U.S. patent application number 12/659370 was filed with the patent office on 2010-09-16 for hydrogen storage alloy, preparation process thereof, and hydrogen storage device.
This patent application is currently assigned to KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO. Invention is credited to Masakazu Aoki, Mamoru Ishikiriyama, Akio Itoh, Tatsuo Noritake, Shinichi Towata, Kota Washio.
Application Number | 20100230299 12/659370 |
Document ID | / |
Family ID | 42729816 |
Filed Date | 2010-09-16 |
United States Patent
Application |
20100230299 |
Kind Code |
A1 |
Aoki; Masakazu ; et
al. |
September 16, 2010 |
Hydrogen storage alloy, preparation process thereof, and hydrogen
storage device
Abstract
The hydrogen storage alloy has, as a main phase thereof, a bcc
structure phase having a composition represented by
Ti.sub.xCr.sub.yV.sub.zX.sub.w wherein 3/2.ltoreq.y/x.ltoreq.3/1,
50.ltoreq.z.ltoreq.75 mol %, 0.ltoreq.w.ltoreq.5 mol %, and
x+y+z+w=100 mol %, and X represents any one or more selected from
Al, Si, and Fe. The hydrogen storage device is a device using the
alloy. The preparation process of a hydrogen storage alloy includes
the steps of: melting/casting raw materials mixed to give the
composition represented by Ti.sub.xCr.sub.yV.sub.zX.sub.w;
heat-treating an ingot obtained in the melting/casting step; and
subjecting the heat-treated ingot to a hydrogen storing/releasing
treatment at least once to activate the ingot.
Inventors: |
Aoki; Masakazu; (Nagoya-shi,
JP) ; Towata; Shinichi; (Nagoya-shi, JP) ;
Noritake; Tatsuo; (Nagoya-shi, JP) ; Itoh; Akio;
(Nagoya-shi, JP) ; Washio; Kota; (Susono-shi,
JP) ; Ishikiriyama; Mamoru; (Fujieda-shi,
JP) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 320850
ALEXANDRIA
VA
22320-4850
US
|
Assignee: |
KABUSHIKI KAISHA TOYOTA CHUO
KENKYUSHO
Aichi-Gun
JP
|
Family ID: |
42729816 |
Appl. No.: |
12/659370 |
Filed: |
March 5, 2010 |
Current U.S.
Class: |
206/.7 ;
164/76.1; 420/424; 420/583; 420/588 |
Current CPC
Class: |
C22C 30/00 20130101;
Y02E 60/32 20130101; C22F 1/18 20130101; C22C 27/02 20130101; Y02E
60/327 20130101; C01B 3/0031 20130101 |
Class at
Publication: |
206/7 ; 164/76.1;
420/424; 420/583; 420/588 |
International
Class: |
B65B 3/00 20060101
B65B003/00; B22D 23/00 20060101 B22D023/00; C22C 27/02 20060101
C22C027/02; C22C 30/00 20060101 C22C030/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 13, 2009 |
JP |
2009-061932 |
Nov 11, 2009 |
JP |
2009-258344 |
Claims
1. A hydrogen storage alloy comprising, as a main phase thereof, a
bcc structure phase having a composition represented by the
following formula (1): Ti.sub.xCr.sub.yV.sub.zX.sub.w (1) wherein,
3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, and x+y+z+w=100 mol %, and X represents
any one or more selected from Al, Si, and Fe.
2. The hydrogen storage alloy according to claim 1, wherein
3/2<y/x.ltoreq.3/1 and 50.ltoreq.z<70 mol %.
3. The hydrogen storage alloy according to claim 2, wherein
55.ltoreq.z<70 mol %.
4. The hydrogen storage alloy according to claim 2, wherein
3/2<y/x.ltoreq.3/1.2.
5. The hydrogen storage alloy according to claim 2, wherein
3/2<y/x.ltoreq.3/1.2 and 55.ltoreq.z<70 mol %.
6. The hydrogen storage alloy according to claim 2, wherein
3/1.65<y/x.ltoreq.3/1.35 and 60.ltoreq.z.ltoreq.68 mol %.
7. The hydrogen storage alloy according to claim 1, wherein
3/2.ltoreq.y/x.ltoreq.3/1 and 70<z.ltoreq.75 mol %.
8. A preparation process of a hydrogen storage alloy comprising: A
melting/casting step of melting/casting raw materials mixed to give
a composition represented by the following formula (1):
Ti.sub.xCr.sub.yV.sub.zX.sub.w (1) wherein
3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents any
one or more selected from Al, Si, and Fe; a heat-treating step of
heat-treating an ingot obtained in the melting/casting step; and an
activation step of activating the heat-treated ingot by subjecting
the ingot to a hydrogen storing/releasing treatment at least
once.
9. A hydrogen storage device, comprising: the hydrogen storage
alloy according to claim 1, a container for placing the hydrogen
storage alloy therein, and a heat exchanger for controlling the
temperature of the hydrogen storage alloy placed in the container.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a hydrogen storage alloy
capable of storing and releasing hydrogen in a reversible manner, a
preparation process of the hydrogen storage alloy, and a hydrogen
storage device using the hydrogen storage alloy.
[0002] Hydrogen energy has recently been drawing attention as a
clean alternative energy in view of environmental problems such as
global warming due to emission of a carbon dioxide gas or energy
problems such as depletion of petroleum resources. For
industrialization of the hydrogen energy, it is important to
develop technologies for storing and transporting hydrogen with
safety. There are some candidates for the storage method of
hydrogen. Among them, a method of using a hydrogen storage material
capable of storing and releasing hydrogen in a reversible manner
are considered as the safest means for storing/transporting
hydrogen. It is expected as a hydrogen storage medium to be
installed on fuel cell cars.
