The effect of electrode area, electrolyte concentration, temperature,
and light intensity (up to 218 sun) on PV electrolysis of water is
studied using a high concentrated triple-junction (3-J) photovoltaic
cell (PV) connected directly to an alkaline membrane electrolyzer
(EC). For a given current, the voltage requirement to run an electrolyzer
increases with a decrease in electrode sizes (4.5, 2.0, 0.5, and 0.25
cm2) due to high current densities. The high current density
operation leads to high Ohmic losses, most probably due to the concentration
gradient and bubble formation. The EC operating parameters including
the electrolyte concentration and temperature reduce the voltage requirement
by improving the thermodynamics, kinetics, and transport properties
of the overall electrolysis process. For a direct PV–EC coupling,
the maximum power point of PV (P
max) is
matched using EC I–V (current–voltage)
curves measured for different electrode sizes. A shift in the EC I–V curves toward open-circuit voltage
(V
oc) reduces the P
op (operating power) to hydrogen efficiencies due to the increased
voltage losses above the equilibrium water-splitting potential. The
solar-to-hydrogen (STH) efficiencies remained comparable (∼16%)
for all electrode sizes when the operating current (I
op) was similar to the short-circuit current (I
sc) irrespective of the operating voltage (V
op), electrolyzer temperature, and electrolyte
concentration.