Progress No

27 Feb 2006

Name:…………………………….

Title: (compulsory)

Introduction: (compulsory for the first progress and early of semester)

Experimental: (compulsory)

Result and Discussion: (compulsory)

Future work: (compulsory)

References: (optional)

Example
Progress 19

Dr Mohamad Azmi Bustam 24 Jan 2006

Title: Development of New Cathode/Anode Material for Li-ion Battery

Introduction
Basic Concept and state of arts in Li ion Rechargeable batteries

charge
<Reaction>
Fig. 1 Schematic diagram and electrode
charger reactions of - e
electrochemical process
Cathode of Li ion rechargeable batteries
LiMO2 Li1-xMO2 + Li +
Xe-
discharge (M=Co,Ni,Fe)
or
cathode anode Li1+YMn2O4 Li1+Y-XMn2O4 +　XLi + Xe-
e- Anode
separator
Current C n + XLi + Xe- CnLiX
collector
Total reaction
LiMO2 + Cn Li1-XMO2 + CnLiX
(M=Co,Ni,Fe)
or
Li1+YMn2O4 + Cn Li1+Y-XMn2O4 + CnLi

electrolyte Li

Oxygen Metal Li Carbon

elements
 Figure 1 shows the scheme of electrochemical process of Li ion rechargeable batteries. The
intercalation electrodes that most commonly used as cathodes are inorganic compound (e.g., LiMO 2(M; Co, Ni,
Fe)) and that for anode is carbon. Basically, it was a combination of negative Li + intercalation electrode material
with another Li+ intercalation material having more positive redox potential, both materials are capable of
reversible intercalation of Li+ cations. During redox process, one electrode will de-intercalate Li +(namely,
oxidation of Li), and the other electrode will intercalate Li +(namely, reduction of Li). The basic electrochemistry
involves only the transfer of Li + cations between two intercalation electrodes. Unless the potential for redox
reaction is within the stability range of electrolyte, so that the electrolyte volume can be minimized to a very thin
film. This principle was firstly proposed by Armand [1] and Lazzari et al. [2] and can be recognized with name
as “rocking-chair” [2], “shuttlecock” [3], “swing” [4], “Li-ion” and ”Lion” [5] batteries.

References
[1] M. Armand. In: D.W. Murphy, J. Broadhead and B.C.H. Steeles Editors, Materials for Advanced Batteries Plenum, New
York (1980) p. 145
[2] M. Lazzari and B. Scrosati. J. Electrochem. Soc., Brief Comm., March, 127, 773 (1980)
[3] K. Sawai, Y. Iwakoshi, T. Ohzuku, Solid State Ionics, 69, 273 (1994)
[4] R. Bittihn, R. Herr, D. Hoge, J. Power Sources, 43-44, 223 (1993)
[5] K. Ozawa, Solid State Ionics, 69, 212 (1994)

Research and Development of Silicone and Compounds as high Capacity Anode Materials for Lithium Ion Cells

Objectives
 To coat Si with carbon (Si-C composite)
 To improve Li insertion properties Si-C composite

Approach
Carbon coated Si

Fig. 2 Synthesis of Carbon coated Si

Experimental
1. Si cut off capacity at 450 Si +Csugar (80:20) with various current conditions(0.25, 0.5 and 1.0mA).

Result and Discussion

Table.2 Summarized result of characterized sample.
No Sample No. Sample Dis. Cap. Cha Cap. Dis. Cha. Eff. Note
(mAh/g) (mAh/g) Pot. (V) Pot. (V) (%)
1. az096(1ST) Si +Csugar 450 150.98 0.8, 0.2 0.4 33.6 0.25mA,450mAh/g
(80:20) dis cut-off
2. az096(2ND) Si +Csugar 450 383.5 0.1 0.5 85.2 0.25mA,450mAh/g
(80:20) dis cut-off
3. az097(1ST) Si +Csugar 450 158.2 0.8, 0.2 0.4 35.2 0.5mA,450mAh/g
(80:20 dis cut-off
4. az096(2ND) Si +Csugar 450 368.1 0.1 0.5 81.8 0.5mA,450mAh/g
(80:20) dis cut-off
5. az098(1ST) Si +Csugar 450 202.9 0.8, 0.2 0.4 45.1 1.0mA,450mAh/g
(80:20) dis cut-off
6. az098(2ND) Si +Csugar 450 358.0 0.1 0.5 79.6 1.0mA,450mAh/g
(80:20) dis cut-off
1MLiPF6 in EC:DMC(1:1vol) was used

2.5 2.5
2nd cycle 1st cycle
1st cycle 2nd cycle
2 2

1.5
Voltage / V

1.5
Voltage / V

1
1

0.5
0.5

0
0 0 100 200 300 400 500
0.0 100.0 200.0 300.0 400.0 500.0 Capacity / mAh/g
Capacity / mAh/g

Fig. 4 1st & 2nd Charge-discharge Si:Csugar(80:20wt%).

Fig. 3 1st & 2nd Charge-discharge Si:Csugar(80:20wt%).
0.5mA, cut-off cap. 450mAh/g
0.25mA, cut-off cap. 450mAh/g

2.5

2 1st cycle
Fig. 3~5 are the discharge-charge
2nd cycle profiles of Si:Csugar(80:20wt%) in various
1.5 conditions of applied current. With cut-off
capacity of 450mAh/g. it was observed that no
1 great influence to the charge capacity with
Voltage / V

increasing current condition. Although high

0.5
current of 1.0mA was used to the composite Si,
0
no reduction of charge capacity can be observed.
0 100 200 300 400 500 Charge capacity in the 1st charging is slightly
-0.5 increase. The reason of increasing in charge
capacity is not clear but it might be came from
-1 the SEI formation in Si composite that may give
Capacity / mAh/g
different electrical properties. The following
st nd
Fig. 5 1 & 2 Charge-discharge Si:Csugar(80:20wt%). cycle (2nd cycle) exhibited decrease in charge
1.0mA, cut-off cap. 450mAh/g
capacity at higher current condition. However, the decreased is very low compared to the non-cut-off method
(Fig. 7). From the results it can be concluded that by using cut off capacity method the current applied have very
less influence to the charge capacity compared with cut-off potential method.

450.0 600.0
400.0
500.0
350.0
1st charge
Capacity / mAh/g

300.0 400.0
2nd charge

Capacity / mAh/g
250.0
300.0
200.0

150.0 200.0

100.0 1st charge

100.0
50.0 2nd charge

0.0 0.0
0.00 0.20 0.40 0.60 0.80 1.00 1.20 0.00 0.20 0.40 0.60 0.80 1.00 1.20

Applied Current / mA Current / mA

Fig. 6 Charge capacity vs Applied Current (Cut-off Fig. 7 Charge capacity vs Applied Current (Cut-off
capacity 450mAh/g) Potential 0.1-2.0V)

Future works
1. Ball mill effect of Si-Csugar ( Received of ZrO2 bowl on 9oct 05, Planetary Mill)
2. BET surface analysis of Si-Csu(KIV)
Problems
1. Not enough battery cycler (limited channels).(1 researcher 1 channel)-----severe
2. Planetary M/C <RM40K ( Kew 7).-Tendered
3. BET surface analysis------ SIRIM HQ