Hydrides

A Züttel, EMPA Materials Sciences and Technology, Dübendorf, Switzerland

& 2009 Elsevier B.V. All rights reserved.

Hydrogen Storage hydrogen at ambient temperature and atmospheric

The Primitive Phase Diagram of Hydrogen
The triple point of hydrogen is at T ¼ 13.803 K and 7.0 kPa.
The density of solid and liquid hydrogen at the triple point
is 86.5 and 77.2 kg m3, respectively. The boiling point at
normal pressure (p ¼ 101.3 kPa) is 20.3 K and the critical
point is at Tc ¼ 33 K and pc ¼ 1293 kPa (Figure 1).
At zero pressure, hydrogen (H2, D2) solidifies in the
hexagonal closed packed (hcp) structure. Data given by
F. Silvera for p-H2 are a ¼ 375 pm, c/a ¼ 1.633, and molar
volume 22.56 cm3 mol1. The spherical J ¼ 0 species (p-
H2, o-D2) undergo a structural transition below 4 K
where the rotational motion of the molecules is quen-
ched, and the molecules are located on the face centered
cubic (fcc) lattice (space group Pa3) with their axes ori-
ented along the body diagonals. At very high pressures
(>2  1011 Pa), solid hydrogen is expected to transform
from a diatomic molecular phase to a monatomic me-
tallic phase with a density >1000 kg m3. This phase may
become a high-temperature superconductor (Table 1).
Owing to the low critical temperature of hydrogen,
liquefaction by compression at room temperature is not
possible.
Hydrogen Storage Methods
Hydrogen storage basically implies reduction of the
enormous volume of hydrogen gas. One kilogram of
pressure takes a volume of 11 m3. The density of
hydrogen can be increased by: (1) increasing pressure;
(2) lowering the temperature; and (3) reducing the
oscillation amplitude of hydrogen atoms or molecules by
interaction with other materials. The crucial parameter is
the ratio of energy (hydrogen) released to the energy
stored in the system (Figure 2).
There are basically six methods to reversibly store
hydrogen with a high volumetric and gravimetric density.
The volumetric hydrogen density (rv) describes the mass
of hydrogen in a material or a system (mH) divided by the
volume (V ) of the material or storage system:
mH
rV ¼ ðkg m3 Þ
V
The gravimetric hydrogen density describes the ratio of
the mass of hydrogen to the mass of the material or
storage system:
mH
rm ¼ ðmass%Þ
mtot
Hydrides
Interstitial Hydrides
Metals, intermetallic compounds, and alloys generally react
with hydrogen and form mainly solid metal–hydrogen

108

H metal Liquid metal

6
10
Pressure (bar)

104
H2
gas
102
Critical point
H2
100 liquid
H2
solid Triple point
H
10–2 gas

100 101 102 103 104 105 106

Temperature (K)

Figure 1 Primitive phase diagram for hydrogen.

440
 Fuels – Hydrogen Storage | Hydrides 441

Table 1 Physical properties of para-hydrogen (p-H2) and normal-hydrogen (n-H2) at the triple and normal boiling point
p-H2 n-H2
Triple point (T ¼ 13.803 K, p ¼ 7.04 kPa)
Temperature (K) 13.803 13.957
Pressure (kPa) 7.04 7.2
Density (solid) (kg m3) 86.48 86.71
Density (liquid) (kg m3) 77.03 77.21
Density (vapor) (kg m3) 0.126 0.130
Heat of melting DHm (J mol1) 117.5
Heat of sublimation DHV (J mol1) 1022.9
Enthalpy DH0 (J mol1)  740.2
Entropy DS0 (J mol1 K1) 1.49
Thermal conductivity (W m1 K1) 0.9
Dielectric constant 1.286
Boiling point at p ¼ 101.3 kPa
Temperature Tb (K) 20.268 20.39
Density (liquid) (kg m3) 70.811
Density (vapor) (kg m3) 1.316
Heat of vaporization DHV (J mol1) 898.30 899.1

Storage Media Volume Mass Pressure Temperature

max. 33 kg H2⋅m−3 13 mass % 800 bar 298 K Composite cylind.

established
Molecular H2

71 kg H2·m−3 100 mass % 1 bar 21 K Liquid hydrogen

20 kg H2·m−3 4 mass % 70 bar 65 K Physisorption

max. 150 kg H2·m−3 2 mass % 1 bar 298 K Metal hydrides

Atomic H

150 kg H2·m−3 18 mass % 1 bar 298 K Complex hydrides

reversibility?

>100 kg H2·m−3 14 mass % 1 bar 298 K Alkali + H2O

Figure 2 The six basic hydrogen storage methods and phenomena. The gravimetric density rm, the volumetric density rv, the working
temperature T, and pressure p are listed. RT stands for room temperature (25 1C). From top to bottom: compressed gas (molecular H2);
liquid hydrogen (molecular H2); physisorption (molecular H2) on materials, e.g., carbon, with a very large specific surface area; hydrogen
(atomic H) intercalation in host metals, metallic hydrides working at RT are fully reversible; complex compounds ([AlH4] or [BH4]),
desorption at elevated temperature, adsorption at high pressures; chemical oxidation of metals with water and liberation of hydrogen.

compounds. Hydrides exist as ionic, polymeric covalent,
volatile covalent, and metallic hydrides (Figure 3).
Hydrogen reacts at elevated temperature with many
transition metals and their alloys to form hydrides. The
electropositive elements are the most reactive, i.e., scan-
dium, yttrium, the lanthanides, the actinides, and mem-
bers of the titanium and vanadium groups.
The binary hydrides of transition metals are pre-
dominantly metallic in character and are usually referred
to as metallic hydrides. They are good conductors of
electricity and possess a metallic or graphite-like ap-
pearance (Figure 4).
Many of these compounds (MHn) show large devi-
ations from ideal stoichiometry (n ¼ 1, 2, 3) and can exist
as multiphase systems. The lattice structure is that of a
typical metal with atoms of hydrogen on the interstitial
sites; for this reason, they are also called interstitial hy-
drides. This type of structure has the limiting com-
positions MH, MH2, and MH3; the hydrogen atoms fit
into octahedral or tetrahedral interstitial lattice sites in
442 Fuels – Hydrogen Storage | Hydrides

1 2 13 14 15 16 17 18
H He
Allred-Rochow Electronegativity Ref: Huheey, J.E. Inorganic Chemistry; Harper & Row: New York, 1983
2.20
LiH BeH2 Ionic hydrides BH3 CH4 NH3 H2O HF Ne
Covalent polymeric hydrides
0.97 1.47 Covalent hydrides 2.01 2.50 3.07 3.50 4.10
Metallic hydrides
NaH MgH2 AIH3 SiH4 PH3 H2S HCI Ar

1.01 1.23 3 4 5 6 7 8 9 10 11 12 1.47 1.74 2.06 2.44 2.83

KH CaH2 ScH2 TiH2 VH CrH Mn Fe Co NiH<1 CuH ZnH2 (GaH3) GeH4 AsH3 H2Se HBr Kr
VH2 (CrH2)
0.91 1.04 1.20 1.32 1.45 1.56 1.60 1.64 1.70 1.75 1.75 1.66 1.82 2.02 2.20 2.48 2.74
RbH SrH2 YH2 ZrH2 (NbH2) Mo Tc Ru Rh PdH<1 Ag (CdH2) (InH3) SnH4 SbH3 H2Tc HI Xe
YH3
0.89 0.99 1.11 1.22 1.23 1.30 1.36 1.42 1.45 1.35 1.42 1.46 1.49 1.72 1.82 2.01 2.21
CsH BaH2 LaH2 HfH2 TaH W Re Os Ir Pt (AuH3) (HgH2) (TIH3) PbH4 BiH3 H2Po HAt Rn
LaH3
0.86 0.97 1.08 1.23 1.33 1.40 1.46 1.52 1.55 1.44 1.42 1.44 1.44 1.55 1.67 1.76 1.90
Fr Ra AcH2

