DEVELOPMENT OF NON-AQUEOUS

ASYMMETRIC HYBRID SUPERCAPACITORS

BASED ON Li-ION INTERCALATED
COMPOUNDS

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

WHAT IS A CAPACITOR?
capacitor is a device used for storing charges and energy in its simplest
form.
A capacitor consists of two conducting surfaces separated by an insulating
material ( Dielectric).
PRINCIPLE:
 What are Supercapacitors?
Supercapacitors are an advanced version of capacitors with
unique ability to combine energy storage capabilities of
batteries and power storage behavior of capacitor.
Hence fill the gap between batteries and conventional
capacitors such as the electrolyte capacitors in terms of specific
energy as well as specific power.
 PROPERTIES OF ENERGY STORAGE
DEVICES

DEVICE CAPACITORS EDLC BATTERY

CHARGING TIME μ sec – m sec m sec - minute Hours

DISCHARGE TIME μ sec – m sec m sec – minute Minutes – months

CYCLE LIFE 106 - 108 106 - 108 200-1000

SPECIFIC POWER > 10,000 1000-3000 <500

(W/KG)
SPECIFIC ENERGY <0.01 0.5-5 50-300
( Wh/KG)
TYPES OF SUPERCAPACITORS
1.EC DOUBLE LAYER CAPACITORS

The term electrochemical double layer capacitor is most

commonly used for carbon based double layer capacitors
because of its high capacitance value.
It generally denotes the supercapacitor having non- faradaic
reactions at both electrodes
CARBON SUPERCAPACITOR
 2.PSUEDOCAPACITOR OR
ULTRACAPACITOR
In a pseudocapacitor, there are two basic reactions, which
lead to electrochemical cell.
Both occur at the interface between a conductor and an
electrolyte and both benefits form very high specific surface
areas at the electrode.
The first mechanism commonly referred to as charge
separation, which is well documented as non-faradaic
mechanism and is the basis for EDLC.
The second reaction commonly referred to as an oxidation –
reduction reaction due faradaic mechanism.
HYBRID CAPACITOR:
Hybrid power system is a new highly reliable
energy storage device. It is a combination of EDLC and a
battery. (eg. C and Li-ion). Hence it is known as capattery
(capacitor battery)
 WHY “HYBRID”?

In supercapacitor two symmetric capacitors are connected in

series and the total capacitance is halved.

1/Ctotal = 1/C + 1/C

Ctotal = C/2.

But in a hybrid supercapacitor, one of the electrodes is

replaced by a battery electrode. So we can get the total
capacitance of the single capacitor electrode with the added
advantage of battery electrode.
Li-CARBON HYBRID SYSTEM
 AIM

Development of hybrid power system combining various

power sources with the supercapacitors is the promising field
of research due to its fundamental advantages of both.
Our work focuses on developing a hybrid system combining
Li-ion battery and Carbon based supercapacitor.
We proposed to study the various supercapacitors based on
cathode material such as LiMn2O4, LiCoO2, LiFeP2O7 and
other such materials.
 CATHODE MATERIAL

Our work starts with making pure and doped lithium

manganate as suitable candidate for Lithium ion based
supercapacitor system
Why Lithium manganate ?
Spinel LiMn2O4 is of great interest as a cathode
material for lithium ion batteries.
Advantage:
 High voltage, low cost and low toxicity
Disadvantage:
Poor cycling behavior because of a fast capacity fading
due to Jahn Teller distortion
 JAHN TELLER DISTORTION AND ITS
REMEDY
Average oxidation state of the manganese in
LiMn2O4 is 3.5 and thus any small perturbation
influencing the oxidation state may alter the ratio of Mn4+
and Mn3+.
When the ratio of Mn3+ increases ,it follows a
disproportionate reaction

2Mn3+ Mn4+ + Mn2+

and causes high solubility of spinel material into the

solution.
Remedy:
Wahihara suggest that partially substituted LiMxMn1-xO4
(M=Co, Cu, Ni, Mn) shows improved cyclability due to the
stronger M-O bonding of octahedron structure in comparison
to that of Mn-O bonding in LiMn2O4.
Hence we studied the both pure and the doped manganate
system
 SYNTHESIS OF CATHODE MATERIAL
SOL-GEL PROCESS:

LiMn2O4 LiCo0.25Cu0.25Ni0.25Mn1.25O4

Li2CO3+MnCO3 in Acetic acid Li2CO3+MnCO3+CuCO3+CoCO3+

Stirring at 500C NiCO3.Ni(OH)3.1.5 H2O in Acetic acid
for 30 minutes

Addition of 50ml of EtOH

Heating at 800C
for 4 hours

Addition of Ammonia solution(30%)

Addition of 2 X Glycine
Heating until
gel formation

Filtering, Drying and Grinding

1.Heating at 5000C for 12 h
2.Firing at 6500C for 12 h
3.Calcining at 7500C for 12h
SEM

Physical characterization XRD

FTIR
 SCANNING ELECTRON
MICROGRAPHS

LiMn2O4 LiCo0.25Cu0.25Ni0.25Mn1.25O4
 X-RAY DIFFRACTION
2000
LiMn2o4:
1800
JCPDS# 35-0782
1600 B a= 9.412 A0, b= 8.233 A0, c=
1400 0
4.1002A0, V= 317.73 A 3
1200
A.U.

