3.6
4.
PVDF LixC6 PVDF 100 SEI
180
3.7
(R ) I2Rt
SEI
5.
5.1
( )
4
5.2
( PE )
B A
A B
A-A
5.3
B-B
5.4
A B
Ai
Ai
Ai
A=
Ai
Ai∆H AiIVt = ΣAi ΣAi
(A) (B)
5
5.5
SEI 5.5
5.6
6
1
HP Notebook PC Fire and Explosion
Dell Apple Panasonic HP Toshiba IBM, Lenovo Sharp Fujitsu Hitachi Sony Notebook PC Notebook PC Notebook PC Notebook PC Pocket PC Notebook PC Notebook PC Notebook PC Notebook PC Notebook PC 4.2 million 0.1 million 1.8 million 6,000 157,000 340,000 830,000 526,000 28,000 287,000 51,000 16,000 90,000 2006.8.14 2006.9.29 2006.8.25 2006.9.5 2006.4.20 2006.9.20 2006.9.29 2006.9.28 2006.10.13 2006.10.4 2006.10.13 2006.10.6 2006.10.17 Sony Sony Sony Sony Sony Sony Sony Refuse to disclose
£ £ £ £
3O2+C3H6O3(DMC)
Lix CoO2 Lix
3
Mg0.05 O2 LiNi0.8Co0.2O2 LiNi3/8Col/4Mn3/8O2
7 LiNiO2 LiNi 0 7Co0.2Ti0.05 LiCoO2 LiMn204 LiFePO4
LiCoxNiyMn1-x-yO2 LiFePO4
2.
Discharge
e
Charge
load
e
_
+ Charge
Li +
e e e e e
Li + Li + Li + Li +
Li +
e e
Discharge
Li +
Li + Li +
Electrolyte
LixC6 Li1-xCoO2
Li +
e
Current Anode Collector
Current Cathode Collector
x
Lix CoO2 Lix NiO2
;
Li xMn2O4
(5/2)O2+C3H4O3(EC)
£ £
£ £
3CO2+2H2O 3CO2+3H2O
Lix NiO2 x NiO2 Li xMn2O4 Lix CoO2 Li xMn2O4 x 200-230
4O2+C4H6O3(PC)
£ £
£ £
4CO2+3H2O
Li0.7C6 (
Li0.8C6(
80-120
100-120
>260
130 41~42.26
210-230
426 Li0.7C6/
240-350
1500 LiC6/PVDF
1182J/g 1044J/g
210-230 1388 LiC6/ 1497 SEI LiC6/ + >260 1647 Li2C6/PVDF
1. 2. 3. 4. 5.
2007-12-14
1.
Dell Notebook PC Fire and Explosion
Dell Notebook PC Fire and Explosion
Dell Notebook PC Fire and Explosion
HP Notebook PC Fire and Explosion
2007.3.2 Lenovo Gateway Notebook PC Notebook PC Notebook PC NTT DoCoMo Mobile Phone Mobile Phone Nikon Camera 205K 14K 27K 130 million 46 million 710K 2007.3.2 2007.6.19 2007.4 2006.12.7 2007.8.14 2006.11.9 2007.6.19 2007.6.27 2007.6.27 2007.7.2 2007.9.22 2007.12.14
230-
290-310 10
¡
Li XC6
LiPF6 LiPF6 LiPF6
¢ ¢ ¢ ¢
DEC PO3F + 2HF
£ £ £ £ £ £ £
2
LiF + PF5
£
PF5 + H2O
C2H5OCOOC2H5 + PF5 C2H5OCOOC2H5 + PF5
£ £
C2H5OCOOPF4HF+C2H4
Li1-XNiO2
¤ ¤
¤ ¤
(1—2x)LiNiO2+LiNi204 ( [Li1-XNi(2X
Li1-XNiO2
¤ ¤
¤ ¤
1)/3 ] [Ni(4-2X )/3 ]O(8-4x )/3+
[(2x
1)
¤ ¤ ¤ ¤
3]O2
(x>0.5)
Li1-XNiO2
(2-x)Li (1-x)/(2-x) Ni 1/(2-x) O+(x/2)O2
1
3.4
(1)SEI (2)Li XC6 Li XC6 SEI Li XC6 I00 x (3) Li X C6 SEI 1mol/L LiPF6 280 15~20 1mol/LiClO4 820-940J/g DEC DMC
¡ ¡ ¡
DMC 370-380J/g DMC DEC LiPF6 LiCIO4 1040 ~1250J/g DEC 500-530J/g
80-120 (CH2OCO2Li)2
2Li+(CH2OCO2Li)2
3.2
SEI
2Li+C3 H4O3(EC) 2Li+C5Hl0O3(DEC) 2Li+C3 H6O3(DMC)
Li2CO3+C2H4 Li2CO3+C4H10 Li2CO3+C2H6
LixC6 1mol/L LiPF6/PC:EC:DMC(1:1:3 vol/vol) 100~120 LixC6 350J/g LiCF3SO3 LiPF6 145 2000J/g LixC6 EC PC DEC DMC LixC6 LiPF6 Li0.7C6( Li0.8C6( Li2C6( 0.8m2/g) 3.8m2/g) 157m2/g) 426J/g 625J/g 1338J/g.
90-290
P257 ( )
1
LixC6/ (J/g) 350 ( ) LixC6/PVDF (J/g) 1025 Li0.8C6/PVDF
LiF + —CH CF— + ½H2
0.8m2/g) 3.8m2/g) 157m2/g) 657J/g 1025J/g 1647J/g
2
Figure 3. Normalized evolved gas composition of ARC cell and electrolyte.
3.5
LiCoO2 LiFePO4 LiNiO2 650 LiMn204
Li0.5CoO2
¤ ¤
¤ ¤
½ LiCoO2+ Co3O4+
¥ ¥ ¥ ¥
6O2 0 5)
2
3.
3.1 SEI
SEI (CH2OCO Li)2 Li2CO3, LiF
SEI MCMB 60 MCMB 80 257J g Li2CO3+CH2=CH2+½O2+CO2 2Li2CO3+CH2=CH2 MCMB 1mol L LiPF6/EC:DEC(1:1 by vol) 1mol L LiPF6/EC:DEC(1:2 by vol) 1mol L LiBF4/EC:DEC(1:1 by vol) 0.82eV 1.4eV 4.8 X1010min-1 4.8 X1017min-1 1mol L LiPF6/EC:DEC(1:2 by vol)
£ £
C2H5OCOOPF4+C2H5F
C2H5OCOOPF4
£ £
£ £
HF+C2H4+CO2+POF3
£ £ £ £
C2H5OCOOPF4
C2H5F+CO2+POF3
£ £ £ £
C2H5OCOOPF4+HF C2H5OH+CH2 CH2
PF4OH+CO2+C2H5F
£ £ £ £
C2H5OC2H5
3.3
260 —CH2—CF2— + Li
x PVDF Li2C6( PVDF SFG-44 MCMB HC-1227 970J/g LixC6 PVDF (PE) 240 PVDF 290 350 LixC6 50mAh/g 44mAh/g 0 , , 482J/g, 336mAh/g 410J/g 375mAh/g 660J/g 315mAh/g