1.00

CeH3 PrH2 NdH2 Pm SmH2 EuH2 GdH2 TbH2 DyH2 HoH2 ErH2 TmH2 (YbH2) LuH2
PrH3 NdH3 SmH3 GdH3 TbH3 DyH3 HoH3 ErH3 TmH3 YbH3 LuH3
1.06 1.07 1.07 1.07 1.01 1.11 1.10 1.10 1.10 1.11 1.11 1.06 1.14
ThH2 PaH2 UH3 NpH2 PuH2 AmH2 Cm Bk Cf Es Fm Md No Lr
NpH3 PuH3 AmH3
1.11 1.14 1.22 1.22 1.22 1.2

Figure 3 Table of the binary hydrides and the Allred–Rochow electronegativity. Most elements react with hydrogen to form ionic,
covalent, or metallic binary hydrides.

fcc hcp bcc

Figure 4 Octahedral (O) and tetrahedral (T) interstitial sites in the face centered cubic (fcc), the hexagonal closed packed (hcp), and
the body centered cubic (bcc) structure. Reproduced from Fukai Y (2005) The Metal–Hydrogen System: Basic Bulk Properties. Springer
Verlag, ISBN 9783540004943.
 Fuels – Hydrogen Storage | Hydrides 443

the metal lattice, or a combination of the two types
(Table 2).
The hydrogen carries a partial negative charge de-
pending on the metal, an exception is PdH0.7 as shown by
G. R. Pearson. Only a small number of transition metals
are without known stable hydrides. A considerable ‘hy-
dride gap’ exists in the periodic table, beginning at group
6 (Cr) up to group 11 (Cu), in which the only hydrides
are palladium hydride (PdH0.7), the very unstable nickel
hydride (NiHo1), and the poorly defined hydrides of
chromium (CrH, CrH2) and copper (CuH). In palladium
hydride, the hydrogen has high mobility and probably a
very low charge density. In the finely divided state,
platinum and ruthenium are able to adsorb considerable
quantities of hydrogen, which thereby becomes activated.
These two elements, together with palladium and nickel,
are extremely good hydrogenation catalysts, although
they do not form hydrides.
Especially interesting are the metallic hydrides of
intermetallic compounds, in the simplest case the ternary
system ABxHn, because the variation of the elements
allows one to tailor the properties of the hydrides. The A
element is usually a rare earth or an alkaline earth metal
and tends to form a stable hydride. The B element is often
a transition metal and forms only unstable hydrides. Some
well-defined ratios of B to A in the intermetallic com-
pound x ¼ 0.5, 1, 2, 5 have been found to form hydrides
with a hydrogen to metal ratio of up to 2 (Table 3).
Interaction of Hydrogen with Metals
The reaction of hydrogen with metals as analyzed by
B. Hammer and J. K. Norskov is a simple two-level
interaction problem. When the electronic states of two
Table 2 The number of interstitial sites per host metal atom
and the size, i.e., the diameter, of the largest possible sphere on
the interstitial site
Structure fcc and hcp bcc
Site O T O T
Number 1 2 3 6
Size 0.414 0.255 0.155 0.291
fcc, face centered cubic; hcp, hexagonal close packed; bcc, body
centered cubic.
atoms overlap, quantum mechanics dictates that they are
to be orthogonal to each other. This drives up the energy
and leads to the so-called Pauli repulsion. However, the
overlapping states will also hybridize and form bonding
and antibonding states. If only the bonding state becomes
occupied, the hybridization effect will be attractive and
will counteract the orthogonalization energy cost. If, on
the contrary, both the bonding and antibonding states
become occupied, no hybridization energy is gained and
the orthogonalization energy cost prevails.
This simple two-level problem can be transferred to
the case of hydrogen chemisorption on the transition
metal and noble metal surfaces. Here, the adsorbate–
surface interaction is most conveniently considered in
two steps. First, the interaction of the hydrogen 1s state
with the metal 4s (Ni and Cu) or 6s (Pt and Au) band
leads to a deep-lying filled bonding state and an empty
antibonding state. This interaction is therefore attractive
and, as the s–s coupling matrix element varies little for
the metals considered, the attraction should be about the
same for all four surfaces. Then follows the interaction of
the bonding state with the metal states. As illustrated in
Figure 5, this results in an extra bonding shift of the
hydrogen-induced state, but also in an antibonding state
right above the metal d-bands. The energy associated
with this hybridization interaction must depend on the
filling of the antibonding state and the coupling matrix
elements Vsd between the s-state and the d-states, and it
is this contribution to the bonding that determines all the
trends in the atomic chemisorption energies.
The calculated density of one-electron states of chemi-
sorbed hydrogen on the four surfaces (Figure 6) resembles
the simple picture of Figure 5 very well. In particular, as
indicated by the upper four arrows in Figure 6, the anti-
bonding states just above the d-bands are clearly seen. Al-
though these antibonding states are empty on nickel and
platinum, they are essentially filled on copper and gold. On
nickel and platinum, the coupling to the metal d-bands
therefore gives rise to an extra attraction on top of the
contribution attributable to the interaction with the metal s-
band, but gives rise to a repulsion for the noble metals
copper and gold as shown by B. Hammer and M. Scheffler.
However, the bond between the hydrogen atom and the

Table 3 The most important families of intermetallic compounds forming hydrides including the prototype and the structure
Intermetallic compound Prototype Hydrides Structure
AB5 LaNi5 LaNi5H6 Haucke phases, hexagonal
AB2 ZrV2, ZrMn2, TiMn2 ZrV2H5.5 Laves phase, hexagonal or cubic
AB3 CeNi3, YFe3 CeNi3H4 Hexagonal, PuNi3 type
A2B7 Y2Ni7, Th2Fe7 Y2Ni7H3 Hexagonal, Ce2Ni7 type
A6B23 Y6Fe23 Ho6Fe23H12 Cubic, Th6Mn23 type
AB TiFe, ZrNi TiFeH2 Cubic, CsCl or CrB type
A2 B Mg2Ni, Ti2Ni Mg2NiH4 Cubic, MoSi2 or Ti2Ni type
A is an element with a high affinity to hydrogen and B is an element with a low affinity to hydrogen.
444 Fuels – Hydrogen Storage | Hydrides

Fermi level
Antibonding for noble metals
Fermi level

Energy
d-bands for transition metals

Adsorbate-induced
level
Bonding
Density of states
(a) (b)

Figure 5 Schematic illustration of the interaction between two electronic states. The downshift of the bonding state is smaller than the
upshift of the antibonding state because the overlap of the initial states gives rise to an energy cost related to the orthogonalization of the
two states. Both the energy associated with the orthogonalization and the hybridization energy associated with the formation of bonding
and antibonding states scale with the square of the coupling matrix element (a). The simple case of two sharp atomic or molecular states
(b). The interaction between a state of an adsorbate outside a metal surface, which has been broadened out to a resonance owing to the
interaction with the metal s-band, and the metal d-bands.

