One step: In situ synthesis of ZnS/N and S co-doped carbon composites via salt templating for lithium-ion battery applications

Article abstract of DOI:10.1039/c9nj02488c

Herein, we report a simple in situ synthetic route to prepare ZnS/carbon composites (ZnS/NSC-x) by using a eutectic salt mixture (LiCl/ZnCl₂) as a template and 2-amino-4-phenyl thiazole as a precursor for carbon materials. The structural and morphological characterization reveals the presence of cubic ZnS (9 nm) nanoparticles embedded in the carbon material. These synthesized heteroatom co-doped composites (ZnS/NSC-x) with moderate surface area, when used as the positive electrode in a lithium-ion battery, gave better performance than pure ZnS both in terms of cycling stability and rate performance. The capacity retention at the high current density of 1500 mA g^-1 is 65% with respect to the capacity obtained at 250 mA g^-1 for ZnS/NSC-800, whereas pure ZnS retained only 28% of the capacity at the same current density. The charge transfer resistance values are also found to be very low for the synthesized composites, which is responsible for their improved kinetics. The heteroatom co-doped carbon matrix besides improving the electronic conductivity also relieved the stress induced by cycling; therefore, the electrode with a high mass loading of up to 4 mg cm^-2 gave stable capacity with 90% of the initial capacity retained over 200 cycles (at 250 mA g^-1) for the same electrode at which the rate performance was carried out.

Full text of DOI:10.1039/c9nj02488c

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Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
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One step in situ synthesis of ZnS/N and S Co-doped Carbon
Composites via salt templating for Lithium-ion battery application
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a,b
b
b,c
d
b
Sadaf Ikram , Marcus Müller , Sonia Dsoke , Usman Ali Rana , Angelina Sarapulova , Werner
b*
a*
b,e
Bauer , Humaira M. Siddiqi , Dorothée Vinga Szabó
Herein, we report a simple in situ synthetic route to prepare ZnS/Carbon composites (ZnS/NSC-x) by using an eutectic salt
mixture (LiCl/ZnCl ) as a template and 2-amino-4-phenyl thiazole as a precursor for carbon material. The structural and
2
morphological characterization reveals the presence of cubic ZnS (9nm) nanoparticles embedded in the carbon material.
These synthesized heteroatom co-doped composites (ZnS/NSC-x) with moderate surface area, used as the positive
electrode in a lithium-ion battery, gave better performance than pure ZnS both in terms of cycling stability and rate
performance. The capacity retention at the high current density of 1500 mA g-1 is 65% respect to the capacity obtained at
2
50 mA g-1 for ZnS/NSC-800, whereas pure ZnS retained only the 28% of capacity at same current density. The charge
transfer resistance values are also found to be very low for the synthesized composites which are responsible for their
improved kinetics. The heteroatom co-doped carbon matrix besides improving the electronic conductivity also relieved the
-2
stress induced by cycling, therefore the electrode with high mass loading of up to 4 mg cm gave stable capacity with 90%
-1
of the initial capacity, over 200 cycles (at 250 mA g ) for the same electrode at which the rate performance was carried
out.
Therefore, in order to fulfill the growing energy demand and to
meet the requirements for large-scale productions, there is a
need to explore novel high capacity anode materials. In this
1
. Introduction
context, various transition metal oxides (MnO, SnO
Fe , ZnO, Co , Ni CoO etc) and metal sulfides (such as
NiS, FeS, ZnS, Co , NiCoS etc) have gained much attention
2
, CuO, NiO,
Lithium-ion batteries (LIBs) are popular rechargeable batteries,
which can store twice the energy stored by other technologies
like nickel and lead batteries . The most common commercial
O
3 4
3
O
S
9 8
4
2
4
1
because of their high natural abundance, high theoretical
anode material used in LIBs is graphitic carbon, which has good
cyclic stability and relatively low cost. However, graphite
5-7
specific capacity and non-toxic nature
. However, in
-1
comparison to metal oxides, the transition metal sulfides have
proven to be a better choice due to their better electrical
conductivity and the large specific capacity. In addition, the
weaker metal-sulfur bond makes the conversion reactions of
suffers from a low theoretical capacity (375 mAh g ), which
2
-4
brings obvious consequences in terms of energy density
.
*
a. Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan,45320
b. Institute for Applied Materials, Karlsruhe Institute of Technology, Hermann-von-
metal sulfides kinetically more favored than those of metal
8-10
*
oxides
.