[0003] As the hydrogen storage material, carbon materials such as
activated carbon, fullerene, and nanotube, and hydrogen storage
alloys such as LaNi.sub.5 and TiFe are known. Of these, hydrogen
storage alloys are promising as hydrogen storage materials for
storing/transporting hydrogen because of a high hydrogen density
per unit volume compared with carbon materials.
[0004] As hydrogen storage alloys that can store/release hydrogen
at about a room temperature and therefore permit easy control, and
are suited for practical use, LaNi.sub.5, TiFe alloy, V--Ti--Cr
alloy, and the like are known. Of these, LaNi.sub.5 and TiFe alloy
have a problem that a hydrogen storage amount per weight is small.
On the other hand, the V--Ti--Cr alloy is characterized in that it
can store a larger amount of hydrogen per weight than the above
two.
[0005] There have been various proposals on the V--Ti--Cr
alloy.
[0006] For example, Patent Document 1 discloses a
Ti.sub.xCr.sub.yV.sub.z alloy (x=from 5 to 70, y=from 20 to 70,
z=from 10 to 30) and a Ti.sub.25Cr.sub.35V.sub.40 alloy having a
regular periodic structure formed by spinodal decomposition.
[0007] According to the document,
[0008] (1) the Ti.sub.xCr.sub.yV.sub.z alloy has a maximum hydrogen
absorption/release amount (1.4H/M) when the apparent lattice
constant of two phases formed by spinodal decomposition is around
0.3040 nm; and
[0009] (2) the Ti.sub.25Cr.sub.35V.sub.40 alloy after
heat-treatment has a hydrogen storage amount (maximum hydrogen
storage amount) of about 3.7 wt %.
[0010] Patent Document 2 discloses a
Ti.sub.28.3Cr.sub.50.3V.sub.19.2Fe.sub.1.7Al.sub.0.5 alloy, a
Ti.sub.30Cr.sub.50V.sub.20 alloy, a
Ti.sub.30Cr.sub.50V.sub.19Cu.sub.1 alloy, a
Ti.sub.25Cr.sub.50V.sub.20Fe.sub.4Ni.sub.1 alloy, and a
Ti.sub.25Cr.sub.55V.sub.5Mo.sub.10Fe.sub.5 alloy.
[0011] According to the document,
[0012] (1) when the alloy after homogenization heat-treatment is
cooled at a cooling rate of from 10 to 200.degree. C./hour to a
mixed phase region of a BCC structure phase and a C15 Laves phase,
the precipitation of needle-like .alpha.-Ti in crystal grain is
suppressed, crystal completeness of the BCC structure is improved,
and the effective hydrogen transfer amount increases, and
[0013] (2) when the alloy after homogenization heat-treatment is
subjected to water quenching treatment, the effective hydrogen
amount is in the range from 235 to 262 cc/g, while when the alloy
after homogenization heat-treatment is slowly cooled at a
predetermined cooling rate, the effective hydrogen amount is in the
range from 261 to 281 cc/g.
[0014] Patent Document 3 discloses a V.sub.70Ti.sub.12Cr.sub.18
alloy, a V.sub.40Ti.sub.24Cr.sub.36 alloy, and a
V.sub.60Ti.sub.16Cr.sub.24 alloy.
[0015] According to the document, when the alloy composition is
optimized, hydrogen absorbed in the alloy in a low-pressure plateau
region or a lower plateau region of a sloping plateau becomes
unstable, making it possible to release hydrogen from these
regions.
[0016] Patent Document 4 discloses a
Ti.sub.15.0Cr.sub.34.7V.sub.49.8Al.sub.0.5 alloy.
[0017] The document describes that addition of Al to a Ti--Cr--V
alloy improves plateau flatness.
[0018] Patent Document 5 discloses a hydrogen storage alloy
available by mechanical milling of a V-10% Ti-20% Cr alloy in a
hydrogen atmosphere.
[0019] According to the document, the milling treatment
simultaneously achieves reduction in the particle size and
homogenization of the composition. This results in a reduction in
the hysteresis.
[0020] Patent Document 6 discloses a
Ti.sub.20Cr.sub.45V.sub.30Mo.sub.5 alloy, a
Ti.sub.25Cr.sub.50V.sub.20Mo.sub.5 alloy, a
Ti.sub.25Cr.sub.40V.sub.25Mo.sub.10 alloy, and a
Ti.sub.25Cr.sub.40V.sub.20Mo.sub.15 alloy.
[0021] According to the document, hydrogen release characteristics
in a low-temperature region can be improved by optimizing the
chemical composition and the crystal structure and lattice constant
of the main phase.
[0022] In order to put a hydrogen storage alloy into practical use,
the initial value of a hydrogen amount (effective hydrogen amount)
that can be stored and released in a reversible manner should be
high and time-dependent deterioration in the effective hydrogen
amount should be less (in other words, cycle durability is
excellent). Conventional alloys, however, are excellent in only one
of the initial effective hydrogen amount and the cycle durability.
An alloy excellent in both has not been developed yet.
[Patent Document 1] Japanese Patent Application Laid-Open No.
H10-110225
[Patent Document 2] Japanese Patent Application Laid-Open No.
2004-169102
[Patent Document 3] Japanese Patent Application Laid-Open No.
2000-345273
[0023] [Patent Document 4] Japanese Patent Application Laid-Open
No. H11-106859
[Patent Document 5] Japanese Patent Application Laid-Open No.
2001-11560
[Patent Document 6] Japanese Patent Application Laid-Open No.
2006-188737
SUMMARY OF THE INVENTION
[0024] An object of the invention is to provide a hydrogen storage
alloy having a high initial effective hydrogen amount and excellent
cycle durability; and a preparation process of the hydrogen storage
alloy.
