Electrical Energy Storage Systems

(MIET2131)

Session 3: PEM Electrolysers, Hydrogen Storage and Safety

A/Prof. Bahman Shabani

1
Outlines

- PEM Electrolysers
- Hydrogen storage options
- Hydrogen safety

2
 Water Electrolysis

• Electrochemical decomposition of water (H2O) into hydrogen (H2) and

oxygen (O2) through a process is known as water electrolysis.
• High-quality hydrogen (≈100% hydrogen) can be produced.

() + 237.13 + 48.7 → +

Electricity Heat

3
 Proton Exchange Membrane (PEM) Electrolyser

Facts to know about PEM Electrolysers

• The heart of a PEM electrolyser is a proton exchange membrane

(or solid polymer) electrolyte
• Operating temp. range: 50 ─ 80 oC
• High current density (0.6-2 mA/cm2)
• High purity of hydrogen (i.e. 99.99%)
• Can be designed for high pressure operation (up to 350 bar)
• Rapid response to the power supply change and operation at
particle load
• Needs noble materials for catalyst and electrodes (i.e. Pt, Ir)
• Gas crossover at high pressure
• Corrosive acidic environment (needs consideration for materials)

4
 Other Types of Electrolysers

Alkaline electrolyser (liquid electrolyte)

• Aqueous potassium hydroxide (KOH) at 20- 30% concentration

as electrolyte
• Operating temperature 40-90 oC
• Well established and a mature technology
• No noble catalyst or electrode (iron, nickel, nickel compounds)
• Long term stability and relatively low cost
• Low current density (0.2-0.4 mA/cm2)
• Gas crossover (degree of purity may not be acceptable for some
applications)
• Low operational pressure (1-30 bar)
• Low partial load range
• Low operational pressure (up to 30 bar)

5
 Other Types of Electrolysers

Solid Oxide Electrolyser (solid cermaic electrolyte)

• Ceramic as electrolyte
• Operating temperature 700-1000 oC
• High efficiency (close to 100%)
• No noble catalyst
• Bulky system design
• Durability and design challenges (sealings, brittle ceramics)

6
PEM Electrolysers Vs PEM Fuel Cells

PEM electrolysis is a process just reverse of a PEM fuel cell process; however
the materials are typically different from PEM-FC

7
Governing equations
Mainly the equations used for fuel cells are applicable for electrolysers
considering that the direction of the reaction is reverse.

The electrical charge applied = 2F× Number of hydrogen moles

The electrical charge applied/time = 2F× Number of hydrogen moles/time
Electrical current = 2F × Number of hydrogen moles/time
Number of hydrogen moles/time = I/2F (moles/s)
If the stack comprises ‘n’ cells then the reaction rate would be: nI/2F

This is the rate of hydrogen production Similarly this is the rate of oxygen production
This equation can be also expressed based This equation can be also expressed based on the
on the stack power (P) and the average cells’ stack power (P) and the average cells’ voltage (Vc):
voltage (Vc):
1 $ 1 $
! = ( !'/') $ != ( !'/')
2# %& 4# %&
Or
1 $
!= ( */')
1000# %& This can be represented in (kg/s) by considering
the molar mass of oxygen (32 g)

8
Governing equations
In practice, not all the hydrogen produced is collected, and actual amount
produced

µ.It/ (1000F) kg
Where µ is the Faraday efficiency of the electrolyser

Energy efficiencies of >90% can be achieved

Energy efficiency = µ (Vmax/V) x 100%

Where V is the voltage across a single-cell electrolyser, and

Vmax for a single cell = 1.48 V (for the efficiency based on HHV)

9
Voltage-current (characteristic curve)

Vc = Vr + η cat + η an + i.R A + η i
ηcat = Cathode activation overpotential

ηan = Anode activation overpotential

i·RA = Membrane resistance overpotential

RA = Area-specific ohmic resistance of

membrane

ηi = interfacial overpotential between

membrane and electrode

10
Voltage-current (characteristic curve)

The cut-in voltage is the minimum voltage that must be applied to

the electrolyser to initiate the electrolysis reaction.

