Lab 4: Direct Methanol Fuel Cell (DMFC)

A Lab Report

Submitted By

Neel Nadpara

ME 3264 Applied Measurements Laboratory

Section 004L

Department of Mechanical Engineering

University of Connecticut

Lab Preformed On:

February 25, 2015

Summary:
In recent years, many efforts have been made to develop sustainable energy solutions such as
fuel cells which do not harm the environment as much as current fuel sources such as fossil fuels.
Fuel cells are devices that can convert the chemical energy stored in fuels to electrical energy by
harnessing electron transfer of chemical reactions. The primary objective of this lab was to
understand the working principles of fuel cells. Other objectives were to learn to operate a direct
methanol fuel cell (DMFC), and to measure the voltage and current output of a DMFC and draw
the polarization and power density curves. Therefore, the experiment was performed with a
single fuel cell then, repeated the same on a stack of four fuel cells first connected in series then
in parallel. The current and voltage outputs were noted down, and analyzed. Power, power
density, and current density were then calculated and plotted. It was observed that as the cells
were connected in series, their voltage increased while current remained the same as a single
cell. Conversely, when they were connected in parallel their voltage remained same as a single
cell but their current increased. There were some uncertainties associated with the voltage and
current measurement devices, and with measurement error associated with measuring proper
volume of methanol solution and error with time measurement also pertain.

Experimental Procedure:
To begin, a fuel cell and how they function must be understood. Fuel cells are in a category of
power generation devices that convert chemical energy from fuel into electricity by means of
electron transfer of chemical reactions. They are very similar to batteries; however they can be
refueled as opposed to being recharged or thrown away. In a DMFC, the chemical utilized is
methanol. When compared to customary power generation methods, such as coal power plants,
fuel cells do not use thermal energy as a transitional stage for energy conversion. Therefore, they
are not ruled by Carnot efficiency. The DMFC is comprised of an anode, where the fuel
(methanol) is oxidized, a cathode, where the oxidizer is reduced, and an electrolyte between
them, where ions transport to complete the flow of current/charge. In a DMFC, the electrolyte is
a proton exchange membrane and oxygen from the air is used as the oxidizer. The methanol
solution stored in the reservoir will diffuse through the anode diffusion layer and reach the anode
catalyst layer. With the aid of the catalyst (PtRu), methanol reacts with water and generates
electrons and protons. Since the proton exchange membrane can only allow proton transport,
electrons will be redirected to flow through the anode current collector to an external circuit. The
protons move through the proton exchange membrane and arrive at the cathode catalyst layer.
Here, they combine with electrons and oxygen supplied from the surrounding air to form water.
Since there are no pumps in this setup, it is considered a passive DMFC. The reactions occurring
at the anode and cathode can be seen below.

Anode: 𝐶𝐻3 𝑂𝐻 + 𝐻2 𝑂 → 𝐶𝑂2 + 3 𝐻2 𝑂 + 6𝑒 − + 6𝐻 +

3
Cathode: 2 𝑂2 + 6 𝐻 + + 6𝑒 − → 3 𝐻2 𝑂 + 𝐶𝑂2

3
Overall: 𝐶𝐻3 𝑂𝐻 + 2 𝑂2 → 3𝐻2 𝑂 + 𝐶𝑂2
According to reactions given above, every methanol molecule can generate 6 electrons, which
also corresponds to 1.5 oxygen molecules consumed at the cathode. The generation rate of
electric current on a unit area of the membrane electrode assembly (MEA), denoted as I, is called
current density. Therefore, the speed of methanol and oxygen consumption on a unit area of the
𝑚𝑜𝑙𝑒𝑠
MEA, with the unit of 𝑚2 ∙𝑠 and can be related to the current density by given equations below
which can be used to calculate how much methanol and oxygen are consumed based on the
measurement of current density over time.

