energies

Article
Silicon-Carbon Composite Electrode Materials
Prepared by Pyrolysis of a Mixture of Manila Hemp,
Silicon Powder, and Flake Artificial Graphite for
Lithium Batteries
Qin Si, Daisuke Mori, Yasuo Takeda, Osamu Yamamoto * and Nobuyuki Imanishi
Graduate School of Engineering, Mie University, Tsu 514-8507, Japan; qin.si@murata.com (Q.S.);
daisuke.mori@chem.mie-u.ac.jp (D.M.); takeda@chem.mie-u.ac.jp (Y.T.); imanishi@chem.mie-u.ac.jp (N.I.)
* Correspondence: yamamoto@chem.mie-u.ac.jp; Tel.: +81-59-231-9420; Fax: +81-59-231-9478

Received: 16 September 2017; Accepted: 6 November 2017; Published: 8 November 2017

Abstract: A high performance lithium anode is a key component for high energy density lithium
batteries. Silicon based lithium anode materials are attractive for the lithium anode due to their high
theoretical capacity. However, a severe problem is the huge volume change that occurs during cycling,
resulting in a poor capacity retention. We have developed a silicon based anode that disperses silicon
particles on a carbon paper made from Manila hemp. The composite silicon electrode materials
showed a high initial coulombic efficiency of 83%. The initial capacity of 566 mAh g−1 based on the
total weight of the electrode was retained at 491 mAh g−1 after 70 cycles at the charge and discharge
rate of 100 mA g−1 and at room temperature.

Keywords: lithium-ion battery; silicon anode; carbon paper; cyclic performance

1. Introduction
Recently, the demand for high energy density batteries as the energy source in electric vehicles
(EV) has significantly increased, with an aim to reduce the CO2 emission from vehicles. The driving
range of EVs with lithium-ion batteries, which have the highest specific energy density at present,
is too short compared to conventional vehicles with internal conversion (IC) engines. This is because
the specific energy density of the lithium-ion battery with carbon anodes and lithiated cathodes used
for recent EVs (around 100 Wh/kg) is approximately one seventh to that of a conventional IC engine
(around 700 Wh/kg) [1,2]. Many types of battery systems beyond lithium-ion batteries have been
proposed. Among them, lithium-air and lithium-sulfur systems [3] are expected to develop batteries
with high specific energy density that is comparable to IC engines. Lithium-air and lithium-sulfur
batteries should be used in lithium metal or lithium content anodes such as Lix Si.
A lithium metal anode is the best candidate for a battery with respect to the specific energy
density due to its high specific capacity (3860 mAh/g) and low electrode potential (−3.04 V versus
normal hydrogen electrode NHE). Rechargeable batteries with the lithium anodes were proposed
40 years ago [4], and there has been intensive research and development effort since. In 1987,
a rechargeable non-aqueous battery with a lithium anode and a MoS2 cathode was commercialized by
Moly in Canada and used for the battery in cellular phones by NTT, Japan. However, these batteries had
serious problems due to lithium dendrite short-circuit. Sony, Japan, then commercialized a lithium-ion
battery with a carbon anode and a lithiated cathode of LiCoO2 . The lithium dendrite formation
was drastically improved by the use of a carbon anode. The specific capacity of the carbon anode is
372 mAh g−1 . Silicon anode materials are one of the other promising candidates for next generation
high specific energy density batteries due to their substantially high theoretical capacity (3578 mAh g−1