After the cut-in voltage, current

increases approximately linearly
with the increase of applied
voltage

The cut-in voltage (Vc,ci) can be between 1.23 V (LHV) to 1.48 V (HHV)

11
Voltage-current (characteristic curve)

The cut-in voltage is the minimum voltage that must be applied to

the electrolyser to initiate the electrolysis reaction.

After the cut-in voltage, current

increases approximately linearly
with the increase of applied
voltage

The cut-in voltage (Vc,ci) can be between 1.23 V (LHV) to 1.48 V (HHV)

12
Do it at home ……

• How much hydrogen in kg is produced by a current of 10 A that flows through

an electrolyser with a Faraday efficiency of 95% for 24 hours?

• How long would it take to generate 4.5 kg of hydrogen (about a full tank for a
Honda FCX Clarity hydrogen fuel cell car) using a 5 kWe PEM electrolyser
(energy efficiency 85% based on HHV) running on average at 80% of
maximum capacity?

13
 PEM Electrolyser Components
Catalyst
Hydrogen side: Supported or unsupported Platinum (loading: 1-6 mg·cm-2).

Oxygen side: Unsupported iridium, ruthenium and their oxides and mixtures (loading: 1-2 mg·cm-2):
Ruthenium oxide (RuO2) is the most active material for OER; yet it is highly unstable (the
oxidation of RuO2 to RuO4 occurs at potentials more positive than 1.387V)
Iridium oxide (IrO2) is the standard material compromising activity and stability. Used pure or
mixed with other precious (e.g. Pt) or non-precious metals.
Binary and ternary unsupported catalysts (SnO2, TaO2, SbO2, TiO2, Ti4O7 …)

GDL

Hydrogen side: Electrode potentials are close to zero;

it is possible to use carbon-based materials such as
carbon papers or felts as known in PEM FCs.

Oxygen side: Graphite or carbon-based materials are

not stable at the anode’s working potential. Carbon
undergoes electrochemical oxidation at voltages > 0.9V
Instead of carbon, porous titanium structures made
from titanium are mainly used (main drawbacks:
formation of oxide layers, high cost).

14
Pressurised PEM Electrolyser Components

• Compact system design with strong/resistant structural

properties allows High operational pressures
• Pressurised PEM electrolyser operation are reported
reaching pressure up to 350 bar
• Delivering hydrogen at a high pressure by electrochemical
compression without any external compressor
• Oxygen side GDL to withstand the back pressure from
hydrogen side. Mostly, Ti based material such as sintered
Ti plate and Ti felt are used for oxygen side GDL

Challenges
• Cross-permeation phenomenon increases with pressure
• Pressures above 100 bar will require the use of thicker
membranes
• Higher cell resistance with thicker membrane

15
Opportunity for direct coupling

16
Hydrogen Storage

17
Hydrogen storage options

18
Current Status and DoE Targets

1 kg H2 ≈ 1 gal gasoline equivalent (gge) on energy basis

https://www.energy.gov/eere/fuelcells/doe-technical-targets-onboard-
hydrogen-storage-light-duty-vehicles

19
DoE Targets

https://www.energy.gov/eere/fuelcells/doe-technical-targets-onboard-
hydrogen-storage-light-duty-vehicles

20
Compressed Gas (350 Bar and 700 Bar)

21
Toyota (Mirai) 700 Bar hydrogen tank

Toyota 700 bar carbon-fibre composite cylinders - ~5.7 wt% = 1.135 kWhe/kg

http://www.johnnycabs.com/news/toyotas-hydrogen-fuel-cell-car-to-arrive-in-the-us/

https://www.news.com.au/technology/innovation/motoring/hitech/toyota-to-bring-
hydrogen-fuelcell-car-to-australia/news-story/a10ead64fda1a413f4146b26b8f8e4ef

Lithium ion batteries

• Gravimetric energy density: up to about 0.27 kWh/kg (larger numbers have been quoted)

