DEVELOPMENT OF NON-AQUEOUS ASYMMETRIC HYBRID SUPERCAPACITORS BASED ON Li-ION INTERCALATED COMPOUNDS

GUIDE Dr.D.KALPANA, SCIENTIST, EEC DIVISION, CECRI, KARAIKUDI. BY NAKKIRAN.A,

An overview of previous presentations
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Introduction Hybrid supercapacitors Synthesis of LiMn2O4 and the same multidoped with Ni, Co and Cu Physical characterization - XRD, SEM, FTIR Cell Fabrication Electrochemical characterizations Comparison of their performances

Study of supercapacitors

Having LiCo1-xAlxO2 as cathodes (where x=0,0.2,0.4 and 0.6)

Lithium Cobaltate(LiCoO2)

Commercially successful The layered structure of LiCoO2 enables easy diffusion of Li-ions in and out of the structure

Why Aluminum

There has recently been considerable interest in Aldoping of lithium intercalation oxides. Al substitution of the transition-metal cation has been shown theoretically and experimentally to increase the cell voltage. Some other advantages of Al are that it is light, nontoxic, and inexpensive

Advantage

The similarity of Al and Co ions in these lithium metal oxides makes Al an attractive choice for doping The end members, a-LiAlO2 and LiCoO2, have the same crystal structure, layered a-NaFeO2 and the metal ions are close in size. These similarities remove the complications of phase transitions and lattice strain when varying doping content.

Synthesis Of Cathode Material

Two cathode materials synthesized are, i) Pure LiCoO2 ii) LiCoO2 doped with Al - LiCo1-xAlxO2 ( x = 0.2, 0.4,0.6 ) The cathode material was synthesized by soft combustion method Compositions were taken on a stoichometric ratio based on following equations,
LiNO3 + Co(NO3)2.6H2O LiCoO2

(for pure substance)
LiCo1-xAlxO2 (for doped substance)

LiNO3 + (1-x) Co(NO3)2.6H2O + xAl(NO3)2.9H2O

Composition of precursors required for synthesis Basis : 0.2 moles of product
Precursor LiNO3 Al(NO3)2.9H2O Co(NO3)2.6H2O Glycine(C2H5NO2) Distilled Water Weight of the material X=0 13.8g 58.2g 30g 100ml X=0.2 13.8 g 15 g 46.56 g 30 g 100 ml X=0.4 13.8g 30g 34.92g 30g 100ml X=0.6 13.8 45g 23.28g 30g 100ml

X= Fraction of Aluminium

The Soft Combustion Process
Weighing of required chemicals Dissolve in 100ml distilled water Stir well at 600C Heat the mixture at 1000C for 8 hours Product is formed following a soft combustion

Physical Characterization
  

Thermal Analysis X-Ray Diffraction FTIR

Thermal Analysis

TGA is used to find the optimum temperature ranges for drying a sample to remove the moisture and impurities from it. In DTA phase transitions or chemical reactions are followed through observation of heat absorbed or liberated.

TGA Curves
1.0

0.9

Weight fraction

0.8

0.7

0.6

0.5

LiCoO2 LiCo0.8Al0.2O2 LiCo0.6Al0.4O2 LiCo0.4Al0.6O2

0.4 0 200 400 600 800
0

1000

1200

1400

Temperature ( C)

DTA Curves
2.0

Temperature difference( C)

1.5 1.0 0.5 0.0 -0.5 -1.0 -1.5 -2.0 0 200 400 600 800
0

0

LiCoO2 LiCo0.8Al0.2O2 LiCo0.6Al0.4O2 LiCo0.4Al0.6O2

1000

1200

Temperature( C)

TGA Curves

The initial weight drop from 300C-1500C is due to moisture removal from the sample. the subsequent weight loss from 1500C to 3000Ccorresponds to elimination of organic compounds from samples. Next weight drop in the temperature range of 3000C-5000C is formed as a result of the reaction of unreacted precursors to give the final product. The stabilization temperature for these samples mostly lay after 8000C. So the samples are heated at 8000C for 4 hours.

FTIR Curves
100

80

% Transmittance

60

40

20

LiCoO2 LiCo0.8Al0.2O2 LiCo0.6Al0.4O2 LiCo0.4Al0.6O2

0 500 1000 1500 2000 2500
-1

3000

3500

Wave numbers(cm )

These are the FTIR spectroscopes of LiCoO2, LiCo0.8Al0.2O2, LiCo0.6Al0.4O2, and LiCo0.4Al0.6O2 respectively For high level of Al substitution, the broadening of the infrared peaks can be interpreted as an increase in CoO6 distortion due to the incorporation of Al3+ in the Co3+ site.

XRD Patterns
(003) (101) (006) (012) (104)

(107)

(108) (110) (113)

(105)

LiCo0.6Al0.4O2

LiCo0.8Al0.2O2

LiCoO2
10 20 30 40 50 60 70 80 90 100

2 theta

(201)

LiCo0.4Al0.6O2

All samples are single phase and have the αNaFeO2 structure (space group R3m). Miller indices (hkl) are indexed in the hexagonal setting. No impurity phase was detected in the XRD patterns of LiAlyCo1−yO2 On Al doping, the (108) peak shifts towards lower 2θ and the (110) peak shifts towards higher 2θ value

XRD Patterns
(108) (110)
66

LiCo0.4Al0.6O2

LiCo0.6Al0.4O2

LiCo0.8Al0.2O2

LiCoO2

64

68

2 theta

Electrochemical Characterizations
 

Cyclic Voltammetry Electrochemical Impedance Spectroscopy Galvanostatic Charge/Discharge

CV of LiCoO2/CNF before cycles
0.0004 0.0002 0.0000

Current(A)

