Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon

SnS2 has been investigated as anode material for lithium ion batteries. To obtain anode material having high

capacity and long-term lifespan, in the present work, a nanostructured composite comprising SnS2 nanosheets and

CMK-3 ordered mesoporous carbon has been designed. The CMK-3/SnS2 composite is fabricated via incipient wetness

impregnation, followed by chemical reduction and chemical conversion in an inert gas at high temperature. The

obtained composite exhibits boosted lithium storage behaviors involving high specific capacity, fast rate response and

stable cyclability. At a discharge-charge rate of 100 mA g-1, the CMK-3/SnS2 electrode delivers a specific capacity of

985.2 mA h g-1 with the utilization efficiency of SnS2 present in the composite of 90.5 %. Even, after 500 cycles testing

at higher discharge-charge rates of 0.5 and 1 A g-1, CMK-3/SnS2 still can maintain specific capacities of 556.2 and

402.9 mA h g-1, respectively, much higher than the theoretical specific capacity of commercialized graphite anode

material. This work demonstrates considerable application potential of the CMK-3/SnS2 anode in Li-ion batteries.

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 1

Trang 1

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 2

Trang 2

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 3

Trang 3

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 4

Trang 4

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 5

Trang 5

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 6

Trang 6

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 7

Trang 7

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon trang 8

Trang 8

pdf 8 trang viethung 5300
Bạn đang xem tài liệu "Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon", để tải tài liệu gốc về máy hãy click vào nút Download ở trên

Tóm tắt nội dung tài liệu: Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon

Fabrication and lithium storage performances of a composite of tin disulfide and ordered mesoporous carbon
Cite this paper: Vietnam J. Chem., 2020, 58(5), 622-629 Article 
DOI: 10.1002/vjch.202000050 
622 Wiley Online Library © 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH 
Fabrication and lithium storage performances of a composite of 
tin disulfide and ordered mesoporous carbon 
Le Thi Thu Hang
*
, Hoang Thi Bich Thuy, Dang Viet Anh Dung, Dang Trung Dung 
School of Chemical Engineering, Hanoi University of Science and Technology, 
1 Dai Co Viet, Hai Ba Trung district, Hanoi 10000, Viet Nam 
Submitted March 31, 2020; Accepted April 28, 2020 
Abstract 
SnS2 has been investigated as anode material for lithium ion batteries. To obtain anode material having high 
capacity and long-term lifespan, in the present work, a nanostructured composite comprising SnS2 nanosheets and 
CMK-3 ordered mesoporous carbon has been designed. The CMK-3/SnS2 composite is fabricated via incipient wetness 
impregnation, followed by chemical reduction and chemical conversion in an inert gas at high temperature. The 
obtained composite exhibits boosted lithium storage behaviors involving high specific capacity, fast rate response and 
stable cyclability. At a discharge-charge rate of 100 mA g
-1
, the CMK-3/SnS2 electrode delivers a specific capacity of 
985.2 mA h g
-1
 with the utilization efficiency of SnS2 present in the composite of 90.5 %. Even, after 500 cycles testing 
at higher discharge-charge rates of 0.5 and 1 A g
-1
, CMK-3/SnS2 still can maintain specific capacities of 556.2 and 
402.9 mA h g
-1
,
respectively, much higher than the theoretical specific capacity of commercialized graphite anode 
material. This work demonstrates considerable application potential of the CMK-3/SnS2 anode in Li-ion batteries. 
Keywords. Tin disulfide, lithium storage, composite, cyclability. 
1. INTRODUCTION 
Since the first commercialization in 1991, lithium 
ion batteries (LIBs) have been regarded as the most 
popular storage technology for mobile and portal 
applications including mobile phones, laptops, 
digital cameras because of their low self-discharge, 
high energy density, nearly zero-memory effect, and 
long lifespan.
[1]
 Graphite is established as a main 
anode active material for commercial LIBs since it 
possesses some advantages such as low working 
potential, low cost, and high stability. Nevertheless, 
it also exhibits some disadvantages such as high 
lithium ion diffusion resistance, harmful lithium 
dendrite growth on the graphite surface, and low 
theoretical specific capacity (372 mA h g
-1
).
[2]
 To 
meet the growing demand on high power density 
and high energy density, the development of new 
electrode active materials with outstanding 
electrochemical properties is indispensable. 
Much effort has been dedicated to developing 
alternatives to graphite anode for LIBs. In this 
context, conversion-alloying anode materials have 
recently received great attention, especially, SnS2, a 
tin based anode material since it possesses 
outstanding properties such as high specific capacity 
(1230 mA h g
-1
), low cost, low working potential, 
environmental friendliness, and ready availability.
[3]
Unfortunately, this material also suffers from large 
stress caused by huge volume expansion during 
lithiation process, which is also found for other 
alloy-type anode materials. This leads to the 
pulverization phenomenon of the active material, 
electrical disconnection between active material 
particles and a current collector, deterioration of the 
solid electrolyte interphase (SEI) layer on the 
electrode, and, eventually, significant degradation of 
the electrochemical performance. 
So far, some strategies have been supposed to 
solve the drawbacks of SnS2. They include 
fabrication of nanostructure,
[4]
 fabrication of 
composites of SnS2 with other active/inactive 