[0025] Another object of the invention is to provide a hydrogen
storage device using a hydrogen storage alloy having a high initial
effective hydrogen amount and excellent cycle durability.
[0026] In order to overcome the above-described problems, a
hydrogen storage alloy according to the invention has, as a main
phase thereof, a bcc structure phase having a composition
represented by the following formula (1):
Ti.sub.xCr.sub.yV.sub.zX.sub.w (1)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents any
one or more selected from Al, Si, and Fe.
[0027] A preparation process of a hydrogen storage alloy according
to the invention includes: a melting/casting step of
melting/casting raw materials mixed to give a composition
represented by the following formula (1):
Ti.sub.xCr.sub.yV.sub.zX.sub.w (1)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents any
one or more selected from Al, Si, and Fe; a heat-treating step of
heat-treating an ingot obtained in the melting/casting step; and an
activation step of activating the heat-treated ingot by subjecting
the ingot to hydrogen storing/releasing treatment at least
once.
[0028] A hydrogen storage device according to the invention has the
hydrogen storage alloy according to the invention, a container for
placing the hydrogen storage alloy therein, and a heat exchanger
for controlling the temperature of the hydrogen storage alloy
placed in the container.
[0029] When the Cr/Ti ratio (y/x) of a Ti--Cr--V alloy is
optimized, an initial effective hydrogen amount can be increased
while keeping a plateau pressure within a practically adequate
range. In addition, when the amount of V is optimized, cycle
durability can be improved while maintaining the initial effective
hydrogen amount at a high level. Further, when the alloy contains
predetermined amounts of Al, Si, and/or Fe, the plateau pressure
can be raised and at the same time, cycle durability can be
improved without causing a drastic decrease in the maximum hydrogen
amount.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 includes X-ray diffraction patterns of alloys after
heat-treatment obtained in Examples 1 to 4;
[0031] FIG. 2 is a pressure-composition isotherm of the alloy
obtained in Example 1 during an initial hydrogen desorption process
at a room temperature;
[0032] FIG. 3 illustrates cycle durability of each of alloys
obtained in Examples 1 and 4, and Comparative Examples 1 and 3 at a
room temperature (Example 1 and Comparative Example 3) and
0.degree. C. (Example 4 and Comparative Example 1 (.largecircle.,
.diamond-solid., .DELTA., and .box-solid. are measured values, each
curve shows an approximate curve of the measured value);
[0033] FIG. 4 illustrates the relationship between a y/x ratio of a
Ti.sub.xCr.sub.yV.sub.z alloy (z=75) and an initial effective
hydrogen amount or cycle durability;
[0034] FIG. 5 illustrates the relationship between a y/x ratio of a
Ti.sub.xCr.sub.yV.sub.z alloy (z=65) and an initial effective
hydrogen amount or cycle durability;
[0035] FIG. 6 illustrates the relationship between a y/x ratio of a
Ti.sub.xCr.sub.yV.sub.z alloy (z=50) and an initial effective
hydrogen amount or cycle durability;
[0036] FIG. 7 illustrates the relationship between a y/x ratio of a
Ti.sub.xCr.sub.yV.sub.z alloy (z=40) and an initial effective
hydrogen amount or cycle durability;
[0037] FIG. 8 illustrates the relationship between z of a
Ti.sub.xCr.sub.yV.sub.z alloy (y/x=1.5) and an initial effective
hydrogen amount or cycle durability;
[0038] FIG. 9 illustrates the relationship between z of a
Ti.sub.xCr.sub.yV.sub.z alloy (y/x=2.0) and an initial effective
hydrogen amount or cycle durability; and
[0039] FIG. 10 illustrates the relationship between z of a
Ti.sub.xCr.sub.yV.sub.z alloy (y/x=2.5) and an initial effective
hydrogen amount or cycle durability.
DETAILED DESCRIPTION OF THE INVENTION
[0040] One embodiment of the present invention will hereinafter be
described specifically.
1. Hydrogen Storage Alloy
[0041] The hydrogen storage alloy according to the invention has,
as a main phase thereof; a bcc structure phase having a composition
represented by the following formula (1))
Ti.sub.xCr.sub.yV.sub.zX.sub.w (1)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents any
one or more selected from Al, Si, and Fe;
1.1. Composition of Alloy
1.1.1. y/x
[0042] The term "maximum hydrogen amount" as used herein means the
maximum hydrogen amount that can be taken out from the alloy
theoretically. In addition, the term "effective hydrogen amount" as
used herein means a hydrogen amount that can be stored and released
in a reversible manner within a range of from 0.01 to 10 MPa.
[0043] The symbol x represents an amount (mol %) of Ti contained in
the alloy. The symbol y represents an amount (mol %) of Cr
contained in the alloy. The y/x means a molar ratio of the amount
of Cr to the amount of Ti (Cr/Ti) in the alloy.
[0044] With a decrease in the y/x ratio (in other words, with an
increase in the Ti amount), the maximum hydrogen amount increases.
When the y/x ratio becomes too small, however, a plateau pressure
decreases. An excessive reduction in the plateau pressure leads to
a reduction in the effective hydrogen amount because pressure
reduction is necessary in order to release hydrogen from the alloy.
Accordingly, the y/x ratio should be 3/2 or greater. The y/x ratio
is more preferably 3/1.65 or greater.
[0045] With an increase in the y/x ratio (in other words, with an
increase in the Cr amount), a plateau pressure increases and
release of hydrogen is facilitated. When the plateau pressure
becomes too large, however, a high pressure should be applied to
store hydrogen. In addition, when the y/x ratio becomes too large,
the maximum hydrogen amount decreases. Accordingly, the y/x ratio
should be 3/1 or less. The y/x ratio is more preferably 3/1.2 or
less, more preferably 3/1.35 or less.
