Department of Materials Science and Engineering Problem 1 PEM Fuel Cells I (8 points, a=5, b=1, c=2)

Examination paper for TMT4287 Hydrogen Technologies, Fuel Cells and Batteries a) Describe the components, and their functionality, of a single PEM fuel cell

Examination date: 25.05.2024 b) Which of these components contain Teflon?

Examination time (from-to): 09:00-13:00 c) Over time, Teflon can degrade in a PEM fuel cell. What is the consequence of the
degradation for each of the components?
Permitted examination support material: C
SI Chemical Data Solution
One approved calculator: Casio FX-82CW, Casio FC100 V2, Casio fx-82ES PLUS Casio a) Components:
fx-82ES PLUS and Casio fx-82EX, Citizen SR-270X College and Citizen SR-270X College, Membrane = proton conducting, thin polymer (Nafion). Anions (sulfonic acid) are
Hewlett Packard HP30S fixed in the structure, so protons are the only ions that can move. Transport of protons
occurs in the water-filled pores of the membrane, through a hopping conduction
Academic contact during examination: Ann Mari Svensson mechanism.
Phone: 98230450
Active layer = layer of electrocatalyst deposited onto the membrane. Electrocatalyst
Academic contact present at the exam location: YES (ca 10:00)
consist of nanosized (2-4 nm) Pt particles deposited onto carbon black particles. The
OTHER INFORMATION active layer is a porous layer containing both supported electrocatalyst and Nafion, to
ensure that the reaction between oxygen (hydrogen) from the gas phase and proton
Get an overview of the question set before you start answering the questions. from the membrane phase can occur on the Pt surface.

Read the questions carefully and make your own assumptions. If a question is Gas diffusion layer = porous layer of carbon fibers in a thin fabric/cloth. Must be
unclear/vague, make your own assumptions and specify them in your answer. The academic compressible, stable and electronically conductive.
person is only contacted in case of errors or insufficiencies in the question set. Address an
invigilator if you suspect errors or insufficiencies. Write down the question in advance. Bipolar plate = plate for electrical connection of PEM single cells. Must be made
from good electronic conductor (metal or graphite). Gas channels are machined into
Hand drawings: For question 2,3,5 and 9 you are meant to answer on handwritten sheets.
Other questions must be answered directly in Inspera. At the bottom of the question you will the plate. Must also be mechanically and thermally stable, and corrosion resistant.
find a seven-digit code. Fill in this code in the top left corner of the sheets you wish to
submit. We recommend that you do this during the exam. If you require access to the codes b) Teflon containing compounds:
after the examination time ends, click “Show submission”.
The membrane and active layer (Nafion). The GDLis typically impregnated with Teflon
File upload: 15 minutes are added for file upload. The time is included in the time shown at the in order to improve the water repellant properties of the GDL
top left of the test, and the time is reserved for file upload.
(One compound is sufficient)
Notifications: If there is a need to send a message to the candidates during the exam (e.g.
if there is an error in the question set), this will be done by sending a notification in Inspera. c) Degradation of Teflon
A dialogue box will appear. You can re-read the notification by clicking the bell icon in the top Degradation of the Teflon backbone will cause detoriation of the membrane, and will thus
right-hand corner of the screen.
reduce the conductivity of the fuel cell electrolyte, and also disturb the water balance.
Withdrawing from the exam: If you become ill or wish to submit a blank test/withdraw from Degradation of the Nafion phase of the active layer will increase the activation loss of the
the exam for another reason, go to the menu in the top right-hand corner and click “Submit fuel cell.
blank”. This cannot be undone, even if the test is still open.
Degradation of Teflon in the GDL will increase the susceptibility of the PEM FC towards
Access to your answers: After the exam, you can find your answers in the archive in flooding, as it ruins the water repellant properties of the GDL.
Inspera. Be aware that it may take a working day until any hand-written material is available
in the archive. (One degradation mechanism is sufficient)