22
Metal Hydride (MH) Hydrogen Storage

23
 MH alloy families

Source: Hydrogen as a Future Energy Carrier Edited by Andreas Zuttel ¨ Andreas Borgschulte Louis Schlapbach

24
Pressure Composition Isotherms (PCI) for MH

Source: Hydrogen as a Future Energy

Carrier Edited by Andreas Zuttel ¨ Andreas
Borgschulte Louis Schlapbach

25
MH Hydrogen Storage Capacity
Commercially available at up to 1.6 wt%: 0.32 kWhe/kg; 0.35 kWhe/L (HHV)

Existing MH materials over 2 wt%: 0.4 kWhe/kg; 0.35-0.47 kWhe/L (HHV)

Above figures are in terms of electrical energy delivered assuming 50%

efficiency for the fuel cell, and do not include the mass of the FC.

Most current commercial MH storages are very expensive

There are other MH options with higher capacity but operating at high
pressure and/or temperatures or rely on expensive rare earth materials

https://www.pragma-industries.com/products/hydrogen-
storage/#mh300b-metal-hydride-tank

26
Comparing energy densities of H storage with
lithium ion batteries: Important points to consider
• Distinguish between material, storage unit and system densities: Include
FC in H2 system
• Include cooling system and control unit in Li ion battery system
• Compare electrical energy delivered in both cases

• Take into account:

Decline in storage capacity with repeated cycling
Depth of discharge (for H2 and battery systems)
Fall in voltage as battery is discharged

• Distinguish between proven independent measurements and company

claims
• Best done on a case by case, rather than generic, basis

27
Let’s do this in the class ……

We are planning to power a 15 W load for ~6 hours using the following

options:

Options 1
Using Li ion battery EEMB LIR18650: 3.7 V, 3500 mAh; mass = 80 g.

• 80% depth of discharge

• A linear drop of voltage of 15% over discharge period
• For simplicity the control and thermal management system is not
included

Calculate the number of batteries needed and the gravimetric energy density
of the battery system.

Options 2
A 30-W PEM fuel cell (50% efficiency) supported by metal hydride canisters:

• The mass of the fuel cell is 385 g (including fans and control system)
• The mass of each canister is100 g (when it is empty)
• The capacity of the MH is 1.2 wt% and can be almost fully discharged

Calculate the number of canisters required and the gravimetric energy

density of this hydrogen system.

28
MH canisters are so heavy (compared to other
Hydrogen storage solutions)
Is this an advantage or a disadvantage?

https://www.toyotaforklift.com/blog/forklift-of-the-future

29
Session 4: Practical activities
Hydrogen Safety

30
Properties of pure hydrogen

Undetectable by human senses:

Tasteless
Odourless
Colourless
Non-toxic

Note : Hydrogen is a simple asphyxiant

Hydrogen can easily displace oxygen and cause oxygen deficiency

31
Properties of pure hydrogen

Flammability range (4 – 75%) In AIR

H2 + 0.5 O2 H2O

Maximum 30 cm3 by each unit and 7 units

in operation: comment on the risk of our
experiment ….

Source: www1.eere.energy.gov

32
Properties of pure hydrogen

Auto-ignition temperature:
The lowest temperature required to spontaneously ignite a fuel at its flammability range

Source: www1.eere.energy.gov

Note: Despite higher auto-ignition temperature of hydrogen the ignition energy

of hydrogen (the energy of the ignition source needed to ignite hydrogen) is
considerably lower than those of other fuels

33
Properties of pure hydrogen

Low electro-conductivity

The electro-conductivity of hydrogen is so low. This means when the hydrogen if flowing in a pipe or
agitated in a storage tank electrostatic charges are developed that can be the source of ignition.
that result in sparks.

