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LI-ION BATTERY ANODE USES NANO SIZED SRI LANKA VEIN GRAPHITE TO ENHANCE BATTERY CAPACITY N.W.B.

LI-ION BATTERY ANODE USES NANO SIZED SRI LANKA VEIN GRAPHITE TO ENHANCE BATTERY CAPACITY

N.W.B. BALASOORIYA, Faculty of Applied Sciences, South Eastern University, Sammanthurai (E.P), Sri Lanka.

Ph. Touzain, LEPMI, ENSEEG, INPG, B.P. 75, 38402 St. Martin d’Hères, France.

P.W.S.K. Bandaranayake, Dept. Of Physics, University of Peradeniya, Sri Lanka

Sri Lanka Natural Vein Graphite

09/24/12

Sri Lanka Natural Vein Graphite 09/24/12 2
Sri Lanka Natural Vein Graphite 09/24/12 2
Sri Lanka Natural Vein Graphite 09/24/12 2

2

Intensity (a.u.)

(a)

(b)

(002) (004) (101) (100) (110) (006) (103) 20 30 40 50 60 70 80 90
(002)
(004)
(101)
(100)
(110)
(006)
(103)
20
30
40
50
60
70
80
90
2 Theta
(002)
(004)
(006)
CaCO 3
SiO 2
(c)
(101)
(103)
20
30
40
50
60
70
80
90
2 Theta
Intensity (a.u.)

X-ray diffractogram of Bogala coarse flakes of radial graphite (BCFR): (b) X-ray diffractogram of nuclei of BCFR: (c) SEM Photograph

around the nuclei.

09/24/12

3

Variation of the rhombohedral phase contents

R

100%

(101)

(101)

H

(1 01 )H (10 1 )R h (1 00 )H 5 0h : B all
(1 01 )H
(10 1 )R h
(1 00 )H
5 0h :
B all
m il led
25 h: B all m ill ed
U n treat ed
40 4 1
4 2
4 3
4 4
4 5
4 6
47
4 8
Intensity (a.u.)

2 Theta

Duration and type of mechanical treatment

L c (nm)

 

L a (nm)

(101) R /(101) H intensity ratio

d 002

d 004

d 006

d 110

d 100

 

%

Untreated (63 m)

84

65

74

152

141

14

After 25 hrs. sieve-shaken (63 m)

61

47

45

125

95

22

After 50 hrs. sieve-shaken (63 m)

57

52

50

122

84

30

After 25 hrs. ball-milled

48

36

39

88

82

44

After 50 hrs. ball-milled

45

36

38

60

89

48

(101)H (101)R (100)H (012)R 50h: Ball milled 25h: Ball milled Untreated 40 41 42 43
(101)H
(101)R
(100)H
(012)R
50h: Ball milled
25h: Ball milled
Untreated
40
41
42
43
44
45
46
47
48
Intensity (a.u.)

2 Theta

Duration and type of mechanical treatment

L c (nm)

 

L a (nm)

(101) R /(101) H intensity ratio

d 002

d 004

d 006

d 110

d 100

 

%

Untreated (63 m)

63

53

65

NA

96

21

After 25 hrs. sieve-shaken (63 m)

68

58

50

90

164

26

After 50 hrs. sieve-shaken (63 m)

65

61

76

136

160

22

After 25 hrs. ball-milled

38

32

38

89

67

52

After 50 hrs. ball-milled

44

30

32

120

88

67

Microstructure

A
A

(a)

C
C

(c)

B
B

(b)

D
D

(d)

(a) partly hexagonal crystal faces and random tacking defects of Kahatagaha/Kolongaha shiny slippery

fibrous graphite,

(b)

partly hexagonal crystal faces and random tacking defects of Bogala shiny slippery fibrous graphite, (

(c)

compact equigranular aggregates of hexagonal crystal faces of Kahatagaha/Kolongaha coarse flakes

09/24/12

of radial graphite and (d) crystallized needles of Bogala shiny slippery fibrous graphite.

5

TEM image of KSSI graphite during 50 hrs. Carbon content measured by Carbon-Sulfur determination method

TEM image of KSSI graphite during 50 hrs.

