Embedding nano-silicon in graphene

nano-sheets by plasma assisted milling

for high capacity anode materials in
lithium ion batteries
Wei Sun, Renzong Hu, Hui Liu, Meiqin Zeng, Lichun Yang,
Haihui Wang, Min Zhu
School of Materials Science and Engineering, South China University of Technology
Journal of Power Sources 268 (2014) 610-618

Antony Raj T
M Sc Student
Chemistry Department
Lakehead University

Material: Embedded nano Silicon in Graphene

nanosheets
Method: Plasma Assisted Milling
Application: Li-ion Battery Anode material
+
Si(30% wt) + Graphite (70%Heatwt)
Mechanical
Milling
nano Si/GN

Specialties:
1. Si act as nano miller and Cutting effect of Nano Si
2. In-situ conversion of Graphite to Graphene
3. Better performance in LIB than Graphite and Silicon alone
4. Graphene Nanosheets act as buffers the Volume change issue
of Si anode
5. Can produce the material Bulk

Why Silicon in Graphene Nano

sheets?
1. Advantages Si & Graphite
Si - Can store Li reversibly, high Theoretical capacity (4200 mAh/g
Li22Si5)
Graphite - Good conductivity, stable crystal structure, rate
capability
2. Disadvantages of Si & Graphite
Silicon- High volume change (>300%) during Alloying De Alloying
with Lithium and its a Semiconductor poor electronic conductivity
causes Poor cyclability
Graphites theoretical capacity is less (372mAh/g LiC 6), so limits the
performance .
(Combination of Both gives better anode)

P-Milling - Synthesis

Journal of Alloys and Compounds 478 (2009)

624629

(1)Electromotor
(2)Elastic joint
(3)Vibration exciter
(4)Base plate
(5)Framework
(6)Vial
(7)Refrigerant tank
(8)Electrode
(9)Steel balls
(10) Spring
(11) DBDP (Dielectric
Barrier Discharge
Plasma) power
supply.
The weight ratio of ball to powder is 50:1.
The ball mill was a vibratory type and the milling cylinder vibrated with a
double amplitude of 7 mm and a frequency of 24 Hz.
The milling was under the protection of pure argon gas.
A.C. electricity (frequency 13 kHz) with the tension higher than 22 kV
was supplied to the electrodes. (depends on the experiment
requirement)
The tension and frequency of DBD was 24 kV and 14.4 kHz, respectively.

Schematic illustration of P-milling

Characterization- overview
CONFORMATION & OPTIMIZATION
a. XRD
b. Raman Spectroscopy
c. SEM
d. TEM
e. BET Surface Area
. CHEMICAL ACTIVITY
a. DSC-TGA
. ELECTROCHEMICAL CHARECTERIZATION
a. Galvanostatic Cycling
b. Electrochemical Impedance
c. Cyclic Voltammetry
d. LSV (for Resistance measurement)

XRD

RAMA
N

TEM
SEM

Galvanostatic Cycling

TGA & DSC

Conductivity is High
Nyquist Plots: Comparing the impedance spectra after the 1 st cycle of Nano Si and
Nano Si/GN composite charge transfer resistance is four times reduced compare to Si.

Volume change is Less during Lialloying and de alloying

Cross Sectional Images of Electrode: Shows volume change of the
electrode made using before p-milling(0 hr) sampleMater
and 20h
pBefor After
ial
e
10
milling sample.

Chang
e in %

Cycli
ng

Cycles

P-0h

9m

19m

211%

P-20h

10m

12m

120%

Nano-Si Dominant Contributor

Initial five cycles (charge/discharge) Cyclic voltammetry peaks confirms

Li-Si alloying and Li-Si de alloying.
First Cycle shows the SEI formation, irreversible reduction of Li from
electrolyte at the surface of anode, which disappears from next cycles.

Columb
ic
Cycle
Efficien
cy
1
71.6%
2
94%
20
98%

Good Reversibility & Rate

Capability
Discharge capacity for 50 cycles plotted at different current rates
shows stable reversible capacities at different current rates.

Full Cell with LiMn2O4 Cathode

Cycle life test in full cell reproduces the same results good reversible
capacity, 600mAh at the end of 30 cycles, Working Voltage greater
than the graphite. Capacity is lower than half cell as cathode could
not provide sufficient Li+.

Critique

Process optimized for good performance is 20hr p-milling is long

duration, other process parameters could be discussed, which may
reduce the hours of milling time.
In DSC/TG, Raman analysis it is confirmed that residual graphite
presence, it could tried for 100% conversion, which may yield
better reversible capacity
From CV it is explained that Si mainly contributes for the high
capacity, contribution of graphite and graphene in capacity is
could be added.
Cycle life test done in half cell for 50 cycles and full cell only for 30
cycles are very less to show the material as promising anode.

THANK YOU

References
1. Synergism of mechanical milling and dielectric barrier discharge
plasma on the fabrication of nano-powders of pure metals and
tungsten carbide, Journal of Alloys and Compounds 478 (2009) 624
629
2. Enhancing the performance of SnC nanocomposite as lithium ion
anode by discharge plasma assisted milling, J. Mater. Chem., 2012,
22, 80228028