Poly(vinyl alcohol) and Chitosan-based Chemical Hydrogel

Electrode Binders for Direct Borohydride Fuel Cells and

Supercapacitors

Nurul Alam Choudhury

Department of Chemistry
Nagaland University
 Introduction
 Direct Borohydride Fuel Cell (DBFC) is an electrochemical energy
conversion device that directly converts chemical energy of BH 4-
fuel into electricity.
 In a DBFC, anode & cathode is separated by an electrolyte.
 Polymers are generally used as electrode binders in fuel cells.
 Binders keeps electrode materials attached to current collectors.
 Binders help ionic conduction to the electrode materials.
 Fuel cell performance depends on the nature of electrode binder.
 Chitosan-based chemical hydrogel is a hydrophilic biopolymeric
binder.
 Chitosan-based binders are useful in intermediate-temperature
fuel cells.
 Direct borohydride fuel cell
Anode:
La10.5Ce4.3Pr0.5Nd1.4Ni60.0Co12.7Mn5.9Al4.7
(Misch metal-based AB5 type alloy.
Cathode: Pd/C
Electrode Binders:
•Poly(vinyl alcohol alcohol) Chemical
Hydrogel (PCH)
•Chitosan Chemical Hydrogel (CCH)
•Nafion®

Fuel: 1.7 M NaBH4 in 7.0 M NaOH

Oxidant: 2.5 M H2O2 in 1.5 M H2SO4

Electrolyte Membrane: Nafion®-117

Anode Reaction: NaBH4 + 8OH− → NaBO2 + 6H2O + 8e− (E◦a = −1.24V vs. SHE)
Cathode Reaction: 4H2O2 + 8H+ + 8e− → 8H2O (E◦c = 1.78 V vs. SHE)

Net Reaction: NaBH4 + 8NaOH + 4H2O2 + 4H2SO4→ NaBO2 +14H2O + 4Na2SO4 Eocell = 3.02V
Schematic Diagram of Electrochemical Capacitor
Energy storage device.

Exhibits high power density.

Comprises two electrodes

separated by an solid or liquid
electrode.

Depending on electrode used, they

are of two types:

Electrical double layer capacitors

(EDLCs): High surface area carbon.

(ii) Pseudocapacitors: Redox active

materials.
 Effect of Temperature on DBFC performance
Increased temperature increases electrode kinetics & hence increases DBFC
performance.
Increased temperature increases ionic conductivity in liquid electrolytes & the
behavior is explained by Arrhenius Equation: σ = σo exp[-Ea/kBT]
Increased temperature increases ionic conductivity in Polymer Electrolyte
Membrane (PEM) & the behavior is explained by Vogel-Tamman-Fulcher Equation:

Here, σ(T) is Ionic Conductivity, A is Pre-exponential factor, B is Pseudo-activation

Energy , kB is Boltzman constant, T is Absolute Temperature, T is Reference
Temperature.
Increased temperature dries up polymer electrolyte membrane (PEM).
Drying of PEM results in decrease of its ionic conductivity.
Decreased ionic conductivity of PEM results in decreased DBFC performance.
High ionic conductivity of PEM can be maintained if its water retention is
enhanced.
High water retention in PEMs at high temperature can be achieved by using
hydrophilic polymers.
 Chitosan Chemical Hydrogel (CCH) - Preparation
Electrode binders need to be insoluble in water to be useful in liquid-based fuel
cells.

In present work, electrode binders have been made insoluble by chemical cross-
linking with a cross-linking agent such as Glutaraldehyde.

Chitosan (CS) is insoluble in

water.

In 1st step, CS is dissolved in

aqueous acetic acid.

In 2nd Step, CS is chemically

cross-linked using
glutaraldehyde.

Cross-linking reaction takes

place at room temperature.
Chitosan Chemical Hydrogel Electrode Binder

Cross-linking reaction
converts liquid solution of CS
into a solid mass.

Cross-linked CS is insoluble in
aqueous medium of DBFC.

CCH retains large amount of

water at elevated temperatures
& useful to obtain high
performance.
Scanning Electron Micrographs of Electrodes

(a) PCH binder-based anode.

(b) CCH binder-based anode.

(c) Nafion® binder-based anode.

(d) PCH binder-based cathode.

(e) CCH binder-based cathode.

(f) Nafion® binder-based cathode.

Power Performance of PVA Chemical Hydrogel (PCH)
Electrode Binder in DBFC

 Nafion®-117 Membrane
Electrolyte.

 OCV = 1.9 V.

 Maximum Power density ≈ 500

mWcm-2 at 70oC.

 Maximum Current density ≈

750 mAcm-2 at 70oC.
Power Performance of Chitosan Chemical Hydrogel
(CCH) Electrode Binder in DBFC

 Nafion®-117 Membrane
Electrolyte.

 OCV = 1.9 V.

 Maximum Power density ≈

600 mWcm-2 at 70oC.

 Maximum Current density ≈

900 mAcm-2 at 70oC.
Power Performance of Nafion® Electrode Binder in DBFC

 Nafion®-117 Membrane
Electrolyte.

 OCV = 1.9 V.

 Maximum Power density ≈

450 mWcm-2 at 70oC.

 Maximum Current density ≈

800 mAcm-2 at 70oC.
Comparative Performance of Electrode Binders

DBFC employs:

 PCH Electrode Binder.

 CCH Electrode Binder.

 Nafion® Electrode Binder.

 Temperature: 30 - 70oC.

 CCH is hydrophilic.

 CCH performs well at high

temperatures.

 CCH is useful for

intermediate
temperature fuel cells.
Charge/Discharge Studies for EDLC with CCH
Electrode Binder
 Ionically Cross-linked Chitosan
Membrane Electrolyte.

 Black Pearls Carbon

Electrodes.

 Tested upto 1400 Cycles at

25oC.

 Capacitance decreases with

increasing cycle numbers.

 Optimization is needed to
obtain better capacitor
performance.
Capacitance & Coulombic Efficiency of EDLC as
a Function of Cycle Number
 Ionically Cross-linked Chitosan
Membrane Electrolyte.

 Black Pearls Carbon Electrodes.

 Tested upto 1400 Cycles at 25oC.

 Capacitance decreases with

increasing Cycle Numbers.

 Coulombic Efficiency increases

first & then becomes steady.

 Optimization is needed to obtain

better capacitor performance.
 Conclusions
 CCH & PCH electrode binders were successfully used in
DBFCs.
 CCH is most hydrophilic among the binders studied.
 CCH retains water most effectively.
 CCH is useful for high-temperature DBFCs.
 CCH is a low-cost & high-performance electrode binder.
 CCH electrode binder was successfully used in EDLCs.
 Optimization of operational parameters is needed for better
capacitor performance.
 Acknowledgements
 Prof. Y. Sahai
 Prof. R. G. Buchheit
 Dr. Jia Ma
 Ohio State University , USA
 Third Frontier Fuel Cell Program of Ohio & ITN Energy Systems
 Dr. Paul W. C. Nortrop
 Mr. Andrew C. Crothers
 Ms. Shruti Jain
 Dr. Venkat R. Subramanian
 Washington University in St. Louis, USA
 Nagaland University
THANK YOU…