Electrical Energy Storage Systems

(MIET2131)
Master of Engineering (Sustainable Energy)
An Introduction into the Hydrogen Systems

A/Professor Bahman Shabani

Session 1

1
1
Outlines

- Course Information
- Hydrogen Early History
- Some Hydrogen Properties
- Hydrogen Systems and Applications
- Hydrogen Fuel Cells
- Fuel cell parts and stacks

2
Course Information
Timetable

3
Course Information
Assessment Tasks:Overview

http://www.ucdsb.on.ca/school/sla/a
boutus/Pages/ExamSchedule.aspx

4
Course Information
Assessment Tasks: Key Dates

http://www.ucdsb.on.ca/school/sla/a
boutus/Pages/ExamSchedule.aspx

Note: Any changes will be communicated with you

5
Course Information
Assessment Tasks: Late Submission and Feedback

http://www.ucdsb.on.ca/school/sla/a
boutus/Pages/ExamSchedule.aspx

6
Course Information
Learning Resources

http://www.db18.com/graphics/exam-time/

7
Group Project

8
Group Project: Presentation and Report

9
Hydrogen History

Source
http://dsc.discovery.com/tags/hydrogen/

“Yes, …water decomposed into its primitive elements,

and decomposed with no double, by electricity, which
will then have become a powerful and manageable
force. Yes, my friends, I believe that water will one day
be employed as fuel, that hydrogen and oxygen which
constitute it, used singly or together, will furnish an
inexhaustible source of heat and light, of an intensity
which coal is not cable.”

Jules Verne, ca. 1874

Source:
“Mysterious Island”
http://www.vulcaniasubmarine.com/JUL
ES%20VERNE.htm

10
 Hydrogen History
1766
Henry Cavendish (1731-1810),
English nobleman, first to isolate
and identify hydrogen, but did
not name the element hydrogen
http://www.neurodive
rsity.com/bio_cavend
ish.html
1785
Lavoisier combined two
elements, one he called
‘oxygen’, the other ‘hydrogen’,
to produce water.
http://en.wikipedia.or
g/wiki/File:Antoine_l
avoisier.jpg
~1800
(6 years after Lavoisier’s execution):
William Nicholson and Anthony
Carlisle discovered H2O
electrolysis
William Nicholson ,
http://en.wikipedia.org/wiki/William_Nicholson_(chemist)
1820
Rev W Cecil proposed an engine using
combustion of hydrogen to produce a motive
force at Cambridge University
1830
William Groves discovered
fuel cell principle
http://en.wikipedia.org/wiki/
William_Robert_Grove
1920s
German engineers developed designs for H2-
powered cars and trains
Rudolf Erren, “brilliant, visionary German engineer”
designed and built trucks, buses, submarines, and
internal combustion engines of many kinds all
running on hydrogen and other fuels. 1930: Erren
Engineering Company founded in UK
J.B.S. Haldane introduced the concept of
renewable hydrogen in his paper, Science and
the Future, by proposing that ”there will be great
power stations where during windy weather the
surplus power will be used for the electrolytic
decomposition of water into oxygen and hydrogen.”
11
 Recent Article by John Bokris
Hydrogen History Bockris, J. O. M. (2013). "The hydrogen economy: Its
history." International Journal of Hydrogen Energy(0).
Dincer, I. and C. Zamfirescu (2012). "Sustainable
hydrogen production options and the role of IAHE."
International Journal of Hydrogen Energy 37(21): 16266-
1962 16286.

(You can download this article through science direct

John Bockris, proposed supply of accessible online via the RMIT library)
US cities with solar-derived energy
via hydrogen

1970
Term ‘hydrogen economy’ coined in discussion
involving Bockris (then consultant to GM) at GM
Technical Centre, Warren, Michigan
1973
Oil shock renews interest in hydrogen as an
alternative fuel
1975
Bockris published Energy: The Solar Hydrogen
Alternative, the first detailed overview of the H2
Find more information about the history of hydrogen here:
economy. http://www.schydrogen.org/documents/Factsheets/factSheet_hi
story.pdf

