Title: Carbonaceous material for hydrogen storage, and method for preparation thereof, carbonaceous material having hydrogen absorbed therein and method for preparation thereof, cell and fuel cell usin
Abstract: A hydrogen-stored carbonaceous material is provided. The present invention relates to a hydrogen-stored carbonaceous material obtained by storing hydrogen in a carbonaceous material heated at more than about 230° C. under pressure in a reducing atmosphere, a battery and a fuel cell using same. The carbonaceous material is heated at more than about 230° C. under pressure in a reducing atmosphere so that its surface can be efficiently cleaned and an area where the surface of the carbonaceous material comes into contact with hydrogen atoms or hydrogen molecules is increased.
Patent Number: 7,014,951 Issued on 03/21/2006 to Kajiura, et al.
| Inventors:
|
Kajiura; Hisashi (Kanagawa, JP);
Shiraishi; Masashi (Tokyo, JP);
Negishi; Eisuke (Tokyo, JP);
Ata; Masafumi (Kanagawa, JP)
|
| Assignee:
|
Sony Corporation (Tokyo, JP)
|
| Appl. No.:
|
221887 |
| Filed:
|
March 16, 2001 |
| PCT Filed:
|
March 16, 2001
|
| PCT NO:
|
PCT/JP01/02125
|
| 371 Date:
|
February 27, 2003
|
| 102(e) Date:
|
February 27, 2003
|
| PCT PUB.NO.:
|
WO01/68522 |
| PCT PUB. Date:
|
September 20, 2001 |
Foreign Application Priority Data
| Mar 16, 2000[JP] | 2000-074446 |
| Current U.S. Class: |
429/218.2; 429/20; 429/231.8; 423/445.R; 423/645; 423/447.2 |
| Current Intern'l Class: |
H01M 4/58 (20060101) |
| Field of Search: |
429/2182,20,231.8
423/445.R,645,447.2
|
References Cited [Referenced By]
U.S. Patent Documents
| 6268077 | Jul., 2001 | Kelley et al.
| |
| 2001/0016283 | Aug., 2001 | Shiraishi et al.
| |
| Foreign Patent Documents |
| 0154 165 | Sep., 1985 | EP.
| |
| 60-247073 | Dec., 1985 | JP.
| |
| 10-72291 | Mar., 1989 | JP.
| |
| 5-270801 | Oct., 1993 | JP.
| |
| 10-72201 | Mar., 1998 | JP.
| |
| 2000/-103612 | Apr., 2000 | JP.
| |
| 2000/-264602 | Sep., 2000 | JP.
| |
| WO 99/4002/3 | Aug., 1999 | WO.
| |
| WO 00/7662/5 | Dec., 2000 | WO.
| |
Other References
Dillon et al., "Storage of hydrogen in single-walled carbon nanotubes"
Nature (1997), vol. 386, pp. 377-379.
Yue-Ying Fan et al., "Hydrogen uptake in vapor-grown carbon nanofibers"
Carbon (1999), vol. 37, pp. 1649-1652.
X. B. Wu et al., "Hydrogen uptake by carbon nanotubes", International
Journal of Hydrogen Energy (2000), vol. 25, pp. 261-265.
ECO Industry Publication, vol. 4, No. 7, pp. 12-18 (1999).
Y. Ye et al., "Hydrogen adsorption and cohesive energy of single-walled carbon
nanotubes," Appl. Phys. Let., vol. 74, No. 16, (1999), pp. 2307-2309.
|
Primary Examiner: Weiner; Laura
Attorney, Agent or Firm: Bell, Boyd Lloyd, LLC
Claims
The invention claimed is:
1. A method of producing a hydrogen-storing carbonaceous material, the method
comprising annealing a carbon nanofiber material at a temperature ranging from
about 400° C. to about 800° C. under pressure in a reducing atmosphere
of about 10.1 Pa, wherein the carbon nanofiber material is produced by chemical
vapor deposition.
2. The method according to claim 1, wherein the carbon nanofiber material has
a large surface and a structural curvature.
