Lecture 3 - Nanotechnology and Its Applications in Sustainable Energy and Environment

CHMT 4032 A
Lecture 3
Nanotechnology and its applications
in sustainable energy and
environment
Prof S Iyuke
-5-Day Adv Chem Eng Course-
E-mail: [email protected]
July 2023
Hybrid-Renewable Energy Training Course.
1
Outline & Acknowledgment with courtesy
• Typical National Nanotechnology Initiative- (NNI);

- Electronics and computing; - Health and medicine
- Energy & Transportation
• Commercial outlook & Impact on various economic sectors
• Investigate the feasibility of using a hybrid fuel cell (HFC) and battery
system to power different load cases.
• Evaluate various renewable and non-renewable energy sources, energy
storage methods and their applicability regarding cost and performance.
• Use software e.g. HOMER (Hybrid Optimization for Electric Renewable) as
a sizing and optimization tool for renewable energy generation.
References
1. M.D. Qandil, R.S. Amano & A.I. Abbas. A Stand-alone Hybrid Photovoltaic,
Fuel Cell and Battery System. Proceedings of the ASME 2018, 12th
International Conference on Energy Sustainability, ES2018 -7121, June 24-
28, 2018, Lake Buena Vista, FL, USA
2. X. Li, Principles of Fuel Cells, Taylor & Francis, New York. 2006.
3. NASA Ames Research Center
2
What is Nanotechnology?
Nanotechnology is the creation of USEFUL & FUNCTIONAL materials,
devices and systems (of any useful size) through control/manipulation of
matter on the nanometer size scale and exploitation of novel phenomena
and properties which arise because of the nanometer length scale:
• Physical
Nanometer • Chemical
• One billionth (10-9) of a meter • Electrical
• Hydrogen atom 0.04 nm • Mechanical
• Proteins ~ 1-20 nm • Optical
• Feature size of computer chips 90 nm • Magnetic
(in 2005) •
• Diameter of human hair ~ 10 µm •

3
What Is Nanotechnology, Cont.?
(Definition from NNI)
Research and technology development aimed

to understand and control matter at
dimensions of approximately 1 - 100
nanometer – the nanoscale
Ability to understand, create, and use
structures, devices and systems that have
Nanoarea Electron Diffraction
fundamentally new properties and functions of Double Wall Carbon
because of their nanoscale structure Nanotube – Zuo, et.al
Ability to image, measure, model, and

manipulate matter on the nanoscale to exploit
those properties and functions
Ability to integrate those properties and
functions into systems spanning from nano- to
macro-scopic scales Source: Clayton Teague, NNI
Corral of Fe Atoms – D. Eigler
4
Examples of Nanostructures
• Examples AFM Image of DNA
- Carbon Nanotubes
- Proteins, DNA
- Single electron transistors
• Not just size reduction but phenomena
intrinsic to nanoscale
- Size confinement
- Dominance of interfacial phenomena
- Quantum mechanics
• New behavior at nanoscale is not
necessarily predictable from what we
know at macroscales.

5
Unique Properties of Nanoscale Materials
• Quantum size effects result in unique mechanical,

electronic, photonic, and magnetic properties of
nanoscale materials
• Chemical reactivity of nanoscale materials greatly

different from more macroscopic form, e.g., gold
• Vastly increased surface area per unit mass, e.g.,

upwards of 1000 m2 per gram
• New chemical forms of common chemical elements, e.g.,

fullerenes, nanotubes of carbon, titanium oxide, zinc
oxide, other layered compounds
Source: Clayton Teague, NNI

6
• Atoms and molecules are generally less than a nm and we study
them in chemistry. Condensed matter physics deals with solids
with infinite array of bound atoms. Nanoscience deals with the
in-between meso-world
• Quantum chemistry does not apply (although fundamental laws
hold) and the systems are not large enough for classical laws of
physics
• Size-dependent properties
• Surface to volume ratio
- A 3 nm iron particle has 50% atoms on the surface
- A 10 nm particle 20% on the surface
- A 30 nm particle only 5% on the surface

7
• Many existing technologies already depend on nanoscale materials
and processes:
- photography, catalysts are “old” examples,
developed empirically decades ago
• In existing technologies using nanomaterials/processes, role of

nanoscale phenomena were not understood until recently;
unexpected discoveries
- with understanding emanating for improvement
• Ability to design more complex systems in the future is ahead

- designer material that is hard and strong but low weight
- medical self-healing materials

