Chapter03 Experimental 2020-03-05

3.
Experimental Methods
In Fuel Cell Research
Lecture Fuel Cell Technology, Chair for Process Systems Engineering (Prof. K. Sundmacher) Winter Term 2019/20 1
Contents
3. Experimental Methods in Fuel Cell Research

3.1 Introduction
3.2 Electrochemical Methods
3.3 Non-electrochemical Methods
Annotation:
In the literature on electrochemistry and electrochemical analytics, the potential difference between two electrodes is referred to
as potential if no current flows between two electrodes or voltage if there is a current flow. Often the symbol E is used for potential
and U is used for voltage. In the following the symbol U is used for both the potential and the voltage. The SI symbol of the unit
“Volt” is V !
Introduction
• Why do we need experimental methods?

 for system characterization  for model validation &
(e.g. fuel cell, fuel cell stack) parameter determination
Introduction
• Which experimental methods are available?
 Electrochemical methods  Non-electrochemical methods
U or I Test I or U X Test Y
system system
X = Mass, Y = Frequency,
Absorbance or
Light intensity…
Transmittance…
Contents

3.1 Introduction
- Cells
- Analytical Devices
- Techniques
Electrochemical Methods - Setup
Setup
• Cell
• Devices
• Techniques
POTENCIOSTAT /
GALVANOSTAT
CE RE WE
Cell
CE – counter electrode
RE – reference electrode
WE – working electrode
Electrochemical methods - Cells
ChemPhysChem 11 (2010) 2714 – 2731
Electrochemical methods - Cells
3 – electrode setup 2 – electrode setup

RE
R
WE CE WE CE
Classical elec- Cyclone flow cell Fuel cell

trochemical cell
Electrochemical Cells: Fuel Cell - 2-Electrode Setup
Working electrode (WE): Fuel cell reaction I

Counter electrode (CE): Fuel cell reaction II
What can be studied?

- Mass transport to and from WE and CE
- Kinetics of electrochemical reactions on WE and CE
- Electrolyte resistance and mass transport through membrane.
What can be measured?
UWE-CE= UWE - RI - UCE

R where:
WE CE R – resistance of the electrolyte
I I – cell current
and UWE= f(I), UCE= f(I) unknown
(depend on kinetics of the reactions)
and UWE-CE measured.
Electrochemical Cells: Fuel Cell - 2-Electrode Setup
 Advantages:
- Real system
- System characterization.
 Disadvantages:
-Cannot distinguish between WE and CE
contribution to overall behaviour.
- All processes inside the cell influence the
measured behaviour simultaneously.
Electrochemical Cells: 3-Electrode Setup
Working electrode (WE): Fuel cell reaction I or II

Counter electrode (CE): Complementary electrochem. reaction to WE
Reference electrode (RE):
Electrode with known equilibrium voltage:URE=f(t)
- installed close to the WE (usually Luggin-Capillary LC)
- measure potential difference between WE and RE
(negligible current flow between RE and WE)
What can be studied?

E – Mass transport to and from WE and CE
– Kinetics of electrochemical reactions on WE and CE.
RE What can be measured?

UWE-RE= UWE - RI - URE
where:
WE R CE R – resistance of the electrolyte
I – cell current
I and URE known
and UWE-RE measured UWE = UWE-RE - RI - URE
Electrochemical Cells: 3-Electrode Setup
Rotating disc electrode (RDE):

- Flat disc electrode with inert outer
ring rotates in electrolyte
- Uniform thickness of hydrodynamic
boundary layer in front of electrode
Outer mass transport is function
of rotation speed
from Bard-Stratman: Encyclopedia of Electrochemistry, Wiley-VCH,2003
 Advantages:
- Possible to distinguish the influence of separate phenomena
- One can study the kinetics of examined reactions independently
- The surface area and mass transport can be well controlled
- Electrodes with well defined surface areas can be used.
 Disadvantages:
- Model system.
- Component characterization.
Electrochemical Cells: Cyclone Flow Cell- 3-Electrode
Setup
Cyclone flow cell:

- Model system, but more realistic than the example shown before
- One can use real electrodes, like in a fuel cell (MEA)
- Mass transfer conditions similar as for a RDE
- Combination of a real fuel cell and the classical 3-electrode set up
from Sundmacher: J.Appl. Electrochem. 29 (1999) 919
Analytical Devices: Potentiostat/Galvanostat
A potentiostat adjusts a desired potential difference between two electrodes and measures
the resulting electrical current:
2-electrode setup 3-electrode setup
Apply Uset / [V] Measure I / [A] Apply Uset / [V] Measure I / [A]
U set
UW ERE
RE
WE CE WE CE
Ohmic drop :U E  RE  I
Define: cell voltage U cell  UWE CE electrode potential vs. reference electrode UWE RE
Features:
- Any potential difference applicable (but usually below 10 V)
- Usually automated ohmic drop compensation (positive feedback or current-interrupt technique)
- Very fast adjustments (usually within milliseconds or even faster)
- Fundamental tool in electrochemistry, many suppliers (but mostly limited max. currents !)
Analytical Devices: Potentiostat/Galvanostat
A galvanostat adjusts a desired electrical current between two electrodes and measures
the resulting electrical potential difference:
- In both, 2-electrode and 3-electrode setup, the current between WE and CE is adjusted
- 2-electrode setup: Total cell voltage U cell  U WECE is recorded
- 3-electrode setup: Voltage between WE and RE U WE RE is recorded
Features:
- Ohmic drop compensation analogous to potentiostat.
- Comparably slower adjustments (usually within 10 to 100 milliseconds).
- Fundamental analytical tool in electrochemistry, see potentiostat.
Cheaper alternative for fuel cell research (only for 2-electrode setup): Electrical loads
- No ohmic drop compensation
- Slow adjustments (usually within a few ten to hundred milliseconds)
- High electric currents possible even for moderately priced units.
Steady-State Methods
Stepwise change of voltage (potentiostat) or current (galvanostat) to determine:

a) Polarization curves (e.g. current-voltage curves, see below) from steady-state responses
b) But: Also the transient response of the systems can yield valuable information:
e.g. Chronoamperometry (i.e. record current change over time for a voltage step)
Input:
dU/dt = 0
Voltage / V
Response:
Non-Steady-State Methods:
(Cyclic) Voltammetry (CV)
dU
Voltage is changed between two levels with a constant sweep rate v  const .
dt
(values between 10-6 and 102 V/s)
Single sweep: Features:

+ fast and simple experiment
Voltage / V
+ good orientation in system properties:

• potential regions
• rate determining steps
• character of reactions
• mass transport towards electrode
Multiple sweeps: Cyclic voltammetry
• etc.
U max + enables determination of active electrode surface
Voltage / V
+ “very slow” sweep rates: quasi-steady-state curves

U start - complicated mathematical description for
Umin U end multistage processes (especially cyclic voltammetry)
CV Diagramms (I)
Ideal polarisable electrode: Pure activation control:
- no reaction, pure double layer charging - with reaction (plus double layer charging)
IDL
I I I reac
UDL
R r C DL R r C DL UDL
I U (t ) U (t )
dUDL
IDL  I   I  Ireac  CDL  v
dt CDL 1 F U U
 RTF
UDL UDL ,0   DL ,0  
I reac  I0   e 
DL
with  e RT 
U (t )  Ur  UDL , when UDL  Ur  I  r  
dU (t ) dUDL I ! I UDL  U (t )  I  r
  v  CDL 
dt dt CDL v
2vo
vo
Voltage / V Voltage / V
CV Diagramms (II)
Reversible reaction + mass transport:
- Reaction: Red Ox + n·e-
c
- plus e.g. diffusion through boundary layer 
cEd
I I reac
R r C DL UDL
I / [mA]
U (t ) t
Mass balance through boundary layer:
cEd ( x, t )  2 cEd ( x, t )
 DEd
t x 2
dcEd ( x, t ) I (t )
x=0 DEd  reac
dx x 0 F
x = δN cEd  N , Ed , t   cEd , t 
where U / [mV]
F (1 )
 U DL (t )U DL, 0   U DL (t )U DL, 0  
I reac (t )  I 0   cEd (0, t )  e RT  cProd (0, t )  e RT 
 Cyclic voltammograms
  for diff. sweep rates
I  Ireac  CDL  v concentration profiles
UDL  U (t )  I  r across boundary layer
Cyclic Voltammetry: Summary
Summary:
Process Peak Dependence on sweep rate v