materials,
[5]
 fabrication of doped SnS2
[6]
 and 
structure design for SnS2-based materials.
[7]
In this work, we report a facile routine to 
synthesize the composite of SnS2 and CMK-3, a 
kind of ordered mesoporous carbon, with the aim of 
application as high performance-anode material for 
LIBs. For this designed composite, SnS2 nanosheets 
are filled inside and deposited partially outside 
mesopores of CMK-3 framework, which works as 
nanocage to confine the SnS2 nanosheets. Owing to 
high porosity and high stable structure of CMK-3, 
the volume expansion of SnS2 nanosheets during 
Vietnam Journal of Chemistry Le Thi Thu Hang et al. 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 623 
lithiation process can be alleviated. Accordingly, the 
composite exhibits remarkable lithium storage 
behaviors in term of cyclability, rate capability, and 
capacity. 
2. MATERIALS AND METHODS 
2.1. Synthesis of CMK-3/SnS2 composite 
CMK-3/SnS2 composite was fabricated via incipient 
wetness impregnation technique, following by heat 
treatment at high temperature. Where, CMK-3 as 
supporting material was synthesized by hard 
template method, which was described in the 
literature.
[8]
 In detail, CMK-3 powder (0.5 g) was 
added in 5 mL of a 50v/50v ethanol/water mixture 
containing SnCl4 and ultrasonicated for 30 mins. 
After drying at 80 C for 5 h, the resultant powder 
continued to be mixed well with 2 g of NaBH4, and 
then storage in the humid air for 48 h. Because 
NaBH4 is a highly hygroscopic substance in 
combination with the presence of oxygen in the air, 
the CMK-3/SnO2 composite could be easily formed 
according to chemical reactions as follows:
[9]
 SnCl4 + 4NaBH4 → Sn +4NaCl +2B2H6 +2H2 (1) 
 Sn + O2 → SnO2 (2) 
After that, the CMK-3/SnO2 sample was rinsed, 
and dried at 100 
o
C, followed by a heat treatment 
process in nitrogen atmosphere at 350 
o
C for 3 h. 
Prior to the heat treatment, CMK-3/SnO2 powder 
was put into a small alumina crucible ... hese 
processes were irreversible and only occurred at the 
first discharge. Meanwhile, the rest cathodic peaks 
exhibited a slight shift because of the structural 
change of the active material after the first cycle. 
For the anodic scan direction, two distinct anodic 
peaks (0.52 V, and 1.89 V vs. Li
+
/Li) were recorded 
for the five cycles of scanning. These peaks imply 
Vietnam Journal of Chemistry Le Thi Thu Hang et al. 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 627 
the dealloying of Li4.4Sn to form Sn, and the 
oxidation of Sn to SnS2.
[25]
 In addition, in 
comparison with figure 5a, two characteristic anodic 
peaks of CMK-3 were found in the CV plot of the 
CMK-3/SnS2 composite. 
Figures 6a,b illustrate the characteristic 
galvanostatic discharge-charge curves of the CMK-3 
and CMK-3/SnS2 composite electrodes at a current 
density of 100 mA g
-1
 for 100 cycles. As seen in 
Figure 6a, as for the first cycle, the CMK-3 electrode 
delivered specific discharge/charge capacities of 
1276.8/628.8 mA h g
-1
. Accordingly, its initial 
coulombic efficiency (CE) was calculated to be 49.2 
%. This obtained low CE resulted from the 
irreversible formation of the SEI layer and parasitic 
reactions. Within first ten cycles, the specific 
capacity had tendency to decrease rapidly for both 
discharge/charge processes due to the marginal 
structure deterioration of porous CMK-3.
[12]
 In the 
subsequent cycles, the microstructure stabilized 
gradually. Accordingly, the discharge-charge 
voltage curves almost overlapped, demonstrating 
highly stable cyclability of the CMK-3. Noticeably, 
no discharge/charge plateaus were observed for the 
CMK-3 electrode. 
In contrast, the CMK-3/SnS2 composite electrode 
exhibited two discharge plateaus (~1.4 V and ~0.4 
V) and two charge plateaus (~0.5 V and ~1.8 V). 
The obtained results are accordance with the CV 
