Development of Low cost, Eco Friendly Electrode Materials For Hybrid Supercapacitor Applications

Karthikeyan Kaliyappan, Ph.D scholar, Energy Conversion and Storage Processing Lab, Chonnam National University, Gwangju.

What is Supercapacitors (SC)
 ‘Super’ implies high capacitance values  SCs have the ability to store and release charge and deliver high power densities over short periods of time Stores energy efficiently and release energy very quickly Can be used where short time backup power and peak power needs are critical Applications in hybrid power systems for EVs, memory back up Bridges the gap between conventional capacitors and batteries

History
1957 – First supercapacitor developed with porous carbon electrode by general electronics 1966 – Standard oil company patented a device that stored energy in double layer interface 1978 – Memory backup devices 1980 – Energy source 2005 – Used to power emergency actuation systems for doors in aircraft

Principle of a Supercapacitor
Activated carbon electrode Electrolyt e Activated carbon electrode

+ + + + + + + + + + + + + + - - - - - - - - - - - - - -

Separator shocked in electrolyte
+ + + + + + + + + + + + + + - - - - - - - - - - - - - -

Capacitance C = ε o ε r A/d

 Double layer is generated when a voltage is applied to electro des in an electrolyte  The charge separation occurs in molecular dimensions (few nanometers) resulting in extremely large capacitance Activated carbon with high surface area (2000 m2/g)

Properties of supercapacitors compared with batteries and traditional capacitors
Property
Charge – Discharge time Operating temperature Life Power density

Capacitors
pico seconds to milli seconds - 20 to + 100 o C > 10 8 Cycles 0.25 to 10,000 kW / kg 0.01 to 0.05 Wh / kg 1 to 10 g

SCs
Milli seconds to minutes - 40 to + 75 o C 30,000 to 10 6 cycles 10 to 100 kW / kg

Batteries
1 to 10 hours

- 20 to + 65 o C 150 to 1500 cycles 0.005 to 0.4 kW / kg 8 to 600 W h / kg

Energy density

1 to 5 W h / kg

Weight

1 to 2 g

1 g to over 10 kg

Comparison of Various Energy systems

Advantages
 Very high cell voltages possible  High power density  No special charging circuits required  Can be charged and discharged in seconds  Long cycle life  No chemical reactions 10 to12 years life

Classification of Supercapacitors

Need for Hybrid Supercapacitor
 HEVs requires energy storage devices that can deliver higher power density as well as higher energy densities Two kind of energy devices 1. Secondary batteries can not be widely used in HEVs due to their low power density and short cycle life 2. Supercapacitors – Low energy density is the major problem  By combining the energy density of a battery with a high power density of a super capacitor, much smaller and lighter battery could be used in cars

Lithium ion capacitors
High specific energy then ECs • Cathode - Lithium intercalated compounds • Anode - High surface activated carbon

Lithium materials
     LiMn2O4 LiCo1/3 Ni1/3 Mn1/3 O2 LiCoPO4 LiCoO2 Li4Ti5O12 High cost Toxic

Metal orthosilicates (Li2MSiO4, M = Fe, Mn)
 Environmental Friendly  Better thermal properties  Competitive energy density  Low cost  Relatively high lithium-ion mobility

Preparation of Li2MSiO4 (M=Fe and Mn)
LiOH Mn2O3 or FeC2O4 SiO2

Adipic Acid Pre calcination at 400 oC for 4h in air

Solid State method
 Bulk production  Easy to handle

Grinding and pellet

Final calcination at 800 oC for 12h in argon

Li2MSiO4 (M=Fe and Mn)

Electrode Fabrication
Anode: Anode 70% of Li2FeSiO4 Li2MnSiO4 or

Cell Fabrication
Coin type cell - CR 2032

20% of Ketjen Black 10% of Teflonized acetylene black Cathode: 70% of Activated carbon Cathode 20% of Ketjen Black 10% of Teflonized acetylene black Separator: Celgard 3401 Separator Electrolyte: 1 M LiPF6 in EC:DMC Electrolyte (1:1 vol%) The mass ratio of cathode to anode was about 2:1

X-Ray diffraction Patterns
 The broad peaks indicate that in neither case the crystallinity is good
Li2FeSiO4

Intensity (au.units)

 Orthorhombic unit cell in space group Pmn2 typical of phases with the low temperature Li3PO4 structure type  The two compounds are isostructural
80

Li2MnSiO4 10 20 30 40 50 60 70

2θ (degree)

