A Written Essay on the topics of Hydrogen Storage Alloy

Applicant: YIN Shi

1. Introduction

Hydrogen energy is one of the most important new energies in the 21st century. As a new type
of the clean energy, low cost hydrogen-production, safe and high-efficient storage and transport,
and large-scale utilization techniques have been received much attention[1]. It is expected to reduce
the dependence of our economy on fossil fuels and alleviate the ever-worsening CO2 pollution that
threatens our environment. In the subject of the expected hydrogen energy, hydrogen storage is
one of the key enabling technologies. It is essential to develop practical and viable hydrogen
storage systems before this new kind of energy can be commercially delivered and utilized.
Hydrogen storage materials, which are important carriers during hydrogen storage and transport,
can absorb and desorb hydrogen reversibly. With various advantages, such as no expanse for
liquefaction and evaporation loss, large condensation (more H2 molecules/vol. than liquid H2) and
safety, this kind of material draws many attractions in the hydrogen energy research[2].

2. Fundamental characteristics and theory on the hydrogen storage material

Traditional source of hydrogen are reformation of fossil fuels, electrolysis of H2O, thermal
splitting of H2O, photo-catalytic of H2O or hydrate, boiling or enzyme catalysis of biomass and
recovery from industrial wastes. Advantage of H2 over electricity is its storability. With the
suitable storage material the hydrogen can be largely compacted to store and transport. From the
Table I it can be seen clearly that metal hydrides can store hydrogen more compactly than liquid
hydrogen in a safe and efficient way, which corresponds to gas storage of 150MPa.
Medium State Density Capacity (wt. %) Capacity(g/ml)
Normal H2 Gas (1 MPa) 1 100 0.00008
High Pressure Gas (150 MPa) 150 100 (0.80) 0.012
Liquid Liquid 778 100 (~5.0) 0.062
MgH2 Solid 1222 7.60 0.098
LaNi5H6 Solid 1148 1.37 0.092
TiFeH1.95 Solid 1056 1.85 0.084
Mg2NiH4 Solid 1037 3.60 0.083
VH2 Solid 1944 3.81 0.156
[3]
Table I. the hydrogen capacity in various media
The metallic storage material covers almost all transitional metal hydrides: IIIB, IVB, VB,
(VIB, VIIB and VIIIB). Because of the metallic bond or ionic bond, it could form different many
different hydrides may form, such as VH, VH2 and TiFeH1.95. Metallic hydrides usually have
larger unit volume than metal and its stability differs greatly from various alloys, which measured
by -∆H (larger -∆H, more stable).
There are three categories of metallic hydrides according
to the stability. The first is very stable (IIIB and IVB) with
large -∆H and very low dissociation pressure, such as
∆HLaH2.7 = -55.4 kcal/mol H2, Pdis, ZrH2= 0.001 atm at 250℃.
The reversible alloy includes the metal in VB at room-temp,
At 0~100℃, Pdiss = 0.01~20 atm; ∆H = ~ -10 kcal/ mol H2. The VIB, VIIB, VIIIB metal can form
a very unstable kind of storage alloy at the surrounding of very high H2 pressure and very low
temp, ∆H>0.
As seen from a typical phase transformation diagrams of hydrogen storage alloy[4], a phase
line encompassed the α+β region incises the thermodynamics region into three parts: α region:
solid solution, (α+β) region: double phases－plateau and β region: hydride phase. In the plateau,
the saturated solid solution α phase absorbs hydrogen and form β phase hydride through phase
transformation[5].

2 2
MH x + H 2 U MH y + Q
y−x y−x
In this process, some key factors determine the different features among the compounds. ΔS˚ is
fairly independent of many metals or compounds (usu. ~-S˚H2 (g)) and negative because the
solution system from disorderly to orderly in the hydrogenation process. ΔH˚ is dependent of the
metals or compounds. Most ΔH˚ are negative and some are positive, which are a criterion for
choosing HSAs[6].

ΔH D ΔS D
ln PH 2 = −
RT R
About the reaction mechanisms, there are several viewpoints put forward. C.N. Park and J.Y.
Lee et al. propose four-step process.
i) chemisorption of hydrogen molecules

H 2 U 2 [ H ]ad

ii) adsorbed H translates into absorbed H

H ad U H ab

iii) H diffusion in α phase and iv) chemical reaction

α+H Uβ
Three-step process proposed by K. S. Nahm et al. (Korea) only includes the step of chemisorption,
diffusion and chemical reaction.