8
Nano Revolution
• 1959 Feynman Lecture “There is Plenty of Room at the
Bottom” provided the vision of exciting new discoveries
if one could fabricate materials/devices at the
atomic/molecular scale.
• Emergence of instruments in the 1980s; STM, AFM
providing the “eyes”, “fingers” for nanoscale
manipulation, measurement…
• Recently, there has been an explosion of

research on the nanoscale behavior
- Nanostructures through sub-micron self
assembly creating entities from “bottom-
up” instead of “top-down”
- Characterization and applications
STM - Highly sophisticated computer simulations
to enhance understanding as well as create
‘designer materials’
Image of Highly Oriented Hybrid-Renewable Energy Training Course.
9
Pyrolitic Graphite
Nanotechnology applications in Renewable Energy
• Renewable energy is gaining popularity around the world, especially
where electricity is either unavailable or unreliable.
• Depending on geographical location – the global solar radiation on

horizontal surface varied between 1.51 and 2.46 MWh/m2/year, for
South Africa it’s between 1.54 – 2.26 MWh/m2/year.
• Implementation of standalone PV system to supply residents may not

currently be economical due to the high cost of installing this system as
compared to the electricity cost from a conventional grid.
• Study has shown the possibility of combining a PV solar system with

another energy source to generate energy efficiently to form a hybrid
setup.
• Simulation results have shown that replacement of conventional

technologies, e.g. diesel generators with batteries and hydrogen
technologies is technologically feasible to reducing emissions, noise,
and fossil fuel dependence.
10
Limiting Problems in Fuel Cell
Fuels Selection based on electrode theoretical voltage:

H2 + ½ O2 ↔ H2O; emf = 1.23 V (STP)
CH4 + 2O2 → CO2 + 2H2O; emf =1.04 V (STP)
2CH3OH + 3O2 → 2CO2 + 4H2O; emf = 1.10 V
• Apart from Hydrogen fuel, CH4 and CH3OH will emit
carbon dioxide. However, onboard reformate of
methanol and methane will supply relatively clean
hydrogen, but CO2 is still an effluent.
• Methanol and methane produced from bio-sources can
be seen to releasing the CO2 that was consumed during
previous photosynthesis.

11
Fuels Selection
Relative electrochemical activities of hydrogen, hydrocarbon and
carbonaceous fuels in basic electrolytes
Fuel Current density Electrical Voltage vs.
(Amp/ft2) theoretical O2 electrodes
Hydrogen 100 0.7
Formaldehyde 50 0.6
Ethanol 35 0.5
Methanol 30 0.4
Propanol 16 0.4
Butanol 16 0.4
Propylene 15 0.5 In a full electric BMW
or Tesla vehicles non
Butylene 15 0.5
of these fuels is
Ethane 3 0.3 needed. Repair
Butane 5 0.3 workshops are now
Methane 2 0.2 increasing in SA

12
Reaction on catalyst particle showing
Mass, electronic and protonic transport
Reaction and transport in
proton-exchange membrane
fuel cells (PEMFC) and direct
methanol fuel cells (DMFC)
Anatomy of a typical direct methanol fuel cell (Koraishy, et al. 2007,

patents.google.com/patent/US7837819B2/en- accessed 06/06/2021)
Nano course 2011 Hybrid-Renewable Energy Training Course.

13
Microporous Layer surfaces by scanning
a nanosecond-pulse laser
Ditch-structured
microporous layers
(MPL) fabricated by
nanosecond-pulse laser
ablation for enhancing
water transport in
polymer electrolyte
membrane fuel cells
through the channels.
Schematics of (a) in-plane water transport through the ditch-structure

carved on the MPL in analogy with water drainage through field ditches
(inset image) and (b) fabrication process for making ditches on the
MPL surfaces by scanning a nanosecond-pulse laser (Lee et al., Mater.
Adv., 2020, 1, 254--261)

14
Transport in microchannels, (BSL 2nd Ed.)
Manipulate and control Measure or compute
Bi-polar
certain observables other observables
plates/MPL
(inputs) (outputs)
Generic balance equation (Conservation law)

New = Old + In – Out + Generation - Consumption
In, Out: Transport mechanisms
1. Convection – Property is “carried”/”mixed” by moving fluid
Intraphase Transport – Constitutive laws
Viscous momentum flux
•
•Thermal heat conduction
•Mass diffusion
Generation & Consumption mechanisms:

1. Chemical reactions; 2. Electrical, radiation heating; 3.
Pressure & body (gravity) forces.
15
Channel flow (e.g. in CVD reactor, blood capillary, etc)
H
X = =h W = width of channel in y – direction
2 x
Flow
X=0 Ct H W>>H, so we neglect changes
y z in y – direction; i.e. (.)
X=
H
=-h 0
2 y
Z = 0, P = P0 Z = L, P = PL
Suppose the flow is (1) Fully developed, i.e. velocity is not a function of flow direction
 (.)
(2) “Steady state” i.e. 0
t
(3) “Incompressible” i.e. r = constant
(4) “Newtonian fluid” i.e.  xz   
dv z
dx
Hypothesis- the solution to the flow field is of the form;
P = P(z) ; v = vz(x)ez , e is a unit vector
Balances: Fluid flow in general, requires up to 4 balances: 1 mass balance and
3 momentum balances (1 for each coordinate direction).