Ni(111) Cu(111) Pt(111) Au(111)

5

0
ε (eV)

H 1s–d antibonding

−5

H 1s–d bonding
−10

Projected DOS (au)

Figure 6 The density of one-electron states (solid lines) for H atomically chemisorbed on the (111) surface of Ni, Cu, Pt, and Au. The
DoS is projected onto the atomic H 1s-state. The surface d-bands DoS (dashed lines) of the four clean metal surfaces are shown for
comparison. The dominant features are the H to metal d-bonding resonances at energies e between  5 and  10 eV. Also prominent
are the H 1s metal d-antibonding DoS peaks (indicated by arrows) directly above the metal d-bands. These antibonding states cause
repulsion on Cu and Au, where they are filled. As indicated by the gray shading, only states below the Fermi energy (which is the energy
zero in all cases) are filled.

noble metals is not weak – the coupling to the metal s-band
gives rise to a considerable attraction, which is only partly
compensated by the repulsive interaction with the d-bands.
However, relative to the bonding in the H2 molecule, the
bond is only marginally stable for copper and completely
unstable for gold. In order to understand why gold is more
noble than copper, we have to consider the absolute mag-
nitude of the coupling matrix element Vsd (and the overlap
Ssd, which is essentially proportional to Vsd). The ortho-
gonalization energy between adsorbate and metal d-states
increases monotonically with (Vsd)2, which is considerably
larger for the 5d-metals than the 3d-metals because of the
more extended 5d-states. The orthogonalization energy cost
therefore increases through the periods of the periodic table
rendering gold less reactive than copper.
The concepts emerging from the above H2-on-metal
considerations now enable a more general discussion of
surface nobleness. The important factors are (1) the de-
gree of filling of the antibonding adsorbate-metal d-states
and (2) the size of the coupling matrix element. The
filling increases to the right in the transition metal series,
and is complete for the noble metals (copper, silver, and
gold); the size of the coupling matrix element increases
down through the periods of the periodic table, making
the 5d-metals the most noble. The coupling matrix
element also decreases to the right in the periodic table
because the d-states become more tightly as the nuclear
charge increases.
The physical picture presented here for the chemi-
sorbed state also holds for the energy barrier for dis-
sociation. For H2 at the transition state, the filled
molecular bonding sg state behaves much the same as the
filled H 1s-state considered above. The molecular anti-
bonding s*m state, however, also interacts covalently with
the metal d-states. The strength of this interaction
completely dominates the trends in the H dissociation
barriers over a broad range of transition metal, noble
metal, and alloy surfaces.
 Fuels – Hydrogen Storage | Hydrides 445

Hydrogen Absorption depends according to the Sieverts equation on the ap-

plied pressure:
The reaction of hydrogen gas with a metal is called the
absorption process and can be described in terms of a 1
M þ x H2 $MHx ½I
simplified one-dimensional potential energy curve (one- 2
dimensional Lennard-Jones potential) (Figure 7).
1 g
Far from the metal surface, the potential of a hydro- m ¼ ma ½1
2
gen molecule and that of two hydrogen atoms are sep-
 
arated by the dissociation energy (1/2H2 - H, 1 g 1 p 1  x 
ED ¼ 218 kJ mol1 H). The first attractive interaction of m þ kT ln ¼ h a  TSnc
a
þ kT ln ½2
2 2 p0 2 r x
the hydrogen molecule approaching the metal surface is
rffiffiffiffi  
the van der Waals force leading to the physisorbed state x p Dgs
¼ exp  ½3
(EPhysE 5 kJ mol1 H) approximately one hydrogen r x p0 RT
molecule radius (E0.2 nm) from the metal surface.
Closer to the surface, the hydrogen has to overcome an The metal lattice expands in proportion to the hydrogen
activation barrier for dissociation and formation of the concentration by B2–3 Å3 per hydrogen atom (2.5 Å3/
hydrogen metal bond (Figure 8). [H/M]) as shown by Y. Fukai. For all binary hydrides
The height of the activation barrier depends on the investigated at infinite dilution and at higher concen-
surface elements involved. Hydrogen atoms sharing their trations, the enthalpy of solution decreases with in-
electron with the metal atoms at the surface are then in the creasing hydrogen content. This general behavior is in
chemisorbed state (EChemE 50 kJ mol1 H). The chemi- many cases related to the lattice expansion accompanying
sorbed hydrogen atoms may have a high surface mobility, hydrogen absorption in a metal. At greater hydrogen
interact with each other, and form surface phases at suf- concentrations in the host metal (H/M40.1), a strong
ficiently high coverage. In the next step, the chemisorbed H–H interaction owing to the lattice expansion becomes
hydrogen atom can jump in the subsurface layer and finally important and the hydride phase (b-phase) nucleates and
diffuse on the interstitial sites through the host metal lattice. grows. The hydrogen concentration in the hydride phase
The hydrogen atoms contribute with their electron to the is often found to be H/M ¼ {1, 2, 3, 4}.
band structure of the metal.
Hydride Phase (b-Phase)
The volume expansion between the coexisting a- and the
Solid Solution (a-Phase)
b-phase corresponds, in many cases, to 10–20% of the
The hydrogen is at small hydrogen to metal ratio (H/ metal lattice. Therefore, at the phase boundary, large
Mo0.1) when exothermically dissolved (solid solution, stress is built up and often leads to a decrepitation of
a-phase) in the metal (Figure 9). The concentration brittle host metals such as intermetallic compounds. The

(a) Hydrogen and metal (b) Physisorption (c) Chemisorption

(d) Subsurface hydrogen (e) Solid solution (α) (f) Hydride (β-phase)

Figure 7 Schematic representation of the six distinct hydrogen absorption steps: (a) The metal lattice is exposed to hydrogen gas in
the nonequilibrium state; (b) at low temperature, hydrogen molecules adsorb at the surface of the metal; (c) dissociation of hydrogen
molecules and chemisorption of hydrogen atoms; (d) subsurface hydrogen; (e) solid solution phase; and (f) hydride phase.
446 Fuels – Hydrogen Storage | Hydrides

300
Gas Interface Metal

2H + M
200

Epot.(kJ mol−1 H) 100

Endothermic

Activated
H2 + M
0

Physisorbed
Chemisorbed Exothermic
−100
d

Figure 8 Lennard-Jones potential of hydrogen approaching a metallic surface. Far from the metal surface, the potential of a hydrogen
molecule and that of two hydrogen atoms are separated by the dissociation energy. The first attractive interaction of the hydrogen
molecule is the van der Waals force leading to the physisorbed state. Closer to the surface, the hydrogen has to overcome an activation
barrier for dissociation and formation of the hydrogen metal bond. Hydrogen atoms sharing their electron with the metal atoms at the
surface are then in the chemisorbed state. In the next step, the chemisorbed hydrogen atom can jump in the subsurface layer and finally
diffuse on the interstitial sites through the host metal lattice.