Problem 2 PEM Fuel Cells (6 points) Problem 3. PEM Electrolyzer (17 points, 6 points for a). b= 2. 3 points for c), d) og e))

A PEM fuel cell is operated at 60 oC, and data for the cell and operating conditions are given PEM water electrolyzers are used for manned expeditions to Mars. Oxygen must be supplied
below: to the astronauts for the trip, and hydrogen will be used as fuel for the journey home. Solar
cells will provide a constant voltage of 36 V for the entire journey. You have space for a
Inlet pressure, Pin = 110 kPa stack of 24 series connected PEM cells where each electrode has an area of 100 cm2. Assume
standard conditions (1 bar and 300 K) inside the spacecraft.
Outlet pressure, Pout = 100 kPa
a) Your water electrolyzer is required to produce 1 L of O2 per minute. What is the current
The air stoichiometry is λ=3 density you need in order sustain this production of O2?

Assume that the PEM cell is fed with fully humidified air. Considering the water balance of b) How much H2 will be produced per minute?
the cell, what is the maximum temperature of the inlet air?
c) What is the overpotential from ohmic losses in each cell if the PEM thickness is 100 μm
Solution and the resistivity is 81 Ω cm?
The maximum inlet temperature corresponds to the condition that RH = 100% at the outlet d) The HER catalyst has an exchange current density (i0) of 10 mA/cm2 and a Tafel slope of
(i.e. the maximum inlet water), as “hot” air can carry more moist than “cold” air. 68 mV. Calculate the kinetic overpotential associated with the HER.
We have:
e) The OER-catalyst has a Tafel slope of 100 mV. What is the minimum exchange current
At the outlet, the maximum airflow is given by the condition that RH = 100%. Thus, (based density needed in order to guarantee the astronauts supply of 1L of O2 per minute?
on the saturation pressure at 60 oC):
𝑃 19.94
= = 0.1994
𝑃 100 Solution

At the inlet we have a)

𝑝 =𝜙⋅𝑝 = 1.0 ⋅ 𝑝 2𝐻 𝑂 → 𝑂 + 4𝐻 + 4𝑒
1
𝑛 = 𝑛
Determine the parameter ψ: 4
𝑃 0.42 + 𝛹 ⋅ 𝜆 𝐼𝑡
= = 0.1994 𝑛 = ×𝑁
𝑃 0.21 + 𝜆 ⋅ (1 + 𝛹) 4𝐹
𝑃𝑉
𝑛 =
3𝛹 − 0.1994 ∙ 3𝛹 = 0.1994 ∙ 0.21 + 3 ∙ 0.1994 − 0.42 𝑅𝑇
𝛹 = 0.0786 4𝐹 𝑃𝑉 1 4 × 96485 𝐶 𝑚𝑜𝑙 0.1 𝑀𝑃𝑎 × 10 𝑚 1
𝑃𝑒𝑟 𝑐𝑒𝑙𝑙: 𝐼 = = = 10.7 𝐴
𝑡 𝑅𝑇 𝑁 60 𝑠 8.314 𝐽 𝑚𝑜𝑙 𝐾 × 300 𝐾 24
𝑃 (𝑖𝑛) 𝑝 𝐼 10.7 𝐴
𝛹= = = 0.0786 𝑖= = = 107 𝑚𝐴 𝑐𝑚
𝑃 − 𝑃 (𝑖𝑛) 𝑃 −𝑝 𝐴 100 𝑐𝑚
𝑝 = 8.016 b)
Based on the table, where psat(40 oC) =7.383 kPa and psat(50 oC) = 12.35 kPa, we estimate the
maximum temperature to be in the range of 41-42 oC
𝐼𝑡 10.7 𝐴 × 60 𝑠
𝑛 = ×𝑁 = 24 = 0.08 𝑚𝑜𝑙
2𝐹 2 × 96485 𝐶 𝑚𝑜𝑙
𝑚 =𝑛 𝑀 = 0.08 𝑚𝑜𝑙 × 2.016 𝑔 𝑚𝑜𝑙 = 161 𝑚𝑔 𝑚𝑖𝑛