analysis results above. In the first cycle, the CMK-
3/SnS2 could offered discharge/charge capacities of 
1570.8/985.2 mA h g
-1
 with an initial CE of 62.7 %. 
In the subsequent cycles, the discharge-charge 
voltage profile of the CMK-3/SnS2 almost 
overlapped in the discharge plateau at ~0.4 V, and in 
the charge plateau at ~0.5 V vs. Li
+
/Li. This 
indicates the high reversibility of alloying/dealloying 
reaction of SnS2 present in the CMK-3/SnS2 
composite. Remarkably, in the first cycle, the CMK-
3/SnS2 could supply a reversible specific capacity of 
985.2 mA h g
-1
. Accordingly, the practical specific 
capacity of only SnS2 component contributing to the 
total capacity of the composite was estimated to be 
1114.3 mA h g
-1
. Accordingly, utilization 
efficiency of the SnS2 active material was estimated 
to be 90.5 %. It means that 90.5 % of the entire 
CMK-3/SnS2 composite material participated in 
electrochemical reactions for lithium storage. This 
resulted from uniform dispersion of SnS2 nanosheets 
on/into CMK-3 framework. This led to avoiding the 
agglomeration phenomenon of SnS2 nanosheets and 
facilitating the contact between the electrolyte and 
the entire active material. After the 100 discharge-
charge cycles, the CMK-3/SnS2 electrode delivered 
a reversible specific capacity of 706.1 mA h g
-1
, 
which is over 1.5 times as high as the CMK-3 
electrode (458.9 mA h g
-1
). Furthermore, during 
cycling test, the CMK-3/SnS2 frequently remained a 
stably high CE of 99 % (figure 6c). 
Figure 6d shows the rate capability of CMK-
3/SnS2 at various current densities for five cycles. It is 
observed that at applied current densities of 0.1, 0.5, 
1, 2, 5, and 10 A g
-1
, the CMK-3/SnS2 could supply 
reversible specific capacities of around 923.9, 725.4, 
661.4, 590.4, 472.1 and 365.8 mA h g
-1
, respectively. 
As the applied current density was returned to the 
initial value of 0.1 A g
-1
, the specific capacity of the 
composite electrode quickly recovered a reversible 
specific capacity of 785.8 mA h g
-1
. This proves the 
remarkable rate capability of the CMK-3/SnS2. 
To further verify the long-term duration of rapid 
cycling, the CMK-3/SnS2 was cycled at different 
high current densities for 500 cycles. In specific, at 
such high current densities of 0.5 A g
-1 
and 1 A g
-1
, 
the electrode frequently offered reversible specific 
capacities of above 550 mA h g
-1
 and 400 mA h g
-1
, 
respectively, during cell operation. These values are 
even much higher than the theoretical value of 
commercialized graphite anode. At an extremely 
high current density of 5 A g
-1
, despite the decay of 
both discharge and charge specific capacities in the 
first 30 cycles, the CMK-3/SnS2 electrode rapidly 
recovered the specific capacity in the subsequent 
cycles. Because of the extremely high rate of 
discharge-charge, it is necessary for lithium ions to 
diffuse from the bulk electrolyte to the whole active 
material. This period is regarded as activation 
process for the electrode. After 500 cycles, the 
reversible specific capacity of the CMK-3/SnS2 
electrode still reached up approximately 
300 mA h g
-1
. Thus, despite operating under such 
hash conditions for a long duration of 500 cycles, 
the CMK-3/SnS2 still showed superior specific 
capacity and high stability. This probably resulted 
from the synergistic effect of the stable structure of 
CMK-3 and nanosized SnS2 sheets. It is well 
established that with the nanosized level, ultrafine 
SnS2 particles can tolerate the huge volume 
expansion caused by the lithiation process.
[26]
 In 
addition, as a supporting material, CMK-3 with the 
mesoporous structure offered plenty of interior void 
spaces for accommodation of the volume expansion 
of SnS2 during lithiation process (inset in figure 6e). 
As a result, the structural integrity of CMK-3/SnS2 
could remain during repetitive discharge-charge 