1.1.2. z
[0046] The symbol z represents an amount (mol %) of V contained in
the alloy. With a decrease in z (in other words, with a decrease in
the amount of V), the cycle durability deteriorates. In order to
achieve higher cycle durability, z should be 40 mol % or greater.
The z is more preferably 50 mol % or greater, still more preferably
55 mol % or greater, still more preferably 57.5 mol % or greater,
still more preferably 60 mol % or greater.
[0047] On the other hand, an excessive increase in the amount of V
causes a decrease in the initial amount of the effective hydrogen
amount (initial effective hydrogen amount). Accordingly, z should
be 75 mol % or less.
[0048] In order to obtain a hydrogen storage alloy especially
excellent in the initial effective hydrogen amount, z is preferably
less than 70 mol %. The z is more preferably 68 mol % or less.
[0049] On the other hand, in order to obtain a hydrogen storage
alloy especially excellent in cycle durability, z preferably
exceeds 70 mol % but not greater than 75 mol %. The z is more
preferably 71 mol % or greater, and still more preferably 72 mol %
or greater.
1.1.3. w
[0050] The symbol w represents an amount (mol %) of an element X
contained in the alloy. The "X" represents any one or more elements
selected from Al, Si, and Fe.
[0051] The element X is not an essential element, but addition of
it can raise the plateau pressure and at the same time, improve the
cycle durability without causing a drastic reduction in the maximum
hydrogen amount.
[0052] When w becomes too large, on the other hand, the effective
hydrogen amount decreases drastically. Accordingly, w should be 5
mol % or less. The w is more preferably 3 mol % or less, still more
preferably 2 mol % or less.
1.2. Specific Example of Alloy Composition
[0053] The hydrogen storage alloy represented by the formula (1)
has a relatively high initial effective hydrogen amount and
relatively high cycle durability. Further optimization of the
components enables to obtain a hydrogen storage alloy having
improved initial effective hydrogen amount and/or cycle durability.
The following are specific examples of such an improved alloy.
1.2.1. First Specific Example
[0054] A first specific example of a hydrogen storage alloy has, as
a main phase thereof, a bcc structure phase having a composition
represented by the following formula (2):
Ti.sub.xCr.sub.yV.sub.zX.sub.w (2)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 50.ltoreq.z.ltoreq.70 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents at
least one element selected from Al, Si, and Fe.
[0055] In the formula (2), an increase in z causes an increase in
the initial effective hydrogen amount. When z becomes too large,
however, the initial effective hydrogen amount sometimes decreases.
In the formula (2), an increase in z leads to improvement in the
cycle durability.
[0056] In order to achieve both a high initial effective hydrogen
amount and high cycle durability, z is preferably 55 mol % or
greater. The z is more preferably 57.5 mol % or greater, and still
more preferably 60 mol % or greater.
[0057] Similarly, in order to achieve both a high initial effective
hydrogen amount and high cycle durability, z is preferably 68 mol %
or less.
[0058] In the formula (2), with an increase in the y/x ratio, the
initial effective hydrogen amount increases. When the y/x ratio
becomes too large, however, the initial effective hydrogen amount
decreases. Similarly in the formula (2), an increase in the y/x
ratio leads to improvement in the cycle durability. However, an
excessive increase in the y/x ratio sometimes causes deterioration
in the cycle durability.
[0059] In order to achieve both a high initial effective hydrogen
amount and high cycle durability, the y/x ratio is preferably
3/1.65 or greater.
[0060] Similarly, in order to achieve both a high initial effective
hydrogen amount and high cycle durability, the y/x ratio is
preferably 3/1.2 or less, and more preferably 3/1.35 or less.
[0061] Further, in the formula (2), an initial effective hydrogen
amount and cycle durability can be satisfied at a high level by
carrying out optimization of the y/x ratio and z in the formula (2)
simultaneously. The following are preferable ranges of the y/x
ratio and z.
(a) 3/2<y/x.ltoreq.3/1.2, 55.ltoreq.z<70 mol % (b)
3/2<y/x.ltoreq.3/1.2, 57.5.ltoreq.z<70 mol % (c)
3/2<y/x.ltoreq.3/1.35, 57.5.ltoreq.z<70 mol % (d)
3/1.65.ltoreq.y/x.ltoreq.3/1.35, 57.5.ltoreq.z<70 mol % (e)
3/2<y/x.ltoreq.3/1.2, 60.ltoreq.z.ltoreq.68 mol % (f)
3/2<y/x.ltoreq.3/1.35, 60.ltoreq.z.ltoreq.68 mol % (g)
3/1.65.ltoreq.y/x.ltoreq.3/1.35, 60.ltoreq.z.ltoreq.68 mol %
1.2.2. Second Specific Example
[0062] The second specific example of a hydrogen storage alloy has,
as a main phase thereof, a bcc structure phase having a composition
represented by the following formula (3). The hydrogen storage
alloy represented by the formula (3) has an adequate initial
effective hydrogen amount and high cycle durability.
Ti.sub.xCr.sub.yV.sub.zX.sub.w (3)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 70.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents at
least one element selected from Al, Si, and Fe.
[0063] In the formula (3), an increase in z leads to improvement in
cycle durability. An excessive increase in z however deteriorates
the initial effective hydrogen amount.
[0064] In order to achieve both a high initial effective hydrogen
amount and high cycle durability, z is preferably 71 mol % or
greater. The z is more preferably 72 mol % or greater.
[0065] Similarly, in order to achieve both a high initial effective
hydrogen amount and high cycle durability, z is preferably 74 mol %
or less.