1000

800 311 LiCo0.25Cu0.25Ni0.25Mn1.25O4:

111
600 400 A
a= 8.162, b= 7.0844, c= 6.235 Å
400 440 0
200 331
511 V= 360.6 A 3
222
0
10 20 30 40 50 60 70 80
2θ
Fig.1. XRD patterns of (A) LiMn2O4 and (B) doped compound.
Pristine LiMn2O4 adopts a cubic Fd3m space group
The XRD data does not shows any structural distortion on
doping which is evident when the doping concentration
increases X<0.5
 FTIR SPECTROGRAPHS
75
70 The 628cm-1 peak is associated with
65
the symmetric Mn-O stretching
60
%

55
vibration of the MnO6 groups.
50
The peaks 558, 512 and 418cm-1 are
Transmittance

45 A
40
attributed to bending mode of CoO6
35 octahedral (558) and Ni2+-O
30 stretching mode (512&418),
B
25 respectively in the doped compound
20
structure.
15
10
1100 1000 900 800 700 600 500 400

Wave number, cm-1

Fig. 2 IR spectra of LiMn2O4 (A) and doped compound (B)

 ANODE MATERIAL
CNF – Carbon Nano Foam
High surface area (1500 m2/g)
Low electrical resistance
No participation in faradaic reactions at the applied voltage
High capacity (100 - 200 F/g)
Unlike AC, CNF combine high surface area with high bulk
density to give large capacitance values
 CELL FABRICATION
CONSTITUENTS:
POSITIVE ELECTRODE - LiMn2O4(80%)
CNF(15%)
NMP(5%)
NEGATIVE ELECTRODE - CNF(95%)
NMP(5%)
ELECTROLYTE - 1M LiClO4 in EC-PC
SEPARATOR - POLYPROPYLENE
CURRENT COLLECTOR - SS
ELECTRODE AREA - 1 cm2
GRINDING AND MIXING AFTER PASTING AND DRYING

COMPLETE SUPERCAPACITOR COMBINED ELECTRODES

ELECTROCHEMICAL CHARACTERIZATION

 Electrochemical Impedance
spectroscopy
 Cyclic voltammetry
 Galvanostatic charge / Discharge
 CYCLIC VOLTAMMETRY
FOR LiMn2O4: FOR LiCo0.25Cu0.25Ni0.25Mn1.25O4 :

Specific capacitance = Avg current/scan rate/weight of the

material
(F/g)
Scan rate
1 mV/s 2 mV/s 5 mV/s
Material

Pure 34 31 29

Doped 22 20 19
IMPEDANCE SPECTROSCOPY

8 Doped
7 Pure
6

5 R
Z''(Ohm)

4
w
3 C
2

-1
5 6 7 8 9 10 11 12 13

z'(Ohm)
 Impedance parameters

PARAMETERS

RS (Ohm) Rct (Ohm) Cdl (mF/g)

MATERIAL

PURE 5.128 0.2917 2.98

DOPED 5.043 0.2394 3.14

 CHARGE-DISCHARGE

DOPED 2.4 PURE

2.0
1.8 2.0
1.6
1.4 1.6
Voltage(V)

1.2

Voltage(V)
1.2
1.0
0.8 0.8
0.6
0.4 0.4
0.2
0.0
6300 6350 6400 6450 6500 6550 6600 6650 900 1000 1100 1200 1300 1400 1500 1600

Time(sec) Time (sec)

 FORMULAE USED

Current x Discharge time

Specific Capacitance = Voltage x weight

Current x Voltage
Specific Power = weight

Current x Voltage x Discharge time

Specific Energy =
weight
 RESULTS

PROPERTY SPECIFIC SPECIFIC SPECIFIC

CAPACITANCE POWER ENERGY
MATERIAL (F/g) (kW/kg) (kWh/kg)

LiMn2O4 15 200 20

LiCo0.25Cu0.25Ni0.25Mn1
6 110 6
.25O4
 FUTURE WORK

Finding the cycle life behavior of this capacitor and

variation of properties with cycle life.
Continuing the same work for the LiCoO2 cathode material
prepared by various methods and comparing their results
with the results of LiMn2O4.
THANK YOU
QUERIES ?