Fabrication of supercapacitors

Eelectric double layer ( EDLC) capacitors

As there is no faradic reaction in EDLCs, electric charge is stored by aggregation of charges at the surface of the electrode
materials. Therefore, an important principal for high performance EDLCs is the use of electrochemically stable electrode
materials with high surface area and conductivity.

Properties of Electrode materials

Electrochemically stable
High surface area
High conductivity
Low cost

Both electrodes and current collectors should be stable under electrolyte in charge and discharge cycles.
 Possible electrode material in EDLC

Carbon-based electrode materials

Activated carbon
Carbon nanotubes or nanofibers
Graphite powder or Graphene film (or powder)

Activated carbons are the

most widely used materials for
supercapacitor electrodes Powder of carbon nanotubes Graphite powder
(surface area 2000-3000 m2/g)

Graphite

Graphene powder
 Electrolyte in Supercapacitors
Electrolyte plays a critical role in supercapacitor performance.

Properties of electrolyte Aqueous solution electrolyte

High electrochemical stability KOH (high concentration like 6 M)

High ionic concentration and conductivity H2SO4 acid
Low viscosity KCl, Na2SO4
Wide voltage window
Low toxicity

Typical cell voltage by aqueous electrolyte is 1.23 V

Ions diameter in aqueous electrolyte is relatively small which allows higher ions absorption by the activated carbon
pores and therefore, lower internal resistance.
 Organic electrolyte (Non-aqueous electrolyte )

Non-aqueous electrolyte is quaternary salts dissolved in organic solvent such acetonitrile, ethylene carbonate, propylene
carbonate etc .

Unlike the aqueous electrolyte, organic ions have bigger diameter which limit the ions penetration or absorption into the
activated carbon pores. The internal resistance of organic electrolyte is bit high compared to the aqueous electrolyte. But it
delivers higher voltage in the range of 3 to 3.5 V.

Common electrolytes used in organic supercapacitors

TEABF4/CAN
TEABF4/PC
TEABF4/HFIP
SBPBF4/ACN

TEABF- Tetraethylammonium tetrafluoroborate

ACN- Acetonitrile savant
HFIP- Hexafluoroisopropanol solvent PC- Propylene carbonate solvent
 A good electrolyte should have the following important features
(i) High ionic conductivity
(ii) Large potential window
(iii) Wide operating temperature range
(iv) High chemical and electrochemical stability
(v) Low volatility and flammability
(vi) Environmentally friendly
(vii) Low cost.

The most commercially available electrolytes are organic electrolytes and have some advantages like large
operating voltage. However, compared with aqueous electrolytes, organic electrolytes are expensive, highly
flammable, and, in some cases, toxic.
 Separator
A separator is a barrier used as spacer between the electrodes to prevent electrodes short circuit. It blocks any
electronic contact (short circuit) in the cell, but on the other hand, it allows ionic transfer between electrodes.

Separators: Cellulose based separators (filter papers) , glass fiber, ceramic, polymer based separator
 Preparation of Supercapacitor electrodes
In general, supercapacitor electrodes are prepared from a mixture of an active material (Activated carbon ~ 80%),
a polymeric binder (~ 5-10%) and conducting carbon powder (acetylene black ~10%). Then a slurry is prepared
mixing with a suitable solvents (Acetone, ethylene glycol,N-methyl-2-pyrrolidone (NMP) etc.) Finally film is
applied on a conducting substrate (AL sheet, graphite sheet etc) followed by drying the electrode at around 100-
190 C.

Polymeric binders

Nafion
Polyvinylidene fluoride (PVDF)
Polytetrafluoroethylene
carboxymethyl cellulose (CMC) (for aqueous electrolyte) Activated carbon applied electrode
Polyvinyl alcohol (PVA) on Al sheet
 Pseudo-capacitive materials
Pseudocapacitive materials store charges through battery-like redox reactions but at fast rates comparable to those of
electrochemical double-layer capacitors.

Pseudo-capacitive materials
Conducting polymers - Polyaniline, polypyrrole, polythiophene and their derivatives
Metal oxides - RuO2, MnO2 and Co3O4 .

• Higher specific capacitance of pseudo-capacitors compared to EDLCs

• Low power density compared to EDLCs

Properties of Electrode materials

Should have two or more oxidation states
High surface area
High electronic conductivity
Low cost

Ruthenium oxide is the one widely studied metal oxide for supercapacitor application because it has good electronic
conductivity and also has three distinct oxidation states in a 0-1.2 V voltage range
Some research done