120
100
80
Heat of solution (kJ mol−1 H2)

60
40
20
0
−20
−40
−60
−80
−100

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn 3rd row
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd 4th row
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg 5th row

Figure 9 Heat of solution of hydrogen in transition metals at infinite dilution. Reproduced from Griessen R (2005) Lecture Script
‘Hydrogen in Metals, Science and Technology’. The Netherlands: Vrije Universiteit Amsterdam.

final hydride is a powder with a typical particle size of two-phase region ends in a critical point Tc, above which
10–100 mm (Figure 10). the transition from a- to b-phase is continuous
The thermodynamic aspects of hydride formation (Figure 11):
from gaseous hydrogen are described by means of pres-  
p
sure composition isotherms in equilibrium (DG ¼ 0). 0
GMH  GH2 ¼ DG ¼ 0 ¼ GMH 0
 GH  RT ln ½4
2
p0
While the solid solution and hydride phase coexist, the
isotherms show a flat plateau, the length of which de-  
termines the amount of H2 stored. In the pure b-phase, 0 p
DG ¼ RT ln ¼ DH 0  T DS 0 ½5
the H2 pressure rises steeply with the concentration. The p0
 Fuels – Hydrogen Storage | Hydrides 447

Tc β-Phase 80
_ ΔS
α-Phase B
100 60
100 °C

E 0 (mV)
40

peq (bar)
10
ΔH 20
α + β-Phase R
25 °C
1 0
0 °C
−20
0.1
0.0 0.2 0.4 0.6 0.8 1.0 2.4 2.8 3.2 3.6
cH (H/M) T (10−3 K−1)

Figure 10 Pressure composition isotherms for hydrogen absorption in a typical metal on the left-hand side. The solid solution (a-
phase), the hydride phase (b-phase), and the region of coexistence of the two phases. The coexistence region is characterized by the
flat plateau and ends at the critical temperature Tc. The construction of the van’t Hoff plot is shown on the right-hand side. The slope of
the line is equal to the enthalpy of formation divided by the gas constant and the interception with the axis is equal to the entropy of
formation divided by the gas constant.

 
p DH 0 1 DS 0
ln ¼  ½6
p0 R T R
ΔH 0 < 0
ΔS 0 < 0
As the entropy change corresponds mostly to the change
from molecular hydrogen gas to dissolved solid hydrogen,
it amounts approximately to the standard entropy of
x/2 H2 + y A + z B
hydrogen (S0 ¼ 130 J K1 mol1) and is therefore DSf E Elements
 130 J K1 mol1 H2 for all metal–hydrogen systems. x M + H2 → x MH2/x
The enthalpy term characterizes the stability of the metal Alloy x/2 H2 + AyBz
hydrogen bond. The decomposition temperature for Equilibrium ΔG = 0

p ¼ p0 ¼ 1 bar is:
DH 0
Tdec jp¼p0 ¼
DS 0
To reach an equilibrium pressure of 1 bar at 300 K, DH
should amount to 39.2 kJ mol1 H2. The entropy of for-
mation term of metal hydrides (change of the hydrogen
gas to a solid) leads to a significant heat evolution DQ ¼T
DS0 (exothermal reaction) during the hydrogen ab-
sorption. The same heat has to be provided to the metal
hydride to desorb the hydrogen (endothermal reaction).
If the hydrogen desorbs below room temperature, this
heat can be delivered by the environment. However, if
the desorption is carried out above room temperature,
the heat has to be delivered at the necessary temperature
from an external source, which may be the combustion of
the hydrogen. The ratio of the hydriding heat (DQ) to the
upper heating value (DHV) is approximately constant:
DQ DS 0
¼ T ¼ 4:6  104 T
DHV DHV
The stability of metal hydrides is usually presented in the
form of van’t Hoff plots. The most stable binary hydrides
ΔH 0
ΔS 0 = S0(H2) = 130 J K mol−1
Hydride Ay BzHx
½7 Figure 11 Formation of an interstitial hydride from an
intermetallic compound. The enthalpy of the hydride formation is
measured between the intermetallic compound and the metal
hydride.
have enthalpies of formation of about DHf ¼
 226 kJ mol1 H2, e.g., HoH2. The least stable hydrides
are FeH0.5, NiH0.5, and MoH0.5 with enthalpies of for-
mation of DHf ¼ þ 20 kJ mol1 H2, DHf ¼ þ 20 kJ mol1
H2, and DHf ¼ þ 92 kJ mol1 H2, respectively, given by
R. Griessen and T. Riesterer.
Owing to the phase transition upon hydrogen ab-
sorption, metal hydrides have, in view of the application,
the very appreciated property of absorbing large amounts
of hydrogen at a constant pressure, i.e., the pressure does
not increase with the amount of hydrogen absorbed as
long as the phase transition takes place. The character-
istics of hydrogen absorption and desorption can be tai-
½8
lored by partial substitution of the constituent elements
in the host lattice. Some metal hydrides absorb and de-
sorb hydrogen at ambient temperature and close to at-
mospheric pressure (Figure 12).
448 Fuels – Hydrogen Storage | Hydrides

T (°C)
700 500 300 200 150 100 50 20 0 −20
10
Mg2FeH6 Na3AIH6 NaAIH4
6 MnNi5H6
LiBH4 TiCr1.8H1.7
4
Mg2NiH4
2 TiFeH
PdH0.6 CaNi5H4
Pressure (MPa) 1
6
4

0.1
6
4 MgH2 LaNi5H6

2
LaNi3.5AI1.5H5 LaNi AIH
4 5
0.01
1.0 1.5 2.0 2.5 3.0 3.5 4.0
1/T (10−3 K−1)

Figure 12 van’t Hoff plots of some selected hydrides. The stabilization of the hydride of LaNi5 by the partial substitution of nickel with
aluminum in LaNi5 is shown as well as the substitution of lanthanum with mischmetal (e.g., 51% La, 33% Ce, 12% Nd, 4% Pr).
Reproduced from ReillyJJ and Sandrock GD (1980) Metallhydride als Wasserstoff-Speicher. Spektrum der Wissenschaften 53–59.

0
Energy

0

Figure 13 Potential for one hydrogen atom in a metal. The potential minima correspond to interstitial lattice sites.

Lattice Gas b. the interaction has a finite range, so that U(r) ¼ 0 for
r>b
The behavior of a hydride is very well described by the c. U(r) is nowhere  N
lattice gas model (Figure 13). This model is precisely
defined by T. D. Lee and C. N. Yang as follows: a This means that two hydrogen atoms cannot occupy the
lattice gas is a monoatomic gas with the interaction po- same interstitial site and that there is an interaction be-
tential tween two H dissolved in a metal. The energy of
X hydrogen atoms dissolved in a metal given by Lacher
U¼ U ðjRi  Rj jÞ ½9 follows:
i;j

where Ri indicates the position of the ith atom and E ¼ NH e0 þ NHH e ½10

a. the atoms have a finite impenetrable core of diameter where NHH is the number of nearest neighbor H pairs
a, so that U(r) ¼ N for roa and e is the H–H pair interaction. We take the zero of
 Fuels – Hydrogen Storage | Hydrides 449

energy at the energy of a single H atom outside the number of atoms. The chemical potential, mH, of
metal. If N is the total number of sites, then NHoN. In hydrogen in a metal is
order to determine the thermodynamic properties of the
metal–hydrogen system, the free energy F ¼ U  TS is @F 1 @F
mH ðcH ; T Þ ¼ ¼ ½17
calculated by means of the relation @NH T ;V N @cH T ;V

X  
NH e0 þ NHH e
F ¼ kT ln exp  ½11 cH
kT mH ¼ kT ln þ e0 þ encH ½18
1  cH
where the sum (the partition function) is taken over all
At thermodynamic equilibrium, the chemical potentials
configurations of NH atoms distributed over N sites. NHH,
of the two phases (H2 gas and MH solid) are equal
the number of H–H pairs for each distribution of the NH
atoms, is given by the equivalent (formally) Ising model;  
1 p cH
however, it has not yet been solved analytically for a eb þ kT ln ¼ kT ln þ e0 þ encH ½19
2 p0 ðT Þ 1  cH
three-dimensional gas (system). The simplest approxi-
mation was formulated by W. L. Bragg and E. J. Williams where eb is the binding energy of H2 molecules. This
and assumes that there is no short-range order around equation describes the solubility isotherms in the one-
hydrogen atoms. This is of course true only in the limit of phase region. In the limit of small hydrogen gas pressure,
weak interaction between two H atoms. The use of the we have simply
Bragg–Williams approximation leads to
1 p
NH 1 kT ln DkT ln cH
NHH ¼ NH n ½12 2 p0 ðT Þ ½20
N2
p-0 cH -0
with n the number of nearest neighbors interstitial sites
(e.g., n ¼ 12 for octahedral sites in an fcc lattice) and NH/ which is known as Sievert’s law.
N the probability of finding a nearest neighbor around a Equation [19] may, however, be unphysical at tem-
given H. The factor 1/2 avoids counting the H–H pairs peratures ToTc, where Tc is the critical temperature of
twice. We have thus the MHx system under consideration:
 
e N2 1 p
E ¼ e0 NH þ n H ½13 eb  en þ kT ln  2e0 ¼ f ðcH Þ ½21
2 N 2 p0 ðT Þ

where
The energy E of a configuration depends thus only on
NH, which is of course the same for all pairs. This implies  
cH 1
that f ðcH Þ ¼ kT ln þ en cH  ½22
1  cH 2
"
A necessary condition for equilibrium is
F ¼  k TN ln N  NH ln NH  ðN  NH ÞlnðN  NH Þ