3. A method of producing a hydrogen-stored carbonaceous material, the method
comprising storing hydrogen in a carbon nanofiber material annealed at a temperature
ranging from about 400° C. to about 800° C. under pressure in a reducing
atmosphere of about 10.1 Pa, wherein the carbon nanofiber material is produced
by chemical vapor deposition.
4. The method according to claim 3, wherein the carbon nanofiber material has
a large surface and a structural curvature.
Description
RELATED APPLICATION DATA
The present application claims priority to Japanese Patent Application No. P2000-074446
filed on Mar. 16, 2000, herein incorporated by reference to the extent permitted
by law.
BACKGROUND OF THE INVENTION
The present invention relates to a hydrogen-storing carbonaceous material and
a method for producing it, a hydrogen-stored carbonaceous material and a method
for producing it and a battery and a fuel cell using a hydrogen-stored carbonaceous
material, and more particularly to a hydrogen-storing carbonaceous material and
a method for producing it, a hydrogen-stored carbonaceous material and a method
for producing it and a battery using the carbonaceous-stored carbonaceous material
and a fuel cell using the hydrogen-stored carbonaceous material.
Fossil fuel such as gasoline, light oil, or the like has and continues to
be widely employed as the energy source for producing an electric power as well
as the energy source of motor vehicles or the like. The fossil fuel not only may
possibly degrade a global environment, but also is exhaustible and questionable
whether or not the fossil fuel can be stably supplied.
Hydrogen has been paid attention to in place of the fossil fuel having the
above described possibilities. The hydrogen is contained in water, inexhaustibly
exists on the earth and includes a large quantity of chemical energy per amount
of material. Further, the hydrogen has advantages as a clean and inexhaustible
energy source by which the fossil fuel is replaced, because the hydrogen does not
discharge harmful substances or global greenhouse gas or the like when it is used
as the energy source.
Especially recently, the fuel cell that an electric energy can be generated
from the hydrogen energy has been studied and developed and it has been expected
that the fuel cell is applied to a large-scale power generation, an onsite private
power generation, and further, to a power supply for a motor vehicle.
On the other hand, since the hydrogen is gaseous under ambient temperature and
ambient pressure, it is treated with more difficulty than liquid or solid. Since
the density of the gas is extremely small as compared with that of liquid or solid,
the chemical energy of the gas is small per volume. Further, it is inconveniently
difficult to store or transport the gas. Still further, since the hydrogen is gas,
it is liable to leak. When the hydrogen leaks, the danger of explosion is undesirably
generated, which results in a great trouble in utilization of the hydrogen energy.
Thus, in order to employ an energy system using the hydrogen energy to practical
use, the development of a technique that the gaseous hydrogen is efficiently and
safely stored in a small volume has been promoted. There have been proposed a method
for hydrogen storage as high pressure gas, a method for hydrogen storage as liquefied
hydrogen and a method for using a hydrogen-storing material, or the like.
In the method for hydrogen storage as the high pressure gas, since a very strong
metallic pressure proof vessel such as a cylinder needs to be used as a storage
vessel, the vessel itself becomes extremely heavy and the density of the high pressure
gas is ordinarily about 12 mg/cc. Accordingly, not only the storage density of
the hydrogen is disadvantageously terribly small and a storage efficiency is low,
but also there has a problem in view of safety because of high pressure.
On the contrary, in the method for hydrogen storage as the liquefied hydrogen,
the storage density is ordinarily about 70 mg/cc. Although the storage density
is considerably high, it is necessary to cool hydrogen down to lower than -250°
C. in order to liquefy, so that an additional device such as a cooling device is
required. Therefore, not only a system has been undesirably complicated, but also
energy for cooling has been needed.
Further, hydrogen-stored alloys are most effective materials among the hydrogen-stored
materials. For instance, there have been known lanthanum-nickel, vanadium, and
magnesium hydrogen-stored alloys. The practical hydrogen storage density of these
hydrogen-stored alloys is generally 100 mg/cc. Although the hydrogen is stored
in these hydrogen-stored alloys, the hydrogen storage density of these alloys is
not lower than that of liquefied hydrogen. Therefore, the use of the hydrogen-storing
materials is the most efficient among conventional hydrogen storage methods. Further,
when the hydrogen-storing alloy is used, the hydrogen can be stored in the hydrogen-storing
alloy and the hydrogen can be discharged from the hydrogen-storing alloy at around
room temperature. Further, since the hydrogen storage condition is controlled under
the balance of the partial pressure of hydrogen, the hydrogen-storing alloy is
advantageously treated more easily than the high pressure gas or the liquefied hydrogen.