c)
 𝑙 100 𝜇𝑚 Problem 4. Hydrogen storage (10 points, a=3, b=3, c=4)
𝑅 =𝜌× = 81 Ω 𝑐𝑚 × = 8.1 𝑚Ω
𝐴 100 𝑐𝑚
a) The journey to Mars takes 210 days. Calculate how much H2 you will have produced
𝜂 = 𝐼𝑅 = 10.7 𝐴 × 8.1 𝑚Ω = 87 𝑚𝑉 during this time based on your calculation in the previous question (Question 3b).
2
d) The HER catalyst has an exchange current density (i0) of 10 mA/cm and a Tafel
slope of 68 mV. Calculate the kinetic overpotential associated with the HER? b) You have been granted a volume of 1000 L storage for the H2. Estimate the maximum
pressure required of a gas tank using the figure below.

𝑖 107 𝑚𝐴 𝑐𝑚 c) What means of H2 storage would you suggest? Discuss the various alternatives and
𝜂 = 𝑏𝑙𝑜𝑔 = 68 𝑚𝑉 × log = 70 𝑚𝑉 describe why you want to choose one over the others.
𝑖 10 𝑚𝐴 𝑐𝑚

If you used the natural logarithm in the Tafel equation, you will also be given full score.
𝑖 107 𝑚𝐴 𝑐𝑚
𝜂 = 𝑏𝑙𝑛 = 68 𝑚𝑉 × ln = 161 𝑚𝑉
𝑖 10 𝑚𝐴 𝑐𝑚

e) The OER-catalyst has a Tafel slope of 100 mV. What is the minimum exchange current
density needed in order to guarantee the astronauts sufficient supply of O2?

36 𝑉 𝑉
𝑉 = = 1.5
24 𝑐𝑒𝑙𝑙𝑠 𝑐𝑒𝑙𝑙
𝜂 <𝑉 −𝐸 −𝜂 −𝜂 = 1.5 𝑉 − 1.23 𝑉 − 0.087 𝑉 − 0.070 𝑉 = 0.113 𝑉
𝑖
𝜂 = 𝑏𝑙𝑜𝑔
𝑖
Solution
𝑖 = i × 10 = 107 𝑚𝐴 𝑐𝑚 × 10 = 7.93 𝑚𝐴 𝑐𝑚
a) The journey to Mars takes 210 days. Calculate how much H2 you will have produced
during this time based on your calculation in the previous question (Question 3b).
If you used the natural logarithm in the Tafel equation, you will also be given full score.
𝑚 = 161 𝑚𝑔 𝑚𝑖𝑛 × 302400 𝑚𝑖𝑛 = 48.7 𝑘𝑔
𝜂 <𝑉 −𝐸 −𝜂 −𝜂 = 1.5 𝑉 − 1.23 𝑉 − 0.087 𝑉 − 0.161 𝑉 = 0.022 𝑉
𝑖
𝜂 = 𝑏𝑙𝑛 b) You have been granted a volume of 1000 L storage for the H2. Estimate the maximum
𝑖
pressure required of a gas tank using the figure below.
𝑖 =i×e = 107 𝑚𝐴 𝑐𝑚 ×e = 86 𝑚𝐴 𝑐𝑚 48.7 𝑘𝑔
𝜌 , = = 48.7 𝑘𝑔 𝑚
1𝑚

