Materials Letters 171 (2016) 6367

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Amorphous carbon shell on Si particles fabricated by carbonizing of

polyphosphazene and enhanced performance as lithium ion battery anode
Caili Zhang a, Angang Song a,b,1, Peiling Yuan a,b, Qian Wang a,b, Peng Wang a,b,
Shilin Zhang a,b, Guoqin Cao a,b, J.H. Hu a,b,n
a
b

School of Architecture Engi., Zhongyuan University of Tech., Zhengzhou, China

School of Materials Sci. & Engi., Zhengzhou University, Zhengzhou 450052, China

art ic l e i nf o

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.

conductive materials with wonderful structural stability. Different

types of Si-based composites (Si/metal [4], Si/C [57], Si/oxide [8],
Si/nitride [9]) have been investigated to overcome the disadvantage of low conductivity of silicon anode. Among them, the
combination of silicon and carbon is considered as a very efcient
method to accommodate the mechanical stress and improve the
electronic conductivity of silicon anode. Even after break of Si
particles, Si are still conned within the carbon shell and will not
fall off electrode. We employed a route to synthesized Si/C composites materials by in situ polymerization on Si particle surface,
followed by carbonization at 900 C under Ar atmosphere. Polyphosphazene was employed as carbon precursor. The cycle performance of lithium ion battery was signicantly improved.

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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C. Zhang et al. / Materials Letters 171 (2016) 6367

Fig. 1. (a) FT-IR spectrum of the polymer layer. (b) XRD of Si and Si/C.

annealing at 900 C under a argon atmosphere for 2 h. Fourier

transform infrared spectroscopy (FT-IR, Bruker VERTEX70, Germany) was performed to ensure completely carbonization. The
crystallographic properties of powder samples were characterized
by X-ray diffraction(XRD) using a Rigaku Ultima IV diffractometer
with Cu K radiation between 10 and 90. The morphology and
microstructure of samples was observed using a Sirion 200 eldemission scanning electron microscopy (FE-SEM) and JEOL-2010
transmission electron microscopy (TEM). The anode electrode was
prepared by mixing 80 wt% of the active material with 10 wt%
carbon black and 10 wt% polyvinylidene uoride (PVDF) binder in
N-methy1-2- pyrrolidinone (NMP) solvent to get homogeneous
slurry via continue stirring. The slurry was coated onto Cu foil
(9 m thick). Then, the coated electrode was dried at 80 C for 12 h
under vacuum, and pressed into 100 m in thickness using a rolltype mill. Lithium plate (15.6  0.45 mm) was used as counter
and reference electrodes. The coin cells (CR 2016) were assembled
in an argon glove box. The electrolyte was 1 m LiPF6 EC/DMC
(ethylene carbonate/dimethyl carbonate1:1 by volume) and Celgard 2400 as a separator, foam nickel as a support. Subsequently,
the electrochemical performance of sample was evaluated using
LAND battery test system and electrochemical workstation (AMETEK Parstat 4000).

3. Results and discussion

FT-IR spectrum before carbonization was detected and the
result was shown in Fig. 1a. The FT-IR spectrum indicated
transmittance peaks at 1142 to 1097 cm  1, which was ascribe to
the phosphazene. The absorption peak of some other reactant
was located at 1185, 1295, 1152, 1588 and 1490 cm  1 [9]. The
absence of these peaks proved the reaction was complete. After
carbonization, the Si/C campsite was characterized by XRD and
showed in Fig. 1b. All the diffraction peaks of pure Si particle can
be obviously observed (JCPDS no. 27-1402). The pattern of Si/C
composite material shows identical diffraction peaks as compared. No diffraction peaks from crystalline carbon were observed in Si/C sample, indicating the amorphous structure of the
carbon.
Fig. 2 shows the TEM image of Si/C composite. It is very clear that
the dispersive particles are in a diameter 50100 nm and the obvious contrast from different phases can be observed. The distribution of some Si powders were indicated by arrows in Fig. 2a. A typical Si particle was shown in Fig. 2b in detail. The Si particle was
coated by an uniform amorphous carbon layer and a clear boundary
was indicated by a dash line. The thickness of carbon layer on the
particle was about 6 nm. The Si core was characterized by HRTEM
(Fig. 2c) and the lattice fringes agreed well with the standard Si. The

C. Zhang et al. / Materials Letters 171 (2016) 6367

65

Fig. 2. TEM of Si/C composite.

Fig. 3. Galvanostatic charge-discharge voltage proles of Si (a); Si/C composite (b).

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

and electrolyte, and the formation of SEI on the electrode surface

[8,9]. However, the composite samples showed a superior cycle
stability than pure Si after two cycles. This is mainly attributed to the
amorphous carbon effectively prevent the direct contact and reactions between electrode material and electrolyte.
The cycle performance and coulombic efciency is compared
and shown in Fig. 4. The Si/C composite sample exhibited a
high discharge capacity 2024 mA h/g at the rst cycle. After 100
cycles, the specic capacity can also be kept at 740 mA h/g,
which is far superior to that of pure Si. And the coulombic efciency is as high as 99%. Although the Si anode showed a higher
charge/discharge capacity in 1st round, it decayed rapidly to
lower than 200 mA h/g. Compared with the Si/C anode, pure Si
anode also showed a rather lower coulombic efciency (Fig. 4b).
The electrochemical impedance spectra from 100 kHz to 10 mHz
of pure Si and Si/C composite samples were measured and

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C. Zhang et al. / Materials Letters 171 (2016) 6367

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.

amorphous carbon also increased interfacial reaction kinetics and

conductivity of electrode, which contributed to the improvement
of rate performance. This work provides a simple way to evidently
improve the cycling performance of Si based anode.

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.

C. Zhang et al. / Materials Letters 171 (2016) 6367

[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

Si-SiO2-C composites as the negative material for Li-ion batteries, J. Power

Sources 195 (2010) 43044307.
[9] Peng Zhang, Lijie Wang, Xi Zhang, Changlu Shao, Junhua Hu, Guosheng Shao,
SnO2-core carbon-shell composite nanotubes with enhanced photocurrent and
photocatalytic performance, Appl. Catal. B: Environ. 166167 (2015) 193201.