However, since the hydrogen-stored alloys consist of metallic alloys, these
are heavy and the amount of stored hydrogen is limited to approximately 20 mg/g
per unit weight, which may not be said to be sufficient. Further, since the structure
of the hydrogen-storing alloy is gradually destroyed in accordance with the repeated
the cycle of storing and discharging of hydrogen gas, a performance is undesirably
deteriorated. Still further, there may arise problems associated with resource
and environmental concerns depending on the composition of the alloy.
Thus, for overcoming the above described issues of the conventional methods
for hydrogen storage, a carbon material is paid attention to as the hydrogen-storing material.
For example, Japanese Patent Application Laid-Open No. hei. 5-270801 proposes
a method that the addition reaction of hydrogen is applied to fullerene to store
hydrogen. In this method, since a chemical bond such as a covalent bond is formed
between a carbon atom and a hydrogen atom, this method is to be called an addition
of hydrogen rather than a hydrogen storage. Since the upper limit of the amount
of hydrogen which can be added by the chemical bonds is essentially restricted
to the number of unsaturated bonds of carbon atoms, the amount of stored hydrogen
is limited.
Further, Japanese Patent Application Laid-Open No. hei. 10-72201 proposes
a technique that fullerene is used as the hydrogen-storing material and the surface
of the fullerene is covered with catalytic metal such as platinum deposited by
a vacuum method or a sputtering method to store hydrogen. In order to employ platinum
as the catalytic metal and cover the surface of fullerene with it, much platinum
needs to be used so that not only a cost is increased, but also a problem is generated
in view of resources.
Known methods for hydrogen storage may be problematic from a practical standpoint
when hydrogen energy is utilized. Especially, when the hydrogen energy is employed
as an energy source for motor vehicles, marine vessels, general domestic power
supplies, various kinds of small electric devices, or the like or when a large
amount of hydrogen needs to be conveyed, the conventional methods for hydrogen
storage is not practical.
SUMMARY OF THE INVENTION
It is an advantage of the present invention to provide a hydrogen-storing carbonaceous
material and a method for producing it, a hydrogen-stored carbonaceous material
and a method for producing it and a battery and a fuel cell using a hydrogen-stored
carbonaceous material which are light-weight, can be repeatedly used in a safe
manner and employ materials in virtually unlimited supply with minimal, if any,
impact on the environment during use.
The inventors of the present invention have found that a hydrogen-storing carbonaceous
material can be obtained by heating a carbonaceous material at more than about
230° C. in a pressure reducing atmosphere.
In order to store a large amount of hydrogen in the carbonaceous material, it
is an important factor to increase an area where the surface of the carbonaceous
material comes into contact with hydrogen atoms or hydrogen molecules when a storing
is carried out in the form of a chemisorption or when the storing is carried out
in the form of a proton storage. Therefore, it is important to clean the surface
of the carbonaceous material and efficiently remove impurities on the surface.
It is known that the carbonaceous material can be subjected to a heating process
at 150° C. or 220° C. under a vacuum for the purpose of removing water
content existing on the surface of a sample (See, for example, Appl. Phys. Let.,
by Y. Ye. et. al., Vol. 74, No. 16, (1999) 2307-2309). In order to more improve
a hydrogen storage capacity, it is necessary to remove not only the water content,
but also functional groups or metallic oxides or the like and increase an area
where the surface of the material comes into contact with hydrogen. In this regard,
the inventors have found that the carbonaceous material was heated at about 230°
C. or higher in the pressure reducing atmosphere so that the surface of the carbonaceous
material was efficiently cleaned and the area where the surface of the carbonaceous
material came into contact with the hydrogen atoms or the hydrogen molecules could
be greatly increased.
The present invention provides, in an embodiment a hydrogen-storing carbonaceous
material by heating the carbonaceous material at more than about 230° C. under
a pressure reducing atmosphere.