Among several metal sulfides, ZnS attracted considerable
attention because of its easy synthesis, low cost, non-toxicity,
and high theoretical capacity (962 mAh/g), but the practical
application of ZnS is hindered due to its poor electrical
Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany
c. Helmholtz-Institute Ulm for Electrochemical Energy Storage (HIU), P.O. Box 3640,
D-76021 Karlsruhe, Germany
d. Sustainable Energy Technologies (SET) centre, college of engineering, PO−Box
11
conductivity and large volume change during cycling . As the
8
00, King Saud University, Riyadh 11421, Saudi Arabia
Li insertion/extraction mechanism on ZnS involves conversion
and alloying reactions during Li insertion/extraction, it suffers
from rapid expansion/shrinkage. This dramatic change in
volume results into the loss of electrical contact from the
collector foil, thus causing a rapid capacity fading. Moreover,
e. Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology,
Hermann-von-Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany
*Corresponding authors: werner.bauer@kit.edu (W. Bauer); humairas@qau.edu.pk
(Humaira M. Siddiqi)
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poor electronic conductivity is also responsible for its poor rate distilled water 26. Here for the first time, we have used a
performance 1
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2, 13
DOI: 10.1039/C9NJ02488C
eutectic mixture (LiCl/ZnCl ) as a template to prepare the
2
.
To address these problems, various strategies have been porous ZnS/NSC-x composites. This salt mixture not only helps
devised. One of the strategies is to reduce the ZnS particle size in ordering and increasing the surface area of the material, but
to the nanoscale as this shortens the transport pathways for also acts as a source of zinc ions for in situ formation of ZnS
ion and electrons movement, thus facilitating the charge during the carbonization process. On the other side, the use of
storage process at high current rates and improving the rate 2-amino-4-phenyl thiazole as precursor serves as the single
capability 1
4,
15
. Nevertheless, nanosizing also increases the source for both N and S doping. Moreover, in situ synthesis
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interface exposure to an electrolyte, resulting in excessive leads to ZnS composites having good contact with the carbon
solid electrolyte interphase (SEI) formation. In another matrix that helps in buffering the volume change of ZnS on
approach, to alleviate the poor conductivity and electrode lithiation/delithiation. This developed synthesis route has also
pulverization problem, hybridization of ZnS with the variety of the advantage to be simple, low cost, and high yield.
nanostructured carbonaceous materials including graphene,
reduced graphene oxide, carbon nanotubes, and
micro/mesoporous carbons, etc. has been done
3
, 16-18
2. Experimental
.
In this respect amorphous porous carbon-based composites
also provide extra storage sites but at the expense of poor
conductivity due to less graphitization. So to overcome this
problem heteroatom doping (such as N, P, S or B) has been
proven beneficial as it improves the electronic structure by
2
.1. Synthesis of the precursor for carbon material
The synthesis of 2-Amino-4-phenyl thiazole was carried out
2
7
according to the procedure reported in the literature . The
reactants consisting of acetophenone (0.1 moles), iodine (0.1
moles) and thiourea (0.2 moles) were mixed in a ceramic
mortar and the mixture was transferred to a 250 mL round
bottom flask for heating at 110°C for 24 h. The reaction
mixture was extracted with ether to remove the excess
unreacted iodine and acetophenone. The residue from the
aqueous layer was further dissolved in boiling water and on
cooling; it was made alkaline using ammonium hydroxide
solution. The obtained solid was filtered and washed multiple
times with distilled water. Finally the separated solid was
recrystallized in ethanol.
1
9, 20
shifting the Fermi level to the valence or conduction band
.
N and S are the extensively studied dopants; N doping
improves the electronic conductivity and S because of its large
size increase interlayer spacing which creates micropores for
ion storage. Moreover, its polarizable lone pairs can change
the adjacent carbon charge state which improves the
adsorption ability. Importantly when these interactive
heteroatoms are co-doped their synergistic effects can be
generated which is helpful in improving electrochemical
stability2
1-23
.
Mostly, the ZnS composites have been prepared by first
synthesizing ZnS and then applying a carbon coating with
2
.2. Synthesis of active materials
2
4
various precursors such as glucose, polydopamine, etc. . Li et The carbon precursor (2-Amino-4-phenyl thiazole) was mixed
2
4
al prepared ZnS/Nitrogen-doped composite by following the with LiCl (23 mol %) /ZnCl (77 mol %) in a 1:3 ratio. The dry
2
same strategy using polydopamine as a source of nitrogen mixing of precursor and salt mixture was done in a ceramic
doped carbon coating. Metal-organic frameworks (MOFs) have mortar with pestle. The well-ground mixture was transferred
also been used as precursors for the synthesis of ZnS/Carbon to the crucibles and carbonized at 800 and 900°C in a furnace
Composites. Fu et al12 prepared nitrogen doped porous carbon at a heating rate of 5°C/min under Ar flow. The maximum
from MOFs that displays a capacity of 438 mAh/g at a current temperature was held for 2 h. The materials prepared by
density of 0.1A/g after 100 cycles. The introduction of various carbonization followed by ball milling were further stirred with
heteroatoms (N, S, etc.), beneficial for improving the carbon distilled water for 2-3 h; this mixture was filtered and
conductivity, involves extra nitrogen and sulfur sources like subsequently washed with warm distilled water to get rid of
thiourea, urea, 2-amino thiophenol, etc. . The previous excess salt or other side products. The resulting material was
studies focused on the synthesis of composites, where the finally dried at 80°C for 1h.