𝑖 𝑚𝑉 107 𝑚𝐴 𝑐𝑚 c) What means of H2 storage would you suggest? Discuss the various alternatives and
𝜂 = 𝑏𝑙𝑛 = 30 × ln = 71 𝑚𝑉 describe why you want to choose one over the others.
𝑖 𝑑𝑒𝑐 10 𝑚𝐴 𝑐𝑚
Pressurizing the H2 would require very high pressures (≈1500 bar) which would require a lot
of energy to pressurize and high requirements towards the choice of storage material as
demonstrated by the figure.
Liquid hydrogen has a higher density than the requirement and could therefore be used as
potential storage. Storing H2 as a liquid on earth is very energy intensive with almost 40 % of
the hydrogen energy needed for the liquefaction. However, you could argue that in space,
cooling of H2 is not a big problem due to the very low temperatures.
Metal hydrides could also be used as they have excellent volumetric efficiency, but their high
mass would not be ideal during takeoff. Also, the large amounts of H2 would result in
significant heating and cooling upon filling and release, respectively.

Liquid hydrogen has a higher density than the requirement and could therefore be used as Solution
potential storage. Storing H2 as a liquid on earth is very energy intensive with almost 40 % of
a) The volume of the electrolyte is 100 cm3, and thus contains 130 g of H2SO4.
the hydrogen energy needed for the liquefaction. However, you could argue that in space,
The number of moles of H2SO4 participating in the discharge of the battery is
cooling of H2 is not a big problem due to the very low temperatures.
therefore (1L = 1000 cm3):

The 6M solution contains: 0.6 mol H2SO4

Problem 5. Lead Acid Battery (8 points)
The 2M solution contains: 0.2 mol H2SO4

Thus, a total of 0.4 mol of H2SO4 is available for the discharge reaction. As 2 moles of
The electrode reactions of a Lead-Acid Battery are given below: electrons are involved in the discharge per 2 moles of H2SO4, this corresponds to a
charge of 0.4*F Coulomb = 38594 C = 38594 As = 10.72 Ah.
Negative electrode (anode):
𝑃𝑏𝑆𝑂 + 𝐻 + 2𝑒 ⎯⎯⎯⎯⎯⎯ 𝑃𝑏 + 𝐻𝑆𝑂 Eo = -0.36 Energy is thus: 10.72 Ah ∙ (1.69-(-0.36))V =22 Wh.

Positive electrode (cathode): The reaction requires 0.2 mole of PbO2 and 0.2 mole of Pb (i.e. 0.4 mol/2), assuming
that all the available electrode material take part in the reaction (i.e. theoretical
𝑃𝑏𝑂 + 𝐻𝑆𝑂 + 3𝐻 + 2𝑒 ⎯⎯⎯⎯⎯⎯ 𝑃𝑏𝑆𝑂 + 2𝐻 𝑂 Eo= 1.69 V
maximum capacity).

Total reaction The weight of all components in the cell is:

Electrolyte = 130 g
𝑃𝑏𝑂 (𝑠) + 𝑃𝑏(𝑠) + 2𝐻𝑆𝑂 + 2𝐻 ⎯⎯⎯⎯⎯⎯ 2𝑃𝑏𝑆𝑂 + 2𝐻 𝑂 Weight of 0.2 mole of PbO2 = 0.2∙239.2 g/mol = 47.84 g
Weight of 0.2 mole of Pb = 0.2 ∙ 207 g/mol =41.4 g

Assume that during discharge, the concentration of the H2SO4 electrolyte changes from 6M to Total weight = 219.24 g
2M. Assume that the density of H2SO4 is 1.3g/cm3, regardless of concentration. Calculate the
theoretical maximum energy density of a Lead Acid Battery with the following dimensions: Which gives a theoretical maximum energy density of 100 mWh/g (100 Wh/kg)

Problem 6 Lead Acid Battery b) (6 points)

a) The figure below illustrates the effect of temperature on various properties of the Lead
Acid battery. Explain what is shown in Figure a) and b).
 Solution Li2S4 + 6Li+ +6e-→4Li2S (liquid-solid transition)