Important note: Hydrogen pipes and storage tanks have to be properly grounded

34
Properties of pure hydrogen

Invisible flame

Invisible and low heat radiation while the flame

temperature is quite high (2318 K in air)

Source: http://h2bestpractices.org/h2introduction/hazards/flames.asp

35
Hydrogen Safety
Undetectable by human sense (discussed earlier)

Adding an odorant may not be a good solution for this for a few reasons:

- Devices like fuel cells are very sensitive to hydrogen impurities such as
carbon or sulphur
- Hydrogen diffuses faster that any kind of odorant that might be added to
that. So in such situation an odorant may not be of any help to detect
hydrogen.

Then how to detect hydrogen/ (see next slide)

36
Hydrogen Safety

Leakage: Hydrogen leakage like any other fuel is hazardous

- Hydrogen molecules are small a property that increases

the chance of leakage
- Hydrogen embrittlement is another property of hydrogen
that increase the chance of leakage
http://www.onsitegenerating.
com/gas_leak_detection.html

How to detect hydrogen leakage?

- Monitoring the pressure of hydrogen storage tanks and lines

- Using specially designed hydrogen detectors

Note: Such detectors should be installed close to hydrogen

equipment and at highest point in the ceiling

http://www.fuelcellstore.com/en/pc/vie
wPrd.asp?idproduct=482

37
Hydrogen Safety

Ignition Control
As mentioned earlier hydrogen air-mixture (within its flammability range of 4-
75%) can be easily ignited by a low energy source of ignition. Hence such
sources (as below) in a hydrogen working environment has to be avoided.

- Thermal sources
- Electrical sources (including electro-static charges)
- Mechanical sources (e.g. machining, hammering, friction, …)
- Chemical and catalytic sources (lower chance of ignition than the others)

http://www.electroboom.com/?p=29
http://www.kennesaw.edu/ehs/newsletters/Apr_11.html

38
Hydrogen Safety

Hydrogen flame control (post ignition)

Hydrogen flame is not visible hence if needed special thermal/optical sensors

are to be used to detect hydrogen flame

http://news.thomasnet.com/fullstory/Program
http://www.azosensors.com/equipm
mable-Detector-senses-invisible-hydrogen-
ent-details.aspx?EquipID=164
flames-505262

39
Hydrogen Safety

Some safety tips (summary):

- People who use hydrogen facilities are to be

well trained and well aware of hydrogen
properties and due safety procedures
- Do not store hydrogen more than what is
required
- Sources of ignition should be removed from
the hydrogen site
- Specially-designed sensors should be
installed around the site to detect hydrogen
- Hydrogen equipment have to be checked
with handheld hydrogen sensors
- Proper material should be used to store and
transfer hydrogen (e.g. storage and pipe
material)
- Hydrogen equipment are better to be kept
outside or if they are kept inside, they have
to be used in a well ventilated enclosure
(example: hydrogen cylinders on the bus
roof)
- The enclosed environment chosen to use
hydrogen must be well ventilated

40
Hydrogen Safety

Safety Interlock systems for hydrogen systems

Leak detected

Active Auxiliary
Shut the hydrogen solenoid ventilation equipment off Activate the audible
valves should be kept Water pump and visual alarm
ON Air Compressor

41
Hydrogen Safety

Safety Interlock systems for

hydrogen systems

42
Hydrogen Safety

Safety Interlock systems for

hydrogen systems

43
Hydrogen Safety

Safety Interlock systems for

hydrogen systems

44
Hydrogen Safety

Safety Interlock systems for

hydrogen systems

45
Some additional notes related to pressurised systems

- Good to add check valves to the system as well. This check valve is recommended
to be as close to the source of hydrogen (e.g. pressurised gas) as possible.
- Some regulators (e.g. in this case) may act as check valves as well
- Use flexible tubes where the connections are undone regularly
- Make sure pressure relieve devices are used in the hydrogen line (multiple relief
valves are recommended where possible)
- Keep the storage away from the occupants of the building (outside the building)
- Protect the storage from direct sunlight to avoid thermal stresses on the cylinder,
pipes and connectors
- Keep the storage tank in a secure place away from public access
- Release the unused hydrogen from the houses when the system is not going to be
operated for a relatively long time
- Put the flashback arrester close to the potential flame source where possible

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