12
 Hydrogen Systems

Check this one: Solar H2 Centre Baglan Energy Park, Wales, UK

http://www.h2wales.org.uk/pages/hydrogen-centre/hydrogen-centre.html

13
Renewable Paths to Hydrogen

14
Solar Hydrogen Demonstration Unit

http://www.h-tec.com/en/education/products/demonstration/eco-exhibition/

15
Whydrogen?
• Source Flexibility
- Regional variations in traditional energy resources are
no longer an issue
- Every region has some indigenous fossil or renewable
resources that can be used to make hydrogen

• Energy Security
- Can replace imported petroleum as a transportation fuel

• Urban Air Quality

- Water and heat are the only products when hydrogen is
used in a fuel cell for power and heat generation
- In combustion systems – produces heat, water, and
small amounts of NOx

• Global Climate Change

- Renewable hydrogen can reduce greenhouse gas
emissions
- Fossil-based production of hydrogen will require capture
and sequestration of CO2

16
Hydrogen applications to be covered in this course

- In general, energy storage applications (e.g. for renewables)

- Stationary and portable power supply applications (buildings, telecom

towers. Etc.)

- Vehicle applications (bikes, cars, scooters, buses, trucks, etc.)

17
Properties of pure hydrogen

While hydrogen properties can make this fuel quite useful, they may make this
fuel very dangerous if it is not handled properly!

In fact hydrogen is a different gas to those commonly used and hence it should
be handled in a different way.

In other words:

It is important to appreciate this fact that hydrogen is only a different gas

and not a dangerous one!

18
Properties of pure hydrogen

Boiling point: 20 °k (or -253 °C)

Melting Point: 14 °k (or -259 °C)

Cryogenic hydrogen exists at temperatures between -259 °C and -253 °C

Note: liquids at temperatures below -73 °C are called cryogenic

Due to very low boiling temperature (-253 °C), storing hydrogen at normal
atmospheric condition (where people normally live) is a bit challenging,
because simply fuels that stay liquid at this condition can occupy less
space which makes storing them more convenient.

Does applying pressure significantly work to increase the boiling

temperature of hydrogen?

Contrary to many other fuels the answer to this question for hydrogen in particular is NO
Increasing the pressure to 13 bar above atmospheric pressure would decrease the boiling point to
only -240°C while additional pressures beyond this point is not going to further increase the boiling
point.

19
Properties of pure hydrogen

Density (at 1 atm)

• Hydrogen vapour 0.08376 kg/m3g/m3
• Liquid hydrogen 70.8 kg/m3
• Gasoline 700 kg/m3

Note: Hydrogen is the lightest element existed

Note: The expansion ration of hydrogen is 845
(The density of liquid hydrogen over the density of hydrogen vapour at 1 atm)

Does this suggest a challenge for storing hydrogen in liquid form?

20
Properties of pure hydrogen

Energy Content

Source: www1.eere.energy.gov

21
Properties of pure hydrogen

Energy Density (Energy per unit volume: energy content × density)

Source: www1.eere.energy.gov

22
Properties of pure hydrogen
Hydrogen Equation of State

Low Pressure (let’s say less than 50 bar)

Source: www1.eere.energy.gov
Ideal gas equation of state is only
applicable at low pressures.

PV=mRT

R=4124 J/kg°K
m= mass of hydrogen
P= Pressure (Pa)
T= Temperature (Kelvin)

High Pressure
At high pressure a real gas equation of state must be
used

23
Properties of pure hydrogen
Real Gas Equation of State for Hydrogen

Source: www1.eere.energy.gov
For example:

- Using compressibility factor (Z)

PV=ZmRT

Question: based on the graph shown on this slide,

comment on the comparability factor of hydrogen
if it is more or less than unity. Let’s discuss this in
the class…

15 .84 P
Z = 1+
Note: There are some other
empirical equations with good
8.314T accuracies. Check this one for
example:

P : MPa http://www.eolss.net/Sample-
Chapters/C08/E3-13-07-01.pdf
T : oK
Source: C. San Marchi, B.P. Somerday, S.L. RobinsonPermeability, 2007,
solubility and diffusivity of hydrogen isotopes in stainless steels at high gas
pressures, International Journal of hydrogen Energy, 32 (1)