Further, the present invention in an embodiment provides a hydrogen-stored
carbonaceous material obtained by storing hydrogen in the carbonaceous material
heated at more than about 230° C. under the pressure reducing atmosphere.
The hydrogen-stored carbonaceous material according to the present invention
is obtained by heating the carbonaceous material at more than about 230° C.
in the pressure reducing atmosphere to store hydrogen.
Further, the present invention in an embodiment relates to a battery having
an anode, a cathode, an electrolyte interposed therebetween, and the anode and/or
the cathode includes a hydrogen-stored carbonaceous material obtained by storing
hydrogen in the carbonaceous material heated at more than about 230° C. under
the pressure reducing atmosphere.
When a battery of the present invention in an embodiment is applied to an alkaline
storage battery in which aqueous alkaline solution such as potassium hydroxide
solution is employed for the electrolyte, a proton moves to the anode from the
cathode through the aqueous alkaline solution to store the proton in the anode
during a charging process. The proton can be moved to the cathode side from the
anode side through the aqueous alkaline solution during a discharging process.
Further, when the present invention in an embodiment is applied to a hydrogen-air
fuel cell in which perfluorosulfonic acid polymer electrolyte film or the like
is used for the electrolyte, a proton previously stored in a hydrogen electrode
by a charging or storing process is supplied to an air electrode through the polymer
electrolyte film during the discharging process. Accordingly, in the hydrogen-air
fuel cell, an electric power can be generated in a stable manner.
Further, the present invention in an embodiment relates to a fuel cell including
a laminated structure having an anode, a proton conductor and a cathode, and a
hydrogen storage part including a hydrogen-stored carbonaceous material obtained
by heating the carbonaceous material at more than about 230° C. under the
pressure reducing atmosphere to store hydrogen, discharging the hydrogen and supplying
it to the anode.
Since the fuel cell according to the present invention in an embodiment has
the laminated structure of the anode, the proton conductor and the cathode, and
the hydrogen storage part including the hydrogen-stored carbonaceous material obtained
by heating the carbonaceous material under the atmosphere of gas including hydrogen
gas and substantially including no reactive gas as impurity gas to store hydrogen,
discharging hydrogen and supplying it to the anode, the hydrogen discharged from
the hydrogen storage part produces a proton in accordance with a catalytic action
in the anode. The produced proton moves to the cathode together with a proton produced
by the proton conductor so that the protons combine with oxygen to produce water
and generate an electromotive force. Thus, according to the present invention,
there can be provided the fuel cell in which the hydrogen can be more efficiently
supplied than a case in which the hydrogen storage part is not provided and the
conductivity of the protons is improved.
In the present invention, in an embodiment the hydrogen used and stored in the
carbonaceous material includes hydrogen molecules, hydrogen atoms, a proton as
the atomic nucleus of hydrogen the like or combinations thereof.
The pressure reducing atmosphere in the present invention in an embodiment designates
an atmosphere of about 1.01×10
4 Pascal, preferably about 1.01×10
2
Pascal, and more preferably 1.01×10
1 Pascal.
The carbonaceous material employed in the present invention in an embodiment
is preferably heated at lower than about 1500° C. In an embodiment, the carbonaceous
material is heated at a temperature ranging from about 400° C. to about 800° C.
As the carbonaceous material employed for the present invention, in an embodiment
a carbonaceous material having a large surface and a structural curvature is employed.
According to the study of the inventors of the present invention, since the carbonaceous
material belongs to a s-p non-orthogonal electron system, it is found that HOMO
and LUMO are lower than those of a s-p orthogonal electron system. Therefore, the
carbonaceous material with the curvature can become a strong electron acceptor
and separate the hydrogen into an electron and a proton (atomic nucleus of hydrogen)
to store the hydrogen with high density in the form of the proton having no volume.
Further, the carbonaceous material in the present invention is preferably
composed of a carbonaceous material including fullerene, carbon nanofiber, carbon
nanotube, carbon soot, nanocapsule, bucky onion, carbon fiber, the like or mixtures
thereof. As the fullerene, any spheroidal carbon molecules may be used and all
spheroidal carbon molecules having the number of carbons such as 36, 60, 70, 72,
74, 76, 78, 80, 82, 84, the like or combination thereof can be utilized.