process. Furthermore, the electrical contact between 
SnS2 nanosheets filled inside the mesopores of 
CMK-3 retained stably. Consequently, the CMK-
3/SnS2 exhibited superior cycling stability. In 
specific, the capacity loss per cycle at current 
Vietnam Journal of Chemistry Fabrication and lithium storage performances 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 628 
densities of 0.5, 1, and 5 A g
-1
 was ~0.082, 0.078, 
and 0.079 %, respectively. The achieved results 
demonstrated highly practical potential of CMK-
3/SnS2 as high-performance anode material for 
LIBs, which can be deployed in the near future. 
4. CONCLUSION 
The CMK-3/SnS2 composite has been synthesized 
successfully using incipient wetness impregnation 
technique, in combination with chemical reduction, 
and subsequent heat treatment process at the inert 
gas. The resultant sample exhibited a polycrystalline 
phase structure with the unique morphology of 
worm-like-nanorods. Because of the synergistic 
effect of nanosized SnS2 sheets and the stable 
framework of CMK-3 enclosing these nanosheets, 
the CMK-3/SnS2 composite demonstrated excellent 
lithium storage behaviors including long-term 
cyclability and high specific capacity. At a high rate 
of discharge and charge, 1 A g
-1
, the CMK-3/SnS2 
still supplied a high reversible specific capacity of 
more than 400 mA h g
-1
, corresponding to 0.078 % 
capacity loss per cycle. Thereby, the CMK-3/SnS2 
nanocomposite is expected as a promising candidate 
for advanced anode materials in next-generation 
LIBs. 
Acknowledgements. This research is funded by 
Vietnam National Foundation for Science and 
Technology Development (NAFOSTED) under grant 
number 104.99-2017.305. We also gratefully 
acknowledge Professor Chan-Jin Park for use of his 
equipment in Materials Electrochemistry Laboratory 
at Chonnam National University (South Korea). 
REFERENCES 
1. T. Kim, W. Song, D. -Y. Son, L. K. Ono, Y. Qi. 
Lithium-ion batteries: outlook on present, future, 
and hybridized technologies, J. Mater. Chem. A, 
2019, 7, 2942-2964. 
2. M. Li, L. Cong, J. Zhao, T. Zheng, R. Tian, J. Sha, 
Z. Su, X. Wang. Self-organization towards complex 
multi-fold meso-helices in the structures of Wells-
Dawson polyoxometalate-based hybrid materials for 
lithium-ion batteries, J. Mater. Chem. A, 2017, 5, 
3371-3376. 
3. Y. Wang, J. Zhou, J. Wu, F. Chen, P. Li, N. Han, W. 
Huang, Y. Liu, H. Ye, F. Zhao, Y. Li. Engineering 
SnS2 nanosheet assemblies for enhanced 
electrochemical lithium and sodium ion storage, J. 
Mater. Chem. A, 2017, 5, 25618-25624. 
4. L. Wang, L. Zhuo, Y. Yu, F. Zhao. High-rate 
performance of SnS2 nanoplates without carbon-
coating as anode material for lithium ion batteries, 
Electrochim. Acta, 2013, 112, 439-447. 
5. H. Li, Q. Su, J. Kang, H. Feng, P. Huang, M. Feng, 
M. Huang, G. Du. Fabrication of MoS2@SnO2-SnS2 
composites and their applications as anodes for 
lithium ion batteries, Mater. Res. Bull., 2018, 108, 
106-112. 
6. H. Jia, C. Chen, O. Oladele, Y. Tang, G. Li, X. 
Zhang, F. Yan. Cobalt doping of tin 
disulfide/reduced graphene oxide nanocomposites 
for enhanced pseudocapacitive sodium-ion storage, 
Commun. Chem., 2018, 1, 86. 
7. L. Liu, F. Xie, J. Lyu, T. Zhao, T. Li, B. G. Choi. 
Tin-based anode materials with well-designed 
architectures for next-generation lithium-ion 
batteries, J. Power Sources, 2016, 321, 11-35. 
8. L. T. T. Hang, D. V. A. Dung. Lithium storage 
performance of SnO2@CMK-3 composites, Vietnam 
J. Chem., 2019, 57, 747-752. 
9. H. T. T. Le, D. T. Ngo, X. -M. Pham, T. -Y. 
Nguyen, T. -D. Dang, C. -J. Park. Graphitic N-
CMK3 pores filled with SnO2 nanoparticles as an 
ultrastable anode for rechargeable Li-ion batteries, J. 
Power Sources, 2019, 440, 227104. 
10. M. Wu, J. Wang, Z. Wu, H. L. Xin, D. Wang. 
Synergistic enhancement of nitrogen and sulfur co-
doped graphene with carbon nanosphere insertion 
