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Maximum Work Analysis of a SOFC

There follows an analysis of a hydrogen oxidising, oxygen ion conducting fuel cell
electrochemical membrane, which determines the maximum electrochemical work
that can be drawn from the cell.

Consider the electrochemical membrane in steady operation (Figure 1). Applying the
First Law of Thermodynamics by means of the Steady Flow Energy Equation (SFEE)
and invoking the Second Law in the form of the Maximum Work Theorem allows the
maximum work output to be determined.

Environment, T

H2
O2
H2O

Anode Control Cathode

volume

Figure 1. Steady flow process across fuel cell membrane.

In figure 1, the molar flows are such that the overall electrochemical reaction (1)
results in constant composition on both sides of the membrane.

That is, in order to satisfy:

1
H 2 + O2 → H 2 O (1)
2

Molar fluxes (per mol H2) must be:

1
n H 2 = 1mol , n H 2O = 1mol , nO2 = mol
2

Other gases (such as N2 on the air side and CO2 on the fuel side) may be present, but
as they are not involved in the electrochemical reaction and do not pass through the
membrane, they do not need to be considered in the SFEE.

1
Hence, the SFEE:

1
Q − W = hH 2O − hH 2 − hO2 (2)
2

Where Q and W are the heat transferred into the control volume and the work
transferred out of the control volume, respectively; and h is the specific (molar)
enthalpy of the reactants and products.

If the process is reversible, then W=Wmax (Maximum work Theorem) and according
to the Second Law:

1
Q = T ( s H 2 O − s H 2 − s O2 ) (3)
2

Where T is the temperature at which heat is transferred to the system and s is the
specific (molar) entropy of the reactants and products.

Combining equations 2 & 3 gives:

1 1
Wmax = ( hH 2 + hO2 − hH 2O ) − T ( s H 2 + sO2 − s H 2O ) (4)
2 2

This work must be the electrochemical work as there is no other work possible in
steady flow with environment at temperature T. Hence, assuming all gases are semi
perfect, the maximum electrochemical work per mol of H2 supplied is given by (5):

 1   1 
Wmax =  hH 2 (T ) + hO2 (T ) − hH 2O (T ) − T  s H 2 (T , p H 2 ) + sO2 (T , pO2 ) − s H 2O (T , p H 2O )
 2   2 

N.B It is the assumption that all gases are semi-perfect which gives:

h = h(T ) , s = s(T , p ) .

Equation (5) defines the maximum work output. The next few steps are additional
manipulations to give the result in terms of readily available quantities. There is
considerable advantage in using the manipulated equations as they isolate the effect
on the maximum work of the fuel and oxidiser composition, which are design
variables.

Splitting Entropy terms into Standard Pressure ( po = 1bar ) and System Pressure
terms (eqn (6)):

 1 
Wmax =  hH 2 (T ) + hO2 (T ) − hH 2O (T ) Enthalpy Terms
 2 

2
  1 
− T  s H 2 (T , po ) + sO2 (T , po ) − s H 2O (T , po ) Std p Entropy
 2 

 
+ T  s H 2 (T , po ) − s H 2 (T , pO2 ) Entropy pH2
 

 
+ T  sO2 (T , po ) − sO2 (T , pO2 ) Entropy pO2
 

 
+ T  s H 2O (T , po ) − s H 2O (T , p H 2O ) Entropy pH2O
 

Now using the equation for the Entropy Change of an Ideal Gas (derived from the
T∂S equation with ideal gas relations)

 p 1 p p 
Wmax = − ∆GT0 + T  − R ln( 0 ) − R ln( 0 ) + R ln( 0 ) (7)
 pH2 2 pO2 p H 2O 

Where, ∆GT0 is the Gibbs function change for one mol of H2 at temperature T when
all reactants and products enter and leave at p0=1bar, R is the Universal gas constant.

Rearrange using Log Laws:

 p H 2 pO2 1 
Wmax = − ∆GT0 + RT ln ( )( ) 2 (8)
p
 H 2O p 0 

Hence, the expression for Maximum Work has been divided into two terms. The first
term gives the Maximum Work for a hypothetical reaction in which the partial
pressure of both reactants and products is 1bar (such as could only be attained if H2O
were removed along the plane of the of the membrane and no dilutent gases were
present) and the second term accounts for the entropy change due to mixing of the
product water with the reactant hydrogen (this term would also show the effect of
additional dilutents gases)

Performing the same analysis for the case of carbon monoxide (9) and methane (10)
oxidation gives:

 p pO 1 
Wmax = −∆GT0 + RT ln ( CO )( 2 ) 2  (9)
 pCO2 p0 

3
  pCH 4 pO2 2 
Wmax = −∆GT0 + RT ln ( )( )  (10)
p
 CO2 p H 2O 

References
This work closely follows an analysis made by my supervisor J.B. Young at
Cambridge University Engineering Dept. 26/3/2001.

 Ben Todd 2002

Last Updated: September 4, 2003