Electrochemical Systems

Means to store hydrogen

Sistemi elettrochimici - Mezzi di stoccaggio dellidrogeno -

Hydrogen storage - Means mainly used in prototypes

Compressed hydrogen (CH)
Hydrogen is compressed and stored in tanks. Traditional Oxyhydrogen bottles are charged up to
20 MPa.
Today for transport systems are normally considered pressures up to 35 MPa, that are
considered in Italian recharging Facility regulation, but not yet allowed to be transported.
Pressures up to 70 MPa are already obtained in tanks and are expected to appear in prototype
vehicles within a few years

Liquid hydrogen (LH)

Hydrogen is cooled down and maintained at a temperature of 22 K. Evaporated gas is used for
propulsion; in stand-by external energy is needed for cooling.
This option offers large amounts of energy stored per unit of mass and volume; disadvantages
are: complexity, energy wasted for cooling and maintaining cool. Today is not frequently
considered for road vehicles

Metal hydrides (MH)

These are components common in electrochemical batteries. They exploit the capacity of
hydrogen of being dispersed in a metallic matrix.
Several prototypes developed during nineties; latest is from in Toyota car (from Panasonic)
In comparison with CH are normally heavier, but more compact and safety is easier

Hydrogen storage methods under evaluation

Carbon nanofibres
Nanofibres are applications of nanotechnologies.
They promise very high efficiencies (hydrogen mass reaching up to 67% of reservoir
mass have been reported); reproducible results are much worse: below 3%.)
This solution, therefore, although under research, has not supplied practical
applications yet.
Chemical methods (Artificial fuels)
They are based upon the creation of compounds able to carry large quantities of
hydrogen.
To be competitive, this solution must resort to productive process that are simple
and use a little energy; hydrogen release should be simple and energy efficient as
well.
Some studied examples:
Methanol (partial oxidation reforming: 2CH3OH+O22CO2+4H2)
Ammonia (NH3:, see next slide)
Methanol /mnol/ Alkali /aelklai/

Hydrogen storage methods under evaluation

Some Ammonia
characteristics:

Specific energy:
5100 Wh/kg
Hydrogen content:
higher than liquid
hydrogen
Hydrogen content
exceeds DOE targets
liquid below 0.9 MPa
hydrogen can be
easily extracted

mildly toxic

Ammonia cracking energy.

DG f=-26,5 kJ/mol
Therefore to crack an ammonia mole requires 26,5 kJ , a rather small energy (compare with
237 kJ to crack a mole of water)

Hydrogen storage Comparison parameters (1/2)

Volumic and massic parameters
Massic Energy (Wh/kg) normally called specific energy (Italian: energia massica o specifica)
Volumic Energy (Wh/l) normally called energy density (Italian: energia volumica o densit di
energia)
From thermodynamics to Engineering parameters
Standard thermodynamics condition: 298K, 101,3kPa, R=8,314 J K-1 mol-1
From DH to LHV or UHV. When the enthalpy DH of an oxidation (combustion) reaction is
considered, it indicates the heat generated per unit of mole. Therefore, if the compound molar
mass Mm is known: LHV DH g / M m UHV DH l / M m (Italian: LHV->PCI; UHV->PCS)

Volume of a mole. pV nRT if n 1 V RT / p 8,314 * 298 / 101,3k 24,46 L (*)

From Massic to Volumic energy (Ev to Em).
For given gas pressure p, and one mole:

Em
E/m V
RT / p

Ev
E /V
m
Mm

The more frequent compressed gas pressure is 20 MPa, and this is considered in the table
reported in the next page.

(*) The more common value of 22,42 L per mole refers to a temperature of 0C

Hydrogen storage Comparison parameters (2/2)

LHV DH g / M m UHV DH l / M m
Ev
Mm
E /V
m

Em
E/m V
RT / p

R 8,314 JK -1mol -1
p 20 MPa T 298 K

DHg(kJ/mol)
(*)

Mm

(g/mol)

LHV
(kJ/g)

LHV
(Wh/kg)

Ev/Em
(g/L)

Volumic LHV
(Wh/L)

Methane (CH4)

802,0

16,04

50,00

13900

129,5

1800

Hydrogen (H2)

242,0

2,016

120,0

33340

16,27

542

(*) Oxidation enthalpy. For hydrogen the value is the water formation enthalpy; for methane, see example developed
in the Elements of Thermodynamics and Chemical kinetics presentation.

Fuel and reservoir parameters

It is necessary to distinguish between fuel and reservoir parameters.
Indeed, the empty tank may be well heavier than the contained fuel. It is common to resort to
the reservoir efficiency concept: the ratio of stored fuel mass or volume and reservoir with that
fuel. E.g., a 30 MPa composite tank has typically a mass efficiency of about 3% and a volume
efficiency of around 65%

Hydrogen storage Compressed

Compression work
(ideal gas isotherm process)

nRT
dV
p1
p1
V
V
p
nRT ln 2 nRT ln 2
V1
p1
p2

L pdV

p2

L=8,314*298*ln2=1717 J/mol;
DH(H2,g)=242kJ/mol =>L/DH=0,0071
In case of ideal gas isotherm process
every pressure doubling implies a work onto
the gas of 0,7% of the hydrogen energy contents
Starting from atmospheric pressure, to reach 51,2 MPa
9 doublings are needed, therefore a work of 6,5% of
the final tank energy is to be transferred to the fluid.
Normally the gas compression energy is not exploited,
and therefore this energy is a net loss.