for the electrocatalytic oxygen reduction reaction, J. 
Mater. Chem. A, 2015, 3, 7727-7731. 
11. Z. D. Wang, M. Yoshida, B. George. Theoretical 
study on the thermal decomposition of thiourea, 
Comput. Theor. Chem., 2013, 1017, 91-98. 
12. H. T. T. Le, T. -D. Dang, N. T. H. Chu, C. -J. Park. 
Synthesis of nitrogen-doped ordered mesoporous 
carbon with enhanced lithium storage performance 
from natural kaolin clay, Electrochim. Acta, 2020, 
332, 135399. 
13. P. Dibandjo, F. Chassagneux, L. Bois, C. Sigala, P. 
Miele. Comparison between SBA-15 silica and 
CMK-3 carbon nanocasting for mesoporous boron 
nitride synthesis, J. Mater. Chem., 2005, 15, 1917-
1923. 
14. J. Liang, H. Li, Z. Sun, D. Jia. N-doped CMK-3 
anchored with SnS2 nanosheets as anode of lithium 
ion batteries with superior cyclic performance and 
enhanced reversible capacity, J. Solid State Chem., 
2018, 265, 424-430. 
15. I. J. Antonyraj, R. Vijay, D. L. Singaravelu. 
Influence of WS2/SnS2 on the tribological 
performance of copper-free brake pads, Ind. Lubr. 
Tribol., 2019, 71, 398-405. 
16. Z. Fan, B. Wang, Y. Xi, X. Xu, M. Li, J. Li, P. 
Coxon, S. Cheng, G. Gao, C. Xiao, G. Yang, K. Xi, 
S. Ding, R. V. Kumar. A NiCo2O4 nanosheet-
mesoporous carbon composite electrode for 
enhanced reversible lithium storage, Carbon, 2016, 
99, 633-641. 
Vietnam Journal of Chemistry Le Thi Thu Hang et al. 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 629 
17. X. Wang, J. Wang, D. Wang, S. Dou, Z. Ma, J. Wu, 
L. Tao, A. Shen, C. Ouyang, Q. Liu, S. Wang. One-
pot synthesis of nitrogen and sulfur co-doped 
graphene as efficient metal-free electrocatalysts for 
the oxygen reduction reaction, Chem. Commun., 
2014, 50, 4839-4842. 
18. X. Li, H. Wang, J. T. Robinson, H. Sanchez, G. 
Diankov, H. Dai. Simultaneous Nitrogen Doping 
and Reduction of Graphene Oxide, J. Am. Chem. 
Soc., 2009, 131, 15939-15944. 
19. J. Du, L. Liu, Y. Yu, Y. Zhang, H. Lv, A. Chen. N-
doped ordered mesoporous carbon spheres derived 
by confined pyrolysis for high supercapacitor 
performance, J. Mater. Sci. Technol., 2019, 35, 
2178-2186. 
20. S. Kundu, W. Xia, W. Busser, M. Becker, D.A. 
Schmidt, M. Havenith, M. Muhler. The formation of 
nitrogen-containing functional groups on carbon 
nanotube surfaces: a quantitative XPS and TPD 
study, Phys. Chem. Chem. Phys., 2010, 12, 4351-
4359. 
21. L. Yan, J. Yu, J. Houston, N. Flores, H. Luo. 
Biomass derived porous nitrogen doped carbon for 
electrochemical devices, Green Energy Environ., 
2017, 2, 84-99. 
22. Z. Nie, Y. Huang, B. Ma, X. Qiu, N. Zhang, X. Xie, 
Z. Wu. Nitrogen-doped carbon with modulated 
surface chemistry and porous structure by a stepwise 
biomass activation process towards enhanced 
electrochemical lithium-ion storage, Sci. Rep., 2019, 
9, 15032. 
23. J. Hou, C. Cao, F. Idrees, X. Ma. Hierarchical 
porous nitrogen-doped carbon nanosheets derived 
from silk for ultrahigh-capacity battery anodes and 
supercapacitors, ACS Nano, 2015, 9, 2556-2564. 
24. R. Xie, Y. Cui, T. Zhou, J. Ren, L. Zhuo, J. Luo, C. 
Li, X. Liu. Unveiling the structural evolution of 1T 
SnS2 anode upon lithiation/delithiation by TEM, 
Chem. Comm., 2019, 55, 7800-7803. 
25. X. Man, P. Liang, H. Shu, L. Zhang, D. Wang, D. 
Chao, Z. Liu, X. Du, H. Wan, H. Wang. Interface 
Synergistic effect from layered metal sulfides of 
MoS2/SnS2 van der Waals heterojunction with 
enhanced Li-ion storage performance, J. Phys. 
Chem. C, 2018, 122, 24600-24608. 
26. H. Mou, W. Xiao, C. Miao, R. Li, L. Yu. Tin and tin 
compound materials as anodes in lithium-ion and 
sodium-ion batteries: A Review, Front. Chem., 
2020, 8. 
Corresponding author: Le Thi Thu Hang 
 Hanoi University of Science and Technology 
 1 Dai Co Viet, Hai Ba Trung district, Hanoi 10000, Viet Nam 
 E-mail: hang.lethithu@hust.edu.vn. 

File đính kèm:

  • pdffabrication_and_lithium_storage_performances_of_a_composite.pdf