on the graphene contents: 1209 mAh/g active material
for ML-Gr-32.51; 777 mAh/g active material for ML-Gr-8.86; 749 mAh/g active material for
ML-Gr-1.91, respectively. Therefore, the dissolution of sulfur/sulfide compounds into the
electrolytes is effectively blocked, and the shuttle effects can be possibly controlled. The
formation of graphene multilayers also facilitated the effective charge transfer, too. Moreover,
the lithium intercalation capability of ML-Graphene was calculated to be 2232.4 mAh/g.

of
Such high capacity was hybridized with the theoretical capacity of sulfur (1675 mAh/g) to

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give a high performance of the ML-Graphene composite with sulfur compounds as a cathode
material for the stable Li-S battery.

Acknowledgment -p
re
This research was supported by Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the Ministry of Education (2013009768) and
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the Creative Materials Discovery Program (2015M3D1A1068061), and Climate Energy

Funds Austria of the research energy program in 2014 under Grant No. 5131261. One of the
a

authors, Ramphal Sharma thanks to NRF Brainpool Program in Korea for financial support.
rn

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 Credit Author Statement

JoonHee Han, Ramphal Sharma and Sung-Hwan Han : proposed and supervised the research.

Hoa Thi Bui, Hyungil Jang: prepared EG, DEG samples, and coin cell and characterized the

cell performances. Doyoung Ahn, Keumnam Cho: prepared PPG samples and coin cell, and

characterized the cell performances. Byeongsun Jun, Sang Uck Lee, Myung-Mo Sung,

Vishnu Kutwade and Ramphal Sharma carried out theoretical calculations. Schwarz Sabine,

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Michael Stoeger-Pollach, and Karin Whitmore took SEM and TEM pictures.

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Declaration of interests

☒ 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.

☐The authors declare the following financial interests/personal relationships which may
be considered as potential competing interests:

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Declaration of competing interest

All the authors declare no conflict of interest.

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Highlights

 Transition metal chalcogenides (MoS2) were synthesized by applying a closed reflux

system.
 Multilayered graphene was formation from Carbon (C) precursor through heat treatment
process and calculated graphene-theoretical capacity value 2231.4 mAh/g.
 Liquid-solid interfaces facilitate rapid ion transport and low interfacial impedance
 Polysulfide shuttle effects prevented through multilayered graphene structure as an
efficient platform for the cathode of Li-S battery.

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 Reporting here also a new class of other cathode of Li2S, there is no conductive additive
of carbon black to the active material.

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