16
Microscale mass balance
y
New = Old + In - Out
vz vz z  z
z x
z
( rxyz ) t  t  ( rxyz ) t  ( rvz xyt ) z  ( rvz xyt ) z  z

mass
 mass  vol
 time  mass
vol time
r t  t  r t rvz z  rvz
 xyzt ;  z  z
t z
lim r  ( rvz )
t , z  0
 Use flow characteristics; steady, incompressible:
t z
 (v z )
 0; so vz  f ( z ) , this is consistent with our hypothesis.
z
17
Nanoscale momentum balance
• Momentum is vector-valued ( r v), so we have 3 equations

• For this case, we have v  z x ( x)e, z
• General balance;
New = Old + In – Out + ΣForces
Transport forces act as a “generation” or
“consumption” of momentum
• Important quantities and units:

1. Momentum (of mass): mv[=]m.L/t
2. Force (on a mass): ma[=] m.L/t2
3. Force x time [=] momentum
m L momentum
4. Momentum (of a continuum) rv[] 3
 [ ]
L t vol.
5. Momentum flux  [=]
momentum [=] force
area  time area

18
Effects considered in balance:
1. p – pressure accelerates fluid in z-direction

2. gz – gravity body force in z - direction
3. rvz – z component of fluid momentum
4. xz – viscous momentum flux of z – momentum in x-direction
Consider the same fluid element;
 xz x  x
y
rvz z rvz z  z
gz x
pz p z  z
z
 xz x
19
Now the nanoscale momentum balance:
( rvz xyz ) t  t  ( rvz xyz ) t  rxyzg z t z  pxyt z  pxyt z  z

momentum vol. mass accel. time force  time
vol.
force  time  momentum
 (vz xy)( rvz )t ) z  (vz xy)( rvz )t ) z  z

vol. momentum
  time
time vol
  xz yzt x   xz yzt x  x
momentum
 area  time
area  time
 xyzt :
rvz  rvz p z  pz rvz vz z  rvz vz  xz x   xz
t  t t
 rg z  z  z
 z  z
 x  x
t z z x
20
Now the nanoscale momentum balance, Cont.
lim  p  
t , x, z  0 ( rv z )  rg z   ( rv z v z )  ( xz )
t z z x
Steady state Neglect

Mass balance, vz≠ f(z)
 p
Therefore, ( xz )   Now we need a constitutive law
x z for the momentum flux.
Newton’s Law of Viscosity

dv z Momentum is transported “down” the velocity
 xz    gradient; “fast”-moving fluid will accelerate
dx neighboring fluid
For some fluids, it can be shown experimentally that the momentum flux is
proportional to the velocity gradient, while the proportionality constant is –.
d 2vz dp
• ODE becomes;  2 
dx dz
21
Solution:- Pressure
• Note that the ODE LHS = f(x), ODE RHS = g(z), so both sides are constant
d d2p
• (.) both sides: 0  2 so, p = C1z + C0 (general solution)
dz dz
• BCs for pressure: p = p0 at z = 0, p = pL at z = L
• Solution: p( z )   pL  p0    p  dp p ≡ p0-pL pressure drop

 L  L dz
use this in original ODE

22
Solution:- Velocity
• From pressure solution;
• 2 BCs: x = 0 (centre line) d dv z

0
(.) , dx
(symmetry, max. velocity)
dz 0
H
x h (top wall) vz(h) = 0 (no slip)
2
0 by BC # 1
 dvz   p dvz  p
• Integrate once;  d    dx ,  x  C2
 dx  L dx L
 p  p 2
•Integrate twice:  dvz   xdx, v z ( x)  x  C3
L 2L
 ph 2 2 ph 2
BC # 2 0 x  C3 C3 
2L 2L
23
Parabolic velocity profile
Therefore; ph2  x ; 
2
a parabolic velocity profile
v z ( x)  1    
2L   h  
Solution: - Applications
(1) What is the maximum velocity, vz, max. ?
(2) What is the average velocity, <vz> ?
(3) What is the volumetric flow rate, Q ?
(4) What is the friction factor, fF ?

24
Solutions and Applications
ph 2   x 
2

(1) Maximum velocity; at x = 0, v z  vmax  , so v z  vmax 1    
2L  h 
 
v dA   v dxdy
w h
(2) Average velocity; vz 

z
 0 h
z
 dA   dxdy
w h
0 h
h
 x  3
 x 2 
 3h 
vmax
h
2w vz dx   2
vz  0
 0
 vmax  vz
2wh h 3
4
(3) Volumetric flow rate Q 
 vz dA  2wh vz  whv max
3 3
2 pwh
Q
3 L
25
Solutions and Applications
(4) Friction factor; fF = Fk/AK
where, A = wetted surface area
K = kinetic energy of fluid, per volume
Fk = frictional loss (force)
for this problem: A = 2wL (top & bottom plates)
force
1 
, k  2 
w L
K  r vz
2
F
0 0
xz h dzdy xz = momentum flux area
2
dv z   ph  ph
 xz h       
dx h  L  L
ph 2wL (ph / L) 3 vz / h 6
Fk  2wL
L
 fF 