In case of a real gas isotherm process,

compressibility factor z must be taken into
account.
Moreover, the thermal temperature raise during
typical compressions makes the compression work
to rise; finally compression is made by a
compressor that is an electromechanical device
that has mechanical and electromechanical losses.
So, bringing hydrogen to 51,2 MPa requires an
energy of around 10% of the energy finally stored

pV znRT

Hydrogen storage metal hydrides (1)

DH<0
M+H2 MH2
Charge process
Hydrogen is supplied slightly over 100kPa, the reaction proceeds towards the right
side, and is slightly exothermic; it normally stops if heat is not drawn from the
hydride.
The charge process is rather fast (may last a few minutes if the reservoir is cooled)
When the reservoir is full, at a constant hydrogen flow, pressure tends to rise;
typically at about 200 kPa it is considered to be full.
Discharge process
The reservoir is connected to a system at a pressure lower than that present
internally; reaction moves towards left.
Pressure drops and hydrogen is released slowly; since the reaction is
endothermic, heating the hydride makes the discharge much faster; in case of no
heating, the inner pressure is very low, as the amount of hydrogen: this is
advantageous for safety.

Hydrogen storage metal hydrides (2)

+

Measures

FC
System

H2 tank

heat
exchang.

Measures

ON/OFF

Measures

heat
exchang.
ON/OFF

sea
water

Heat management system

An example system: naval auxiliary electrical source

Hydrogen storage metal hydrides (3)

MH
massic energy
Volumic energy

CH
+

Life

cost

LaNi5Hx
xmax=6,5=>
max=3,2% (in practice <2%)
also: in negative-pin NiMH batt.s

Hydrogen storage metal hydrides (3)

The host metal initially dissolves some hydrogen as a solid solution (a-phase).
As the hydrogen pressure together with the concentration of H in the metal is increased,
interactions between hydrogen atoms become locally important, and we start to see
nucleation and growth of the hydride (b) phase.
While the two phases coexist, the isotherms show a flat plateau, the length of which
determines how much H2 can be stored reversibly with small pressure variations. In the
pure b -phase, the H2 pressure rises steeply with the concentration. The two-phase
region ends in a critical point TC, above which the transition from a- to b-phase is
continuous.

Hydrogen storage note

In the following slides data from project FRESCO are quoted.
It was a European commission financed STReP(*) research project
aimed to realise a scooter whose propulsion energy should come
from a hydrogen-fed fuel cell system and a Supercapacitor.
Department of Electrical Systems and Automation of University of
Pisa conducted a lot of work for this project
(*) Specific Targeted Research Project FP6
Note regarding LHV.
As has been seen in other parts of the course it can be obtained from the reaction DH
converting moles into kgs.
E.g., in case of hydrogen combustion with production of water in form of vapour, it is DH =
242 kJ/mol, that corresponds to 1000/2,016*242=120MJ/kg, or 33,3 kWh/kg.

Hydrogen storage comparison of different methods (1)

fuel (Wh/kg)

mass (%)

reservoir
(Wh/kg)

fuel
(Wh/L)

Compressed H2 (20-30MPa)

33300

1,5-3 (*)

500-1000 (*)

500-700

FRESCO (30 MPa)

33300

2,83

950

700 ()

Liquid H2

33300

10

3300

2400

Metal hydrides (ENEA 04)

33300

1,04,8

330-1300

1000-2000

13000 (+)

15

1950

1800-2000

Methanol

5500

90

5000

4500

Petrol

12400

90

11200

9300

32

100

32

150

160
(cell)

100

130
(system)

350

Natural gas @ 20 MPa

Traction Lead Battery

Li-polymer battery
(tract., energy-oriented)

(*) 20MPa steel tank, and 30MPa composite tank respectively

(+) value usually higher than methane because of the presence of heavier hydrocarbons: C2H6 (Ethane),
C3H8, (Propane), C4H10 (Butane); actual value function of actual composition.
biblio: fig. 2 of M. Contes paper
H2 liq data: Zafira in http://www.gmeurope.com/marathon/1/131_factsheet.htm

() tank: : 440 Wh/l

Hydrogen storage comparison of different methods (2)

Energy density Wh/L

Specific Energy Wh/kg

Petrol
Methanol

Liquid H2
CH4 @ 20 MPa
Metal hydrides
H2 @ 30 MPa

32 Wh/kg

Pb Battery

2000

4000

6000

8000

10000

12000

14000

16000