Energies 2017, 10, 1803; doi:10.3390/en10111803 www.mdpi.com/journal/energies

Energies 2017, 10, 1803 2 of 9

for Li14 Si5 ) and the fact that their lithium extraction potential is lower than 0.5 V, compared to that
of Li+ /Li [5–8]. However, a severe problem related to their high gravimetric capacity is the large
volume change that occurs during cycling (300% expansion), which leads to high mechanical stress
and breakdown of the conductive network of the composite electrode [9]. Much research has been
conducted on silicon anodes aimed at addressing these limitations. The approaches include carbon
containing nano-dispersed silicon [10–12], the development of a Si/C composite [13], the distribution
of the silicon particles in a matrix of carbon [14–16], and the use of electrolyte additives such as
fluoroethylene carbonate [17]. Some of them drastically improved the cycling performance of the
silicon anode, but they used expensive materials such as nano-size silicon [18] and mesoporous
silicon nanotube [19]. Dimov et al. [20] and Karulkar et al. [21] reported the cyclic performance of
a simple mixture of a conventional silicon powder and graphite. A 30 wt % Si/graphite composite
results in a theoretical capacity of 1330 mAh g−1 . When the capacity was restricted to 500 mAh g−1 ,
these composites operated reliably up to 90 cycles. In the previous paper [15], we have proposed
a new Si/C composite using a carbon paper (CP) as a three dimensional conductive substrate.
The three-dimensional structure can incorporate the active material into a current collecting network,
in particular, by the improvement of adhesion between the carbon fiber of the paper and the carbon
coated Si (Si/C) composite, wherein the carbon paper was prepared from a mixture of Manila
hemp and poly(acrylonitrile) fiber at 2600 ◦ C. An initial capacity of 1720 mAh g−1 of silicon and
an initial Coulombic efficiency of 90% at 0.12 mA cm−2 wereobserved, and the reversible capacity
of 1200 mA g−1 of silicon was retained even after 100 cycles. However, the volume density of the
silicon dispersed in carbon paper anode is as low as 0.35 g cm−3 , and the specific capacity based on the
total weight of the electrode materials was as low as 300 mAh g−1 . In this study, we have examined
a new silicon anode material, with a high specific capacity dispersed over a carbon paper, using less
expensive starting materials and preparation processes. The cast performance of the batteries in EVs is
one of the most important requirements [22].

2. Experimental
The silicon dispersed carbon paper with artificial flake graphite (Si/G/CP) was prepared according
to the following procedure. Manila hemp (2.5 g, Industrial technology Center, Gifu, Japan), artificial
flake graphite (0.5 g, average particle size of around 15 and 150 µm, Ito Graphite Ltd., Kuwana, Japan),
polyvinyl alcohol binder (0.125 g, Nacalai Tesque, Kyoto, Japan), and silicon powder (0.25 g, average
particle size of 5 µm and 1 µm, Kinsei Matec, Osaka, Japan) were homogenously dispersed in water.
A paper was made from the slurry by using a homemade machine. The handmade paper with graphite
(G) and Si was pressed at 120 ◦ C for 15 min. The dried paper was heated at 600 ◦ C for 1 h and then at
700~1100 ◦ C for 2 h under nitrogen gas flow. The thickness of the Si/G/CP was around 150 µm.
Coin-type cells (2032 type) were used for the electrochemical measurement of the Si/G/CP
composite electrode. The cell consisted of Si/G/CP and lithium counter electrode in 1 M LiClO4 in
an ethylene carbonate (EC) and diethyl carbonate (DEC) mixture (1:1 volume ratio). Microporous
polyethylene separator (Toray, Japan) was used between the Si/G/CP electrode and the lithium
electrode. After electrochemical measurements, the cells were carefully disassembled, and the
composite electrodes were rinsed in dimethyl carbonate (DMC) to remove residual electrolyte and then
dried at room temperature to reveal the surface and cross section for observation. The charge-discharge
cyclic performances of the coin-type cells were measured at room temperature between 0.005 and
1.500 V versus Li+ /Li at a constant current density of 100 mA g−1 (0.53~0.88 mA cm−2 ), with a rest time
of 30 min. after every charging and discharging, using Nagano BTS 2004H, Japan. The current density
was calculated based on the total weight of the Si/G/CP electrode materials. The amounts of the
electrode materials were 6~10 mg, and the surface area of the electrode was 1.13 cm2 . The morphology
of the electrodes was observed using scanning electron microscopy (Hitachi SEM 5-4800, The Central
Microscopy Research Facility, Iowa City, IA, USA). The coin type full cell consisted of an Si/G/CP
anode, LiFePO4 cathode (Hosen, Yokohama, Japan), and ethylene carbonate (EC), fluoroethylene
Energies 2017, 10, 1803 3 of 9

carbonate (FEC), and DMC (2:2:6 volume ratio) electrolyte of around 200 µL. The cathode consisted
of a mixture of carbon coated LiFePO4 vapor growth carbon fiber (Showa Denko, Tokyo, Japan,
0.15 µm diameter and 20 µm long), and polyvinylidene difluorite (PVDF) (90:4:6 weight ratio).
The thicknesses of the cathode and anode were around 70 µm. The resistance of the composite
electrode was measured by a conventional four point probe method using a Mitsubishi Analytech
MCP-PD51 (Yamato, Kanagawa, Japan). The X-ray diffraction (XRD) analysis was carried out using
a Rigaku RINT2500. Diffractometer (Rigaku, Tokyo, Japan) with CuKα radiation. The X-ray CT scan
image was obtained using a SKY1272 (RJL Lid. Japan).