24
Properties of pure hydrogen
Equation of state: example

What volume does 1 kg of H2 occupy at 25 °C

and 1 atmosphere pressure?
R=4127 J/mol/K
T = 273+25 = 298 K
P= 101.325 kPa
m=1kg
V=mRT/P
=1x4127x298/(101.325x103)
= ~12.2 m3

25
Hydrogen Fuel Cells
A fuel cell is a device that uses hydrogen (or hydrogen-rich fuels) and oxygen to
create DC electricity by an electrochemical process.
Applications
Any systems running on electricity, such as:

- Mobile applications (bikes, cars, scooters, buses, trucks,

etc.)
- Stationary applications (buildings, telecom towers. Etc.)

Advantages
- Low to zero emissions
- Quiet
- Low maintenance (no moving part)
- Low in-operation cost

Disadvantages
- Still a bit expensive: high capital cost
- Hydrogen infrastructure: not well developed yet
- Safety standards and regulations to be further
developed
- Social acceptance
- Lifetime: needs further improvement
26
Types of Fuel Cells

• Proton Exchange (Polymer Electrolyte) Membrane (PEM)

• Phosphoric Acid (PAFC)
• Direct Methanol (DMFC)
• Alkaline (AFC)
• Molten Carbonate (MCFC)
• Solid Oxide (SOFC)

27
Hydrogen Fuel Cell Parts
Electrodes (made from carbon-fiber papers coated by
catalyst)
• Anode
o Hydrogen side (it is called the negative post of the fuel
cell)
• Cathode
o Oxygen side (also called the positive side of the fuel
cell)
• Catalyst
o Rough & porous to increase the surface area and
hence hydrogen and oxygen reaction rate
o e.g. in PEM fuel cells: Usually a thin coat of platinum Source:
powder on the carbon-fiber paper (faced to the http://www.futureenergies.com/modules.php?op
=modload&name=News&file=article&sid=959
membrane) that facilitates reaction of oxygen and
hydrogen

Electrolyte
Membrane Electrode Assembly (MEA)
e.g. in PEM fuel cells (Polymer Electrolyte Membrane or Proton
Exchange Membrane): It only conducts positively charged ions
while it does not allow electrons to pass through (electrical
insulator)

Polar plates and gaskets (to be explained later)

Source: Fuel cell systems explained, Larminie and Dicks, 2003

28
Proton Exchange or Polymer Electrolyte Membrane
(PEM) Fuel Cells
“H+ ions must pass through the electrolyte. An Acid is a fluid with H+ ions, and so serves this
purpose very well. Certain polymers can also be made to contain mobile H+ ions. These materials
are called Proton Exchange Membranes, as H+ is also a proton”
(Larminie and Dicks, 2003).

• high power density (power/volume) and specific power (power/mass)

• low weight and volume
• solid polymer as an electrolyte
• porous carbon electrodes containing a platinum catalyst
• the platinum catalyst is also extremely sensitive to CO poisoning
• operate at relatively low temperatures (less than 100 °C)
• quick start (less warm-up time)
• good durability
• low sensitivity to orientation
• used primarily for transportation applications and some stationary applications

Anode Reaction

2 H 2 → 4 H + 4e −
+

Cathode Reaction Overall Reaction

O2 + 4e− + 4H + → 2H 2O O2 + 2 H 2 → 2 H 2O Click on this link to see the video

http://www.youtube.com/watch?v=_MsG9REFN3s

Electrical Energy Storage Systems 29

Proton Exchange or Polymer Electrolyte Membrane (PEM)

Source:
http://www.getters.kr/product/fuelcellmart01.htm?part_idx=15

Source: Fuel cell systems explained,

Electrical Energy Storage Systems Larminie and Dicks, 2003 30
 Proton Exchange or Polymer Electrolyte Membrane (PEM)
- Usually using Sulphonated Fluoro Polymer (e.g. fluoroethylene).
- The most common type of this, which is used in PEM fuel cells, is called Nafion

Source: http://www.ndt-
ed.org/EducationResources/CommunityCollege/M
aterials/Structure/polymer.htm