-0.0002

-0.0004

-0.0006 1mV/s 2mV/s 5mV/s 2000 1000 0 -1000 -2000

-0.0008

Voltage(mV)

CV of LiCoO2/CNF after 500 cycles
0.0002

0.0000

Current(A)

-0.0002

-0.0004

1mV/s 2mV/s 5mV/s
1500 1000 500 0 -500 -1000 -1500

Voltage(mV)

CV of LiCo0.8Al0.2O2/CNF before cycles
0.0004 0.0002

Current(A)

0.0000

-0.0002

-0.0004

-0.0006 1500 1000 500 0 -500

1mV/s 2mV/s 5mV/s

-1000

-1500

Voltage(mV)

CV of LiCo0.8Al0.2O2/CNF after 500 cycles
0.0002 0.0001

Current(A)

0.0000

-0.0001

1mV/s 2mV/s 5mV/s
-0.0002 1500 1000 500 0 -500 -1000 -1500

Voltage(mV)

CV of LiCo0.6Al0.4O2/CNF before cycles
0.00015 0.00010

Current(A)

0.00005

0.00000

-0.00005

-0.00010

1mV/s 2mV/s 5mV/s
1500 1000 500 0 -500 -1000 -1500

-0.00015

Voltage(mV)

CV of LiCo0.6Al0.4O2/CNF after 500 cycles
0.0006 0.0004

Current(A)

0.0002

0.0000

-0.0002

-0.0004

1mV/s 2mV/s 5mV/s
2000 1000 0 -1000 -2000

-0.0006

Voltage(mV)

CV of LiCo0.4Al0.6O2/CNF before cycles
0.0004

Current(A)

0.0002

0.0000

-0.0002

-0.0004

1mV/s 2mV/s 5mV/s
1500 1000 500 0 -500 -1000 -1500

Voltage(mV)

CV of LiCo0.4Al0.6O2/CNF after 500 cycles
0.00010

0.00005

Current(A)

0.00000

-0.00005

1mV/s 2mV/s
-0.00010 1500 1000 500 0 -500 -1000 -1500

Voltage(mV)

Specific capacitance (F/g)

from CV
Scan rate Composition
5mV/s 0 Before cycles 0.2 0.4 0.6 15.93 11.6 21.74 6.1 2mV/s 18.75 15.25 26.93 7.63 1mV/s 20.09 16.3 27.61 8.3

0 After cycles 0.2 0.4 0.6

4.113 8.274 16.225 -

5.29 10.33 19.74 5.1

11.95 12.93 21.51 6.4

Impedance Spectroscopy – Before Cycles
-80

-60

LiCoO2 LiCo0.8Al0.2O2 LiCo0.6Al0.4O2 LiCo0.4Al0.6O2

Z (Ohm)

Im

-40

-20

0 0 20 40 60 80 100

ZRe(Ohm)

Impedance Spectroscopy – After 500 Cycles
-250 -200

LiCoO2 LiCo0.8Al0.2O2 LiCo0.6Al0.4O2 LiCo0.4Al0.6O2

Z (Ohm)

-150

Im

-100

-50

0 0 50 100 150 200 250

ZRe(Ohm)

Results of Impedance Spectroscopy
Property x 0 Before cycles 0.2 0.4 0.6

Rs
Ohm

Cdl
mF

3.747 2.392 4.551 5.649

0.6194 0.5518 0.5491 0.6328

0 0.2 After cycles 0.4 0.6

4.721 6.253 4.782 6.211

0.6567 0.5778 0.621 0.711

Galvanostatic Charge-Discharge behaviour of LiCoO2/CNF
2.0
2.1

1.6
1.4

Voltage(V)

1.2

0.8
0.7

0.4

0.0 350 400 450 500 550 600

Voltage(V)
0.0 5600 5610 5620 5630 5640 5650

Time(s)

Time(s)

First cycle

500th cycle

Galvanostatic Charge-Discharge behaviour of LiCo0.8Al0.2O2/CNF
2.0
1.6

1.6

0.8

Voltage(V)
26 28 30 32 34 36 38 40 42

Voltage(V)

1.2

0.8

0.4
0.0

0.0 1337 1338 1339 1340 1341 1342 1343 1344

Time(s)

First cycle

500th cycle

Time(s)

Galvanostatic Charge-Discharge behaviour of LiCo0.6Al0.4O2/CNF
2.0
2.0

1.6
1.6

1.2

Voltage(v)
600 650 700 750 800 850 900

1.2

Voltage(V)

0.8

0.8

0.4

0.4

0.0

0.0 9120 9140 9160 9180 9200

Time(s)

First cycle

500th cycle

Time(s)

Galvanostatic Charge-Discharge behaviour of LiCo0.4Al0.6O2/CNF
2.0 2.0 1.6 1.6

Voltage(V)
105 110 115 120 125 130 135 140 145

Voltage(V)

1.2

1.2

0.8

0.8

0.4

0.4

0.0

0.0 11732 11736 11740 11744 11748 11752

First cycle

Time(s)

500th cycle

Time(s)

Results of Galvanostatic Charge-Discharge Analysis
Properties Composition
Specific capacitanc e (F/g) 11.17 0.415 11.41 1.53 Power density (kW/kg) 312.5 303.03 333.3 322.58 Energy density (kWh/kg) 12.41 0.44 12.68 1.075

0 Before cycles 0.2 0.4 0.6

0 After cycles 0.2 0.4 0.6

1.8 0.303 3.83 0.88

312.5 303.03 333.33 322.58

2.01 0.336 4.25 0.986

Conclusion

LiCoO2 is a good cathode material for hybrid supercapacitor since it is having specific capacitance of 11 F/g. In the doped cathode materials, LiCo0.6Al0.4O2 is having good capacitance and cycle behaviour.

Thank You

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