3. Various alloy system of hydrogen storage material

a) Rare Earth Based Hydrogen Storage Alloys

Rare earth based hydrogen storage alloys are mainly categorized into three kinds, namely
Rare Earth Based Binary HSAs (LaNi5), Rare Earth Based Multi-component HSAs (MmNi5 based
alloys, MNi5 based alloys), AB5 type Rare Earth Based Electrode Alloys.
At the beginning of 1970’s, Metal hydride electrode (MHE) was put forward. LaNi5 firstly
tested as electrode material, whose maximum capacity can reach 320 mAh/g (theoretical capacity
379 mAh/g). However, the plateau pressure of LiH5 is too high (PH2= 2.2atm > 1atm) and bad
cycling stability in 6M KOH, R100 Cycles < 60%. Decay mechanism of LaNi5 result from intrinsic
disproportionation, surface segregation and pulverization. In the former phenomenon, LaNi5Hx
hydride tends to decompose into lanthanum hydride and nickel due to the thermodynamic
instability of LaNi5Hx.

LaNi5 H 6 → LaH 2.7 + Ni (g − s reaction)

This phenomenon destroys the CaCu5-type crystal structure of alloy and reduces the capacity.
Partial substitution of Ni with Al, Sn in LaNi5 can restrain its intrinsic disproportionation and the
rate of intrinsic disproportionation is slight in the cycling degradation of Re-based electrode alloys.
In the process of surface segregation La is inclined to surface enrichment because the surface
energy of La is lower than that of Ni. So La and Ni apt to the surface enrichment and the sub layer
enrichment respectively. La on surface can be easily oxidized to La(OH)3 and La2O3. However,
La(OH)3 or La2O3 cannot absorb hydrogen and cannot be deoxidized.[7]
2LaNi5 + 6H 2 O → 2La(OH)3 + 10Ni + 3H 2
LaNi5 + 13OH - → La(OH)3 + 5Ni(OH) 2 + 13e-
4LaNi5 + 13O 2 → 2La 2 O3 + 20NiO
In 1984, J.J.G. Williams in Philips Research Lab firstly began multi-component alloying for
LaNi5. La0.8Nd0.2Ni2.5Co2.4Si0.1 with good anti-oxidation, maximum capacity Cmax= 290 mAh/g
and 70% cycling retention after 1000 cycles have been developed as a promising alloy. T. Sakai
put forward three amending way from micro-structure, alloy composition and surface structure to
design good electrode alloys. Tracing the mechanism of the hydrogen storage, there are several
approaches to enhance the storage capacity. From the La-side optimization T. Sakai developed
La1-xCex(NiCoAl)5, La1-yNdy(NiCoAl)5 two multi-composition alloy systems in 1990’s. Up to now,
the majority of international scholars have done much research on the other side–Ni side
optimization. The representative alloy series are ReNi5-x-y-zMnxAlyCoz (0≤x≤0.4; 0≤y≤0.3;
0≤z≤0.75), such as MmNi3.55Mn0.4Al0.3Co0.75 (Cmax= ~320 mAh/g, R1000= ~80 %),
MlNi5-x-y-zCoxMnyTiz (0.5≤x≤1.0; 0.3≤y≤0.6; 0.01≤z≤0.1), such as MlNi3.45(CoMnTi)1.55 (Cmax =
~303 mAh/g, R540 = ~86.5 %). The third method to improve the ability is lowering Co or Co-free
alloys which is usually substituted with Fe, Cu, Sn, Si etc. The cobalt in the alloy with 10% of
weight spends 30% cost of alloy. LmNi4.3-xAl0.4Mn0.3(CoFe)x, such as LmNi3.8Al0.4Mn0.3Co0.3Fe0.2
(Cmax = 295mAh/g; good life.) prepared by A. Zuttel and ReNi3.75Mn0.4Ti0.05Co0.8-xFex (x＝0~0.8),
ReNi3.5Mn0.4Al0.3Co0.8-xFex (x＝0~0.8) by Lixin Chen are the representative alloy series of this
kind[8].
b) Magnesium Based Hydrogen Storage Alloys
The high capacity, such as MgH2 7.6 wt%, Mg2NiH4 3.6 wt%, and low cost of the alloys
draw most of attraction in the international research. However, the Mg - H system is extensively
studied to overcome its disadvantage, which is a very stable hydride, easily corroded in 6M KOH
electrolyte and possesses poor kinetics.
D
300 − 400 C
Hydriding : Mg + H 2 ⎯⎯⎯⎯
24 − 400 atm
→ MgH 2
D
≥ 287 C
Dehydriding : MgH 2 ⎯⎯⎯→
1atm
Mg + H 2
From the two reaction equation, we can see that the Mg-H system is provided with high
hydriding/dehydriding temperature and low hydrogen absorption/desorption rate. Firstly, the
causes of poor kinetics result from four aspects. a) The crystal structure of MgH2 differs from that
of Mg, which transforms from Mg h.c.p. to MgH2 b.c.t. The high expanding stress obstructs the
formation of MgH2. b) the diffusivity of H in Mg-oxide film is low. c) The dissociation of H2 on
Mg surface is difficult and d) the nucleation and growth rate of MgH2 is low due to the bad
catalysis of Mg.
In order to improve hydrogen storage properties of Mg, various modifying methods can be
utilized. The most simple and convenient approach is mechanical ball-milling which enhance the
bonding energy with the graphite and tetrahydrofuran in the h.c.p. Mg. Additive of MgI2 or
MgCl2 and Mixing polynuclear aromatic compounds can be imposed to Mg-H system to increase
the kinetic and H2 dissociation. There are lots of metal hydride catalysts, such as Mg2Ni, Ti-V-Cr,
LaxNiy, leading the increase of kinetic and the fall of thermodynamic stability.
In the main, the Mg based system is categorized into Mg-transition metal systems, Mg-Rare
earth alloys Mg-nontransition metal systems and Amorphous Mg-Ni based alloys which are worth
mentioning. In 1986, K. Sapru published amorphous Mg-Ni film in his US patent 4.623.597(1986)
start the research on this subject. Since then, many scholars in the world have done much research
on this amorphous Mg-based HSAs, involving MA-Mg2-xNix (x=0.2~1.8) alloys, MA-(Mg2Ni + Ni)
by C. Iwakura, MA- Mg2Ni + C (graphite), MA- Mg-Ni-M alloys.[8]
Composition Cmax (mAh/g) HRD (%) R9 cycles (%)
MgNi 387.5 64.4 64.7
MgNi0.9Ti0.1 400 --- 70.2
MgNi0.9Zn0.1 388.3 54.7 71.9
MgNi0.9Mn0.1 345 59.4 57.5
MgNi0.9Cu0.1 343.3 80.1 51.4
MgNi0.9Fe0.1 273.3 73.2 40.5
MgNi0.9Co0.1 247.5 71.7 52.6
MgNi0.9Zr0.1 239.2 --- 65.2
MgNi0.9W0.1 226.7 59.6 47.8
MgNi0.9Cr0.1 204.2 --- 60
MgNi0.9Se0.1 93.3 --- 72.3
MgNi0.9Sb0.1 28.3 --- 73.5
MgNi0.9C0.1 13.3 --- 75.1
Table II. The electrochemical properties of amorphous MgNi0.9M0.1 alloys[8]
c) Ti- Based Hydrogen Storage Alloys
Ti based Hydrogen Storage Alloy includes TiFe, TiNi, TiMn2, TiCr2, TiCo2 etc. The
combination enthalpy of Ti-H systems is usually –34.5 kcal/mol.H2 (–144.40 kJ/mol.H2),
Maximum capacity is 4.177 wt. % H2.[9]
D
400~500 C
ZZZZZZ
Ti + H 2 YZZZZZ X
Z TiH 2
> 600D C