[0066] In the formula (3), the greater the y/x ratio, the greater
the initial effective hydrogen amount. An excessive increase in the
y/x ratio, however, deteriorates the initial effective hydrogen
amount. In the formula (3), an increase in the y/x ratio leads to
improvement in the cycle durability. However, an excessive increase
in the y/x ratio may rather cause deterioration in the cycle
durability.
[0067] In order to achieve both a high initial effective hydrogen
amount and high cycle durability, the y/x ratio is preferably
3/1.65 or greater.
[0068] Similarly, in order to achieve both a high initial effective
hydrogen amount and high cycle durability, the y/x ratio is
preferably 3/1.2 or less, more preferably 3/1.35 or less.
[0069] Further, an initial effective hydrogen amount and cycle
durability can be satisfied at a high level by simultaneously
optimizing the y/x ratio and z in the formula (3).
[0070] When priority is given to the initial effective hydrogen
amount, the following are preferable ranges of the y/x ratio and
z.
(a) 3/2.ltoreq.y/x.ltoreq.3/1.2, 70<z.ltoreq.75 mol % (b)
3/1.65.ltoreq.y/x.ltoreq.3/1.35, 71.ltoreq.z.ltoreq.75 mol %
[0071] When priority is given to the cycle durability, on the other
hand, the following are preferable ranges of the z and y/x
ratio.
(a) 3/1.35.ltoreq.y/x.ltoreq.3/1, 70.ltoreq.z.ltoreq.75 mol % (b)
3/1.2.ltoreq.y/x.ltoreq.3/1, 71.ltoreq.z.ltoreq.75 mol %
1.3. bcc Structure Phase
[0072] The hydrogen storage alloy having, as a main phase thereof,
a bcc structure phase represented by the formula (1) can be
obtained by mixing raw materials so as to give the above-described
composition and melting and casting the resulting mixture. The
hydrogen storage alloy is preferably composed only of a bcc
structure phase, but may contain an inevitable impurity. Examples
of the inevitable impurity include pure Ti and TiCr.sub.2 (Laves
phase). An inevitable impurity adversely affecting the hydrogen
storage/release characteristics is preferably as small as
possible.
[0073] In the invention, the term "has, as a main phase thereof, a
bcc structure phase" means that the hydrogen storage alloy contains
the bcc structure phase in an amount of 80 vol. % or greater. The
amount of the bcc structure phase is more preferably 90 vol. % or
greater.
1.4 Particle Size
[0074] The particle size of the hydrogen storage alloy has an
influence on the storage/release characteristics of hydrogen. In
general, an excessive decrease in the particle size of the alloy
leads to an increase in the surface area thereof, which results in
an increase in the surface oxidized layer and a decrease in the
hydrogen storage amount. By pulverizing treatment for many hours
with a view to decreasing the particle size, a strain is introduced
into the hydrogen storage alloy. This results in a decrease in the
hydrogen storage amount or deterioration in the plateau flatness.
Accordingly, the particle size of the hydrogen storage alloy is
preferably 0.1 mm or greater prior to the activation treatment.
[0075] An excessive increase in the particle size of the hydrogen
storage alloy, on the other hand, decreases the surface area. This
requires the activation treatment for many hours, at a high
temperature, and/or at a high pressure. It also increases the
frequency of the activation treatment. Accordingly, the particle
size of the hydrogen storage alloy is preferably 10 mm or less
prior to the activation treatment.
[0076] The term "particle size of the hydrogen storage alloy" means
the size of a sieve opening to be used in a classification test
with a sieve (mesh).
2. Preparation Process of Hydrogen Storage Alloy
[0077] The preparation process of a hydrogen storage alloy
according to the invention has a melting/casting step, a
heat-treatment step, and an activation step.
2.1. Melting/Casting Step
[0078] The melting/casting step is a step of melting/casting raw
materials which have been mixed to give a composition represented
by the formula (1). The details of the formula (1) have already
been described above so that description on them is omitted.
Ti.sub.xCr.sub.yV.sub.zX.sub.w (1)
wherein 3/2.ltoreq.y/x.ltoreq.3/1, 40.ltoreq.z.ltoreq.75 mol %,
0.ltoreq.w.ltoreq.5 mol %, x+y+z+w=100 mol %, and X represents any
one or more selected from Al, Si, and Fe.
[0079] No particular limitation is imposed on the melting/casting
method of the raw materials and various methods such as arc melting
and high-frequency induction melting can be employed.
[0080] In order to prevent deterioration of alloy properties due to
incorporation of a large amount of oxygen, the melting/casting of
the raw materials is performed preferably in a non-oxidizing
atmosphere such as inert gas atmosphere, reducing gas atmosphere,
or vacuum (1.times.10.sup.-1 to 1.times.10.sup.-6 Torr (13.3 to
1.33.times.10.sup.-4 Pa)). Although no particular limitation is
imposed on the melting temperature and melting time, those
permitting to obtain a uniform melt are preferred.
2.2 Heat-Treatment Step
[0081] The heat-treatment step is a step of heat-treating the ingot
obtained in the melting/casting step.
[0082] In general, the bcc structure phase of a TiCrV alloy is a
high-temperature equilibrium phase. Heat-treatment (homogenization
heat-treatment) in a high temperature region where the bcc
structure phase is stable becomes necessary in order to reduce
solidification segregation of each component (particularly,
dendrite-like solidification segregation of Ti and V components)
formed during melting/casting. The homogenization heat-treatment
can increase the plateau flatness and thereby improving the
storage/release characteristics of hydrogen.
[0083] Heat-treatment is performed at a temperature of preferably
1200.degree. C. or greater in order to diffuse the structural
components for a short period of time and homogenizing the
components.
