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Sulfur cathode material conductivity improving by carbons admixture:

technology and characterization

Article in Materials Today Proceedings · January 2018

DOI: 10.1016/j.matpr.2018.05.064

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Materials Today: Proceedings 5 (2018) S109–S114 www.materialstoday.com/proceedings

NanoOstrava_2017

Sulfur cathode material conductivity improving by carbons

admixture: technology and characterization
Gražyna Simha Martynkováa,b*, Karel Chrobáčekc, Lenka Pazourkováa,b, Savas Aydina,d,
Denis Pivoňkaa, Boris Novosadc
a
Nanotechnology Centre, VŠB - Technical University of Ostrava, 17. listopadu 15, Ostrava - Poruba 708 33, Czech Republic
b
IT4Innovation Center, VŠB - Technical University of Ostrava, 17. listopadu 15, Ostrava - Poruba 708 33, Czech Republic
c
Faculty of Electrical Engineering and Computer Science, VŠB - Technical University of Ostrava, 17. listopadu 15, Ostrava - Poruba 708 33,
Czech Republic
d
Institute of Natutal Sciences, Metallurgical and Material engineering, Physics, Sakarya University, Esentepe Campus 54187, Sakarya, Turkey

Abstract

Sulfur (S) is announced as future cathode material with a theoretical specific capacity of 1672 mAh/g,~5 times higher than those of traditional
cathode materials based on transition metal oxides or phosphates. S based battery is partly limited by the problems of low electrical conductivity
of sulfur, dissolution of polysulfides in electrolyte and volume expansion of sulfur during discharge. The high effort to find materials to overtake
these disadvantages is leading to conductive materials like S. The carbons are well known for very good conductivity along the graphene layers.
For this purpose, 2 types of carbons were tested using mechanofusion milling process to create interaction of sulfur and carbon as two inorganic
materials. Conductivity was tested, and improvement was shown. To solve problems with dissolution of polysulfides in electrolytes the
intercalation of sulfur to clay interlayer space was designed.

© 2018 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and Peer-review under responsibility of NanoOstrava2017.

Keywords: Sulphur; exfoliation; organic modification; particles morphology; structural properties.

*Corresponding author. Tel.: +420-597-321-1572.

E-mail address: grazyna.simha@vsb.cz

2214-7853 © 2018 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and Peer-review under responsibility of NanoOstrava2017.
S110 G.Simha Martynková et al./ Materials Today: Proceedings 5 (2018) S109–S114

1. Introduction

Li-S batteries, which have very high theoretical capacities and energy densities, are believed to be one of the most
promising candidates. The sulfur-based electrochemical reaction requires novel electrolytes to replace the classical
carbonate-based electrolyte systems genetic from Li-ion batteries because carbonates are incompatible with the
intermediate polysulfides in Li-S batteries. In addition, the theoretical specific capacities and projected energy
densities of Li-S batteries are difficult to achieve experimentally, mainly because of the electronically insulating
nature of sulfur and lithium sulfide cathodes, and the shuttle effect; this is a significant issue associated with the
dissolution and diffusion of soluble polysulfides in most potential electrolytes that causes rapid capacity fading [1-8].
The commercialization of lithium-sulfur batteries is hindered by low cycle stability and low efficiency, which are
induced by sulfur active material loss and polysulfide shuttle reaction through dissolution into electrolyte. Sulfur-
impregnated disordered carbon nanotubes as cathode material for the lithium-sulfur battery demonstrated superior
cyclability and Coulombic efficiency. More importantly, the electrochemical characterization indicates a new
stabilization mechanism of sulfur in carbon induced by heat treatment [9]. Activated clay (AC) with a nest-like
structure and a large surface area was employed to support sulfur as the cathode for lithium-sulfur batteries. The
special structure may have a similar effect to small filter screens for entrapping sulfur and restricting the diffusion of
polysulfides during cycling. A high capacity of 959.6 mA h g−1 was achieved at a rate of 0.1 C in the first cycle for
the AC/S composite with a sulfur content of 57 wt % and the reversible capacity remained high at up to 700.9 mA h
g−1 even after 50 cycles [10]. Addressing the safety issues of Li-S cells is necessary before they can be used in
practical applications. Efficient Li-S battery with a flame-inhibiting electrolyte and a sulfur-based composite cathode
are on demand. The flame retardant not only makes the carbonates nonflammable but also dramatically enhances the
electrochemical performance of the sulfur-based composite cathode, without an apparent capacity decline over 750
cycles, and with a capacity greater than 800 mA h−1 g−1(sulfur) at a rate of 10 °C [11].