extra carbonaceous material and the heteroatoms are added
in a different step. Additionally, the activation of carbon 2.3. Material characterization
material (necessary to increase the surface area) also requires
2
5
To investigate the crystal structure, X-Ray diffraction (XRD)
another step. Hence all these methods involve multistep and
pattern was recorded with a powder diffractometer (D5000,
complex synthetic procedures. Moreover, the addition of
Siemens; Cu-Kα1, 2 radiations) in the 2θ range between 15° and
0°. Nuclear magnetic resonance spectroscopy (NMR) was
used for structural analysis of the synthesized precursor. The
H and C NMR spectra were recorded on a Bruker
spectrometer at 300 and 75 MHz respectively. The solvent
used for NMR spectroscopy was DMSO-d6. The morphologies
and other structural characteristics were investigated by field
emission scanning electron microscopy (FESEM) (Supra 55,
carbonaceous agents afterward also leads to poor connectivity
of ZnS with the carbon framework.
8
In the present work, we have devised a novel strategy for
facile one step in situ synthesis of ZnS/NSC-x composites via
salt templating method. Salt templating has been proven as an
effective method for controlling the microstructure of
carbonaceous materials. These templates can be easily
removed after carbonization by subsequent washing with
1
13
2
| J. Name., 2012, 00, 1-3
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Zeiss) with an accelerating voltage of 10 kV. For obtaining experiments were carried out by an Arbin battery cycler
more detailed morphological and chemical information (BT2000, Arbin Instruments). The CV was carried out in the
TEM/STEM measurements was conducted using a Tecnai F20 potential range of 0.01-3.0 V vs Li/Li at a scan rate of 0.1 mV s
ST (FEI, Eindhoven, NL) with a field emission gun operated at
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DOI: 10.1039/C9NJ02488C
+
-
1
−1
. CV with varying scan rates (0.1, 0.2, 0.4 and 0.6 mV s ) was
2
00 kV, equipped with an Orius SC600 CCD camera (Gatan, also performed. All the discharge/charge experiments were
+
Pleasanton, CA) and an S-UTW EDX Si(Li) detector (EDAX, also performed in a potential range of 0.01-3.0V vs. Li/Li with
Mahwah, NJ). EDX line profiles were acquired in STEM-mode varying specific currents (25, 50, 100, 250, 500, 1000 and 1500
using drift correction, with a sample tilt of 20° towards the mAg ). The discharge/charge experiments were also
detector. Sample preparation was done by dispersing a spatula conducted with a current density of 250 mA g for long-term
tip of the composite material in ethanol (grade p.a.). After cycling. For electrochemical impedance spectroscopy (EIS),
sedimentation, one drop of solution was spread with a pipette PAT-cells from EL-cells (Germany) were used. These cells were
onto 300 mesh TEM copper grids coated with lacey carbon film assembled with a Li disc as a counter electrode, a glass fiber
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(
Plano, article number S 166-3).
The thermogravimetric analysis was carried out through a as the electrolyte. EIS was carried out in the frequency range
thermogravimetric analyzer (Netzsch STA 490) in 100 kHz – 10 mHz using a multichannel potentiostat (VMP3,
temperature range 25°C to 900°C at a heating rate of 5°C/min Bio-Logic) with test cells inside a Binder climate chamber at 25
in air. For specific surface area analysis N sorption/desorption °C. The EIS were analyzed using Relaxis 3 software (rhd
separator, a Li-ring as a reference electrode and 150 µL of LP30
a
2
analysis was done on Micromeritics (Flowsorb II 2300). Instruments, Germany).
Measurement of the particle size distribution was carried out
by laser scanning (Horiba LA950), Raman spectroscopy was
performed by a Horiba LabRAM HR spectrometer. To study the
surface composition, X-Ray photoelectron spectroscopy (XPS)
was used. Measurements were performed using a K-Alpha+
instrument (Thermo Fisher Scientific, East Grinstead, UK), The simple synthetic scheme of the composites is illustrated in
applying a 400 µm spot size of a monochromated Al Kα X-ray Figure 1. The synthesis of a precursor (2-Amino-4-phenyl
source. The spectra were fitted with Voigt profiles using the thiazole) is followed by the carbonization of its mixture with
Thermo Avantage software. All spectra were referenced to the
C 1s peak of hydrocarbon at 285.0 eV. The uncertainty of the
binding energy is about ±0.1 eV for intense peaks and/or peaks
clearly evidenced by the peak shape. On the other hand weak
peaks for which no direct justification made by the peak shape,
the uncertainty is ± 0.2 eV.
3
. Results and discussion
3
.1. Structural analysis
eutectic salt (LiCl/ZnCl
2
). The inbuilt N and S atoms of the
precursor act as dopants during the carbonization process.