Consumption Rate Equations:

A
mol I ( 2)
mMeOH
̇ [ 2 ]= m
m ∗s A∗s
6F ( )
mol
A
mol I ( 2)
mȮ 2 [ 2 ] = m
m ∗s A∗s
4F ( )
mol

The procedure of this lab was fairly simple and involved taking voltage and current readings
every minute for fuel cells in series, parallel, and single fuel cell. In order to begin, the fuel cell
was inspected and all its parts as labeled in the provided diagram were understood. Afterwards,
the cathode and anode were identified, and connected them to their respective terminals.
Following this, 5 mL of 2M methanol solution was measured and injected into the fuel cell. The
fuel cell was observed/ the voltage change and noted down the open circuit voltage as the voltage
became steady after 5 minutes. Afterwards, the current was changed to different values and
measured the corresponding voltage after 60 seconds. The current was increased in the following
increments: 5, 10, 20, 30, 50, 75, 100, 150, 200, 250, 300, 400 (mA) until the voltage output was
just over 0.05V. The cell voltage was not allowed to drop below 0.05V. Current and
corresponding voltage was recorded. Next, the four cell assembly was connected in series and
the above procedure was repeated. The same was also repeated with the same four cell assembly
in connected in parallel. This marked the end of the performing part of the experiment, thus the
cell’s reservoirs were emptied of the methanol solution and replaced with deionized water. Next,
data was observed and analyzed both graphically and mathematically. The current and voltage
outputs were noted down, and analyzed. Power, power density, and current density were then
calculated and plotted. Uncertainty was analyzed to calculate the propagated error to find out
how much the predicted result deviated from the actual values.
 Figure 1: Schematic of Passive Single Cell DMFC

Figure 2: Schematic of Single Cell with Electric Load

Figure 3: Schematic of wiring for series (Left) and parallel (right)

Results:

DMFC Test Calculation Formulas

Input Measured Measured Calculated Theoretical Measured Calculated

Uncertainty
Current Density

C.D. (mA/cm2)

Power Density
Current (mA)

Current (mA)

Power (mW)
Voltage (V)

(mW/cm2)
(mA/cm2)
I I P RMS =
Given Measured Measured P = IV J= J= S=
A A A √(VδI)2 + (IδV)2

DMFC Single Cell Test

Input Measured Measured Calculated Theoretical Measured Calculated

Uncertainty
(mA/cm2)

(mA/cm2)

(mW/cm2
Current

Current

Current
Voltage

Density

Density
Power

Power
(mW)
(mA)

(mA)

C.D.
(V)

)
0 0 0.53 0 0.000 0.000 0.000 ±0.053
5 4.7 0.4 1.88 0.556 0.522 0.209 ±0.167
10 9.7 0.34 3.298 1.111 1.078 0.366 ±0.167
20 19.7 0.27 5.319 2.222 2.189 0.591 ±0.225
30 29.6 0.22 6.512 3.333 3.289 0.724 ±0.316
50 49.6 0.12 5.952 5.556 5.511 0.661 ±0.500
 DMFC Stacked Series Cell Test
Input Measured Measured Calculated Theoretical Measured Calculated

Uncertainty
(mA/cm2)

(mA/cm2)

(mW/cm2
Current

Current

Current
Voltage

Density

Density
Power

Power
(mW)
(mA)

(mA)

C.D.
(V)

)
0 0 2.37 0 0.000 0.000 0.000 ±0.237
5 4.5 2.04 9.18 0.556 0.500 1.020 ±1.225
10 9.5 1.65 15.675 1.111 1.056 1.742 ±0.995
20 19.5 1.47 28.665 2.222 2.167 3.185 ±0.903
30 29.4 1.35 39.69 3.333 3.267 4.410 ±0.990
50 49.4 1.13 55.822 5.556 5.489 6.202 ±0.933
75 74.4 0.88 65.472 8.333 8.267 7.275 ±0.966
100 99.4 0.65 64.61 11.111 11.044 7.179 ±1.093
150 149.3 0.19 28.367 16.667 16.589 3.152 ±1.501

DMFC Parallel Stack Cell Test

Uncertainty
Input Measured Measured Calculated Theoretical Measured Calculated
(mA/cm2)

(mA/cm2)

(mW/cm2
Current

Current

Current
Voltage

Density

Density
Power

Power
(mW)
(mA)