1.1. Materials and equipment

Sulfur powder (S), 99.98 % trace metals basis, rhombic structure (Sigma Aldrich), carbon black (Cabot)
conductive Black Pearls (CB), natural Ca-montmorillonite (MMT) from Ivancice, CR below 40 m fraction,
graphite flakes (C) (Sigma Aldrich) were used in as received form.
Oven Memmert (heating and drying up to 260 °C), agate mortar, jet mill (Stutevant micronizer), ball mill
(Fritsch) and equipment for electrical measurements.

1.2. Sample preparation

The preparation method for sulfur composite material is simple.

Two types of mixtures are prepared. First composition contains only 2 compounds - sulfur and carbon in ratio
10:1. This mixture is homogenized in agate mortar and passed through jet mill at grinding condition 50 psi: 50 psi of
feeding: working pressure. In case of sulfur- graphite sample is denoted as S/C and carbon black - sulfur as S/CB.
The following step contained incorporation of clay mineral montmorillonite to sulfur - carbon mixture in ratio
10:2. This mixture was ground in ball mill for 15 min and heat treated at 110 °C for 24 h in closed container. Sample
was denoted as MMT/S/C or MMT/S/CB.

1.3. Characterization methods

The X-ray diffraction (XRD) analysis was carried out on the X-ray diffractometer Ultima IV (RIGAKU, Japan).
The XRD patterns were recorded on the powder samples pressed on the glass slide in the symmetrical Bragg-
Brentano diffraction geometry in the 8 - 80° 2θ range under CuKα radiation (λ = 0.1541 nm) and the scintillation
counter detector with a scanning rate of 2°/min at 40 kV and 40 mA.
The particle size (PS) and particle size distribution (PSD) was determined by the HORIBA (Japan) Laser
diffraction particle size analyzer (LA-950 instrument) with a two short-wavelength blue and red light source in
conjunction with forward and backscatter detection.
 G.Simha Martynková et al./ Materials Today: Proceedings 5 (2018) S109–S114 S111

Scanning electron microscope Philips XL30 (Nederland) were used for viewing morphology of powdered
samples. Samples were analyzed as received from experiment.

1.4. Electrical parameters measurements

The goal of measuring electrical properties of compounds (conductivity , permittivity ) was to differentiate
each mixture and its behavior in various frequencies. We proceeded by constructing special measuring chamber,
which has been calibrated and its electrical properties were properly measured, that offered us a starting point for the
whole measurement. Dimensions of measuring chamber were 0.0089 x 0.0047 x 0.031 m with its total volume
1.29673E-06 m³. We used RLC meter Hioki IM3536 (Japan) that allowed us to measure all compounds on frequency
range of 10Hz to 1MHz. Each material was measured on 6 frequencies in 10 cycles. First, chamber was filled with
sample to the top edge and then by the vibrations of the blower, it was shaken down and this process was repeated
until there was no other sample to shake down. This method provides approximately the same amount of sample in
cell during each measurement. In following table are demonstrated changes of conductance and resistivity of each
mixture depending on their additives.

2. Results and discussion

2.1. Characterizations of structure and particle size of samples

The prepared powders have been characterized using X-ray diffraction analysis. The effect of jet milling on the
XRD pattern is not extremely visible, since the sulfur crystallinity is not changed drastically and well-ordered peaks
of orthorhombic sulfur are intensive (Fig. 1). Peaks of carbon, graphite and carbon black equally in mixture with
crystalline sulfur are not visible in XRD pattern. Adding MMT to the mixture in rather high ratio we can observe
basal 001 diffraction at the pattern (d001 = 1.17 nm). However, low crystallinity of MMT resulted in the peak of low
intensity with extended profile (Fig. 1).

