Development Of Non Aqueous Asymmetric Hybrid Supercapacitors Part Ii
1. DEVELOPMENT OF NON-AQUEOUS ASYMMETRIC
HYBRID SUPERCAPACITORS BASED ON Li-ION
INTERCALATED COMPOUNDS
GUIDE
Dr.D.KALPANA, SCIENTIST, BY
EEC DIVISION, NAKKIRAN.A,
CECRI,
KARAIKUDI.
2. An overview of previous presentation
• Introduction
• Hybrid supercapacitors
• Synthesis of LiMn2O4 and the same multidoped
with Ni, Co and Cu
• Physical characterization - XRD, SEM, FTIR
• Cell Fabrication
9. Formula used
Average current
Specific capacitance =
Scan rate x Weight
10. Cyclic Voltammetry
Results
Specific capacitance of
Specific capacitance of LiMn2O4
LiMn1.25Co0.25Ni0.25Cu0.25O4
(F/g)
Condition ( F/g)
1mV/s 2mV/s 5mV/s 1mV/s 2mV/s 5mV/s
Before
34 31 29 22 20 19
cycles
After 5000
27 22 18 18 16 15
cycles
11. Charge-Discharge Profiles of
LiMn2O4
Current density = 500µA/cm2
2.4
2.4
cycle no.2 2.2
2.0 after 5000 cycles
2.0
1.8
1.6
1.6
Voltage(V)
voltage in V
1.4
1.2
1.2
0.8 1.0
0.8
0.4 0.6
0.4
0.0 0.2
0.0
900 1000 1100 1200 1300 1400 1500 1600 700 750 800 850 900 950 1000 1050 1100 1150
Time (sec)
Time in s
12. Charge-Discharge Profiles of
LiCo0.25Ni0.25Cu0.25Mn1.25O4
Current density = 500µA/cm2
2.0 2.0
cycle no.3 after
1.8 1.8 5000 cycles
1.6 1.6
1.4 1.4
Voltage(V)
1.2 1.2
voltage in V
1.0 1.0
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0
6300 6350 6400 6450 6500 6550 6600 6650 450 500 550 600 650 700 750
Time(sec) Time in s
13. Formulae used
Specific Capacitance = Current x Discharge time
Voltage x weight
Current x Voltage
Specific Power = weight
Current x Voltage x Discharge time
Specific Energy =
weight
14. Charge-Discharge results
LiMn2O4 LiMn1.25Co0.25Ni0.25Cu0.25O4
Condition
Specific Specific Specific Specific Specific Specific
capacitance power energy capacitance power energy
F/g kW/kg kWh/kg F/g kW/kg kWh/kg
Before
14.55 200 21.98 5.36 110 5.8
cycles
After 5000
7.85 200 11.83 4.17 110 4.58
cycles
20. Structure Vs capacity fading
• The structural stability of a host electrode to the
repeated insertion and extraction of lithium is
undoubtedly one of the key properties for ensuring
that a lithium ion cell operates with good
electrochemical efficiency
• In transition metal oxides, both stability of the
oxygen ion array and minimum displacements of the
transition metal cations in the host are required to
ensure good reversibility.
22. Structural Change
• the cubic symmetry of Li[Mn2]O4(space group
Fd3m), in which the lithium ions occupy tetrahedral
sites and Mn occupy the Octahedral sites
• On cycling the lithium ions occupy octahedral sites
of Mn ion ,So the cubic symmetry of LiMn2O4 is
reduced to tetragonal Li2[Mn2]O4 (space group
F41/ddm)
24. • This crystallographic distortion, which results
in a 16% increase in the c/a ratio of the unit
cell parameters
• Average Oxidation state of cubic spinel is 3.5
• Average Oxidation state of tetragonal spinel is
3
25. Jahn Teller distortion
When the ratio of Mn3+ increases ,it follows a
disproportionate reaction
2Mn3+ Mn4+ + Mn2+
Where Mn2+ is an acid-soluble species .It
dissolute into solution. And distrust its
structural integrity during cycling.
26. Remedy
• This multi-doped system maintains the
average oxidation state of Mn ion between
3.5 to 4.
• So JT distortion is reduced to the greater
extend
27. Conclusions
• The faster rate of capacity fading in pure
substance than doped one may be attributed
to the onset of Jahn-Teller distortion
• The above point may be confirmed without
any doubts soon after the arrival of XRD
results for the sample after 5000 cycles.
28. Conclusions
• The low IR in the case of doped substance
is also a strong reason for its better
performance
• The impedance profiles too explain clearly
that doped substance is a better candidate
for supercapacitors than the pure one
29. Conclusions
• With LiMn2O4 we were able to reach a high
voltage of 2.4v, while the highest voltage
that has ever been reported for this system
is 1.8v
• This high voltage may be attributed to the
use of organic electrolyte – 1M LiClO4 in
EC-PC
31. Synthesis Of Cathode Material
• Two cathode materials were synthesized,
i) Pure LiCoO2
ii) LiCoO2 doped with Al - LiCo1-xAlxO2 ( x = 0.2, 0.4,…..0.8 )
• 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)
• LiNO3 + 0.8Co(NO3)2.6H2O + 0.2Al(NO3)2.9H2O LiCo0.8Al0.2O2
(for doped substance)
32. Composition For Pure Substance
Basis : 0.1 moles(9.8g) of product
Chemical Weight
LiNO3 6.9 g
Co(NO3)2.6H2O 29.1 g
Glycine ( C2H5NO2) 15 g
Distilled Water 100 ml
33. Composition For Doped Substance
Basis : 0.2 moles of product
Chemical Weight
LiNO3 13.8 g
Al(NO3)2.9H2O 15 g
Co(NO3)2.6H2O 46.56 g
Glycine ( C2H5NO2) 30 g
Distilled Water 100 ml
34. 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
36. Future Work
• Physical characterization of LiCoO2
• Cell fabrication
• Electrochemical characterization
• Comparison of LiMn2O4 and LiCoO2 using
the available data