2wL 1 / 2 r vz
2


1 / 2 r vz
2

hr vz
r vz H
12  12 Laminar flow in a channel. Where, Re 
fF   16 
Hr vz Re Compare with pipe flow fF 
Re
26
Applications: Boundary Conditions in Fluid
Flow (BSL 2nd Ed.)
1. Solid-Fluid:- “No Slip”- the velocity vector of the fluid is the
same as the velocity vector of the wall
y vx = v(y = 0) = 0
i. Stationary wall:
x also: vy(0) = vx(0) = 0
wall
vx= v(y = 0) =V
ii. Translating wall: y vy(0) = vx(0) = 0
x
wall Linear velocity, v
Angular velocity, Ω (rad/s)
iii. Rotating wall: R Vθ(R) = RΩ
r
Vr (R) = Vz(R) = 0

27
Applications: Boundary Conditions in Fluid
Flow Cont.
2. Symmetry plane:- the derivative of each velocity component w.r.t the
direction normal to the symmetry plane is zero.
vx(y) y By symmetry vx(y) = vx(-y)

X=0
so; vx (y)  vx (0) vx (y)  vx (0)
vx(-y) 
x y y
lim dv x dv x dv x
;   0
y  0 dy 0
dy 0
dy 0
3. Fluid-Fluid Interface:- there is a continuity of pressure, velocity and

momentum flux; at interface (here, y = 0):
Phase II, II y vx (0) I  vx (0) II

X=0
Phase I, I
x dvx dvx
 yx (0) I   yx (0) II   I   II
dy 0, I
dy 0, II

28
Applications: Vertical Floating CVD reactor
• Assuming isothermal
• Cvap → CCNT operation, one-dimensional
z by first order steady state, constant r
reaction
dcCvap d 2 cCvap
v0  DCvapC2 H 2  k1cCvap
• Porous plug of dz dz 2
Cvap (slightly
soluble in C2H2) • Diffusion • Rate
C 2H 2 kinetics
BCs: cCvap = cCvap,0 at z = 0;
+ Cat.
cCvap = 0 at z = ∞
cCvap
 exp  1  (4k1 DCvapC2 H 2 / v0 )  1(v0 z / 2 DCvapC2 H 2 )
2
cCvap, 0    

29
Operational limitations and Irreversibility in
PEM Fuel Cell
VI Curve for Generic PEM Fuel Cell
←
1.2
Cathode electrochemical losses
1
Volatge (Volts)
0.8 Linear Region (ohmic losses)
0.6
0.4
0.2
Mass Transfer Region
0
0 200 400 600 800 1000 1200 1400
Current (mA/cm2)
Electricity:
Hydrogen:
Energy = VIt
Chemical Energy
PEM Fuel Cell Heat Energy
Oxygen:
Water
Chemical Energy
Chemical Energy Balancing PEMFC
Energy inputs and
outputs
Exchange Irreversibility:
Irro = ?

30
Single Cell Voltage Expression
Vcell = ENernst + ηact,a + ηact,c + ηohmic + ηconcentration
where,
ENernst = thermodynamic potential
ηact,a = anode activation overvoltage (a measure of the
voltage loss associated with the anode)
ηact,c = cathode overvoltage
ηohmic = ohmic overvoltage (a measure of the IR losses
associated with the proton conductivity of the solid
polymer electrolyte and electronic internal
resistances)
ηconcentration = concentration overvoltage associated with
Stefan-Maxwell multicomponent mass transfer
equations for the reactants through the porous
electrodes
31
Irreversibility due to activation overvoltage
H2H+|| H2OO2 and 2H2 + O2  2H2O (overall cell reaction)

Reaction at the oxygen electrode undergoes equilibrium forwards flow of
electrons from and to the electrolyte, expressed as,
O2 + 4e- + 4H+ 2H2O (causes voltage drop)

Thus, for a PEM fuel cell that has no losses except for the irreversibility on
the oxygen electrode, its voltage may be given as;
 i 
V  E  A ln 
 io 
Where A=RT/2αF, α is referred to as the charge transfer coefficient and it is
proportional to the electrical energy applied in changing the rate of an
electrochemical reaction. F is the Faraday’s constant, R is the gas constant, T is
absolute temperature, i is the current density, while io is the exchange current
density at which the irreversibility (right term of Eq.) begins to move from zero
32
Irreversibility due to activation overvoltage, Cont.
Last equation can be rearranged to;
V  E  A ln i  Irro
⁬ where Irro = Alnio which is termed as the “exchange irreversibility”, and
E the reversible open circuit voltage
• It is obvious therefore that io and eventually Irro is crucial in controlling

the performance of a fuel cell electrode.
• The smaller io is, greater is the irreversibility and thus greater is the
voltage drop of the cell.
• Hence if exchange current density, io is sufficiently high, the surface

area of the electrode is more active and result in current flow to one
particular direction, while the reverse is for water electrolyser.