 ! # @mH @f
n NH 2 ¼ Z0 ½23
N
NH
e0 þ e =kT ½14 @cH p;T @cH
N 2 N
therefore, the part of the isotherm with a negative slope is
Introducing the concentration unphysical. In terms of free energy, it means that FH has a
shape as shown in Figure 14.
NH This figure represents the free energy of an MHx
cH ¼ ½15
N system in a single phase. We shall show now for
capcHpca0 , where the concentrations ca and ca0 are de-
we have termined by the so-called ‘common tangent’ con-
struction, that the free energy of the system can be
FH ¼ kTN ½cH ln cH þ ð1  cH Þlnð1  cH Þ minimized by assuming a mixed phase.
h n i
þ N e0 cH þ e cH2 ½16 The two coexisting phases have concentrations ca and
2
ca0 given by
Note that cH is not necessarily equal to x in a hydride  
MHx, as for certain structures N, the number of inter- ci 1
kT ln þ en ci  ¼0 ½24
stitial sites of a certain type may be different from the 1  ci 2
450 Fuels – Hydrogen Storage | Hydrides

F (cH ) F (cH )

1.0 0.15

0.5
0.10

0
0.05

−0.5
0

−1.0
−0.05

0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1

cH cH

Chemical potential

1000 200

Free energy
800 800
500 100
700 700
Te

Te

600 0 600 Critical 0

m

m
pe

−500 point
pe

500 500 −100

rat

rat

400 −1000 400 −200

u

u
re

re

300 300
0.6 0.8 0.6 0.8
(K

(K

200 0.2 0.4 200 0.2 0.4

)

x x

Figure 14 The function f (cH) and its integral F(cH) for en/kT ¼  7. The dashed red line corresponds to the common tangent
construction implied by Maxwell. In the right panels, we show three-dimensional representations of the chemical potential and the free
energy and the Maxwell construction to determine the coexistence curve corresponding to the red curve in the lower-right panel.

and the corresponding pressure, the dissociation pressure with a maximum at T ¼ Tc. The critical temperature Tc
pdis, is given by eqn [22] is obtained from the maximum of the T(cH) function
(Figure 15). By differentiating eqn [24], we obtain
pdis
kT ln ¼ 2e0 þ en  eb ½25
p0 ðT Þ dT cc 1
k ln þ kTc þ en ¼ 0 ½27
dc T ¼Tc 1  cc cc ð1  cc Þ

The slope of the ln(p) versus 1/T curves is

(2e0 þ en  eb)/k. The binding energy of two H atoms in a Because of the symmetry of the T(c) curve, the maximum
H2 molecule is eb ¼  4.46 eV. T ¼ Tc corresponds to a critical concentration cc ¼ 1/2.
The values of e0 and en may be determined separately Thus
by plotting isotherms for one-phase systems. From eqn
en
[19] we have then Tc ¼  ½28
4k
"  #
p 1  cH 2 2e0  eb þ 2encH
ln ¼ ½26
p0 ðT Þ cH kT Empirical Models

The coexistence curve, which defines the portion of the Several empirical models allow the estimation of the
T–cH diagram where two phases coexist, is given by eqn stability and the concentration of hydrogen in an inter-
[24]. It is a curve that is symmetric relative to cH ¼ 1/2 metallic hydride.
 Fuels – Hydrogen Storage | Hydrides 451

800

700
Coexistence
Temperature T (K) 600 curve
500
Tc 1000

Chemical potential
400
Spinodal 800 500
300 curve 700

Te
0

mp
200 600
−500

e
500

rat
100

u
400

re
−1000

(K
0 300

)
0.0 0.2 0.4 0.6 0.8 1.0 0.8
200
0.2 0.4 0.6
Concentration cH x

Figure 15 Coexistence curve and spinodal curve as determined by eqns [22] and [24] for en ¼  0.2 eV. Note the sharp decrease in the
solubility of hydrogen in the metal near cH ¼ 0 and cH ¼ 1. This is very different for the spinodal curve, which has a finite slope at 0 and 1.

Geometrical Considerations
The maximum amount of hydrogen in the hydride phase is Elements

given by the number of interstitial sites in the intermetallic

compound for which the following two criteria apply. As A. ΔH (ABn)
C. Switendick showed the distance between two hydrogen
atoms on interstitial sites is at least 2.1 Å and the radius of Alloy
the largest sphere on an interstitial site touching all the
neighboring metallic atoms is at least 0.37 Å (Westlake ΔH(ABnH2m )
criterion). The theoretical maximum volumetric density of
hydrogen in a metal hydride, assuming a closed packing of Hydride
Hydride
the hydrogen, is therefore 254 kg m3, which is 3.6 times
the density of liquid hydrogen. ΔH (BnHm ) Binary hydride
As a general rule, it can be stated that all elements
with an electronegativity in the range of 1.35–1.82 do not ΔH (AHm )
form stable hydrides. Exceptions are vanadium (1.45) and
chromium (1.56), which form hydrides, and molybdenum Figure 16 Schematic representation of the energy levels of the
(1.30) and technetium (1.36), where hydride formation alloy or intermetallic compound, the intermetallic hydride, and the
binary hydrides.
would be expected. The adsorption enthalpy can be es-
timated from the local environment of the hydrogen
atom on the interstitial site. the other way around (Figure 16). This model is based
on the fact that hydrogen can participate on a bond with
a neighboring metal atom only if the bonds between the
Stability of the Hydride metal atoms are at least partially broken. The transition
According to the rule of imaginary binary hydrides, the metal A is assumed to have a stronger affinity for
stability of a hydrogen on an interstitial site is the hydrogen than the transition metal B. As a consequence,
weighted average of the stability of the corresponding hydrogen is attracted by the A atoms in the ABn com-
binary hydrides of the neighboring metallic atoms as pound and isolates the A atoms from the surrounding B
shown by I. Jacob and coworkers and A. R. Miedema: atoms. The breaking of A–B bonds is accounted for by
the last term in eqn [31]. In compounds ABn with no5,
1
Am Bn þ x H2 $Am Bn Hx ½29 however, not all A–B bonds are broken up. In successive
2 steps, A. R. Miedema and coworkers generalized the