[0084] The heat-treatment temperature is preferably not greater
than the melting point of the alloy in order to suppress partial
melting of the alloy. The heat-treatment temperature is more
preferably a temperature lower by 20 to 100.degree. C. than the
melting point of the alloy.
[0085] The longer heat-treatment time is generally preferred to
achieve a sufficient homogenizing effect. Specifically, it is
preferably 1 hour or greater.
[0086] Heat-treatment for too many hours, on the other hand, does
not bring about an effect corresponding to an increase in the
heat-treatment time and is therefore of no practical use so that
heat-treatment time is preferably 24 hours or less.
[0087] The heat-treatment is conducted preferably in a
non-oxidizing atmosphere such as inert gas atmosphere, reducing gas
atmosphere, or vacuum (1.times.10.sup.-1 to 1.times.10.sup.-6 Torr
(13.3 to 1.33.times.10.sup.-4 Pa)).
2.3 Activation Step
[0088] The activation step is a step of activating the heat-treated
ingot by subjecting the ingot to hydrogen storing/releasing
treatment at least once.
[0089] The activation treatment is performed by reducing the
pressure while heating the ingot to a predetermined temperature and
then bringing the ingot into contact with pressurized hydrogen.
[0090] An excessively low activation treatment temperature makes it
difficult to store hydrogen in the ingot. The activation
temperature is therefore preferably 300.degree. C. or greater.
[0091] When the activation treatment temperature becomes
excessively high, there is a possibility of the structure, which
has been homogenized, becoming inhomogeneous. Accordingly, the
activation treatment temperature is preferably 450.degree. C. or
less.
[0092] Although no particular limitation is imposed on the pressure
upon pressure reduction and the hydrogen pressure upon hydrogen
storage, they may be pressures at which full activation can be
carried out. The pressure upon pressure reduction is usually about
1.times.10.sup.-4 Torr (about 1.33.times.10.sup.-2 Pa). The
hydrogen pressure upon hydrogen storage is usually about 50 atom
(5.07 MPa).
[0093] In the hydrogen storage alloy according to the invention,
the activation treatment is required to be performed at least once.
It is generally necessary to repeat, several times, the activation
treatment for obtaining a hydrogen storage alloy, but in the
hydrogen storage alloy according to the invention, it is possible
to achieve sufficient activation by the activation treatment only
once.
3. Hydrogen Storage Device
[0094] The hydrogen storage device according to the invention is
equipped with the hydrogen storage alloy of the invention, a
container, and a heat exchanger.
[0095] Details of the hydrogen storage alloy according to the
invention have already been described so that the description on it
is omitted here.
[0096] The container is for storing the hydrogen storage alloy
therein. It is sufficient that the container can maintain the inner
part thereof at a predetermined temperature and a predetermined
pressure at storage/release of hydrogen.
[0097] The heat exchanger is for controlling the temperature of the
hydrogen storage alloy placed in the container. In general, heat
absorption or heat generation occurs upon storage/release of
hydrogen. Accordingly, it is necessary to maintain the temperature
of the hydrogen storage alloy within a predetermined range in order
to stably store/release hydrogen. No particular limitation is
imposed on the structure of the heat exchanger and heat exchangers
having various structures can be used.
4. Effects of Hydrogen Storage Alloy and Preparation Process
Thereof, and Hydrogen Storage Device
[0098] Optimization of the Cr/Ti ratio (y/x) in the Ti--Cr--V alloy
enables to increase the initial effective hydrogen amount while
maintaining the plateau pressure within a practically adequate
range.
[0099] Optimization of the amount of V, on the other hand, enables
to improve the cycle durability while maintaining the initial
effective hydrogen amount at a high level. In addition, a
relatively large amount of hydrogen can be stored/released even by
the single activation treatment.
[0100] Further, addition of one or more elements selected from Al,
Si, and Fe to the Ti--Cr--V alloy enables to increase the plateau
pressure and improve the cycle durability without drastically
reducing the maximum hydrogen amount. As a result, the effective
hydrogen amount can be increased.
EXAMPLES
Examples 1 to 6, Comparative Examples 1 to 3
1. Preparation of Sample
[0101] Raw materials mixed at a predetermined ratio were arc-melted
to obtain an ingot. The ingot thus obtained was heat-treated at
1300 to 1350.degree. C. in an Ar atmosphere. The alloy thus
heat-treated is then subjected to activation treatment once at 300
to 450.degree. C.
2. Test Method
2.1. X-Ray Diffraction
[0102] The X-ray diffraction measurement of the alloy subjected to
the heat-treatment was performed. From the resulting X-ray
diffraction pattern, a lattice constant was determined.
2.2. Hydrogen Storage/Release Characteristics
[0103] The pressure-composition isotherm measurement of the alloy
subjected to the activation treatment was performed for 10 cycles
at a temperature from -20.degree. C. to a room temperature. Based
on the initial effective hydrogen amount and the effective hydrogen
amount at 10th cycle, a maintenance ratio (=(effective hydrogen
amount at 10th cycle).times.100/initial effective hydrogen amount
(%)) was determined.
[0104] Further, the pressure-composition isotherm measurement was
performed for 50 to 100 cycles at a room temperature or 0.degree.
C. to investigate a change in the effective hydrogen amount.
3. Results
[0105] Evaluation results are shown collectively in Table 1. The
composition and heat-treatment conditions of each sample are also
shown in Table 1.
[0106] It is apparent from Table 1 that:
[0107] (1) each of the alloys obtained in Comparative Examples 1
and 2 has a relatively large initial effective hydrogen amount but
has a low maintenance ratio (cycle durability) of the effective
hydrogen amount at 10th cycle;
[0108] (2) the alloy obtained in Comparative Example 3 has high
cycle durability but has a small initial effective hydrogen amount;
and
[0109] (3) each of the alloys obtained in Examples 1 to 6 has a
large initial effective hydrogen amount and high cycle
durability.