33
However, it was reported earlier that at an appropriate exchange current

density, now designated as io,vopl, the irreversibility is equal to the cell voltage
at an optimum voltage, otherwise referred to as the voltage operational limit
Vopl. i.e. Irr = Vopl. (Iyuke et al., 2003)
50 1
Voltage b
a E1
E2
Voltage O perational Limit (V)

40 0.8 E-TEK
E3
Efficiency (%)
30 0.6
20 E1 0.4
E2
E-TEK
10 E3 0.2
Irreversibility
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
2
Exchange C urrent Density (mA/cm ) Exchange C urrent Density (mA/cm )
2

34
Therefore, we may write,
i  io,vopl e E / A E
Thus, when io,vopl ≡ 1 , the equation becomes i e A
Hydrogen fuel usage is defined as,

ni
⁬ H2 usage = , where n is the number of cells
2F
Substituting F = 96485 coulombs, and molecular mass of H2 = 2.02 x 10-3

kg/mol for the single cell, becomes,
E
⁬ H2 usage = 1.05 108 e A kg/s

35
⁬ Putting Equations together with rearrangement will give expression for

voltage operational limit as,
Vopl
 eE / A
 E  A ln 
 i0


 or


Vopl  E  A ln i0,vopl / i0  e E / A  
0.6 0.25
E2 E-TEK
E3 E1
Voltage Operational Limit, Vopl (V)
0.5
0.2
Hydrogen Usage (kg/s)

0.4
Effect of exchange current
0.15 density on voltage
0.3 operational limit and
0.1
0.2 Vopl.exp hydrogen fuel usage in
Vopl.cal
0.05 determining PEM fuel cell
0.1 Hydrogen usage
performance and design
0 0
0 0.25 0.5 0.75 1 1.25 1.5
2
Exchange Current Density (mA/cm )

36
Worked Examples
•

37
Solution 1 Cont.
•
0.01 0.02 0.05 0.1 0.2

Jf(A/cm2) (x 10-3) 1.2150 1.4761 2.6473 7.0083 49.117
Jb(A/cm2) (x 10-3) 0.8231 0.6774 0.3777 0.1427 0.02036
J(A/cm2) (x 10-3) 0.3919 0.7987 2.270 6.866 49.10
38
Comments on Solution 1.
1. It is seen that the current density for the forward reaction increases
quickly, while it decreases rapidly for the backward reaction, so that the
net current density increases significantly as the electrode overpotential
is increased.
2. It is known that among the acid electrolyte fuel cells, the rate of reaction
is the fastest for hydrogen oxidation at the Pt electrode with the
presence of H2SO4 electrolyte. Even so, the current density generated is
still small, as shown in this example. At the electrode potential of
200mV, the current density generated is only about 0.0491 A/cm2.
Therefore, for the practical fuel cells measures need to be taken to
increase the current density, hence the power output, at anode
overpotentials is small as possible. Note that anode overpotential of
200mV is a very large value in H2-O2 fuel cells.
3. Since the hydrogen oxidation occurs at the anode of the fuel cell, the
corresponding electrode overpotential arising from resistance to the
electrochemical reaction in the anode is often referred to as the anode
activation overpotential as calculated in this example.

39
Worked Examples, Cont.
•

40
Solution 2, Cont.
•
-0.01 -0.02 -0.05 -0.1 -0.2

Jf(A/cm2) (x 10-7) 1.1850 0.7021 0.1460 0.01066 5.686x10-5
Jb(A/cm2) (x 10-7) 3.3755 5.6970 27.389 375.08 7.034x104
J(A/cm2) (x 10-7) -2.1905 -4.9949 -27.243 -375.07 -7.034x104

41
Comments on Solution 2
1. The results given in the table above indicate that the current density for the
forward reaction decreases quickly, while it increases rapidly for the backward
reaction, further more, the current density for the forward reaction is smaller
than the backward reaction, so that the net current density is negative, indicating
that the net reaction is in the backward direction. That is, H2O is formed as the
reaction product under the specified condition, as it should be for the cathode
reaction in a fuel cell. It is also seen that the net current density decreases
significantly as the magnitude of the electrode overpotential is increased.
2. Since the net current density is always negative for the present cathodic
reaction, which would take place as, in a fuel cell
O2 + 4H+ + 4e- ⇄ H2O
and for the above reaction, the forward reaction is faster than the backward
reaction so that the net current density associated with this reaction is positive,
along with a positive value of the overpotential.
3. Oxygen reduction occurs at the cathode of a fuel cell and the corresponding
electrode overpotential arising from the resistance to the electrochemical
reaction in the cathode, called the cathode activation overpotential.

42
PEM Fuel Cell Stacking and Commercialisation
Constraints
• A number of PEMFC parameters can be changed to enhance the cell
performance in fairly predictable ways: E.g. temperature, pressure, air
stoichiometry, reactant humidity, membrane hydration, etc.
• This could be done and modelled on:
• Water and heat movement (next tutorial Section)
• Performance of a Single Cell and then modelled into stack of
several cells (chosen for this discussion)
To commercialise PEMFCs successfully, the production cost must be

reduced from the current estimate of $200/kW to $30/kW:
• How does this compare to internal combustion engine?
• Typical single PEMFC can easily be operated, but limited to less than
1 V.
• Multi-volts stack therefore requires several cells connected in series,
in a complex flow network.
• The efficiency and power output of a PEMFC operating within a stack
are lower than the performance of a PEMFC operating independently.