Modifying the basic polymer (e.g.

polyethylene) by substituting fluorine for
the hydrogen making PTFE or Teflon).

perfluorosulphonic acid PTFE copolymer

Sulphonic acid (HSO3)

is added as a side chain
to PTFE (sulphonation).
HSO3 is ionically
bonded to the main
chain (PTFE) with SO3-
and H+ ions
PTFE (Teflon)
Source:
Source: Fuel cell systems explained,
http://www.substech.com/dokuwiki/doku.php?id=polytetrafluoroethylene_ Electrical Energy Storage Systems 31
ptfe_as_solid_lubricant Larminie and Dicks, 2003
Proton Exchange or Polymer Electrolyte Membrane (PEM)

How it works ….
The bonds between the fluorine and the carbon is so
strong, the reason of high mechanical resistance
(the reason that can make in thin films) of the
membrane and its chemical stability (its is hard for
other molecules to break the bonds)
PTFE is highly hydrophobic, the reason that it is also Source: http://www.ion-power.com/resources.html
used in fuel cell membrane to drive the water product
outside fuel cell
HSO3 group is highly hydrophyllic (absorbing lots of
water and creating a hydrated region)
Presence of water within HSO3 region makes a diluted
acid with weak attraction between SO3- and H+ ions,
such that the H+ ions can easily move (H+ conductivity)
through the membrane. A dry membrane has weak H+
conductivity.

Electrical Energy Storage Systems 32

Fuel Cell Bipolar Plates
Bipolar plates requirements

• Uniform distribution of reactants through parallel grooves (there are many flow patterns with
agreement as yet on which one is the best)
• Good electrical (>10 S/cm) and thermal conductivity (>20 W/m.°K for water cooled fuel cell or
>200 W/m.°K for air-cooled fuel cells)
• To carry out humidity from the cathode side and maintain humidity on the anode side
• Seal to avoid fluid and reactants leakage or mixing
• Corrosion resistance and Chemical Stability (corrosion resistant)
• Light (forms nearly 80% of the total weight of the stack)
• Low cost (one of the costliest parts of the fuel cell)

Bipolar plates material development

• Graphite: the material initially used to make fuel cell bipolar plates
o Not a good formability due to its nature of microstructure
o Prone to fracture due to the special structure (the graphite is very brittle)
o Can only be formed by machining processes : a high costs and time consuming process
o Usually post machining process (such as resin impregnation) is needed to avoid gas permeation
o Graphite is porous, and cannot made to be thin (to keep the reactants apart); this adds to the
Source: Schunk – Molded
weight of the system Bipolar Plates for Fuel Cells

• Composite material (carbon/carbon-based ; thermoset-based; thermoplastic-based)

• Metal material (recently used): high mechanical strength and high electrical conductivity
o stainless steel
o aluminum alloys
o titanium alloys For more information see the chapter 5 of the following source:
o nickel alloys
o copper alloys Proton Exchange Membrane Fuel Cells
Materials Properties and Performance
o intermetallic alloys Edited by David P . Wilkinson , Jiujun Zhang , Rob Hui , Jeffrey
o and metal-based composites such as carbon Fergus , and Xianguo Li
o fiber-reinforced aluminum alloys
o carbon fiber reinforced copper alloys
Note: S/cm is Siemens per centimetre. Siemens is the SI unit of electrical conductance; 1 S = 1/R (1/Ω) = I/V (Amp/Volt) 33
Fuel Cell Stacks

The useful voltage supplied by a single cell is about 0.7-0.8 V. Hence, to

produce a useful voltage a number of cells (depending on the level of
voltage required) are to be connected in series.

The combination of such cells connected in series is called fuel cell stack.

Source: http://www.nuvera.com/blog/?cat=71
Source: http://www.serenergy.com/htpem_technology.htm

Electrical Energy Storage Systems 34

Fuel Cell Stacks

How a Hydrogen Fuel Cell System is Made

https://www.youtube.com/watch?v=LDwS31OE7ak&feature=youtu.be

https://www.youtube.com/watch?v=LDwS31OE7ak&feature=youtu.be

Electrical Energy Storage Systems 35