There are three steps within hydrogenation reaction, as follows, involving three different phases, a)
α-phase: cubic structure, solid solution, max solubility=0.1; b) β-phase: square structure, first
hydride phase, TiFeH1.04; c) γ-phase: cubic structure, second hydride phase, TiFeH1.95.
TiFe + H 2 → TiFeH 0.1 ( solid − solution)
2.13TiFeH 0.1 + H 2 U 2.13TiFeH1.04
2.2TiFeH1.04 + H 2 U 2.2TiFeH1.95
The graph below illustrates typical P-C-T of TiFe-H system.
As T<55℃, there are two pressure plateaus due to two hydride
phases. As T>55℃, there is only one pressure plateau due to
non-coexistence of β-phase and γ-phase (γ→β continuously transition). From the graph we can
find Ti- alloy with high capacity of 1.86 wt. % (210 ml/g) at room temperature, good
thermodynamic -∆H= -6.7 kcal/mol.H2 (-28.04 kJ/mol.H2), good kinetics after activation (high
absorption/ desorption rate) and low cost (￥20/kg TiFe, ￥120/kg LaNi5). However, some
demerits limit its application, such as sluggish activation (inactivity), big hysteresis ln(Pa/Pd)TiFe
= 0.64 > ln(Pa/Pd)LaNi5 = 0.19 and easily be poisoned by O2, H2O, CO2, CO, Cl2, etc. Raising
reaction temperature and the pressure of H2－heated at 400~450℃ and 10-3 torr vacuum can
overcome the sluggish activation. Surface modification treatment, such as milling with LaNi5;
soaking treatment in acid or alkali solution, can wipe off the additional impurity.

