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Materials Letters
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a b s t r a c t
Article history:
Received 17 December 2015
Received in revised form
23 January 2016
Accepted 8 February 2016
Available online 9 February 2016
A novel strategy was employed to introduce a carbon layer on Si particle to overcome the intrinsic poor
electrical conductivity and signicant volume change. The carbon layer was fabricated by forming
polyphosphazene coating through a facile precipitation polymerization method, followed by carbonization. As a result of formation of core-shell structure, the Si anode exhibited improved cycling stability
(740 mA h/g remained after 100 cycles) and rate capability (300 mA h/g at a rate 2C). In addition, 99%
coulombic efciency was remained after 100 cycles.
& 2016 Elsevier B.V. All rights reserved.
Keywords:
Secondary battery
Core-shell
Composite materials
Carbon materials
1. Introduction
The rapid development of electric vehicle calls for lithium ion
batteries with higher energy densities, and longer cycling performance. Researchers are searching for substitutional materials for
commercialized graphite anode materials due to their low specic
capacity (372 mA h/g). Several anode materials have been investigated, such as Al, Sn, Si [13]. In particular, silicon with the
highest theoretical specic capacity of 4200 mA h/g corresponding
to forming high lithium content intermetallic phase Li4.4Si, medium voltage platform (about 0.4 V vs Li/Li ) and abundant resource, has attracted wide attention. However, the mechanical
stress resulting from signicant volume change (4 300%) during
charge/discharge cycling leads to pulverization of electrode
structure and breakdown of electrical contact network. As a result,
the silicon anode materials show poor capacity retention [4],
which restricts silicon anode's application seriously. Another
drawback is the low electrical conductivity of silicon anode, which
causes it difcult to cycle at a high current density. A promising
approach to overcome the problems of dimensional instability and
low electrical conductivity is to prepare a composite nanostructure in which silicon particles are uniformly dispersed in the
n
Corresponding author at: School of Architecture Engi., Zhongyuan University of
Tech., Zhengzhou, China.
E-mail address: hujh@zzu.edu.cn (J.H. Hu).
1
Co-rst author.
http://dx.doi.org/10.1016/j.matlet.2016.02.034
0167-577X/& 2016 Elsevier B.V. All rights reserved.
2. Experiment
Si nano particles ( 100 nm in diameter, Alfa Aesar chemical Co.,
Ltd.) 0.01 g were dispersed in a mixed solvent of tetrahydrofuran
(THF) and ethanol (30 ml, 1:1 by volume) under continuous stirring.
Subsequently, hexachlorocyclotriphosphazene (HCCP) 0.01 g, 4, 4sulfonyldiphenol (BPS) 0.02 g and triethylamine (TEA) 2 mL were
added into the solution, with persistent ultrasonic processing for
8 h in an ultrasonic bath (200 W). Polymerization reaction between
HCCP and BPS occurred. After centrifugation at 8000 rpm, the
sample was dried under the vacuum condition at 80 C to remove
THF/ethanol solution.The carbonization process was done by
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Fig. 1. (a) FT-IR spectrum of the polymer layer. (b) XRD of Si and Si/C.
65
selected area diffraction patterns from one particle proved the incident direction [011] of single crystal structure.
Fig. 3 shows Galvanostatic charge/discharge voltage proles between 0.1 V and 3.0 V vs. Li/Li at the 1st, 2nd and 3rd cycles with a
charge/discharge rate of 0.05 C. Fig. 3a exhibited typical voltage
proles of pure Si. A long at plateau in the rst cycle occurs at
0.17 V, indicated the alloying process of silicon with inserted Li .
The initial charge and discharge capacity of pure Si are 2269.6 mA h/
g and 3443.5 mA h/g, respectively. While the discharge capacity
decayed rapidly to 2372.4 mA h/g and 1786.9 mA h/g at the second
and the third cycle, respectively. Commercial silicon powder with an
average particle size 50 nm also showed fast capacity fade to
214 mA h/g after only 2 cycles, as reported in [9].The Si/C composite
sample displayed similar capacity fade trend at the rst and second
cycle. It have been reported that the irreversible capacity of the Si is
closely inuenced by the side reactions between the active material
66
Fig. 4. Cycling performance (a) and coulombic efciency (b) of Si; Si/C composite.
shown in Fig. 5a. The rst semicircle at the high frequency range
displays the resistance of electrolyte. The second semicircle at
the middle frequency range corresponds to the charge transfer
resistance, which relates to the charge move across the electrode/electrolyte interface and the double layer. The inclined line
at the low frequency range indicates the Li diffusion kinetics in
the electrode materials [7,8]. According to Nyquist plots of three
electrode, the resistance at high-to-medium frequency range of
Si/C composite sample is lower than that of pure Si sample. This
indicated that carbon coating is benecial to increase interfacial
reaction kinetics and conductivity of electrode. As a direct result,
the rating performance is also improved. The rate performance
of Si/C electrode from 0.05 C to 2 C was measured and shown in
Fig. 5b. The specic capacity Si/C is over 740 mA h/g at 0.05 C and
up to 300 mA h/g at a higher rate 2 C. Moreover, more than 99%
of the capacity at 0.05 C was recoverable after cycling at different
rates.
4. Conclusion
Si/C core shell material was fabricated by polyphosphazene
coating through a facile precipitation polymerization method and
carbonization by annealing. Such a unique core shell structure
provides a superior cycling performance (740 mA h/g after 100
cycles) and good rate capability (300 mA h/g @ 2 C). In addition,
Fig. 5. (a) Nyquist plots of Si and Si/C electrode. (b) Charge/discharge capacities at
various rates of Si/C composite.
Acknowledgments
The present work is supported nancially by the National Natural Science Foundation of China (Nos. 11472316 and 10902129).
References
[1] Sa Li, Junjie Niu, Yu Cheng Zhao, et al., High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity, Nat.
Commun. 6 (2015) 7872.
[2] P. Zhang, L. Wang, X. Zhang, J. Hu, G. Shao, Three-dimensional porous networks
of ultra-long electrospun SnO2 nanotubes with high photocatalytic performance, Micro Nano Lett. 7 (2015) 8695.
[3] L.F. Cui, R. Ruffo, Y. Cui, et al., Crystalline-amorphous core-shell silicon nanowires for high capacity and high current battery electrodes, Nano Lett. 9 (2008)
491495.
[4] Y. Yu, C. Zhu, et al., Reversible storage of lithium in silver-coated three-dimensional macroporousg silicon, Adv. Mater. 22 (2010) 22472250.
[5] W. Wang, P.N. Kumta, Nanostructured hybrid silicon/carbon nanotube heterostructures: reversible high-capacity lithium-ion anodes, ACS Nano 4 (2010)
22332241.
[6] L.F. Cui, Y. Yang, C.M. Hsu, et al., Carbon-silicon core-shell nanowires as high
capacity electrode for lithium ion batteries, Nano Lett. 9 (2009) 33703374.
[7] L. Wang, C. Ding, L. Zhang, et al., A novel carbon-silicon composite nanober
prepared via electrospinning as anode material for high energy-density lithium
ion batteries, J. Power Sources 195 (2010) 50525056.
[8] Lu Z, Zhang L, Liu X, Microstructure and electrochemical performance of
67