3. Results and Discussion

Figure 1 shows SEM and X-ray CT scan images of the Si/G/CP composite electrode materials,
where the particle size of Si was 5 µm, the contents of Si and G were 16 and 32 wt %, respectively,
and the pyrolysis temperature was 900 ◦ C. The energy dispersive X-ray (EDX) analysis suggested that
the Si particles were dispersed homogenously over the carbon paper matrix. The average diameter of
the carbon fiber was around 5.5 µm; the thickness of the composite electrode materials was around
150 µm; and the density was 0.43 g cm−3 . The density is 20% higher than that of the Si dispersed over
carbon paper reported previously [15]. The specific electrical resistance was estimated to be 100 mΩ
cm for the composite with 15 µm particle size G and 282 mΩ cm for that with 150 µm particle size G at
25 ◦ C. The densities of the composites with 15 and 150 µm G were 0.43 and 0.26 g cm−3 , respectively.
The XRD pattern of the Si/G/CP electrode with 16 wt % and 5 µm Si heated at 900 ◦ C showed that no
diffraction peak of SiC was observed and that the carbon fiber was amorphous. The Si/C/CP heated
at 1200 ◦ C showed a trace diffraction peak due to SiC. The composite electrode was flexural.

Figure 1. Cont.
Energies 2017, 10, 1803 4 of 9

Figure 1. Scanning electron microscopy (SEM) and X-ray CT scan images of Si/G/CP with 16 wt %
and 5 µm Si; (a) surface; (b) cross section; and (c) X-ray CT scan image.

Figure 2 shows the cyclic performance of the Si/G/CP electrode with 16 wt % and 5 µm Si, where
15 and 150 µm G were used. The effect of the particle size of the artificial flake graphite was examined.
The addition of the small size graphite was effective to decrease the electrode resistance and to increase
the density of the electrode. An initial discharge (lithium insertion into Si) capacity of 468 mAh g−1
and an initial coulombic efficiency of 76% for the Si/G/CP with 15 wt % Si and 15 µm G were observed.
The composite electrode with a large particle size G showed a high initial discharge capacity of
540 mAh g−1 but a low initial charge (lithium extraction from Lix Si) and discharge efficiency of 70%.
The capacity retention rate was slightly lower than that of the electrode with 15 µm G. The specific
capacities of 382 and 364 mAh g−1 at the seventieth cycle were observed for the composite electrodes
with 15 and 150 µm G, respectively. The reversible capacity of the Si/G/CP electrode is comparable to
that of the carbon anode of conventional lithium-ion batteries. The Si/G/CP electrode with 5 µm Si
showed an expansion of the electrode by cycling, as shown in Figure 3. The thickness of the Si/G/CP
electrode expanded from 153 to 209 µm after 100 cycles. The degradation of the reversible capacity by
cycling may be due to the expansion of the composite electrode [23]. The initial reversible capacities of
the CP and G/CP electrode without Si were 240 and 270 mAh g−1 , respectively, and these decreased
with cycling. Therefore, some lithium may be intercalated into CP and G, but the main part of the
lithium may be intercalated into Si.

Figure 2. Cyclic performances of the Si/G/CP electrode with 16 wt % and 5 µm Si at 100 mA g−1 and 25 ◦ C.
Energies 2017, 10, 1803 5 of 9

Figure 3. SEM images of the Si/G/CP composite electrode with 16 wt % and 5 µm Si. (a) Initial and
(b) after 100 cycles.

The Si/G/CP composite electrode with 5 µm Si was observed to have some cracking by cycling
because of the expansion and shrinkage by lithium insertion and extraction. To improve the volume
change by cycling, a fine silicon powder with an average diameter of 1.0 µm was used for the composite
electrode. The volume density of the Si/G/CP composite electrode with the 1.0 µm Si was slightly
increased from 0.43 g cm−3 for that with 5.0 µm Si to 0.44 g cm−3 . The density is lower than that of
a nono-size Si, carbon black, and PVDF mixture (4:4:2 weight ratio) of 0.625 g cm−3 [18]. Figure 4 shows
the first cycle charge and discharge profiles and the cyclic performance of the Si/G/CP, with 1.0 µm
and 16 wt % Si as a function of the pyrolysis temperature of the Manila hemp paper with Si and G.
The coulombic efficiency at the first cycle was 61% for the composite electrode prepared at 700 ◦ C, 82%
for that prepared at 900 ◦ C, and 88% for that prepared at 1100 ◦ C. Generally, a low coulombic efficiency
for the first cycle of the Si anode has been reported [18]. The low coulombic efficiency for the composite
electrode prepared at 700 ◦ C may be due to the insertion of more lithium into the amorphous pyrolysis
carbon of the Manila hemp. The electrode resistance of 102 mΩ cm was comparable with that of the
5.0 µm Si. The initial discharge capacity of the composite electrode prepared at 900 ◦ C significantly
increased from 466 mAh g−1 for that with 5.0 µm Si to 565 mAh g−1 . The specific capacity of the
composite electrode corresponds to 2200 mAh g−1 of silicon. The reversible capacity of 491 mAh g−1
was retained even after 70 cycles. The high capacity retention by the charge and discharge cycling
could be explained by the small expansion of the composite electrode by cycling, as shown in Figure 5.
The initial electrode thickness of 153 µm was not changed after 100 cycles at 100 mA g−1 .

