5

Characteristics of Fuel Cell Systems

A. 1. Appleby

5.1. BACKGROUND

Fuel cell power systems possess certain generic characteristics, which may make
them favorable for future power production compared with devices based
primarily on rotating machinery using thermo mechanical processes. Many of
these operational characteristics of fuel cell systems are superior to those of
conventional power generators. The most important are their potentially out-
standing advantages compared to those of other existing or anticipated technol-
ogy, namely thermodynamic efficiency, part-load characteristics, response time,
emissions (including chemical emissions, noise, thermal emissions and visual or
esthetic effects), modularity, and siting flexibility. Other factors which will affect
their future economic viability in respect to their competition are expected to be
their lifetime, on-line availability, reliability, start-up and shutdown characteris-
tics, control, power conditioning, safety, materials, multifuel ability, and finally
the waste disposal of their materials on dismantling of the plant. In this chapter,
fuel cell systems will be characterized with respect to these factors. Finally, their
overall economics, which will be largely dictated by their effective capital cost and
lifetimes, will be considered in general terms.

5.2. EFFICIENCY

5.2.1. General Thermodynamics

The heat absorbed per mole of reactant at constant pressure for a real fuel
cell can be expressed as
Q = !1H + Wclcc (5.1)

A. J. Appleby· Center for Electrochemical Systems and Hydrogen Research, Texas Engineering
Experiment Station, The Texas A&M University System, College Station, Texas 77843-3402.

157
L. J. M. J. Blomen et al. (eds.), Fuel Cell Systems
© Springer Science+Business Media New York 1993
158 A. J. APPLEBY

where Q is the heat produced, !1H is the reaction heat, and 1¥.,lec is the electrical
work delivered by the cell, all in kllmol. Since heat is evolved in essentially all
fuel cell reactions, Q will be negative (i.e., there will be a heat loss by the
system). This expression can be expressed as

(5.2)

where ~ 1111 is the sum of the activation and concentration polarization, I is the
cell output current, Riot is the sum of the ohmic resistances, n is the number of
electrons involved in the overall process, and F is the Faraday (96,500 coulombs
per equivalent). The rate of heat loss per mole in the cell also can be expressed as
an equivalent power loss in watts (thermal), giving the cell cooling requirement

T!1S ~ } 2
~h = I { nF - L..J 1111 - I Riot· (5.3)

The theoretical reversible (or zero current) cell voltage ET at operating

temperature T is given by the free energy of the process (-!1G T , the maximum
work that can be performed by the process at the temperature of operation),
expressed in electron volts (eV, volts per electron or per equivalent). Thus, the
numerical value of the Faraday in joules per equivalent (96.5 kllequ) is equal to
23.06 kcallequ, or 1.0 eV; i.e., -!1GT in kllmole = nFET' where n is the
number of electrons involved in the overall process. This theoretical reversible
potential is related to the standard state potential ETo by the Nernst equation:

RT [lI(r) ]
ET = ETo + nF In I1(p) , (5.4)

where R is the gas constant in llequ and lI(r), lI(p) are the products of the
activities of the total number of equivalents of anode and cathode reactants and
products involved in the overall n-electron process. Finally, the overall cell
potential, V, of an operating fuel cell is given by

(5.5)

where ~ 1111 is an increasing function of current density (see Chapter 3).

5.2.2. Fuel Utilization

All practical fuel cell systems intended for multi kilowatt or multimegawatt
power generation use hydrogen as the fuel, even if the feedstock is a carbon
compound (e.g., a hydrocarbon, alcohol, or coal). The latter must be converted
to hydrogen and carbon dioxide via an endothermic reaction with steam followed
as necessary by water-gas shifting. In a real fuel cell, the objective is to convert
as much as possible of the hydrogen in the anode feedstock to work, in order to
obtain the maximum overall conversion efficiency. The same will be true for the