TABLE-US-00001 Heat- Effective hydrogen amount treatment Lattice
Initial Amount at maintenance temp. Activation Crystal Constant
Measured amount 10th cycle ratio No. Composition (.degree. C.)
treatment Structure (nm) at (mass %) (mass %) (%) Example 1
V.sub.65.0Ti.sub.11.7Cr.sub.23.3 1350 400.degree. C. .times. bcc
single 0.3026 r.t. 2.51 2.38 95 once phase Example 2
V.sub.64.0Ti.sub.11.7Cr.sub.23.3Si.sub.1.0 1350 400.degree. C.
.times. bcc single 0.3020 0.degree. C. 2.32 2.26 97 once phase
Example 3 V.sub.63.5Ti.sub.11.6Cr.sub.23.1Al.sub.1.8 1350
400.degree. C. .times. bcc single 0.3029 0.degree. C. 2.36 2.25 95
once phase Example 4 V.sub.63.9Ti.sub.11.7Cr.sub.23.4Fe.sub.1.0
1350 450.degree. C. .times. bcc single 0.3023 0.degree. C. 2.42
2.37 98 once phase Example 5 V.sub.75.0Ti.sub.8.3 Cr.sub.16.7 1300
400.degree. C. .times. bcc single -- r.t. 2.37 2.31 97 once phase
Example 6 V.sub.40.0Ti.sub.20.0Cr.sub.40.0 1300 400.degree. C.
.times. bcc main -- 10.degree. C. 2.54 2.29 90 once phase Comp. Ex.
1 V.sub.20.0Ti.sub.25.0Cr.sub.50.0Mo.sub.5.0 1300 300.degree. C.
.times. bcc main 0.3019 0.degree. C. 2.20 1.81 82 once phase Comp.
Ex. 2 V.sub.25.0Ti.sub.25.0Cr.sub.50.0 1300 300.degree. C. .times.
bcc main -- -20.degree. C. 2.50 2.10 84 once phase Comp. Ex. 3
V.sub.75.0Ti.sub.10.0Cr.sub.10.0Mo.sub.5.0 1300 300.degree. C.
.times. bcc main -- r.t. 1.99 1.89 95 once phase
[0110] FIG. 1 includes X-ray diffraction patterns of the alloys
obtained in Examples 1 to 4. It has been confirmed from FIG. 1 that
each of the alloys obtained in Examples 1 to 4 had a bcc single
phase.
[0111] FIG. 2 shows a pressure-composition isotherm of the alloy
obtained in Example 1 during the initial hydrogen desorption
process at a room temperature. The initial effective hydrogen
amount of the alloy obtained in Example 1 is 2.51 mass %.
[0112] FIG. 3 illustrates cycle durability of each of alloys
obtained in Examples 1 and 4, and Comparative Examples 1 and 3 at a
room temperature (Example 1 and Comparative Example 3) and
0.degree. C. (Example 4 and Comparative Example 1).
[0113] It is understood from FIG. 3 that in the alloy obtained in
Comparative Example 1, a reduction amount of the effective hydrogen
amount due to an increase in the number of cycles is relatively
large, while in the alloys obtained in Examples 1 and 4, a
reduction amount of the effective hydrogen amount due to an
increase in the number of cycles is relatively small.
[0114] On the other hand, it has been found that in the alloy
obtained in Comparative Example 3, a reduction amount of the
effective hydrogen amount with an increase in the number of cycles
is relatively small but the initial effective hydrogen amount is
smaller than those of the other examples.
Example 7
1. Preparation of Sample
[0115] In a similar manner to Example 1, various
Ti.sub.xCr.sub.yV.sub.z alloys different in y/x ratio and z were
prepared.
2. Test Method
[0116] In a similar manner to Example 1, an initial effective
hydrogen amount and an effective hydrogen amount at 10th cycle were
measured at from 0 to 50.degree. C. and a maintenance ratio (cycle
durability) was determined based on them.
3. Results
[0117] FIGS. 4 to 10 show initial effective hydrogen amounts and
cycle durability of various Ti.sub.xCr.sub.yV.sub.z alloys. FIGS. 4
to 10 reveal the following findings:
[0118] (1) Within a range of 3/1.65.ltoreq.y/x.ltoreq.3/1, the
initial effective hydrogen amount reaches the maximum value and at
the same time, an increase in the y/x ratio leads to improvement in
cycle durability.
[0119] (2) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1 and
65.ltoreq.z.ltoreq.75, the initial effective hydrogen amount
becomes 2.2 mass % or greater and the cycle durability becomes 94%
or greater.
[0120] (3) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1.2 and
50.ltoreq.z<65, the initial effective hydrogen amount becomes
2.2 mass % or greater and the cycle durability becomes 91% or
greater.
[0121] (4) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1 and
50.ltoreq.z.ltoreq.75, the initial effective hydrogen amount
becomes 2.2 mass % or greater and the cycle durability becomes 91%
or greater.
[0122] (5) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1.2 and
40.ltoreq.z<50, the initial effective hydrogen amount becomes
1.8 mass % or greater and the cycle durability becomes 90% or
greater.
[0123] (6) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1.5 and
40.ltoreq.z<50, the initial effective hydrogen amount becomes
2.3 mass % or greater and the cycle durability becomes 90% or
greater.
[0124] (7) Within a range of 3/1.5.ltoreq.y/x.ltoreq.3/1.2 and
65.ltoreq.z.ltoreq.75, the initial effective hydrogen amount
becomes 2.3 mass % or greater and the cycle durability becomes 95%
or greater.