Size of the particles
δ = 0.9λ /β cosθ Li2FeSiO4 – 62 nm Li2MnSiO4 – 150 nm

SEM Images
(a ) (b )
(a) - Li2FeSiO4 (b) - Li2MnSiO4

Compound Li2FeSiO4 Li2MnSiO4

Average particle size (nm) 50 - 75 100-150

Well-developed particles Narrow size distribution Better for diffusion of lithium ions

CV Studies
9
abcd2 mV/s 5 mV/s 10 mV/s 20 mV/s Li2FeSiO4/AC capacitor
Li2MnSiO4/AC capacitor

9

6

6

a - 2 mV/s b - 5 mV/s c - 10 mV/s d - 20 mV/s

Current (mA)

3

Current (mA)

3

0

a b c d

0
b c

a

-3

-3

d

-6

-6 0.0 0.5 1.0

Voltage (V)

1.5

2.0

2.5

3.0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Voltage (V)

 CV test was employed to find out the capacitive performance of the material • Voltage window - 0-3 V • Scan rates – 2, 5, 10 and 20 mV/s  The rectangular-like behavior revels that both have good capacitive behavior and high reversibility  The curve remains in good rectangular like shape even at high scan rates

Specific capacitance
CSC = I/s*m

I = Applied current (A) S – Scan Rate (mV/s) M – weight of the active material

Li2FeSiO4/AC Cell
Scan rate (mV/s) 2 5 10 20 Csc (F/g) 58.1 42.6 40.8 36.2

Li2MnSiO4/AC Cell
Scan rate (mV/s) 2 5 10 20 Csc (F/g) 76.92 64.13 48.07 38.15

Charge Discharge Characteristics
3
Li2FeSiO4/AC Cell

3

Li2MnSiO4/AC Cell

Voltage (V)

Voltage (V)
1
0 2000 4000 6000 8000 10000

2

2

1

0

0 0 2500 5000

Time (sec)

Time (s)

7500

10000

 Linear and symmetrical feature can be observed from curves  Excellent electrochemical reversibility and good capacitance behavior  Both systems have low ohmic drop

Discharge Specific capacitance The average internal resistance Sdc = 4 (I * t) /(V * M)
Li2FeSiO4/AC Cell

R = Vcharge – Vdischarge /2l
Li2MnSiO4/AC Cell

Current Density Discharge Current Density Discharge (mA/cm2) Capacitance (F/g) (mA/cm2) Capacitance (F/g) 1 2 4 6 8 10 Resistance (Ω) 58 1 2 4 6 8 10 Resistance (Ω) 43.2 34.8 33.5 32 30.6 30 70

120
Li2MnSiO4/AC Cell

120

100
100

Li2FeSiO4/AC Cell

100

100

Discharge Capacitance (F/g)

Coulombic Efficiency (%)

80

80

Discharge Capacitance (F/g)

60

60

60

60

40

40

40

40

20

20

20

20

0 0 200 400 600 800 1000

0

(b)
0 200 400 600 800 1000

Cycle Number

Cycle Number

Li2FeSiO4/AC Cell Cycle Number 1 1000 Capacity loss (%) Columbic Efficiency (%) Discharge Capacitance (F/g) 49.5 43.5 12 More then 99.5

Li2MnSiO4/AC Cell Cycle Number 1 2 Capacity loss (%) Columbic Efficiency (%) Discharge Capacitance (F/g) 43.2 36.7 15 More then 99.5

Coulombic efficiency (%)

80

80

Li2FeSiO4/AC Cell
Energy density (Wh/kg) Power Density (W/kg)

Li2MnSiO4/AC Cell
Energy density (Wh/kg)
54 43 41 40 38 37

Power Density (W/kg)
150 300 600 900 1200 1500

Electrochemical impedance spectroscopy
20
Li2MnSiO/AC Cell 4

Li2FeSiO/AC Cell 4

12

15

9

-Z ima (ohm)

10

-Z ima (ohm)
10 20 30 40 50

6

5

3

0

0 5 10

Zreal (ohm )

Zreal (ohm)

15

20

System

Solution Resistance (Ω)

Charge transfer Resistance (Ω)

Capacitance (F/g) C = -1/2pfZim m
40 56

Conductivity (S/cm) σ = δ/Rct * A

Li2FeSiO4/AC Cell Li2MnSiO4/AC Cell

Conclusion
 Nano sized low cost, less toxic materials Li2MSiO4 (M = Fe and Mn) have been developed for hybrid supercapacitor application.  Hybrid EC capacitors gives about 43.2 and 49.5 F/g specific capacitance based on the electrode activematerial in 1 M LiPF6 in EC:DMC  Delivered high Specific energy and Specific power then conventional EDLC.  Both system exhibited excellent cycling performance (more then 1000 cycles) with more then 99.5% efficiency

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