2
+
However, the Zn ions from the eutectic salt mixture combine
with the sulfur, liberated from the precursor during the
carbonization and thus form in situ ZnS. The structure
1
confirmation of the synthesized precursor was done by the H
13
and C NMR as presented in Figure S1.
2
.4. Electrochemical characterization
The working electrodes were prepared by coating uniform
slurry on a 10 µm thick copper foil (current collector). The
components of the slurry were active material (86 wt. %),
carbon black (Super C65, Imerys Graphite and Carbon, 6 wt.
%
), carboxymethyl cellulose (CMC, CRT2000, Dow Wolff
Cellulosics, 6 wt. %) and styrene-butadiene (SBR) copolymer
latex (TRD2001, JSR Corporation, 4 wt. %). All the components
of the slurry were mixed in deionized water by a dissolver
mixer (VMA Getzmann). For the preparation of bare ZnS
working electrode, the electrode slurry with the same
composition was used. The mass loading on each electrode
was kept between 3-4 mg cm . Before assembling of the cells Figure 1: Schematic representation of the synthesis of ZnS/NSC-800
the punched electrodes (12 mm) were dried in a vacuum oven
at 120 °C. Swagelok type cells with two electrodes were
assembled in an Ar-filled glove box with lithium metal used as
-2
and ZnS/NSC-900
The synthesis and phase purity of in-situ synthesized ZnS is
confirmed by XRD (Figure 2a). The peaks present at 2Ɵ 28.5°,
both counter and a reference electrode. A glass fiber foil
4
7.6°, and 56.4° correspond to (111), (220) and (311) single
(
Whatman®-GF/D) was used as a separator and the electrolyte
was BASF LP30 [1M LiPF in ethylene carbonate/dimethyl
carbonate (1:1, w/w)]. The electrolyte quantity was 80 µL in
8
phase crystal planes of cubic zinc sulfide structure . The
average crystal size of the synthesized composites calculated
by the Debye Scherer equation from the most intense XRD
6
each cell. The capacity of composite anodes was calculated on peak was 9 nm. The diffraction peaks related to the
the basis of the whole active material mass. Cyclic heteroatom-doped carbon in composites cannot be observed,
voltammetry (CV) and galvanostatic charge/discharge which displays the amorphous nature of the carbon matrix. In
This journal is © The Royal Society of Chemistry 20xx
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addition, no peaks related to impurities are observed, which In comparison to ZnS/NSC-800, the high magnificVaiteiwoAnrtiscpleeOcntlirnae
shows the purity of the synthesized composites.
of S 2p and N 1s for ZnS/NSC-900 (Fi
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smaller peak intensities, suggesting the decrease of nitrogen
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and sulfur content with increasing pyrolysis temperature
.
Thus, the XPS analysis demonstrates the successful doping of N
and S at the graphite edges. It is presumed that the electrical
conductivity and lithium storage performance for the
heteroatom doped composites will be improved because of
the introduction of more electrochemically active sites and the
additional defects introduced by dopants.
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Figure 2: (a) XRD Diffraction patterns of ZnS/NSC-800 and ZnS/NSC-
9
00 (b) Raman spectra of composites (ZnS/NSC-800, ZnS/NSC-900)
and NSC-800
To further study the structure of carbon material in
composites, Raman spectroscopy was carried out as presented
in Figure 2b. The characteristic peaks arising at 1350 and 1590
cm were ascribed to D and G bands 28. The D band arises
from the deformation in the carbon matrix and the G band
appears because of vibrations induced from the graphite-like
-1
D G
carbon. The I /I value determines the degree of deformation
in the carbon matrix, a higher value shows a higher
deformation and less graphitization in the material 2 . The
extent of deformation induced by heteroatom doping by
calculating I /I (see Table 1), decreases with the increase of
D G
the temperature. Moreover, the carbon material prepared
without the use of salt mixture (NSC-800) show the smaller
values for composites. This decrease of I /I with use of salt
D G
mixture indicates that the salt template has resulted in the
formation of more ordered composites.
8, 29
Figure 3: XPS. (a) Zn 2p and S 2p; (b) N 1s spectra of ZnS/NSC-800 and
(c) Zn 2p and S 2p; (d) N 1s spectra of ZnS/NSC-900
D G
Table 1: I /I ratios obtained from Raman spectra
The morphologies of the as-synthesized composites (ZnS/NSC-
800 and ZnS/NSC-900) were investigated by Field emission
scanning electron microscopy (FE-SEM), as presented in Figure
4. The high magnification SEM micrographs show that the
particle size of ZnS/NSC-900 is finer than ZnS/NSC-800. Some
graphitic sheets like morphology, in addition to globular
structures, can also be observed in these materials. The cross-
sectional SEM images of the composite electrodes in Figure S3
show ZnS particles well enclosed in the carbon layer. However,
some of the nanocrystals were also found scattered on the
surface of the carbon material. Moreover, the porosity,
resulting from the use of salt mixture can also be seen in these
images. The composites analyzed by EDX spectra shows the
presence of Zn, S, C and N elements (Fig S4 h). The presence of
embedded ZnS was also confirmed from the elemental
mapping (Figure S4) and the existence of Zn and S peaks in 1:1
atomic ratio in the corresponding EDX spectra (Table S1).
