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 Separator shocked in electrolyte
e + + + + + + + + + + + + + +
- - - - - - - - - - - - - -
Activated carbon
electrode

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 Capacitors SCs Batteries

Charge – Discharge pico seconds to Milli seconds to 1 to 10 hours
time milli seconds minutes

Operating temperature - 20 to + 100 o C - 40 to + 75 o C - 20 to + 65 o C

Life > 10 8 Cycles 30,000 to 10 6 cycles 150 to 1500 cycles

Power density 0.25 to 10,000 10 to 100 kW / kg 0.005 to 0.4

kW / kg kW / kg

Energy density 0.01 to 0.05 1 to 5 W h / kg 8 to 600 W h / kg

Wh / kg

Weight 1 to 10 g 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 High cost
 LiCoPO4 Toxic
 LiCoO2
 Li4Ti5O12

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
Solid State method
Pre calcination at 400 oC  Bulk production
for 4h in air
 Easy to handle

Grinding and pellet

Final calcination at 800 oC

for 12h in argon

Li2MSiO4 (M=Fe and Mn)

 Electrode Fabrication
Cell Fabrication
Anode:
Anode 70% of Li2MnSiO4 or Coin type cell - CR 2032
Li2FeSiO4
20% of Ketjen Black
10% of Teflonized acetylene
black
Cathode:
Cathode 70% of Activated carbon
20% of Ketjen Black
10% of Teflonized acetylene
black
Separator:
Separator Celgard 3401
Electrolyte:
Electrolyte 1 M LiPF6 in EC:DMC
(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
Intensity (au.units)

Li2FeSiO4
 Orthorhombic unit cell in space
group Pmn2 typical of phases with the
low temperature Li3PO4 structure type
Li2MnSiO4  The two compounds are isostructural
10 20 30 40 50 60 70 80
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 Average particle size Well-developed particles

(nm)

Li2FeSiO4 50 - 75 Narrow size distribution

Li2MnSiO4 100-150 Better for diffusion of lithium

ions
 CV Studies
Li2FeSiO4/AC capacitor Li2MnSiO4/AC capacitor
9
9
a - 2 mV/s
a- 2 mV/s
6 b - 5 mV/s
b- 5 mV/s
c - 10 mV/s
c- 10 mV/s 6
d - 20 mV/s
d- 20 mV/s

3
Current (mA)

Current (mA)
0 a 0 a
b
b c
c -3
-3 d

d
-6
-6

0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Voltage (V) 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 I = Applied current (A)
S – Scan Rate (mV/s)
CSC = I/s*m
M – weight of the active
material

Li2FeSiO4/AC Cell Li2MnSiO4/AC Cell

Scan rate Csc (F/g) Scan rate Csc (F/g)

(mV/s) (mV/s)
2 58.1 2 76.92

5 42.6 5 64.13

10 40.8 10 48.07

20 36.2 20 38.15
 Charge Discharge Characteristics
Li2FeSiO4/AC Cell 3 Li2MnSiO4/AC Cell
3

2 2
Voltage (V)

Voltage (V)
1 1

0 0
0 2000 4000 6000 8000 10000 0 2500 5000 7500 10000
Time (sec) Time (s)

 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) R = Vcharge – Vdischarge /2l

Li2FeSiO4/AC Cell Li2MnSiO4/AC Cell

Current Density Discharge Current Density Discharge
(mA/cm2) Capacitance (F/g) (mA/cm2) Capacitance (F/g)

1 1 43.2
2 2 34.8
4 4 33.5
6 6 32
8 8 30.6
10 10 30
Resistance (Ω) 58 Resistance (Ω) 70
 120 120
Li2MnSiO4/AC Cell Li2FeSiO4/AC Cell
100 100
100 100

Coulombic Efficiency (%)

Discharge Capacitance (F/g)

80 80

Coulombic efficiency (%)

Discharge Capacitance (F/g)
80 80

60 60
60 60

40 40 40 40

20 20 20 20

0 0 (b)
0 200 400 600 800 1000
0 200 400 600 800 1000
Cycle Number Cycle Number

Li2FeSiO4/AC Cell Li2MnSiO4/AC Cell

Cycle Number Discharge Capacitance Cycle Number Discharge Capacitance
(F/g) (F/g)
1 49.5 1 43.2
1000 43.5 2 36.7
Capacity loss (%) 12 Capacity loss (%) 15

Columbic Efficiency (%) More then 99.5 Columbic Efficiency More then 99.5
(%)
 Li2FeSiO4/AC Cell Li2MnSiO4/AC Cell

Energy density Power Density Energy density Power Density

(Wh/kg) (W/kg) (Wh/kg) (W/kg)
54 150

43 300

41 600

40 900

38 1200

37 1500
 Electrochemical impedance spectroscopy
Li2MnSiO4/AC Cell Li2FeSiO4/AC Cell
20
12

15
9
-Z ima (ohm)

-Z ima (ohm)
10
6

5
3

0 0
10 20 30 40 50 5 10 15 20
Zreal (ohm ) Zreal (ohm)

System Solution Charge transfer Capacitance Conductivity

Resistance (Ω) Resistance (F/g) (S/cm)
(Ω) C = -1/2pfZim m σ = δ/Rct * A
Li2FeSiO4/AC Cell 40

Li2MnSiO4/AC Cell 56
 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 active-
material 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