(mA)

C.D.
(V)

)
0 0 0.64 0 0.000 0.000 0.000 ±0.064
5 4.5 0.57 2.565 0.139 0.125 0.071 ±0.345
10 9.5 0.49 4.655 0.278 0.264 0.129 ±0.309
20 19.5 0.44 8.58 0.556 0.542 0.238 ±0.328
30 29.4 0.41 12.054 0.833 0.817 0.335 ±0.411
50 49.4 0.39 19.266 1.389 1.372 0.535 ±0.564
75 74.4 0.37 27.528 2.083 2.067 0.765 ±0.788
100 99.4 0.34 33.796 2.778 2.761 0.939 ±1.022
150 149.3 0.29 43.297 4.167 4.147 1.203 ±1.511
200 199.4 0.25 49.85 5.556 5.539 1.385 ±2.002
250 249.4 0.2 49.88 6.944 6.928 1.386 ±2.498
300 299.4 0.16 47.904 8.333 8.317 1.331 ±2.996
350 349.4 0.12 41.928 9.722 9.706 1.165 ±3.495
400 399.3 0.07 27.951 11.111 11.092 0.776 ±3.993
 DMFC Single Cell Polarization & Power Density vs.
Current Density
0.6 0.800
0.700

Power Density (mW/cm2)

0.5
0.600
0.4
Voltage (V)

0.500
0.3 0.400
0.300
0.2
0.200
0.1
0.100
0 0.000
0.000 1.000 2.000 3.000 4.000 5.000 6.000
Current Density (mA/cm2)

Voltage vs Current Density Power Density vs Current Density

DMFC Stacked Series Cell Polarization & Power

Density vs. Current Density
2.5 8.000
7.000

Power Density (mW/cm2)

2
6.000
5.000
Voltage (V)

1.5
4.000
1 3.000
2.000
0.5
1.000
0 0.000
0.000 2.000 4.000 6.000 8.000 10.000 12.000 14.000 16.000 18.000
Current Density (mA/cm2)

Voltage vs Current Density Power Density vs Current Density

 DMFC Stacked Parallel Polarization Curve and Power
Density Curve
0.6 1.600

Power Density (mW/cm2)

1.400
0.5
1.200
0.4
Voltage (V)

1.000
0.3 0.800
0.600
0.2
0.400
0.1
0.200
0 0.000
0.000 2.000 4.000 6.000 8.000 10.000 12.000
Current Density (mA/cm2)

Voltage vs Current Density Power Density vs Current Density

RMS vs Current (Single Cell)

0.600

0.500

0.400
RMS

0.300

0.200

0.100

0.000
0 10 20 30 40 50 60
Current (mA)
 RMS vs Current (Stacked Series)
1.600

1.400

1.200

1.000
RMS

0.800

0.600

0.400

0.200

0.000
0 20 40 60 80 100 120 140 160
Current (mA)

RMS vs Current (Stacked Parallel)