43
PEM Fuel Stack

44
Mathematical Modelling
Stack performance, often measured in terms of the stack voltage, Estack
can be expressed as;
N cell N cell
Estack  E1
cell   cp
1
(1)
where Ncell= total number of fuel cells in the stack

Ecell = voltage of each cell
ηcp = ohmic loss due to a cooling plate (similar bipolar plate)
Single Cell Model

Ecell = Erev- ηa-| η c|-2 ηbp-2 ηe- ηm (2)
where Erev = reversible cell voltage
ηa, ηc = overpotential at anode and cathode, respectively,
ηbp, ηe, ηm= voltage losses caused by the bipolar plate,
electrode backing and polymer electrolyte membrane,
respectively

45
Stack Flow Modelling
Mass Conservation
Molar flow rates of hydrogen and oxygen to the anode and cathode of the
stack can be expressed as;
 S a N cell IAcell S c N cell IAcell

N H2 
stack
,

N O2 
stack
2F 4F
where Sa, Sc = stack anode and cathode stoichiometries, respectively
I = current density
Acell = active area of a PEMFC
F = Faraday constant
For all anodes; total mass flow into and out of each node in the flow
network are equal as;
 m   m
in
t
out
t
(3)

46
Mathematical Modelling, Cont.
As the fuel and oxidant undergo electrochemical reactions, the reactants
are consumed while water is produced. The general expression for the
amount consumed is;
N r   r
 i (4)
N
i  species
At the anode hydrogen is consumed. The excess water molecules produced are
considered to migrate through the PEM towards the cathode side as a net result
of electroosmotic drag and back diffusion as;
IAcell
N rH 2   and N Anode  N rH 2  N drag
H 2O (5)
2F
The net water transport from anode to the
cathode through the electrolyte membrane
At the cathode catalyst layer, the species present are O2, N2 and H2O, but
N2 does not take part in the reaction. Thus O2 consumed and water
produced can be written as;

47
 IAcell  IAcell
N r  
O2
N r  
H 2O
(6)
4F 2F
Molar accumulation at the cathode consists of the water molecules produced, those
dragged from the anode side and reacting oxygen are expressed as,
N cathode  N rO2  N rH 2O  N drag

H 2O (7)
Energy Conservation
To satisfy conservation of energy, the sum of pressure changes around
each flow loop must be zero as
N branch

j 1
i, j Pi , j  0 (i= 1, 2, 3, ……., Nloop) (8)
where θi,j is a sign convention representing the direction of flow in the

branch j of loop i. θi,j =+1 when fluid flows in clockwise direction and -1 if
the direction is reversed. Total pressure drop in branch, j of loop, i is;
48
Pi , j  Pf ,i , j  Pm,i , j (9)
where the last two terms (Eq 9) are frictional and local or minor losses,
respectively. The frictional pressure drop may be determined by the Darcy
Weisbach expression as;
Li , j ri , jVi ,2j (10)
Pf ,i , j  C f ,i , j
Dh,i , j 2
where Li,j = branch or control volume length, Dh,I,j = hydraulic diameter
ρi,j = fluid average density; Vi,j = average velocity in the branch, j of
the loop of i.
The friction coefficient, Cf,i,j may be expressed as a function of Reynolds
number as;
r i , jVi , j Dh ,i , j
 16 Re 1
Re i , j  2000 Re i , j 
C f ,i , j  i, j
1 / 4
where i , j
0.079 Re i, j Re i , j  4000 (11)

49
Example & Solution Method
Since the relationships are non linear between the pressure losses and mass flow
rates in the stack manifolds and gas flow channels, the mass flow rate and
pressure distributions may be calculated using interactive method. Make
assumptions where necessary.
Example: Solve these equations and use a plot to explain the effects of pressure
changes (pressure ratio 1 to 10) on the net voltage change per volts. You may
use the following hints:
If pressure is increased from P1 to P2, an increase or gain in voltage is;
 P2 
Vgain  C ln  Volts (12)
 P1 
where C is a constant, whose value depends on how the exchange
current density, io is affected by pressure, and also on R, T and F.
50

50
P 
Power gain  C ln 2  In Watts
 P1  (13)
where I = current in Ampere

n = number of cells in the stack

T1  P2 
0.286

 
4
Compressor/electrical  3.58 10   1 In Watts (14)
 mc  P1  
power lost 

T1  P2 
0.286


    Volts
4
 Vloss  3.58 10     1 (15)
 mc  P1  
 
where the inlet gas temperature T1 = 150C.
•Efficiency of the electric drive for the compressor, ηm is between 0.9 to
0.95
•Efficiency of the compressor, ηc is between 0.70 to 0.75
•Stoichiometry, λ is between 1.75 to 2.0
51
Thus, plot ten curves of Net ΔV = Δ Vgain- Δ Vloss for different values of
P2/P1
Parameters:
Voltage gain is between 0.06 to 0.10
Essence of the Problem:

• Running a fuel cell at higher pressure perhaps due to increase in cells
stack or to reduce cathode activation overvoltage, will increase the
power, but it also involves the expenditure of power, and there is the
cost, weight and space taken up by the compression equipment.
• To consider the pros and cons of adding the extra apparatus, a

quantitative cost/benefits analysis must be made.

