K. Kanamura et al., PERFLUORO-ETHYLENE-1,2-BIS-PHOSPHONIC ACID FUEL-CELL ELECTROLYTE, Journal of the Electrochemical Society, 143(9), 1996, pp. 2765-2770
Concentrated aqueous perfluoroethylene-1,2-bis-phosphonic acid, (OH)(2
)OPCF2CF2PO(OH)(2), has been investigated as an alternative to phospho
ric acid as the electrolyte in the H-2/O-2 acid fuel cell. Phosphoric
and bis-phosphonic acid solutions were equilibrated with pure O-2 (P =
1 atm) and were used in (i) chronoamperometry experiments performed w
ith a Pt microelectrode to estimate the O-2 diffusion coefficient, D,
and solubility, C, and (ii) O-2 electroreduction polarization studies
done with a gas-fed Teflon-bonded carbon electrode with a high surface
area Pt catalyst in a microfuel cell. At 22 degrees C in 85% bis-phos
phonic acid, C was found to be 3.4 +/- 0.3 x 10(-4) mol/liter and D wa
s 5.0 +/- 0.5 x 10(-7) cm(2)/s as compared with C = 2.8 +/- 0.3 x 10(-
4) mol/liter and D = 1.2 +/- 0.1 x 10(-6) cm(2)/s in 85% phosphoric ac
id at T = 22 degrees C. The overpotential for O-2 reduction on the mic
rofuel cell cathode was smaller in 85% bis-phosphonic acid than in 85%
phosphoric acid for current densities up to 200 mA/cm(2) at 100 degre
es C. This indicates that the oxygen electroreduction kinetics on Pt i
ncreased when phosphoric acid was replaced with the perfluorinated bis
-phosphonic acid. At higher current densities (greater than or equal t
o 200 mA/cm(2)) where mass transport may influence cathode performance
, the performance with bis-phosphonic acid was not as good as with pho
sphoric acid at 100 degrees C, which is consistent with the higher vis
cosity and lower D found for bis-phosphonic acid relative to phosphori
c acid at 22 degrees C. As the temperature was raised from 100 to 200
degrees C, the cathode performance improved with the bis-phosphonic ac
id electrolyte. The enhanced O-2 reduction kinetics with the bis-phosp
honic acid persisted in the fuel cell environment at temperatures up t
o 200 degrees C for 500 h which demonstrated a major improvement in st
ability for a high performance perfluorinated fuel cell electrolyte us
ed at higher temperatures such as 200 degrees C.