4. Improvement of recent Hydrogen Storage Alloy

a) Exploring new materials that have ultra large adsorption area

A major mechanism for hydrogen storage is physical or chemical adsorption of hydrogen
molecules onto a material’s surface. It is believed that the enhancement of hydrogen storage
capacity can be achieved with an increase in surface area.
One kind of material is a nanostructured continuous three-dimensional metal alloy. The
nanostructure will have a large surface area. In addition, the surface could be continuous and open,
which not only enhances the hydrogen storage capacity, but also facilitates materials
transportation, and therefore increases the hydrogen adsorption and desorption kinetics.
For nanoporous polymers, aromatic polymer backbones and pendant groups will be utilized
to enhance H2 binding. Pyrolysis of the resulting materials is believed that it can potentially
increase surface area and H2 binding. Such solid state organic compounds contain large void space
in their solid state structure, and are supposed to be able to store sufficient amounts of hydrogen.
Additional expectations are that the hydrogen release will occur with a small temperature change,
which requires only a small amount of energy.
b) Incorporating highly active sites into adsorption areas
While exploring materials with larger surface area, Alivisatos et al.[10] are attempting to
incorporate highly active adsorption sites into absorption areas.With the perception that H2
binding enthalpies vary with changes in coordinatively unsaturated metal M, they propose to
introduce square pyramidal [Co(CN)5]3− into nanoporous coordination solids. They expect that the
rigid framework of aromatic rings in the nanoporous solids will pin coordinatively unsaturated
metal centers thus preventing aggregation. Such a structure would give a larger number of open
coordination sites and enhance H2 uptake capability.
c) Introducing new adsorption/desorption mechanisms
In their research on carbon-doped nanocomposite materials, Stefanakos et al. [10] introduced
new mechanisms to the hydrogen adsorption process. They believe that ionization of the host
materials as well as hydrogen molecules could enhance hydrogen adsorption. Similarly, Yaghi and
Matzger also proposed a structure polarization approach to further enhance hydrogen adsorption
capability in their MOF materials.
A project under investigation by Shelby and Hall[10] is aimed at storing hydrogen in hollow
glass microspheres (HGM). In this process, hydrogen diffuses through the thin wall of the HGM at
elevated temperatures and pressures, and the gas is then trapped in the HGM uponcooling to room
temperature. They introduced a “photo-enhanced out gassing” mechanism. The mechanism has
been validated with a monolithic glass plate, from which the release rate of hydrogen was greatly
accelerated by radiation emitted from an infrared lamp.
Alivisatos et al. [10] have a similar view on this new mechanism, i.e. improving hydrogen
storage capability through modification of the electronic configuration of host materials. The
nanoporous polymers they will investigate include conductive polymers, which may be able to
store hydrogen through a charge transfer into the conduction band, resulting in an electrically
activated uptake and release mechanism.
d) Seeking high hydrogen-content compounds
While conventional metal hydrides appear inadequate for hydrogen storage due to their low
gravimetric hydrogen uptake, Shaw et al. [10] have turned their attention to lithium nitridebased
materials. Their effort is to reduce the hydrogen sorption/desorption temperatures and to further
increase hydrogen storage capacity in the basic compound LiNH2.
Damle’s group[10] started a project to investigate the feasibility of boron nitrogen hydride for
hydrogen storage. The compound is named aminoborane and has a chemical formula of NH3BH3.
Their primary research tasks are to find a method to efficiently heat the aminoborane for hydrogen
release and a way to hydrogenate the boron nitride back into aminoborane economically.
Another novel material, under investigation by Hwang et al.[10], is called perhydride. The
concept of perhydride materials is based on the versatile bonding capability of hydrogen and its
ability to form various ion clusters. So far the reported hydrogen ion clusters that have been
identified and isolated include H+5, H+7, H+9, H+11, H+13, H+15, H−16.[11,12] Furthermore,
observations of complex structures composed of hydrogen ion clusters and water molecules,
H3O+(H2)2,H3O+(H2)3 and H3O+(H2)4, and even H3O+(H2)10 have been reported.

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