Figure a) illustrates the cycle life of a Lead Acid battery, and the fact that it decreases Phase IV: Eventually, the reaction tail of solid state Li2S2 produces insoluble Li2S.
as the depth of discharge increases (i.e. complete discharge of the battery reduces the
cycle life). Similarly, increasing the temperature will decrease the cycle life, as all Li2S2 +2Li+ +2e-→2Li2S (solid-solid transition).
degradation reactions (sulfation, corrosion etc.) are accelerated when the temperature
is increased.
Problem 8. Li-sulphur battery b) (4 points)
Figure b) illustrates that a higher temperature and a slow discharge will enable the
highest discharge capacity of the battery. This is because a high current and a low The average voltage of Li-S batteries (2.2 V) is lower than Li-ion batteries (3.5 V).
temperature is associated with a high polarization, and thus the cut-off voltage will be Therefore, the Li-S battery areal capacity will need to be around 6 mAh/cm2 to compete with
reached before the battery is fully discharged (i.e. full capacity cannot be utilized). Li-ion batteries.
The opposite is true for low current, as well as a high temperature, which is associated
with low polarization. What is the active mass loading of sulfur (in mg/cm2) required to achieve the areal capacity
of 6 mAh/cm2 in a Li-S battery?

Problem 7. Li-sulphur battery a) (5 points) Solution

Areal capacity (mAh/cm2 ) = [Theoretical spec. cap. (1675 mAh/g ) × Sulfur loading]/1000
Figure below shows a typical discharge curve of assembled Li-S battery with distinct phases For an areal capacity of 6mAh/cm2, a minimum sulfur loading of 3.58 mg/cm2 is required.
(Phase I to Phase IV) evolving during discharge at specific voltages. Write down the In practice the theoretical specific capacity of sulfur is difficult to achieve. Therefore, a higher
reactions taking place at each phase. sulfur loading is needed to produce an areal capacity of more than 6 mAh/cm2.

Problem 9. Li-sulphur battery c) (5 points, a=3, b=2)

a) A Li-S battery with an areal capacity of 6 mAh/cm2 is assembled utilizing a composite

cathode coated on aluminium disc containing sulfur S8 as active material, carbon black as
conductive additive and PVDF as polymeric binder. Lithium metal is used as anode and 1M
LiTFSI in DOL:DME (1:1 vol) as electrolyte. The cell parameters are given in the table
below.

What is the energy density (Wh/kg) of the assembled Li-S battery with an areal capacity
of 6 mAh/cm2 and an average voltage of 2.2 V?

Material Thickness Density

aluminium disc (12 mm dia.) 15 μm 2.7 g/cm3

Solution
Phase I: The solid sulfur is electrochemically reduced upon reaction with the migrating Li + lithium disc (14 mm dia.) 100 μm 0.534 g/cm3
forming soluble Li2S8. Material Mass Loading
S8 + 2Li+ + 2e-→Li2S8 (solid-liquid transition) electrolyte + separator 4.5 mg/cm2

Phase II: The Li2S8 is further lithiated to produce soluble Li2S4. Carbon black +binder 1.93 mg/cm2

Li2S8 + 2Li+ + 2e- →2Li2S4 (liquid-liquid transition)

What is the energy density (Wh/kg) of the assembled Li-S battery with an areal capacity of 6
Phase III: The soluble Li2S4 is further lithiated to produce soluble solid Li2S2 or Li2S. mAh/cm2?

Li2S4 + 2Li+ + 2e- →2Li2S2 (liquid-solid transition)