S. No
Sample
NSC-800
D G
I /I
1
2
3
1.37
1.24
1.10
ZnS/NSC-800
ZnS/NSC-900
X-Ray photoelectron spectroscopy (XPS) was performed in
order to study the heteroatoms doping and chemical bonding
of elements in ZnS/NSC-x composites. The XPS survey spectra
(
Figure S2) show the presence of Zn, C, S, and N in the
synthesized composites. The high-resolution Zn 2p spectra of
ZnS/NSC-800 inserted in Figure 3(a) shows peaks at around
1
2
044.8 eV and 1021.8 eV, which correspond to Zn 2p1/2 and Zn
3/2 peaks of ZnS. The presence of ZnS is further confirmed by
p
the peak in the S 2p spectrum, with the characteristic binding
Figure 4g shows a TEM bright field image, and from the same
area a STEM HAADF image (Figure 4h) of ZnS/NSC-900, tilted
0° towards the EDX detector. In the TEM image, ZnS
crystallites appear with dark contrast. They are partly
agglomerated, in some cases single dark spots of around 10nm
can be observed (see red arrow). The ZnS-crystallites are
embedded in an amorphous appearing matrix. In STEM, the
ZnS particles appear bright, whereas the carbon exhibits less
contrast. The EDX line profile (location is the yellow line)
18
energy at 161.5 eV . The other two weak peaks at 163.5 eV
and 167.9 eV are ascribed to C-S-C covalent bond and to C-SO -
x
C sulfone bridges respectively
functionalities of ZnS/NSC-800, the
deconvoluted into three peaks with binding energies (398.1
eV), (399.9 eV) and (401.5 eV) which are assigned to pyridinic-
N, pyrrolic-N, and quaternary N respectively (Figure 3b)
2
3
0, 31
. To identify the nitrogen
1s peak was
N
3
2, 33
.
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indicates clearly that STEM-signal intensity, Zn and S-intensity loss results from the loss of coordinated water VaienwdArtoicxleyOgnelinne-
evolve in parallel (Figure S5). The HR-TEM image (Figure 4h) containing groups in the samples. Howe
shows a ZnS particle, where (111) fringes with a distance of loss in the third step, from 400 to 800°C, is the result of both
D
v
O
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:
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1
t
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03
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a
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j
9
o
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w
02
e
4
ight
8
8
C
2
4
0
.31 nm corresponding to planes of ZnS crystals are visible. the combustion of carbon and oxidation of ZnS to ZnO [ ]. The
Around the particle, carbonaceous matrix can be detected.
conversion of ZnS to ZnO was confirmed by the XRD of the TGA
residue presented in Figure S5. As ZnS was fully converted to
Further, the particle size distribution of the two composites ZnO, the quantity of ZnS from ZnO was calculated by the
24, 37
(
Figure 5a) displays the decrease of particle size with the following formula
.
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increase in pyrolysis temperature. The average particle size of
ZnS/NSC-800 and ZnS/NSC-900 was found to be 3.9 and 2.8
µm, respectively. The Brunauer–Emmett–Teller (BET) surface
area was also determined by the N adsorption isotherm, as
2
shown in Figure 5(b). These isotherms can be categorized as
ZnO% = WZnO / WTotal
ZnS % = ZnO% × MZnS / MZnO
Where WZnO is the weight of ZnO, WTotal is the total weight of
the composite while MZnS and MZnO are the molecular masses
of ZnS and ZnO respectively. The content of ZnS determined by
the above formula was 52 and 40.5% for ZnS/NSC-800 and
ZnS/NSC-900, respectively. The relatively lower content of ZnS
in the composite prepared at 900°C results from the more loss
of heteroatoms and heteroatom based carbon fragments at
higher temperatures.
Type IV which is indicative of the presence of micropores and
mesopores 35. The measured surface areas for ZnS/NSC-800
2
and ZnS/NSC-900 were 131 and 156 m /g, respectively, which
signifies that the use of salt mixture has resulted into the
composites with a good surface area, which can lead to more
contact between the electrolyte and active material interface,
thus facilitating the electrochemical reactions. The relatively
higher surface area of ZnS/NSC-900 is the result of high-
temperature treatment as mentioned before, which is also in
3
6
correspondence with the particle size measurement .