 equation to the case of ABn compounds with n as small as
DH ½Aa Bb H ¼ DH ðAm Hxa=ðaþbÞ Þ þ DH ðBn Hxb=ðaþbÞ Þ ½30
1 and proposed that
More general is the rule of reversed stability (A. R.
DH ðABn H2m Þ ¼ DH ðAHm Þ þ DH ðBn Hm Þ
Miedema model): the more stable an intermetallic
compound, the less stable the corresponding hydride and  ð1  F ÞDH ðABn Þ ½31
452 Fuels – Hydrogen Storage | Hydrides
The term (1  F) represents the extent to which A–B
contacts between atomic cells are broken by hydrogen. In
ABn compounds, it is empirically found that 90% of the
A–B contacts are broken, whereas only 40% are broken
in AB compounds.
A. L. Shiiov and coworkers proposed a relation for the
heats of formation of ternary hydrides based essentially
on parameters derived from A. R. Miedema’s model.
Effective Medium Theory
As Nordlander, J. K. Norskov, and F. Besenbacher
showed, the binding energy of a hydrogen atom as a
function of the electron density of the environment can
be calculated by means of the effective medium theory.
The binding energy of the hydrogen atoms shows a
maximum at low electron densities and decreases with
increasing electron density. When a hydrogen atom ap-
proaches a metal surface, an electron density with a
maximum binding energy is always found. On the way
through the metal lattice, the electron density is usually
too high except on vacancies (Figure 17).
Electronic Structure
Hydrogen absorption is electronically an incorporation
of electrons and protons into the electronic structure of
the host lattice. The protons lower the energy of a part of
the d-electrons and they lead to new states about 4 eV
below the Fermi energy EF. On the other side, the elec-
trons fill empty states at the Fermi energy EF and
therefore increase the Fermi energy (Figure 18).
Metal
(a)
H in a homogeneous electron gas
3
Helium
2
hom (eV)
1 Hydrogen
0
ΔE eff
−1
−2
Eb(H)
−3
0 002 004 006 008
—(au)
ideal n0 n0
Figure 17 The energy of hydrogen and that of helium in a homogeneous electron gas are shown in the lower left corner. Hydrogen
absorption in the effective medium theory. (a) Hydrogen atom on a path to the surface of a metal and through the lattice. (b) Electron
density along the path of the hydrogen atom. (c) Potential energy of the hydrogen atom along the path.
The effect of hydrogen on the electron structure of
transition metals is shown in Figure 19. The d-band of
the host metal contains N electrons, where N is less or
equal to 10. The lowest band hybridizes with the s–p-
band and builds a band with mainly s-character on the
sites of H, which contains two electrons. The inter-
calating hydrogen lowers the s-type band typically by 3–
4 eV. The remaining part of the d-band can hold a
maximum of eight electrons and is occupied by N  2
electrons.
The Local Band-Structure Model
The heat of formation of binary hydrides MHx is related
linearly to the characteristic band energy parameter
DE ¼ EF  Es, where EF is the Fermi energy and Es the
center of the host metal electronic band with a strong s
character at the interstitial sites occupied by hydrogen
(Figure 20).
Griessen and Driessen showed that for most metals, Es
can be taken as the energy that corresponds to one
electron per atom on the integrated density-of-state
(DoS) curve. The semiempirical model mentioned above
allows an estimation of the stability of binary hydrides as
long as the rigid band theory can be applied. The en-
thalpy of solution at infinite dilution is
pffiffiffiffiffi X 4
DH̄ N ¼ a DE W Rj þ b ½32
j
where a ¼ 18.6 kJ mol1 H Å4 eV3/2 and b ¼  90kJ
mol1 H. However, the interaction of hydrogen with the
electronic structure of the host metal in some binary
n n
(b) r ΔE hom
ΔE eff
hom
r
(c)
 Fuels – Hydrogen Storage | Hydrides 453

Endothermic
EF

Exothermic

s, p
n(E )

Figure 18 Schematic representation of the hydrogen absorption (left) and the influence on the electronic structure (right).

hydrides and especially in the ternary hydrides is often

M
E
MH more complicated. In many cases, the crystal structure of
E
Q′ = 9 – N the host metal, and therefore also the electronic struc-
Q ′ = 10 – N
ture, changes upon phase transition, and the theoretical
EF EF
calculation of the stability of the hydride becomes very
Q′ = N – 2 Q′ = N – 1 complicated if not impossible.

Hydrogen Sorption Kinetics

Q′ = 2
Q′ = 2 The hydrogen sorption kinetics is determined by several
subsequent steps with different interfacial reservoirs
Q=N Q=N+1
(Figure 21):
n(E) n(E )
1. gas diffusion to the surface;
Figure 19 Schematic representation of the change in the 2. chemisorption at the surface;
electronic structure of a transition metal upon hydride formation. 3. diffusion in the solid solution phase;
Integrated density of states

Y Ru
Density of states

100 W 8
Ir
3
Ru
∞ (kJ mol H)

50
1
Rh Fe Pt 1
−1

Mo Co −6 −4 −2 0 2 4 −8 −6 −4 −2 0 2
0 Ni Cr E s E F E(eV) Es EF
Pd
ΔH exp

V Pd Ag
_

Hf
–50 Nb Ta 11
Ti 10
La Zr
Y
Sc
–100
–100 –50 0 50 100
_ 1 1
ΔH mod −1
∞ (kJ mol H)
−8 −6 −4 −2 0 2 −8 −6 −4 −2 0 2
Es EF Es EF

Figure 20 The local band-structure model correlation, between experimental values of the enthalpy of hydrogen solution at infinite
dilution and the calculated values. Relative positions of EF and Es for representative metals are shown. Reproduced form V. L. Moruzzi
and coworkers and R. Griessen.
454 Fuels – Hydrogen Storage | Hydrides

4. nucleation of the hydride phase; and pressure, m for the mass of the hydrogen molecule, and k
5. growth of the hydride phase. (k ¼ 1.380 662  1023 J K1) for the Boltzmann constant.
One of the most fundamental reactions, the dissociative
chemisorption of H2 on metal surfaces, can be treated
Gas Diffusion
accurately using quantum mechanics as shown by
By using the Hertz–Knudsen equation, J. Barrett and C. A. Gross and M. Scheffler. Density functional theory
Clement have shown that the gas diffusion to the surface allows one to compute the molecule–surface interaction,
leads to and the motion of the hydrogen atoms is simulated using
p quantum dynamics, modeling all six molecular degrees of
Rads ¼ ka ð1  yÞpffiffiffiffiffiffiffiffiffiffiffiffiffiffi ½33 freedom.
2pmkT
The H2 þ Pd(100) system is a classic example of a
where ka stands for the sticking coefficient, y ¼ N(H2)/NS nonactivated system, the potential energy surface being
for the surface coverage, p for the gas (hydrogen partial) barrierless at some sites (like the bridge site), although
having a barrier at others (like the top site)
H2 (Figures 22(a) and 22(c)). At moderate collision energies
(temperature), dissociation is feasible if the molecule is
Desorption lying parallel to the surface – so that both atoms can form
Activated
Adsorption bonds to the surface upon dissociation – but not if the
complex
Mobility molecule is standing upright. The H2 þ Cu(100) system
is a classic example of an activated system, dissociation
Recombination proceeding over a potential barrier above all sites
(Figures 22(e)–22(h)). For H2 þ Cu(1 1 1), the barrier to
dissociation varies considerably with surface site and
Intercalation orientation of the molecule. The reaction of H2 on
Pd(100) is much more exothermic, and the associated
barrier height is much lower (or zero) than for the
Figure 21 The steps of hydrogen absorption reaction. Upon H2 þ Cu(100) system. This difference can be explained
chemisorption, the hydrogen atoms diffuse at the surface and into from the position of the center of the metal d-band
the lattice. relative to the Fermi level. The center of the d-band lies

H2 + Pd(100) H2 + Cu(100)
2.5 1.5 2.5 1.5
1.0 (θ = 45°, φ = 0°)
2.0 θ = 0° 2.0
0.5 1.0
1.5
(θ = 90°, φ = 45°) 0.0 1.5 0.50 eV
Molecule–surface distance (Å)