b) Assume that the assembled Li-S battery is discharged at a 0.05C and charged at 0.3C, Problem 10. Solid State Batteries (6 points, a=3, b=3)
calculate the corresponding applied current densities “j”.
a) Describe the advantages and disadvantages of solid electrolytes:
i) Argyrodite Li6PS5Cl solid electrolyte and ii) Lithium garnet Li7La3Zr2O12 solid electrolyte.
Solution
a) Energy density = (Qd.Eave)/ (∑mx)
b) Discuss the challenges and the mitigation strategies in solid-state batteries assembled with
Where Qd is the areal capacity (6 mAh/cm2), Eave is the average voltage (2.2 V) and ∑mx is the Li metal anode and high voltage metal oxide cathodes such as LiCoO2 or
sum of all the masses of all the components in g/cm2. LiNi0.8Mn0.1Co0.1O2 and Li7La3Zr2O12 solid electrolyte.
Areal mass of cathode = mass of sulfur + mass of carbon black +mass of binder
Solution
= 3.58 mg/cm2 + 1.93 mg/cm2
a)
2 2
= 5.51 mg/cm = 0.00551 g/cm
i) Argyrodite Li6PS5Cl solid electrolytes:
Qd = 6 mAh/cm2
Li6PS5Cl has high room temperature conductivity.
∑mx = mass of cathode + mass of aluminium disc + mass of lithium disc + mass of electrolyte Li6PS5Cl is easy to process.
and separator
This family of electrolytes have very low electrochemical and chemical stabilities making them
(Mass = density × volume (= density × area × thickness)) unsuitable with metallic lithium anode and high voltage metal oxide cathodes.
Volume = thickness × area Li6PS5Cl reacts easily with H2O to produce the toxic gas H2S.

Area of aluminium disc = 1.13 cm2 ii) Lithium garnet Li7La3Zr2O12 solid electrolytes:
Volume of aluminium disc = 0.0017 cm3 Cubic phase of Li7La3Zr2O12 possess high Li+ conductivity because Li+ ions have more
available sites for migration than in the tetragonal phase.
Mass = density × volume = 2.7 g/cm3 × 0.0017 cm3 = 0.0046 g Li7La3Zr2O12 is electrochemically stable with Li metal and possess wide electrochemical
Areal mass of aluminium disc = 0.0046 g / 1.13 cm2 = 0.00407 g/cm2 window.

Similarly, areal mass of lithium = 0.00533 g/cm2 Li7La3Zr2O12 requires higher processing temperatures > 1100 °C.
Li7La3Zr2O12 reacts with air and moisture forming Li2CO3 and LiO2.
∑mx = 0.00551 g/cm2 + 0.00407 g/cm2 + 0.00533g/cm2 + 0.0045 g/cm2 = 0.01941 g/cm2
Energy density = (Qd.Eave)/ (∑mx) = [6 mAh/cm2 × 2.2 V]/ [0.01941 g/cm2] = 680 Wh/Kg b)
(1mAh.V/1g = 1Ah.V/1Kg = 1Wh/1kg) ii) Challenges in solid-state batteries containing lithium garnet Li7La3Zr2O12 solid electrolytes:
The challenges at the lithium anode-Li7La3Zr2O12 electrolyte interface include:
b) Areal capacity of Li-S is 6 mAh/cm2 Insufficient contact due to pore formation on lithium metal or bad cell assembly.
j (mA/cm2) at 1C = 6 mA/cm2 Contamination layers on Li7La3Zr2O12 surface such as Li2CO3 formed due to exposure of
j (mA/cm2) at 0.05C = 6 × 0.05 = 0.3 mA/cm2 Li7La3Zr2O12 to ambient atmosphere prior to deposition of the Li anode. The surface
contamination results in large interface resistance in a battery.
j (mA/cm2) at 0.3C = 6 × 0.3 = 1.8 mA/cm2
Grain boundary resistance in Li7La3Zr2O12 resulting in slow Li+ transport.
Surface defects or surface flaws on Li7La3Zr2O12 causing stress to build-in during deposition
of lithium. The gradually increasing stresses cause the mechanical failure of Li7La3Zr2O12 solid
electrolyte.
Mitigation strategies include enabling uniform and dense Li deposition and increase the
fracture resistance of the Li7La3Zr2O12 solid electrolyte.
The challenges at the LiCoO2 cathode-Li7La3Zr2O12 electrolyte interface include:
The diffusion of cobalt into Li7La3Zr2O12 into during co-sintering of LiCoO2 cathode-
Li7La3Zr2O12 electrolyte at higher temperature. During high temperature sintering Co from
LiCoO2 can diffuse into Li7La3Zr2O12 solid electrolyte and react to form secondary phases electrolyte. The value of the capacitance is given by the charge stored at the interface
(contaminating the Li7La3Zr2O12) such as Li2CO3, La2Zr2O7, and LaCoO3/La2CoO4 (poor Li+ vs. the applied voltage
conductors). The high conductive Li7La3Zr2O12 electrolyte transforms into tetragonal
Li7La3Zr2O12 at the interface with reduced Li+ conductivity. Loss of Co not only results in high b) Nyquist plot
cell resistance at cathode-electrolyte interface but also fast cell failure.
c) Re = 0.0025 Ohm. This is extracted from the value of Z(real) at the highest
To mitigate the diffusion of Co into Li7La3Zr2O12 a thin protective interlayer of Nb metal can
frequencies.
be introduced at the cathode-electrolyte interface. A thin Nb coating can form a stable and Li+
Rf = 13.9 Ohm. This value is found from the value at the lowest frequencies, with Re
conductive amorphous phase Li-Nb-O layer preventing Co diffusion into Li7La3Zr2O12.
subtracted
Cdl = 0.0009. This is found from the following relations:

Problem 11. Equivalent circuit (14 points, a = 4, b= 4, c= 4, d= 1, e= 1) At the maximum of the semicircle of the Nyquist plot (i.e. where Z(imaginary) has the
highest value, we have:
In the sheet attached (Impedance equivalent circuit.pdf), you will find data for the impedance
of the equivalent circuit below, representing a PEM fuel cell or a battery. The cell has an area
1
of 10 cm2, and the thickness of the electrolyte is 30 µm. Operating temperature of the cell is =𝑅 𝐶
T=50 oC. Answer the questions a) to f) below. 𝜔
𝜔 = 2𝜋𝑓

From the data, we see that the maximum in Z(imaginary) occurs at f =12.589 Hz.
This gives Cdl = 0.0009

d) The conductivity of the membrane is given by:

30𝜇𝑚
𝑅 =
𝜎 ∙ 10𝑐𝑚

𝜎 = 0.12 𝑆/𝑐𝑚

e) The linear approximation gives:

a) Describe the underlying physical mechanisms behind each of the components in
the equivalent circuit. 𝑖 𝑛𝐹
𝑖= ∆𝐸
b) Determine the values of the components of the equivalent circuit. 𝑅𝑇

𝑖 𝑛𝐹
c) Calculate the conductivity of the electrolyte. 𝐼= ∆𝐸 ∙ 𝑎𝑟𝑒𝑎
𝑅𝑇
d) Assume that the activation overvoltage is given by the linear approximation,
𝑅𝑇
and determine the exchange current density of the cell from the impedance data. 𝑅 =
𝑖 𝑛𝐹 ∙ 𝑎𝑟𝑒𝑎
e) At time t = 0, the cell is subject to a voltage step of ∆V= 50 mV. Determine
the corresponding current at t = 0, and after a long time, I(t = 0) and I(t →∞) Thus, io = 0.0001 A/cm2

Solution
f) We have:
a) Re = ohmic resistance of the cell. The main contribution is from the ionic resistance of
I(t = 0) = ∆V/Re = 0.05 V/0.0025 Ohm = 20 A
the electrolyte. Additional contributions could come from electronic conduction in the
I(t →∞) = ∆V/(Re+Rf) = 0.05 V/(0.0025+13.9)Ohm = 0.0036 A
gas diffusion layer, bipolar plate or connecting wires
Rf = Charge transfer resistance, the resistance associated with the electrochemical
reactions in the cell. The main contribution to the charge transfer resistance comes
from the oxygen reduction reaction at the cathode.
Cdl = double layer capacitance. This capacitance is related to the double layers (space
charge layers), which always form at the interface between the solid electrode and the

Problem 12. Multiple choice (11 points)