In order to calculate the percentage content of ZnS and carbon
in composites, thermogravimetric analysis was carried out, as
presented in Figure 6. The TGA shows the three-step weight
loss for both composites. The weight loss from 25°C to 150°C
Figure 4: FESEM images. Higher and Lower magnification FESEM images of ZnS/NSC-800 (a, b, c) and ZnS/NSC-900
d, e, and f), TEM, STEM and HRTEM (g, h, i) of ZnS/NSC-900
(
can be attributed to the adsorbed water. The second weight
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Figure 6: TGA curves of ZnS/NSC-800 and ZnS/NSC-900
Figure 5: PSD and BET isotherms (a) Particle size distribution of the
synthesized composites (b) N
and ZnS/NSC-900
Moreover, when the current density was again lowered to
50mA g after 46 cycles of cycling at various current
densities, the reversible capacity of the composites can be
recovered approximately to the initial capacities. By further
lowering the current density to 25 mA g , about 84% of the
2
adsorption isotherms of ZnS/NSC-800
-1
2
3.2. Electrochemical characterization
-1
initial capacity is recovered for ZnS/NSC-800. However, bare
To investigate the electrochemical behavior of the synthesized ZnS could only regain 53% of its initial capacity at the same
composites, cyclic voltammetry (CV) on bare ZnS and on the current density. Hence, this also shows the structural stability
two composite electrodes was carried out. Figure S6 (a, b and of the composite electrodes even under high rate cycling.
c) shows the cyclic voltammogram of bare ZnS, ZnS/NSC-800
and ZnS/NSC-900 for the first four cycles. In the cathodic scan, Table 2: The specific discharge capacities of the two composite
several small reduction peaks appear below 0.8V, indicating
the alloying and reduction of ZnS to metallic zinc in multiple
steps. However, the small oxidation peaks, detected in the
same potential range, represents the multistep dealloying of
Li-Zn. A strong oxidation peak at 1.3V is attributed to the
regeneration of ZnS from Zn. The CV curves are consistent with
electrodes and bare ZnS at various current densities
Current
densities
(mA/g)
S. No
Specific discharge capacities
mAh/g)
(
38
the previous literature . However, the important point to
note here is that the CV of bare ZnS is similar to the
synthesized composites, but a rapid degradation can be
observed. On the other side, the CV curves of both composites
are well overlapped, showing the good electrochemical
reversibility of the composite materials.
Bare ZnS
898
459
320
208
114
80
ZnS/NSC-800
895
ZnS/NSC-900
960
1
2
3
4
5
6
7
8
9
25
50
586
577
100
250
500
1000
1500
250
25
508
490
429
370
To further explore the electrochemical superiority of the
composites, the uninterrupted rate performance was studied
in half cells. Figure 7(a) shows the comparison of the rate
performance of the composite materials (ZnS/NSC-800 and
ZnS/NSC-900) with bare ZnS. The initial Coulombic efficiency of
ZnS/NSC-800 is 74% however, only after a few cycles; this
value becomes nearly 100%, which demonstrates the good
electrochemical reversibility of the material. For ZnS/NSC-900
the relatively lower initial Coulombic efficiency (66%) is
because of the comparatively higher surface area, which is
responsible for large contact between the electrolyte-
electrode interfaces, thus leading to more irreversible side
reactions during SEI formation. However, after a few cycles,
the Coulombic efficiency of ZnS/NSC-900 also becomes nearly
357
286
317
225
60
279
200
205
403
360
241 (53%) 555 (84%)
534 (87)
The discharge/charge profiles of ZnS/NSC-800, ZnS/NSC-900,
and bare ZnS at various current densities are presented in
Figure 7(b, c, d). In these discharge/charge curves, the rapid
capacity drop, from 898 to 60 mAh g , can be visibly seen in
case of bare ZnS. Moreover, the capacity retention of ZnS/NSC-
-1
1
00%. Table 2 shows the specific capacities of the two
composite electrodes and bare ZnS at various current
densities. It can be seen that in comparison to the two
composites, bare ZnS exhibits much lower capacities.
8
00 is 65% on increasing current density from 250 to 1500 mA
-
1
g . The capacity retention of bare ZnS is only 28% which is
much less than the one of the composites. This shows the
excellent rate performance of the composites compared to
bare ZnS. Among the two composites, ZnS/NSC-800 performs
better with higher specific capacity and capacity retention with
the subsequent increase in current densities. The possible
explanation for the better rate performance of ZnS/NSC-800 is
the presence of a relatively higher percentage of ZnS and more
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dopants (N and S) that can also provide more
electrochemically active sites and defects which are
responsible for extra lithium storage.