TEM image of KSSI graphite during 50 hrs. Carbon content measured by Carbon-Sulfur determination method 09/24/12

Carbon content measured by Carbon-Sulfur determination method

Impurity contents of vein graphite

09/24/12

1.2 SiO2 C aO 1 Fe2O 3 Tot. MgO 0.8 Al2O3 0.6 0.4 0.2 0
1.2
SiO2
C aO
1
Fe2O 3 Tot.
MgO
0.8
Al2O3
0.6
0.4
0.2
0
BSSI
KSSI
BCFR
BSCF
KSCF
BNPG
KNPG
E1099
KCFR
UF4
1200
1000
800
600
Cu (ppm )
400
200
0
BS SI
KSSI
BCFR
KCFR
BSCF
KSCF
BNPG
KNPG
C o nte nt
Percentage
(ppm)

7

(a) (c) (b) ( d )  Energy Dispersive X-ray (EDX) analysis is one of

(a)

(a) (c) (b) ( d )  Energy Dispersive X-ray (EDX) analysis is one of the

(c)

(a) (c) (b) ( d )  Energy Dispersive X-ray (EDX) analysis is one of the

(b)

(a) (c) (b) ( d )  Energy Dispersive X-ray (EDX) analysis is one of the

( d )

Energy Dispersive X-ray (EDX) analysis is one of the versatile techniques available for the investigation of the distribution of the materials. EDX analysis was performed on a JSM 6400 scanning electron microscope equipped with an Energy Dispersive Microanalyser to identify the materials in the

samples.

09/24/12

8

Evolution of Raman spectra of untreated and ball-milled natural vein graphite

600 KSSI (Untreated) G KSSI (25h., ball milled) 500 400 300 D 200 100 0
600
KSSI (Untreated)
G
KSSI (25h., ball milled)
500
400
300
D
200
100
0
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
Intensity (a.u.)

Wave number (cm -1 )

Raman spectrometry is a unique tool to characterize structure defects in graphite and gives complementary information to XRD. In graphite there are two main Raman active modes in first order. The G-mode appears at 1580-1585 cm -1 and D-mode at 1350 cm -1 . The second order Raman mode appears at 2725 cm -1 . The G-mode is associated with C-C plane bond stretching (E 2g mode) while the D–mode is attributed to the finite size effect.

Li/graphite cell assemble

Liquid electrolyte Separator Graphite composite electrode Stainless steel plate Li metal : reference electrode
Liquid
electrolyte
Separator
Graphite composite
electrode
Stainless steel plate
Li metal :
reference electrode
O-ring

Then coin type cells (CR2430): metallic lithium counter electrode and composite membrane as the working electrode

Separator: A micro-porous polypropylene sheet (Celgard 2400)

Electrolytes: 1M LiPF 6 and 1M LiClO 4 in EC/ DMC (1:1)

Electrochemical experiments were performed with a MacPile multichannel potentiostat-galvanostat (Biologic, France).

09/24/12

10

3 A BSSI KSSI 2.5 E1099 0.35 KS25 0.3 2 0.25 0.2 E B 1.5
3
A
BSSI
KSSI
2.5
E1099
0.35
KS25
0.3
2
0.25
0.2
E
B
1.5
0.15
F
0.1
1
0.05
G
C
0
0
0.2
0.4
0.6
0.8
1
1.2
1.4
x in Li x C 6
0.5
D
E
0
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+
Potential (V) vs. L/Li
+
Potential (V) vs. Li/Li

x in Li x C 6

a) First discharge-charge curve for Li/graphite (KSSI) cell for different electrolytes with a current rate C/20, at 25 °C,

(b) Li/ natural graphite (Sri Lanka and Madagascar) and synthetic graphite (KS25) cells in 1M LiPF 6 (EC/DMC), at current rate C/40.

09/24/12

Inset: Detail of the curves corresponding to the Li intercalation.