Molecule–surface distance (Å)

1.0 0.5

Potential energy, V (eV)

–0.5
Potential energy, V (eV)

1.0
0.5 –1.0 (θ = 90°, φ = 0°)
0.0
0.0 –1.5 0.5
(a) (b) (e) (f)

2.5 1.5 2.5 1.5

θ = 0° 1.0
2.0 (θ = 45°,
2.0
0.15 eV 0.5 φ = 0°) 1.0
1.5 0.63 eV
0.0 1.5
1.0 –0.5 0.5
(θ = 90°, φ = 45°) 1.0
0.5 –1.0
(θ = 90°, φ = 0°) 0.0
0.0 –1.5 0.5
0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Bond length (Å) Reaction coordinate (Å) Bond length (Å) Reaction coordinate (Å)
(c) (d) (g) (h)

Figure 22 Potential energy surfaces (PESs) for H2 þ Pd(100) (a)–(d) and H2 þ Cu(100) (e)–(h). Two-dimensional cuts through the
PES are shown for the molecule being parallel to the surface, for the bridge-to-hollow (a) and top-to-hollow (c) configurations for
H2 þ Pd(100), and for the bridge-to-hollow (e) and top-to-bridge (g) configurations for H2 þ Cu(100). The configurations are visualized in
the insets, viewing the system from above. The contour lines are for potential energies 0.1 eV apart. For each cut, the potential along the
reaction path is shown on the right as a function of the reaction coordinate for the molecule in a parallel (y ¼ 901) and in a tilted (y a 901 –
is the azimuthal angle of orientation of the molecular axis) geometry.
 Fuels – Hydrogen Storage | Hydrides 455

E = 0.01 eV

(a) t = 0 fs t = 140 fs t = 160 fs t = 215 fs

E = 0.12 eV

(b) t = 0 fs t = 60 fs t = 80 fs t = 165 fs

Rotations: experiment

Desorption temperature (K)

0.8 (v = 1, j = 0) 800 Rotations: theory
Sticking probability

Vibrations: experiment
Vibrations: theory
0.6 600

0.4 (v = 0, j = 0) 400

0.2 (v = 0, j = 4) 200

0.0 0
0.0 0.1 0.2 0.3 0.4 0 200 400 600 800 1000

(c) Kinetic energy (eV) (d) Surface temperature (K)

Figure 23 Computational and experimental results are shown for H2 þ Pd(100). Snapshots of classical trajectories of H2 molecules
impinging on Pd(100) that illustrate the steering effect are shown for an initial kinetic energy of 0.01 eV (a) and 0.12 eV (b) for otherwise
identical initial conditions. The computed reaction probability is shown as a function of normal incidence energy for the rovibrational
ground state (v ¼ 0, j ¼ 0), for a rotationally excited state (v ¼ 0, j ¼ 4), and for the vibrationally excited state (v ¼ 1, j ¼ 0) (c). Theoretical
predictions for the rotational and vibrational temperatures are compared with experimental measurements on hydrogen associatively
desorbing from Pd(100) (d).

farther below the Fermi level in copper, resulting in a
greater filling of the molecule-surface and atom-surface
antibonding levels at the barrier and in the exit channel,
respectively (Figure 23).
Phenomenologically, the reaction rate is proportional
to the concentration or pressure of hydrogen and a
temperature-dependent parameter (k):
Rchem ¼ kðT ÞpðH2 Þ
The temperature dependence of the reaction parameter
k is based on the collision energy required to overcome
the activation barrier. The equation was first proposed
by the Dutch chemist J. H. van’t Hoff in 1884; 5 years
later, the Swedish chemist Svante Arrhenius provided a
physical justification and interpretation for it:
 
EA
kðT Þ ¼ k0 exp
kT
where k0 is the preexponential factor or simply the
prefactor and R is the gas constant. The units of the
preexponential factor are identical to those of the rate
constant and will vary depending on the order of
the reaction. If the reaction is first order, it has the
units s1, and for that reason it is often called the fre-
quency factor or attempt frequency of the reaction. It can
be seen that either increasing the temperature or de-
creasing the activation energy (e.g., through the use of
catalysts) will result in an increase in the rate of reaction
½34
(Figure 24).
The activation energy (EA) is influenced by the
binding energy of the surface elements. A material that
reduces the activation energy of a reaction is called a
catalyst. For hydrogen dissociation, the best catalysts are
elements that do not form hydrides. It is required that the
binding energy is sufficient to favor dissociation but small
enough to allow the hydrogen atoms to diffuse away from
½35 the reaction site, otherwise the dissociated hydrogen
atoms block all active surface sites.
The self-diffusion of hydrogen describes the random
diffusion in the absence of a concentration gradient. The
456 Fuels – Hydrogen Storage | Hydrides

mean distance traveled by a hydrogen atom is given by The tracer diffusion requires a concentration gradient,
the Einstein equation: which leads to a gradient in the chemical
-
potential and
therefore a driving force. The flow J is
s̄2 ¼ Dnt ¼ Dt ½36
-
J ¼ D r ½37
where D stands for the diffusion coefficient with the unit
m2 s1, n the number of jumps, p the time for one jump, with a tracer diffusion coefficient
and t the time. D @m
D ¼ r ½38
kT @r
A cm−2
The chemical potential of an ideal solution is given by
10−2 enthalpy and the ratio of occupied to unoccupied sites
Pd Pt Ir (expressed by the concentration):
Os  
10−4 Rh Ru r
Co m ¼ h þ kT ln ½39
Ag Re r0  r
Ni
Exchange current density j0

10−6 Fe Au
Sb Cu Cr lim ðD Þ ¼ D ½40
Ge Nb w r-0
As Ti Mo
Mn Ta
10−8 The diffusion is an activated process and, therefore, the
Bi Al
Sn coefficient D is temperature dependent:
Cd
Ga  
10−10 Zn Ediff
Te D ¼ D0 exp ½41
Pb
kT
l In
Hg
10−12 The diffusion coefficient at 25 1C of hydrogen in
metals varies between 105 cm2 s1 (vanadium) and
0 2 4 6 8 ⋅ 105 J mol−1
1011 cm2 s1 (nickel). The diffusion of hydrogen in body
Heat of sublimation Ls
centered cubic (bcc) metals is faster than in fcc and hcp
Figure 24 Catalytic activity (exchange current density) as a metals because the distance between interstitial sites is
function of hydrogen binding energy (heat of sublimation). smaller in bcc metals as compared to fcc and hcp metals.