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Figure 7: Uninterrupted rate performances and discharge/charge profiles. (a) Rate performance of bare ZnS,
ZnS/NSC-800 and ZnS/NSC-900 (b, c, d) Discharge/Charge profiles of ZnS/NSC-800, ZnS/NSC-900, and bare ZnS
respectively at different specific currents
-1
Figure 8: Cycling performance. Cycle performance at a current density of 250 mA g for 258 cycles
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The cycling stability of the composite electrodes was also
tested and compared with bare ZnS, as presented in Figure 8. to the one of ZnS. Moreover, ZnS/N
The identical electrodes were used for both rate performance charge transfer resistance at low potentials respect to both,
and cycling tests. The electrodes already cycled at various ZnS/NSC-800 and bare ZnS. The higher graphitization degree in
current densities were again discharged/charged at a current ZnS/NSC-900 leads to smaller interlayer distance, thus
R
CT (charge transfer into the graphitic carbon), whViiecwhAroticvlee rOlnalpines
D
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density of 250 mA g for about 200 cycles and the capacity inducing sluggish intercalation. Hence, the decreased
retention for ZnS/NSC-800 is 90%. However bare ZnS retained interlayer spacing can be the possible reason for the high
only 31% of initial capacity after 200 cycles at same current charge transfer resistance of ZnS/NSC-900 at low potentials.
density (see Figure S7). This result displays that the composite The impedance measurements show that the in situ
electrode already cycled under a stress environment of various synthesized ZnS/NSC-800 has very low Rct which is beneficial
current densities when subjected to further cycling, maintain for achieving improved kinetics. Moreover, with 50% of ZnS
good capacity retention that illustrates the good electrode content and moderate surface area the storage capacities for
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structure integrity.
ZnS/NSC-800 are comparable to the composites of higher
surface area having larger ZnS content and low initial
In order to study the reaction kinetics of the electrode Coulombic efficiencies11, 12, 39
materials and to have a better insight into the superior
performance of composites, electrochemical impedance 3.3. Kinetic Analysis
spectroscopy (EIS) was measured at different potentials. Figure
.
To further have an understanding about the electrometrical
performance, kinetic analysis through CV was performed. In
this purpose, CV measurements at different scan rates were
performed, as presented in Figure 10 (a, b). The charge storage
9
(a) shows the Nyquist plots related to the composites and the
+
bare ZnS at 1.3 V vs Li/Li . These spectra can be fitted with the
equivalent circuit shown in Figure 9(a). The resistance of
separator, cell connections, and electrolyte (named REL) is
retrieved by the intercept with the real axis. At very high
frequencies a small semicircle can be identified, which is
related to the contact resistance and the resistance of the SEI
4
0
process generally involves different mechanisms and the
broad categorization of the storage mechanisms can be done
by the CV data obtained at different scan rates by using the
34
following relation :
s S
(R ) and the associated capacitance (C ). At medium
i = avb
(1)
(2)
frequencies, a second semicircle represents the charge
transfer resistance (RCT) and the related capacitance (CPECT).
This is followed by the solid diffusion in the particle bulk
log (i )= b log (v) + log (a)
(
Warburg impedance, W) and by the capacitance at very low
Where i represents the measured current density, v is the scan
rate, while a, and b are the constants. A value of 0.5b indicates
a pure diffusion-controlled (faradaic intercalation/insertion)
frequencies (here named CPE ). The RCT of ZnS/NSC-800 is the
3
smallest one among the three materials. On the other side,
bare ZnS shows the highest RCT. The low RCT for composites
imply that the heteroatom-doped carbon matrix is beneficial
for the improvement of reaction kinetics. The resistance
evolution from the Ohmic drop (as calculated from the
charge/discharge curves of cycled electrode) also shows that
after cycling the IR drop is much higher for ZnS than ZnS/NSC-x
electrodes.
4
1, 42
process, whereas b=1.0 means a pure capacitive behavior
.
Figure 9: Electrochemical impedance results and Rct at various
potentials. (a) Nyquist plots of Bare ZnS, composites and an equivalent
circuit model for EIS (b) Comparison of charge transfer resistance at
various potentials
Figure 9(b) shows the charge transfer resistance of the three
electrodes at different potentials. It can be seen that the value
of Rct related to the pure ZnS is smaller at low potentials and
dramatically increases at higher potentials. The higher charge
transfer resistance related to the composites at low potential 800 and ZnS/NSC-900 for LIBs ranging from 0.1 to 0.6 mV s-1 (c, d) log
can be explained by considering that Li insertion into carbon (i) vs log (v) plots for calculation of b value
layers takes place at low potentials, giving rise to an additional
Figure 10: Multiscan cyclic voltammetry. (a, b) CV curves of ZnS/NSC-
8
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Figure 11: Quantification of capacitive current. (a, b) v1/2 versus i/v1/2 plots at various potentials used for
calculating k and k (c, d) Contribution ratio of capacitive and diffusion-controlled capacities at a scan rate of
.2 mV s (e, f) Contribution ratio of capacitive current to Li storage at different scan rates (0.1-0.6 mV s )
1
2
-
1
-1
0
-1
the 57% at a scan rate of 0.6 mV s , which shows the
dependence of capacitive current on scan rate. The higher
capacitive contribution at high current densities leads to the
To determine the b value for the synthesized composites at
various potentials, log i was plotted against log v, as presented
in Figure 10 (c, d). At 1.3V, the calculated b value of anodic
peak is 0.54 for ZnS/NSC-800. However, for ZnS/NSC-900, the b
value is 0.63. This higher b value indicates a predominance of
diffusion controlled process with a slight surface capacitive
contribution. The reason for the higher b value for ZnS/NSC-
900 is the relatively higher carbon percentage and surface
area, which can also contribute to the capacitive storage via a
double layer mechanism. To further quantify the capacitive
contribution in relation to the total stored capacity in ZnS/NSC-
10
good rate capability of these materials .