4.500

4.000

3.500

3.000

2.500
RMS

2.000

1.500

1.000

0.500

0.000
0 50 100 150 200 250 300 350 400 450
Current (mA)
Discussion:
In the first table, the equations used to calculate all of the important values (power, theoretical
and measured current density, and power density) are shown. For the single cell, the power
IV
density equation used was P = A and the area used was 9 cm2. The voltage vs current density
starts at a certain value (.53V) and decays at an exponential rate. Then the current density vs
power density curve starts at a low value and increases to a maximum and then starts decreasing
(an upside down parabolic relationship). For the series stack, the power density can be calculated
V(4I)
by the formulaP = A . Thinking about the situation logically, when four cells are connected in
series, the current between the cells combines to be 4 times the input current, therefore the
voltage should also increase. The power density of the stacked parallel can be calculated as P =
I(4V)
. From the data that was collected there are several observations that can be made. First off,
4A
it was observed that as the cells are connected in series, their voltage increases while current
remains the same as single cell. On the other hand when they are connected in parallel, their
voltage remains the same as single cell but their current increases. Therefore, series combination
is used when higher voltage output is needed while parallel combination is used when higher
current output is needed. It was also observed that the current and voltage never remained
constant at a given time. It kept fluctuating within a small value. This was the uncertainty
associated with the electronic measurement device use. Also, when looking at the polarization
curves it can be seen that the overall shape for each of the tests is fairly similar while the
magnitudes are different (a single cell is obviously going to have a lower current/power density
than a set of 4 cells in either series or parallel). We know that the polarization curve is comprised
of three regions (the activation, the Ohmic, and the mass transport regions). In the activation
region, the voltage drop is mainly directed by the electrochemical kinetics, which serves as the
driving force for the reactions. The voltage drop in the Ohmic region is primarily triggered by
the resistance of charge transfer ions moving through the PEM. When the current density
increases further, the mass transport of reactants into the catalyst layers becomes the limiting
factor earning the name of mass transport region. One of the only really obvious flaws is with the
power density vs current density curve for the single cell. It should have a more parabolic shape
as the other two tests do. However, it looks more like a logarithmic curve. This is likely
attributed to error that is associated with that particular cell.

Data and Error Analysis:

To begin the discussion of error, we must start with error propagation. In the experiment there
are three variables’ that have certain uncertainties and these uncertainties can affect the
uncertainty of a function based off of them. Therefore, we must analyze the uncertainties to
determine how the error propagates. In order to do this the three variables in question must be
identified. They are: 1) the measurement of current, 2) the measurement of voltage, and 3) the
effective area of the DMFC. Now, the uncertainty of the area of the fuel cell can be considered
negligible as the fuel cell is a precision made device and therefore the uncertainties are
minimized. Therefore, only the uncertainties in the current and voltage measurements remain.
Then the equation for root mean square (RMS) can be derived as seen below:

a. P = IV
 b. δP = δ(IV)
∂P ∂P
c. δP = ∂I δI + ∂V δV
d. δP = VδI + IδV
𝐑𝐌𝐒 = √(𝐕𝛅𝐈)𝟐 + (𝐈𝛅𝐕)𝟐

For this experiment the uncertainties of the measurement box for voltage is ±.01 V while the
uncertainty for current is ±.0001 A. With this information the uncertainties were calculated in the
tables above and plotted in the RMS vs current curves above. Also, there are some other error
considerations to take into account. First, the amount of fuel used in the cells was measured by
syringe which is not a very good piece of measuring instrument. The time in-between current
input changes could also be a important factor leading to error (not constant between
measurements) and perhaps more time would have led to better more consistent results (the
voltage would stabilize). Additionally, the differentiation of the current vs power density curves
that was discussed above would likely be attributed to two important factors. First, the single cell
is only one cell, therefore if it is not running perfectly it will greatly alter the results. Secondly,
the fuel reservoir is connected for the stacked setups. Other errors in this lab could include the
resistance of the wires that are used to connect the cells to the power box. Also, there are likely
to be errors in the mixing of the fuel solution so that it may not be exactly 2M methanol solution.
Also, once the lab is completed the fuel reservoir is filled with deionized water and it is not
possible to remove all of it, therefore there is still some water that can reduce the concentration
of the methanol which can adversely affect the data collected. One can point out flaws all day;
however the overall results of this lab were fairly accurate, though certain things such as
measurement tools could be improved upon.

Conclusion:
Overall, it can be concluded that a fuel cell can be used to convert chemical energy stored in the
fuel to electrical energy. These cells can be stacked in series or parallel combination. When the
cells are connected in series, their voltage increases while current remains the same as single
cell. On the other hand when they are connected in parallel, their voltage remains the same as
single cell but their current increases. Basically, series combination is used when higher voltage
output is needed while parallel combination is used when higher current output is needed. It was
observed that the current and voltage never remained constant at a given time. It kept fluctuating
within a small value. This was the uncertainty associated with the electronic measurement device
use. There were some uncertainties also associated with measurement error of proper volume of
methanol solution. Minor rounding errors, and error with time measurement also pertain. The
fuel cell is simple yet very powerful concept and can revolutionize our energy supply.