Figure 4. Cont.
Energies 2017, 10, 1803 6 of 9

Figure 4. (a) Charge and discharge profiles and (b) cyclic performance of the Si/G/CP electrode with
16 wt % and 1.0 µm Si at 100 mA g−1 and 25 ◦ C as a function of the pyrolytic temperature.

Figure 5. SEM images of the Si/G/CP composite electrode with 16 wt % and 1.0 µm Si. (a) Initial and
(b) after 100 cycles.

To improve the specific capacity of the composite electrode, the Si content in the composite
electrode was increased. Figure 6 shows the cyclic performance of the Si/G/CP with 24 wt % and
1.0 µm Si at 100 mA g−1 , where the pyrolysis temperature of the composite was 900 ◦ C. The initial
reversible capacity of 750 mAh g−1 was significantly decreased to 293 mAh g−1 after 100 cycles. The low
capacity retention by cycling for the Si/G/CP with a high content of Si could be explained by the
large expansion of the electrode, as shown in Figure 7. The initial thickness of the composite electrode
of 148 µm was expanded to 219 µm after 100 cycling. The porosities of the composite electrolytes
with 16 and 24 wt % Si were estimated to be 80% using the densities of the sum of components
and the apparent densities of the composite electrodes. After discharging up to 3000 mAh g−1 of
Si, the porosities for the composite electrodes with 16 and 24 wt % Si were reduced to 50 and 18.5%,
respectively, where the specific gravities of Lix Si were calculated using the lattice parameters reported
by Dahn et al. [24]. These calculations suggest that the carbon paper matrix could accommodate
around a 250% volume change by lithium insertion and extraction.
Energies 2017, 10, 1803 7 of 9

Figure 6. Cyclic performances of the Si/G/CP electrode with 24 wt % and 1.0 µm Si at 100 mA g−1
and 25 ◦ C.

Figure 7. SEM images of the Si/G/CP composite electrode with 24 wt % and 1.0 µm Si. (a) Initial and
(b) after 100 cycles.

Figure 8 shows the charge and discharge profiles and cyclic performance for the Si/G/CP with
16 wt % and 1.0 µm Si/1M LiPF6 in EC-FEC-DMC (2:2:6 volume ratio)/LiFePO4 at 0.1 C (based on the
cathode and around 0.3 mA cm−2 ) and 25 ◦ C, where the anode capacity was higher than that of the
cathode and an excess electrolyte was charged [25]. The initial coulombic efficiency was 96%. A steady
reversible capacity of 133 mAh per g−1 of LiFePO4 was observed for 10 cycles.

Figure 8. Cont.
Energies 2017, 10, 1803 8 of 9

Figure 8. Charge and discharge profile and cyclic performance of the Si/G/CP with 1.0 µm and
16 wt % Si/1 M LiPF6 in EC-FEC-DMC (2:2:6 vol. ratio)/LiFePO4 cell at 0.1 C and 25 ◦ C.

4. Conclusions
We have proposed a less expensive silicon anode material for lithium batteries, which was
prepared by the pyrolysis of a paper prepared from a mixture of silicone powder, artificial flake
graphite, Manila hemp, and polyvinyl alcohol at 900 ◦ C, where the pyrolysis temperature was as
low as 900 ◦ C and no expensive starting materials were used. The less expensive anode material
is quite attractive for large size batteries for EV and staminal power storage. The composite anode
with 16 wt % and 1.0 µm Si powder showed a good cyclic performance, with an initial reversible
capacity of 565 mAh g−1 and 249 mAh cm−3 and a capacity of 491 mAh g−1 and 216 mA cm−3 after
70 cycles were observed. No electrode expansion was observed for the composite electrode with
16 wt % Si. The specific mass capacity of the composite anode is about 1.5 times higher than that of
the conventional carbon anode. However, the low specific volume capacity should be improved by
further study.

Author Contributions: Q.S., Y.T. and N.I. conceived and designed the exeriments; Q.S. performed the experiments;
D.M. and O.Y. analyzed the data; Q.S. contributed reagents/materials/analysis tools; Q.S., D.N. and O.Y. wrote
the paper. Authorship must be limited to those who have contributed substantially to the work reported.
Conflicts of Interest: The authors declare no conflict of interest.

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