[0125] (8) Within a range of 3/1.5.ltoreq.y/x.ltoreq.3/1.2 and
50.ltoreq.z.ltoreq.65, the initial effective hydrogen amount
becomes 2.2 mass % or greater and the cycle durability becomes 92%
or greater.
[0126] (9) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1.2 and
65.ltoreq.z.ltoreq.75, the initial effective hydrogen amount
becomes 2.3 mass % or greater and the cycle durability becomes 94%
or greater.
[0127] (10) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1.5 and
50.ltoreq.z.ltoreq.65, the initial effective hydrogen amount
becomes 2.3 mass % or greater and the cycle durability becomes 91%
or greater.
[0128] (11) Within a range of 3/2<y/x.ltoreq.3/1 and
50.ltoreq.z<70 mol %, the hydrogen storage alloy has adequate
cycle durability and a high initial effective hydrogen amount.
[0129] Particularly, within a range of
3/1.65.ltoreq.y/x.ltoreq.3/1.35 and 60.0.ltoreq.z.ltoreq.68 mol %,
the resulting hydrogen storage alloy can achieve both cycle
durability and an initial effective hydrogen amount at a high
level.
[0130] (12) Within a range of 3/2.ltoreq.y/x.ltoreq.3/1 and
70<z.ltoreq.75 mol %, the hydrogen storage alloy has an adequate
initial effective hydrogen amount and high cycle durability.
[0131] Particularly, within a range of
3/1.65.ltoreq.y/x.ltoreq.3/1.35 and 71.ltoreq.z.ltoreq.75 mol %,
the resulting hydrogen storage alloy has a high initial effective
hydrogen amount.
[0132] Within a range of 3/1.2.ltoreq.y/x.ltoreq.3/1 and
71.ltoreq.z.ltoreq.75 mol %, the resulting hydrogen storage alloy
has considerably high cycle durability.
Example 8
[0133] A V.sub.40Ti.sub.18.4Cr.sub.41.6 alloy was prepared by arc
melting V, Ti, and Cr and then heat-treating the resulting ingot at
1300.degree. C. in an Ar atmosphere. The X-ray diffraction analysis
of the resulting alloy was performed. It revealed that the alloy
had, as a main phase thereof, a BCC phase. Pressure-composition
isotherm measurement of the heat-treated alloy at 0.degree. C. was
performed 10 cycles. The initial effective hydrogen amount was 2.29
mass %. On the other hand, the effective hydrogen amount at the
10th cycle was 2.07 mass % (90% of the initial amount).
Comparative Example 4
[0134] A V.sub.40Ti.sub.25Cr.sub.35 alloy was prepared by arc
melting V, Ti, and Cr and then heat-treating the resulting ingot at
1260.degree. C. in an Ar atmosphere. The X-ray diffraction analysis
of the resulting alloy was performed. It revealed that the alloy
had a BCC single phase. Pressure-composition isotherm measurement
of the heat-treated alloy at 50.degree. C. was performed 10 cycles.
The initial effective hydrogen amount was 2.26 mass %. On the other
hand, the effective hydrogen amount at the 10th cycle was 2.00 mass
% (88% of the initial amount).
Comparative Example 5
[0135] A V.sub.20Ti.sub.35Cr.sub.45 alloy was prepared by arc
melting V, Ti, and Cr and then heat-treating the resulting ingot at
1350.degree. C. in an Ar atmosphere. The X-ray diffraction analysis
of the resulting alloy was performed. It revealed that the alloy
had, as a main phase thereof, a BCC phase. Pressure-composition
isotherm measurement of the heat-treated alloy at 50.degree. C. was
performed 10 cycles. The initial effective hydrogen amount was 2.17
mass %. On the other hand, the effective hydrogen amount at the
10th cycle was 1.81 mass % (84% of the initial amount).
Comparative Example 6
[0136] A V.sub.25Ti.sub.42Cr.sub.33 alloy was prepared by arc
melting V, Ti, and Cr and then heat-treating the resulting ingot at
1260.degree. C. in an Ar atmosphere. The X-ray diffraction analysis
of the resulting alloy was performed. It revealed that it had, as a
main phase thereof, a BCC phase. Pressure-composition isotherm
measurement of the heat-treated alloy at 50.degree. C. was
performed 10 cycles. The initial effective hydrogen amount was 0.34
mass %. On the other hand, the effective hydrogen amount at the
10th cycle was 0.28 mass % (83% of the initial amount).
Comparative Example 7
[0137] A V.sub.21Ti.sub.50Cr.sub.29 alloy was prepared by arc
melting V, Ti, and Cr and then heat-treating the resulting ingot at
1260.degree. C. in an Ar atmosphere. The X-ray diffraction analysis
of the resulting alloy was performed. It revealed that the alloy
had, as a main phase thereof, a BCC phase. Pressure-composition
isotherm measurement of the heat-treated alloy at 50.degree. C. was
performed 10 cycles. The initial effective hydrogen amount was 0.26
mass %. On the other hand, the effective hydrogen amount at the
10th cycle was 0.23 mass % (88% of the initial amount).
[0138] Although some embodiments of the invention have been
described herein specifically, it is to be understood that the
invention is not limited to or by these embodiments and that
various changes and modifications may be effected therein without
departing from the scope of the invention.
[0139] The hydrogen storage alloy and preparation process thereof
according to the invention can be used, respectively, as a hydrogen
storage medium to be used as a hydrogen storage unit for fuel cell
system or a hydrogen storage body for chemical heat pump, actuator,
or metal-hydrogen storage battery and preparation process of the
hydrogen storage alloy.
* * * * *