double layer charging no I DL ~ v
activation control no independent
diffusion control (rev.) yes IP ~ v1/2; d(Up) / d(log v) = 0
(irrev.) yes Ip ~ v1/2; d(Up) / d(log v) = 30 mV
adsorption/desorption (rev.) yes Ip~ v; d(Up) / d(log v) = 0
(irrev.) yes Ip ~ v; d(Up) / d(log v) = 120 mV
Things to keep in mind about Cyclic voltammetry (CV):
- Fast and simple as experiment,

- Good orientation in system’s properties: potential regions, rate determining steps,
- Enables determination of real surface area,
- Determination of double layer capacity and
- Mass transport phenomena.
Non-Steady-State Methods:
Electrochemical Impedance Spectroscopy (EIS)
EIS means linear analysis of the system at a given steady-state operating point:
• Voltage U is changed sinusoidal around steady-state voltage Uss
• Small voltage amplitudes ΔU (usually below 10 mV) to ensure that system response is
quasi-linear
• Frequencies between millihertz and megahertz (usually between 1 Hz and 100 kHz)
• Current response is recorded
• Usually a whole impedance spectrum is recorded covering a broad range of frequencies
I /[A]
typical polarization curve: polarization curve, Iss (U )
U
tangent to polarization curve
I ss
one operating point, Iss (Uss )
U /[V ]
Uss
EIS Principle
• Potential U(t) is changed slightly around a steady-state Uss:
~ ~
U(t )  Uss  U(t )  Uss  Uˆ  sin(t ) U ( j )  Uˆ  e jt U (t )
• with a given angle velocity,  [rad s-1]: ~ I (t )
U
• Cell current I(t) is recorded: Uss,Iss
~ ~ ~ ~
I (t )  I ss  I (t )  I ss  Iˆ  sin( t  ) I ( j )  I  e j (t  ) I
• Define DC impedance as function of frequency:

~
U ( j )  /
Z ( j )  ~  Z   jZ   Z  e j  Z  (cos   j sin  )
I ( j ) U
~
Z is a complex value, with Z  and Z  
~
• Typical plotting methods: I
a) NYQUIST plot: -Z’’ over Z’ Z
b) BODE plot: log Z and Z over log(f) Z
• Equivalent to Transfer Function (Lecture SVT, PD, RT)  Z 
Y ( s)
G( s) 
U ( s)
Z
Adopted from Bard-Stratman: Encyclopedia of Electrochemistry, Wiley-VCH,2003
EIS Diagramms (I)
The impedance spectroscopy was originally invented for analysis of electrical circuits.
Most electrochemical systems behave similar to such equivalent circuits, e.g.:
a)Pure ohmic resistor b) Double layer charging

• e.g. electrolyte resistance • No electrode reactions
• No frequency dependence • e.g. double layer
• Constant phase
Z  0
Z   R;  Z   0  angle of +90°
1
Z   
C
Double layer capacity C
c) Double layer + resistor: series d) Double layer + resistor: parallel

• No electrode reactions • e.g. Electrode with reactions
• e.g. double layer + CR  1 • Typical result in

finite conductor (electrolyte)  electrochemical systems
• Sum of a) and b)
• c.f. transfer functions! R
Semicircle with radius R
EIS Diagramms (II)
General electrochemical cell: double layer
external resistances
(electrolyte, cables etc.)
Mass transport resistances
charge transfer resistances
(Warburg impedance)
(electrochemical reactions etc.)
Double layer at non-ideal electrode
(rough surface, inhomogeneities etc.)
depressed semicircle
1 1  iCR
n
1
 , Z CPE 
Z R iAn Mass transport comparably slow
ideal capacitor constant phase only in low frequency domain
-Z’’ Element CPE:
Cdl 
ZW
CPE
Re Z’ Rct Re Rct Z’
Electrochemical Impedance Spectroscopy: Summary
Potential Other dependencies,