Density: 5 g cm−3 2 g cm–3 1 g cm–3 0.7 g cm–3

160 +
H¯ AIH3 AI(BH4)3
BaReH9 Mg FeH dec. <273 K
dec. 373 K
m.p. 208 K
Hcov
140 2
<373 K,1 bar 6
620 K, 1 bar
LaNi5H6 NaBH4
Volumetric H2 density (kg H2 m–3)

liq. LiBH4
120 300 K, 2 bar MgH2 dec. 680 K NH 3
H2 Chemisorbed
liq. b.p. 238.7 K dec. 553 K on carbon
Mg2NiH4 620 K, 5 bar C8H18
LiH
FeTiH1.7 550 K, 4 bar dec. 650 K liq.
100 NaAIH4 CH4
300 K, 1.5 bar LiNH2
liq. b.p. 12 K
dec. >520 K
KBH4 LiAIH4 C4H10
80 dec. >580 K
dec. 400 K b.p. 272 K

H2 H2liq.
60 20.3 K
500 200
120
40 80
80 H2 physisorbed
50 50
on carbon
20 20 pres. H2
gas 20 pressurized H2gas
13
13 (steel) (composite material)
p (Mpa) p (Mpa)
0
0 5 10 15 20 25
Gravimetric H2 density (mass%)

Figure 25 Volumetric and gravimetric hydrogen density of some selected hydrides. Mg2FeH6 shows the highest known volumetric
hydrogen density of 150 kg m3, which is more than double that of liquid hydrogen. BaReH9 has the largest H/M ratio of 4.5, i.e., 4.5
hydrogen atoms per metal atom. LiBH4 exhibits the highest gravimetric hydrogen density of 18 mass%. Pressurized gas storage is
shown for steel (tensile strength sv ¼ 460 MPa, density 6500 kg m3) and a hypothetical composite material (sv ¼ 1500 MPa, density
3000 kg m3).
 Fuels – Hydrogen Storage | Hydrides 457

The transformation of the solid solution phase into ED dissociation energy

the hydride phase starts at a few distinct spots in the EF Fermi energy
lattice (nucleation), e.g., as a result of random concen- EPhys energy at physisorbed state
tration variations or defects in the host lattice. From these F free energy
spots, the hydride phases grow and merge together. The G Gibbs free energy
Johnson–Mehl–Avrami–Kolmogorov equation describes ~
F flow
the fraction of hydride phase formed as a function of k Boltzmann constant
time. A necessary requirement for the growth of the k0 preexponential factor
hydride phase (b-phase) is the supersaturating of the ka stinking coefficient
solid solution phase (a-phase). In the case of a constant mH mass of hydrogen
nucleation rate, a constant growth rate of the hydride mtot total mass
phase, and a random distribution of the hydride phase in n number of nearest neighbors
the volume, the fraction of hydride phase is given by interstitial sites
 p  N nucleation rate
f ðt Þ ¼ 1  exp  Nv3 t 4 ½42 NHH number of nearest neighbor H pairs
3
p normal pressure
where N represents the nucleation rate and v the growth pc critical pressure
rate of the nuclei. In general, the Johnson–Mehl–Avrami pdis dissociation pressure
equation is Ri position of the ith atom
t time
f ðt Þ ¼ 1  expðkt n Þ ½43 T temperature
Tc critical temperature
where the Avrami exponent n is between 1 and 4, e.g., for Tdec|p ¼ p0 decomposition temperature for
two-dimensional phase transition (thin film) the ex- p ¼ p0 ¼ 1 bar
ponent is 3, and k depends on the nucleation and growth U interaction potential
rate and is temperature dependent. n growth rate of the nuclei
V volume
Hydrogen Density DH 0 enthalpy
DHm heat of melting
One of the most interesting features of the metallic hy- DHV heat of sublimation
drides is the extremely high volumetric density of the DQ hydriding heat
hydrogen atoms present in the host lattice. The highest DS 0 entropy
volumetric hydrogen density known today is 150 kg m3 e H–H pair interaction
found in Mg2FeH6 and Al(BH4)3. Both hydrides belong eb binding energy of H2 molecule
to the complex hydrides. Metallic hydrides reach a lH chemical potential of hydrogen
volumetric hydrogen density of 115 kg m3, e.g., LaNi5. qm gravimetric hydrogen density
Most metallic hydrides absorb hydrogen up to a hydro- qV volumetric hydrogen density
gen to metal ratio of H/M ¼ 2 (Figure 25). Abbreviations and Acronyms
Greater ratios up to H/M ¼ 4.5, e.g., BaReH9, have bcc body centered cubic
been found by K. Yvon; however, all hydrides with a DoS density of state
hydrogen to metal ratio of more than 2 are ionic or co- fcc face centered cubic
valent compounds and belong to the complex hydrides. hcp hexagonal closed packed
PES potential energy surface

Nomenclature
Symbols and Units See also: Fuels – Hydrogen Storage: Complex
cc critical concentration Hydrides; High Temperature Hydrides.
cH hydrogen concentration
D diffusion coefficient
D* tracer diffusion coefficient Further Reading
E energy of hydrogen atoms
EA activation energy Asheroft NW (1968) Physical Review Letters 21: 1748.
EChem energy at chemisorbed state Barrett J and Clement C (1992) Journal of Colloid and Interface Science
150: 352; Journal of Chemical Physics 106: 5677
458 Fuels – Hydrogen Storage | Hydrides
Bragg WL and Williams EJ (1934) Proceedings of the Royol Society of
London Series A 145: 699.
Fukai Y (1989) Zeitschrift fur Physikalische Chemie 164: 165.
Fukai Y (2005) The Metal–Hydrogen System: Basic Bulk Properties.
ISBN 9783540004943. Springer Verlag.
Griessen R (1988) Physical Review B 38: 3690--3698.
Griessen R (2005) Lecture Script ‘Hydrogen in Metals, Science and
Technology’. The Netherlands: Vrije Universiteit Amsterdam.
Griessen R and Riesterer T (1988) Heat of formation models.
In: Schlapbach L (ed.) Hydrogen in Intermetallic Compounds I
Electronic, Thermodynamic, and Crystallographic Properties,
Preparation, vol. 63, pp. 219--284. Springer Series Topics in Applied
Physics.
Gross A and Scheffler M (1998) Physical Review B 57: 2493--2506.
Hammer B and Norskov JK (1995) Nature 376: 238--240.
Hammer B and Scheffler M (1995) Physical Review Letters 74:
3487--3490.
Huheey JE (1983) Inorganic Chemistry. New York: Harper & Row.
Jacob I, Bloch JM, Shaltiel D, and Davidov D (1980) Solid State
Communications 35: 155.
Kroes GJ, Gross A, Baerends EJ, Scheffler M, and McCormack DA
(2002) Accounts of Chemical Research 35: 193--200.
Lacher JR (1937) Proceedings of the Royal Society of London Series A
161: 525; (1938) Proceedings of the Cambridge Philosophical
Society 34: 518
Lee TD and Yang CN (1952) Physical Review 87: 404. 410
Miedema AR (1973) Journal of Less-Common Metals 32: 117.
Moruzzi VL, Janak JF, and Williams AR (1978) Calculated Electronic
Properties of Metals. New York: Pergamon.
Mueller WM, Blackledge IR, and Libowitz GG (eds.) (1968) Metal
Hydrides. New York: Academic Press.
Norskov JK and Besenbacher F (1987) Journal of Less-Common
Metals 130: 475--490.
Pearson GR (1985) Chemical Reviews 85: 41--49.
Reilly JJ and Sandrock GD (1980) Metallhydride als Wasserstoff-
Speicher. Spektrum der Wissenschaften 53--59.
Rittmeyer P and Wietelmann U Hydrides. In: Ullmann’s Encyclopedia of
Industrial Chemistry, vol. A13: High-Performance Fibers to Imidazole
and Derivatives, 5th Completely Revised Edition, pp. 199–226. VCH.
Shiiov AL, Kost ME, and Kutsnetsov NT (1985) Journal of Less-
Common Metals 105: 221.
Silvera F (1980) Reviews of Modern Physics 52: 393.
Switendick AC (1979) Zeitschrift fur Physikalische Chemie N.F. 117: 89.
Van Mal HH, Buschow KHJ, and Miedema AR (1974) Journal of Less-
Common Metals 35: 65.
Weinberg MC, Birnie DP , III, and Shneidman VA (1997) Journal of Non-
Crystalline Solids 219: 89--99.
Westlake DJ (1983) Journal of Less-Common Metals 91: 275--292.
Yvon K (1998) Complex transition metal hydrides. Chimia 52(10):
613--619.