11

42 C/20 Untreated 41 40 Sieve-shaked: 50hrs. Ball-milled: 50hrs. C/40 39 38 C/40 C/20 37
42
C/20
Untreated
41
40
Sieve-shaked: 50hrs.
Ball-milled: 50hrs.
C/40
39
38
C/40
C/20
37
C/60
36
C/80
35
34
33
32
C/80
31
C/20
30
C/60
29
28
C/40
21
22
23
24
60
62
64
66
68
70
C irr (%)

Rhombohedral phase content (%)

480 460 Discharge cap. (1M LiPF 6 ) 440 Charge cap.(1M LiPF 6 ) Discharge
480
460
Discharge cap. (1M LiPF 6 )
440
Charge cap.(1M LiPF 6 )
Discharge cap. (1M LiClO 4 )
420
Charge cap. (1M LiClO 4 )
400
380
360
340
320
300
09/24/12
0
2
4
6
8
10
Capacity (mAh/g)

Number of Cycles

Variation of the irreversible capacity loss in relation with the rhombohedral phase content for untreated and treated KSSI graphite at different current rates in 1M LiPF 6 (EC/DMC).

Relationship between the charge and discharge capacity as a function of the cycle number.

12

375 370 Untreated Sieve-shaked: 50hrs. Ball-milled: 50hrs. 365 360 355 350 345 340 335 0
375
370
Untreated
Sieve-shaked: 50hrs.
Ball-milled: 50hrs.
365
360
355
350
345
340
335
0
5
10
15
20
Reversible capacity (mAh/g)

Variation of the reversible capacity as a function of the different cycles for untreated and treated KSSI graphite at a C/40 current rate within 1M LiPF 6 (EC/DMC).

Cycle number

150 BSSI 100 KSSI E1099 50 0 A B -50 C D -100 E -150
150
BSSI
100
KSSI
E1099
50
0
A
B
-50
C
D
-100
E
-150
-0,5
0
0,5
1
1,5
2
2,5
3
3,5
Potential (V) vs. Li/Li +
09/24/12
Specific current (mA/g)

cyclic voltammogram of Li/graphite (Sri Lanka and Madagascar) cells

13

Duration and

 

Current rate

 

(101) R /(101) H intensity ratio

type of

 

C/20

 

C/40

 

C/60

 

C/80

 

mechanical

C

rev

C irr %

C

rev

C irr %

C

rev

C irr

C

rev

C

irr

%

treatment

(mAh/g)

(mAh/g)

(mAh/g)

%

(mAh/g)

%

Untreated (63 m)

 

301

46

 

341

23

 

266

64

 

345

 

54

14

After 50hrs.

 

334

43

 

362

35

 

358

34

 

354

 

37

48

ball-milled

         

After oxidative treatment in air

 

359

17

 

391

13

 

398

4

 

396

 

8

21

After oxidative treatment in (NH 4 ) 2 S 2 O 8

 

371

9

 

387

12

 

394

6

 

396

 

10

18

Duration and

 

Current rate

 

(101) R /(101) H intensity ratio

type of

 

C/20

 

C/40

 

C/60

 

C/80

 

mechanical

C

rev

C irr , %

C

rev

C irr %

C

rev

C irr %

C

rev

C

irr

%

treatment

(mAh/g)

(mAh/g)

(mAh/g)

(mAh/g)

%

Untreated (63 m)

 

307

31

 

354

28

 

300

30

 

355

 

32

24

After 50hrs.

 

369

38

 

366

40

 

365

37

 

370

 

36

67

ball-milled

         

After oxidative treatment in air

 

369

18

 

397

16

 

399

6

 

379

 

25

21

After oxidative treatment in (NH 4 ) 2 S 2 O 8

 

365

10

 

398

7

 

396

18

 

389

 

11

20

First reversible and irreversible capacities of treated and untreated (a) BSSI and (b) KSSI graphite

Conclusions

The present study confirms that Sri Lankan natural graphite is promising as intercalation anode material in rechargeable lithium battery applications due its unique morphology, low cost and high purity.

The electrochemical properties of nano sized BSSI and KSSI graphite can further be enhanced by simple ball-milling or chemical treatments, which can be used for value addition to Sri Lanka graphite.

Future Plan

Purification of graphite: using flotation and mechanical processing methods and chemical treatments.

Electrochemical and other industrial applications

New technological applications