Process Z() value Nyquist
dependence remarks
Ohmic drop, should be kept at

RW 0.1-10 W no
cables minimum
CDL: 10-200 concentration, adsorption,
Double layer 1/iCDL not or little
mF cm-2 roughness (CPE)
Charge 0.1-105
Rct strongly concentration, temperature
transfer Wcm2
Mass transfer 0.1-100
A/(i1/2 no A ~ 1/c
a) Warburg Wcm2s-1/2
b) finite (B/x)tanh(x) x=(i/D)1/2
c) finite
(B/x)coth(x) x=(i/D)1/2
(porous)
Adsorption as R||C semicircle yes
Electrochemical Impedance Spectroscopy: Summary
Things to keep in mind about EIS:

• Used to analyze dynamic electrode/cell behaviour at a certain operating point
• Sinusoidal potential variation with small amplitude around steady-state value
• Current response recorded complex DC impedance as function of frequency
• Broad range of frequencies applied to obtain impedance spectrum
• All kinds of electrode phenomena can be analyzed:
- nature and parameters of reactions
- adsorption/desorption phenomena
- nature and parameters of double layer and electrode surface
- mass transport phenomena (close to electrode surface, e.g. film diffusion)
• Equivalent circuits can be used to interpret and simulate the measured behaviour
Contents

3.1 Introduction
Non-electrochemical methods:
Catalyst characterization
Transmission electron microscopy (TEM)

• Particle size determination
• Particle size dispersion
• Particle dispersion on the support
25
20
( N / Ntotal )*100 / %
15
10
0 1 2 3 4 5 6 7
d / nm
Catalyst characterization
X – ray diffraction (XRD):

• Particle size determination
• Crystal phase
• Element determination
Component & System Characterization
Scanning electron microscopy (SEM):
~200 mm 1 mm
Catalyst layer
Nafion® 105
SE HV 5kV
MEA cross section graph

Nafion® 105 C
Catalyst layer
F
Unsupported PtRu (1:1) Pt
Johnson Matthey,
Back diffusion layer (BDL)
Loading: 5 mg cm-2
Teflonised carbon cloth
Ru
HV 5kV
Energy dispersive X-ray spectroscopy (EDX):

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3.

3. Experimental Methods in Fuel Cell Research

• Why do we need experimental methods?

• Which experimental methods are available?

 Electrochemical methods  Non-electrochemical methods

3. Experimental Methods in Fuel Cell Research

ChemPhysChem 11 (2010) 2714 – 2731

3 – electrode setup 2 – electrode setup

Classical elec- Cyclone flow cell Fuel cell

Working electrode (WE): Fuel cell reaction I

What can be studied?

What can be measured?

UWE-CE= UWE - RI - UCE

Working electrode (WE): Fuel cell reaction I or II

What can be studied?

RE What can be measured?

Rotating disc electrode (RDE):

Cyclone flow cell:

from Sundmacher: J.Appl. Electrochem. 29 (1999) 919

Stepwise change of voltage (potentiostat) or current (galvanostat) to determine:

Single sweep: Features:

+ good orientation in system properties:

+ “very slow” sweep rates: quasi-steady-state curves

Process Peak Dependence on sweep rate v

Things to keep in mind about Cyclic voltammetry (CV):

- Fast and simple as experiment,

• Define DC impedance as function of frequency:

a)Pure ohmic resistor b) Double layer charging

c) Double layer + resistor: series d) Double layer + resistor: parallel

Adopted from Bard-Stratman: Encyclopedia of Electrochemistry, Wiley-VCH,2003

General electrochemical cell: double layer

Potential Other dependencies,

Ohmic drop, should be kept at

b) finite (B/x)tanh(x) x=(i/D)1/2

Things to keep in mind about EIS:

3. Experimental Methods in Fuel Cell Research

Transmission electron microscopy (TEM)

X – ray diffraction (XRD):

MEA cross section graph

Energy dispersive X-ray spectroscopy (EDX):

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