52
Delivering Fuel Cell Power
Power delivery involves power electronics and electrical engineering, which are not
covered in details in this discussion. Four technologies particularly required are:
 Regulation: Electrical output power from fuel cell is certainly not constant.
Voltage regulators, DC/DC converters, and chopper circuits are used to control
and shift the fuel cell voltage to a fixed value, which can be higher or lower than
the operating voltage of the fuel cell.
 Inverters: Fuel cells generate their electricity as direct current, DC (good for
small systems), while larger systems the DC must be converted to alternating
current, AC.
 Electric Motors: Motors are required to drive compressors, pumps, fans, etc.
within fuel cell systems. Thus the electrical power from fuel cell can be delivered
to modern electric motors with very high efficiencies.
 Hybrid system: Fuel cell cost/watt is still expensive. Thus hybrid system with
battery or capacitor can be used. E.g. for transport and communications
equipment where average power needed is much lower than peak power. To
lower cost therefore, hybrid systems can be designed, where the fuel cell runs at
the average power, with the battery or capacitor provide the peak power.

53
Hybrid Optimization of Multiple Energy Resources
(Homer) Software and Hybrid Design
 The economic viability of a stand-alone solar PV system is to be analysed
on a life-cycle cost basis, and a complete system optimization will be
conducted with the aid of the HOMER software.
 This software can be used to design and evaluate technically and
financially the options for off-grid and on-grid power systems for remote,
stand-alone and distributed generation applications. It allows users to
consider many technology options to account for energy resource
availability and other variables.
 HOMER simulates the operation of any system by making energy balance
calculations for each of the 8,760 hours in a year. For each hour, HOMER
compares the electric and thermal loads in the hour to the energy that the
system can supply in that hour.
 For systems that include batteries or fuel-powered generators, HOMER
also decides for each hour how to operate the generators and whether to
charge or discharge the batteries.
 If the system meets the loads for the entire year, HOMER estimates the
lifecycle cost of the system, accounting for the capital, replacement,
operation and maintenance, fuel and interest costs
54
Photovoltaic Array
The vast majority of market solar cells are made of crystalline silicon.
Mono-crystalline cells are the most efficient. However, cheaper Poly-
crystalline cells are also popular. The cheapest would be amorphous
silicon cells which are also available and used widely for small consumer
products but rarely used for power systems.
Several aspects characterize the selection of a solar panel type, which can
be summarized as follows:
1. Cell’s Type: In most situations, the use of quality polycrystalline solar
panel is recommended for solar power systems.
2. Size and Watts: The size or output (in Watts) of the solar panel directly
affects the cost, as solar panels are usually priced and compared in
dollars per Watt, and the physical size.
3. Durability/Longevity/Warranty: Reputable solar panels will have a
warranty period of at least 10 years of artistry, and 25 years of output.
4. Cost: The cost of a solar panel is determined in part by the size (in
Watts), the physical size, the brand, the durability/longevity (or warranty
period) and any certifications the solar panel might have.
55
Homer Software and Simulation
To decide whether to use poly-crystalline or mono-crystalline modules is
not easy, it requires weighing costs against efficiencies, and since the
cost has a higher importance in the configuration of this system due to
the large number of modules expected to be needed in some cases, poly-
crystalline modules are more likely to be selected, bearing in mind that its
efficiency has also to be considerably high. Thus Homer should be used
to predict design, cost, operations, replacement, etc of the following
systems.
• Photovoltaic System
• Electrolyzer
• Hydrogen Storage Tank
• Battery
• Converter

56
Hybrid energy storage system
• Hybrid electric vehicles (HEVs) are getting attention due to

their importance in the transport Industry
• Fuel cell based electric vehicles have many advantages
over conventional vehicles.
• The fuel cell is a massive source of clean energy that
overcomes the issues of conventional vehicles such as;
global warming and high fuel cost.
• The hybrid energy storage system (HESS) of the proposed
vehicle consists of three power sources; fuel cell (FC),
battery, and a super-capacitor (SC), which are connected
to the DC bus through the DC-DC power converters.
• DC bus is further connected to DC-AC inverter which is
used to run the electric motor of vehicle.
57
Hybrid energy storage system (HESS)
• FC is a non-rechargeable source while the battery and supercapacitor
are rechargeable.
• Ideal HESS should have a high energy density, long life, and more
storage capacity.
Block diagram of HESS model.