Conclusions
The two composites ZnS/NSC-800 and ZnS/NSC-900 were
successfully synthesized with ZnS nanoparticles (9 nm)
embedded into the carbon matrix via the salt templating
method. The simple devised strategy of one step in situ
synthesis produced ZnS nanoparticles well encapsulated into
the N and S co-doped carbon matrix. The use of the salt
mixture, besides providing zinc ions for the in situ formation of
ZnS, also induces good surface area to the composites. The
synthesized nanocomposites were used as a positive electrode
for lithium-ion battery and they exhibit better rate
performance and cycling stability than pure ZnS. Among the
two composites, the storage capacities are higher for ZnS/NSC-
3
4
8
00 and ZnS/NSC-900, following relation was used .
v1/2
i(V) = k
1
v +k
2
(3)
By rearranging equation (3)
i(V)/v1/2= k
v1/2 + k
2
(4)
1
1 2 1
where k and k are constants for a given potential V. The k v
-1
8
00, with the initial specific capacity of 895 mAh g . This can
represents the current contribution related to the capacitive
process, while the k
1
/2
be attributed to the higher %age of ZnS and the relatively
lower carbon percentage. Upon long repeated cycles, the pure
ZnS displays a rapid degradation; while N and S co-doped
carbon coated ZnS give stable capacities. Indeed ZnS/NSC-800
retains 90% of the initial capacity after 200 cycles. Besides the
good cycling stability, the composites also show better rate
performance in comparison to pure ZnS. The capacity
2
v
represents the current contribution
and k values
due to the diffusion-controlled storage. The k
were obtained by plotting i(V)/v vs v
11(a, b) where k
1
2
1
/2
1/2
as shown in Figure
is determined from the slope 4, 43-45.
3
1
Figure 11 (c, d) shows the capacitive contribution (shaded
blue) of synthesized composites (ZnS/NSC-800 and retention of ZnS/NSC-800 is 65% on increasing current density
ZnS/NSC900) in relation to the total measured current at a from 250 to 1500 mA g , while pure ZnS retains only 28% of its
scan rate of 0.2 mV s . The higher percentage of capacitive initial capacity at the same current densities. The better rate
current for ZnS/NSC-900 (60%) is the result of relatively higher
surface area and carbon percentage as mentioned before. The
quantification of capacitive current for other scan rates (0.1,
0.2, 0.4 and 0.6 mV s ) was also done as presented in Figure
11 (e, f). It can be seen that for ZnS/NSC-800, 44% of the total
-1
-1
capability can be ascribed to the improved conductivity of the
in situ synthesized composites. EIS analysis also shows the
smallest charge transfer resistance for ZnS/NSC-800, thus
further confirming the better electronic conductivity of
composites. Moreover, the good cycling stability of the
composites respect to the pure material shows that the carbon
-1
-
1
capacity is capacitive at a scan rate of 0.2 mV s and it reaches
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coating also helps in buffering the volume change. This simple 15.
synthetic strategy can be easily applied to synthesize and
explore also other composites in the future. Moreover, by the
adjustment of heating rate and carbonization temperature,
the quantity of ZnS in composites can be increased to more
than 50% which can result in further high storage capacities.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgments
The authors acknowledge the scholarship funding by the
Higher Education Commission of Pakistan under IRSIP program 22.
for this research. We acknowledge the support from Karlsruhe
Nano Micro Facility (KNMF, www.knmf.kit.edu ), a Helmholtz
23.
research infrastructure at Karlsruhe Institute of Technology
(KIT, www.kit.edu). This work contributes to the research
24.
performed at CELEST (Centre for Electrochemical Energy
Storage Ulm-Karlsruhe). The K-Alpha+ instrument was
financially supported by the Federal Ministry of Economics and
Technology on the basis of a decision by the German
Bundestag.
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DOI: 10.1039/C9NJ02488C
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One step in situ synthesis of ZnS/N and S Co-doped Carbon Composites via
salt templating for Lithium-ion battery application
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a,b
b
b,c
d
b
Sadaf Ikram , Marcus Müller , Sonia Dsoke , Usman Ali Rana , Angelina Sarapulova , Werner
b*
a*
b,e
Bauer , Humaira M. Siddiqi , Dorothée Vinga Szabó
Entry for Table of Contents
Eutectic salt mixture (LiCl/ZnCl ) as a template plays a dual role by rendering sufficient
2
2+
surface area and a source of Zn for in situ formation of ZnS. Phenyl thiazole is a precursor
for self-doped N and S carbon material. The resulting ZnS/ N and S Co-doped carbon
composites as anode for Li-ion battery exhibit superior performance than pure ZnS.