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Experimental and theoretical analysis of a thermogalvanic undivided flow cell with two aqueous electrolytes at different temperatures

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Abstract

The electrochemical and thermal performance of a new thermogalvanic undivided flow cell using two aqueous electrolytes maintained at different temperatures between platinum electrodes is described. Measurements on the Fe(CN) 3−6 /Fe(CN) 4−6 redox system in NaOH medium yield a thermoelectric effect between −1.1 and −1.4mV/degree depending on the composition of the electrolytes. The influence of different parameters (temperature gradient, concentration of the electroactive species, fluid velocities and channel thickness) on the power output are determined. The experimental results show that electrical power is largely limited by charge and mass transfer overvoltages, but that it is possible to maintain the temperature gradient between the electrodes, i.e. the thermal boundary layers developing at the interface between the electrolytes do not reach the electrodes. A model based on the generalized Butler-Volmer kinetic equation is found to be in very good agreement with the experiments in terms of the current-voltage relationship and power output. This model is used for the prediction of the maximum electrochemical performance. From a practical point of view the efficiency of these devices remains very low due to the high thermal flux between the hot and cold electrolytes.

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Abbreviations

C,C A,C B :

molar concentrations (mol m−3)

C p :

mass heat capacity (J kg−1 K−1)

D :

molecular diffusion coefficient (m2 s−1)

d h :

hydraulic diameter of the cell (m)

E :

equilibrium cell potential (V)

F :

Faraday's constant=96487 C mol−1

I :

cell intensity (A)

l :

current density (A m−2)

i L :

limiting current density (A m−2)

i * :

dimensionless current density (defined in Equation 14)

i 0 :

exchange current density (A m−2)

k d :

mass transfer coefficient (m s−1)

L :

length of channel (m)

P :

electrical power (W)

p :

specific electrical power (W m−2)

Q m :

mass flowrate (kg s−1)

R :

external electrical resistance (Ω)

R i :

overall internal cell resistance (Ω or Ω m2)

R m :

membrane specific resistance (Ω m2)

R ′i :

ohmic internal resistance (Ω or Ω m2)

Re :

Reynolds number

Sh :

Sherwood number

Sc :

Schmidt number

t :

time (s)

T :

temperature (K)

u :

mean fluid velocity (m s−1)

U c :

cell voltage (V)

x :

parameter defined in Equation 14

y :

coordinate normal to electrode (m)

α:

electrochemical transfer coefficient (−)

Δ:

half channel thickness (m)

ΔT :

temperature difference (T c−T f) (K)

γe :

number of electrons involved in the electrochemical reactions

η:

overpotential (V)

Φ:

thermal flux at the interface between the two flowing fluids (W)

ϕ:

specific thermal flux (W m−2)

λ:

parameter defined in Equation 8 (s−1/2)

γ:

electrical conductivity (Ω m−1)

A:

relative to species A

a:

at the anode

B:

relative to species B

C:

relative to the hot electrode (anode)

c:

at the cathode

e:

at the electrode

f:

relative to the cold electrode (cathode)

opt:

optimal

S:

in the bulk

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Authors and Affiliations

  1. Laboratoire des Sciences du Génie Chimique CNRS-ENSIC-INPL, BP. 451, 54001, Nancy, France

    J. M. Hornut & A. Storck

  2. I.U.T. B. Université de Nancy I, Le Montet, 54600, Villers les Nancy, France

    J. M. Hornut

Authors
  1. J. M. Hornut
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  2. A. Storck
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Hornut, J.M., Storck, A. Experimental and theoretical analysis of a thermogalvanic undivided flow cell with two aqueous electrolytes at different temperatures. J Appl Electrochem 21, 1103–1113 (1991). https://doi.org/10.1007/BF01041456

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  • DOI: https://doi.org/10.1007/BF01041456

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