58
Energy management strategy
Energy management stores the extra and reversible energy and also
delivers the energy for different load conditions. Energy management
algorithm for HESS is given as follows:
• Negative Load: FC doesn’t work during the negative peak of load
current and battery and super-capacitor (SC) can recover the
regenerative energy. So, battery and SC will be in charging mode.
• Low Load: During low load conditions, FC supplies the current
constantly and the battery can be in charging or discharging mode
depending upon its state of charge.
• High Load: During this condition, FC and battery both supply the
power to meet the load requirements.
• Start-Up Condition: SC will supply the power peak during the start-up
condition. FC cannot provide a start-up peak demand. SC has the
property of fast discharging so it can provide an instant peak for the
start-up.

59
HESS management algorithm
General Motors further demonstrating the steps

a hybrid-car uses to increase efficiency

60
HESS management algorithm
Detail presentation of the HESS

management and control can be found at
Ahmad & Malik, J. Energy Storage 29
(2020) 101365
61
HESS Circuit & HEV working characteristics
Mathematical modelling of system
where z1, z2, z3 and z4 denote the FC current,

battery current, SC current and DC bus voltage
respectively. While R, C and L are adjustable
parameters and denote resistance, capacitance,
and inductance respectively. vfc, vbat, vsc and io
denote the FC voltage, battery voltage, SC
voltage and load current. Similarly, u1, u23 and u45
Circuit diagram of HESS. are the control inputs of the system.
62
Take Home Assignments for assessment
Design controllers for tracking performance of a HEV that is equipped

with PEM fuel cell, battery and super capacitor for 300 miles (483 km)
routine trip to their reference values, voltage regulation of DC bus and
the global stability of the system, and simulate the controllers using
MATLAB/Simulink or any other software to analyse their comparative
performance. It is noted that Double integral sliding mode controller
(DISMC) could alleviate the steady-state error significantly.
Submit your report of not more than 10 pages within a week.
The Rubric will be uploaded shortly.
Replaced with practical session for 2022!

63

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CHMT 4032 A

• Typical National Nanotechnology Initiative- (NNI);

Hybrid-Renewable Energy Training Course.

Research and technology development aimed

Ability to image, measure, model, and

Hybrid-Renewable Energy Training Course.

• Quantum size effects result in unique mechanical,

• Chemical reactivity of nanoscale materials greatly

• Vastly increased surface area per unit mass, e.g.,

• New chemical forms of common chemical elements, e.g.,

Hybrid-Renewable Energy Training Course.

Hybrid-Renewable Energy Training Course.

• In existing technologies using nanomaterials/processes, role of

• Ability to design more complex systems in the future is ahead

Hybrid-Renewable Energy Training Course.

• Recently, there has been an explosion of

• Depending on geographical location – the global solar radiation on

• Implementation of standalone PV system to supply residents may not

• Study has shown the possibility of combining a PV solar system with

• Simulation results have shown that replacement of conventional

Fuels Selection based on electrode theoretical voltage:

Hybrid-Renewable Energy Training Course.

Hybrid-Renewable Energy Training Course.

Anatomy of a typical direct methanol fuel cell (Koraishy, et al. 2007,

Nano course 2011 Hybrid-Renewable Energy Training Course.

Schematics of (a) in-plane water transport through the ditch-structure

Nano course 2011 Hybrid-Renewable Energy Training Course.

Generic balance equation (Conservation law)

•Thermal heat conduction

Generation & Consumption mechanisms:

Nano course 2011 Hybrid-Renewable Energy Training Course.

( rxyz ) t  t  ( rxyz ) t  ( rvz xyt ) z  ( rvz xyt ) z  z

• Momentum is vector-valued ( r v), so we have 3 equations

• Important quantities and units:

Nano course 2011 Hybrid-Renewable Energy Training Course.

1. p – pressure accelerates fluid in z-direction

Consider the same fluid element;

( rvz xyz ) t  t  ( rvz xyz ) t  rxyzg z t z  pxyt z  pxyt z  z

 (vz xy)( rvz )t ) z  (vz xy)( rvz )t ) z  z

Steady state Neglect

Newton’s Law of Viscosity

• BCs for pressure: p = p0 at z = 0, p = pL at z = L

• Solution: p( z )   pL  p0    p  dp p ≡ p0-pL pressure drop

use this in original ODE

Nano course 2011 Hybrid-Renewable Energy Training Course.

• From pressure solution;

• 2 BCs: x = 0 (centre line) d dv z

Nano course 2011 Hybrid-Renewable Energy Training Course.

(2) Average velocity; vz 

Nano course 2011 Hybrid-Renewable Energy Training Course.

vx(y) y By symmetry vx(y) = vx(-y)

3. Fluid-Fluid Interface:- there is a continuity of pressure, velocity and

Phase II, II y vx (0) I  vx (0) II

Nano course 2011 Hybrid-Renewable Energy Training Course.

Nano course 2011 Hybrid-Renewable Energy Training Course.

0.8 Linear Region (ohmic losses)

Hybrid-Renewable Energy Training Course.

H2H+|| H2OO2 and 2H2 + O2  2H2O (overall cell reaction)

O2 + 4e- + 4H+ 2H2O (causes voltage drop)