12000
MMT/S/CB
10000 S/CB
S
8000
Intensity

6000
sulfur
4000
MMT
2000

5 10 15 20 25 30 35 40

°2CuK

Fig.1. XRD patterns of obtained milled samples and original sulfur powder.

Reviewing particle size data, we can state that the smallest particles were obtained in case of S/CB sample and
followed by S/C sample (Table 1). Adding MMT average particle size rised because of two facts; original particle is
quite high (< 40 m) and ball milling of mixture is not such efficient as jet milling. Ball milling is in this case as
method for homogenization of mixture rather than for mechanofusion of composite powder.
S112 G.Simha Martynková et al./ Materials Today: Proceedings 5 (2018) S109–S114

Table 1. Particle size parameters of original and prepared samples.

Sample Mean Median Mode Span

(μm) (μm) (μm)
S 48.9 69.1 27.9 2.6
CB 12.6 22.1 12.4 1.2
S/CB 5.8 10.7 6.2 1.1
S/C 7.8 12.3 8.1 1.2
MMT/S/CB 12.5 22.0 9.4 1.3
MMT/S/C 11.6 18.4 6.5 1.9
C 60.1 87.6 29.6 3.1

2.2. Morphology of milled particles

The important characteristic of prepared samples is morphology study of ground materials. During the
mechanofusion process the particles via self-grinding method are being shaped into fine uneven powder particles.
Carbon particles are distributed evenly over the sulfur particles. Graphite visible fine flakes (Fig. 2a) are covering
relatively big sulfur particles. Carbon black particles (Fig. 2b) are finer and cover the sulfur particles in thin
homogenous layer. This phenomenon corresponds with the particle size measurement.

Fig. 2. SEM images using secondary electron detector of samples (a) S/C, (b) S/CB after jet milling.

2.3. Electrical parameters measurement of samples

Electrical parameters measurement of prepared mixtures via mechanofusion exposed following facts.
An interesting material is mixture graphite S/C, where conductivity is high and stable in wide frequency range of
tested condition (Fig. 3). Most probably the dropped value at 1000 kHz is cause by sudden unusual conditions and
could be considered as unexpected nonlinearity of linear curve.
Similar character of  and is observed in case of S/CB (Fig. 4).
 G.Simha Martynková et al./ Materials Today: Proceedings 5 (2018) S109–S114 S113

Fig.3. Chart of electrical parameters dependency of conductivity , permittivity on frequency of sample S/C.

The addition of MMT to mixture S/CB decreased conductivity at lower frequency. However, the conductivity
curve is exponential, where breaking point can be considered at 10 kHz. Conductivity gradually increased but
positive values of conductivity are low: For graphite conductivity within layers was  = 3 x 105 S/m and
perpendicular to layers was  3.3 x 102, and for sulfur was  1 x 10-15 S/m.

Fig. 4. Chart of electrical parameters dependency of conductivity , permittivity on frequency of sample MMT/S/CB.

3. Conclusion

Enhancing very low conductivity of sulfur with carbons was proven in presented work. Two types of carbon
materials, graphite and special conductive carbon black was tested. Using jet mill sulfur powder and carbon powders
were compounded in jet mill chamber. There is good coverage of sulfur by carbon in both cases that was viewed
analyzing morphology of milled samples. Particle size was found dropped by about 4 times from several hundreds
of micrometers to tens micrometers.
Adding clay mineral montmorillonite to S/C or S/CB mixtures we found that conductivity slightly decreased
compare to previous mixture, but it was still higher than sulfur alone. Therefore, we presume that shearing forces of
S114 G.Simha Martynková et al./ Materials Today: Proceedings 5 (2018) S109–S114

ball mill followed with heat treatment is changing the interaction of montmorillonite with sulfur and are keeping
clay with less crystallinity, as shown by XRD patterns.

Acknowledgements

The authors gratefully acknowledge the support by projects from Ministry of Education, Youth and Sport of Czech
Republic (SP2017/86) and from the National Programme of Sustainability (NPU II) project “IT4Innovations
excellence in science – LQ1602”.

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