Still further, the carbonaceous material used in the present invention in an
embodiment includes on its surface fine particles made of metal or a metallic alloy
having a function for separating hydrogen atoms from hydrogen molecules, or further,
separating protons and electrons from the hydrogen atoms. The average size of the
fine particles made of the metal or the alloy in an embodiment is about 1 micron
or smaller. As the metal, there is preferably employed metal or an alloy including
iron, rare earth elements, nickel, cobalt, palladium, rhodium, platinum or alloys
composed of one or two or more of these metals or the like.
When the carbonaceous material having the curvature of fullerene, carbon nanofiber,
carbon nanotube, carbon soot, nanocapsule, bucky onion and carbon fiber or the
like in an embodiment is produced by an arc discharge method, the metal or the
alloy thereof is preferably mixed into a graphite rod before the arc discharge.
At the time of the arc discharge, the above described metals or the alloys thereof
are allowed to exist, the yield of the carbonaceous material can be enhanced and
the hydrogen-storing carbonaceous material with the curvature can result from the
catalytic action of these metals or the alloy thereof. It has been known that these
metals or the alloys thereof perform a catalytic action when the carbonaceous material
such as fullerene, carbon nanofiber, carbon nanotube and carbon fiber or the like
is produced by a laser ablation method. The carbonaceous material such as fullerene,
carbon nanofiber, carbon nanotube and carbon fiber or the like may be collected,
added to and mixed with the hydrogen-storing carbonaceous material so that the
surface of the hydrogen-storing carbonaceous material includes these metals or
the alloys thereof.
In the present invention, in an embodiment the carbonaceous material including
these metals or alloys thereof or the carbonaceous material including no metal
or no alloy is deposited at least on its surface metallic fine particles of 10
wt % or less which have a catalyzing function for separating hydrogen atoms from
hydrogen molecules, and further, separating protons and electrons from the hydrogen
atoms. In an embodiment, a metal having such a catalyzing function can include
platinum or a platinum alloy or the like. In order to deposit these metals on the
surface of the carbonaceous material, methods such as a sputtering method, a vacuum
deposition method, a chemical method, a mixture or the like may be used.
Further, when platinum fine particles or platinum alloy fine particles are
deposited on the carbonaceous material, a method using solution containing platinum
complexes or an arc discharge method using electrodes including platinum may be
applied thereto. In an embodiment, chloroplatinic acid solution is treated with
sodium hydrogen sulfite or hydrogen peroxide, then, the carbonaceous material is
added to the resultant solution and the solution is agitated so that the platinum
fine particles or the platinum alloy fine particles can be carried on the carbonaceous
materials. In an embodiment, in the arc discharge method, the platinum or the platinum
alloy is partly attached to the electrode part of the arc discharge, and is subjected
to the arc discharge to be evaporated so that the platinum or the platinum alloy
can be adhered to the carbonaceous material housed in a chamber.
The above described metals or the alloys thereof are deposited on the carbonaceous
material, so that the hydrogen storage capacity can be more improved than that
when the metals or the alloys thereof are not deposited on the carbonaceous material.
Further, it is found that fluorine or molecules thereof serving as an electron
donor or an amine molecule such as ammonia is mixed or combined with the carbonaceous
material to efficiently generate a charge separation.
As described above, hydrogen composed of protons and electrons is supplied to
the hydrogen-storing carbonaceous material as a strong electron acceptor on which
the above mentioned metals or the alloys are mounted, hence the hydrogen is stored
in the form of protons. Therefore, its occupied volume is greatly reduced and a
large amount of hydrogen can be stored in the hydrogen-storing carbonaceous material
as compared with the storage by the conventional chemisorption of hydrogen atoms.
That is, the hydrogen is separated into electrons and protons from the state of
atoms, and the electrons are efficiently stored in the hydrogen-storing carbonaceous
material so that a large amount of high density hydrogen can be finally stored
in the state of protons. Accordingly, when the above described metals or the alloys
are deposited on the surface of the hydrogen-storing carbonaceous material, the
hydrogen can be more efficiently stored and a larger amount of hydrogen can be
stored. The above described hydrogen-storing carbonaceous material is light-weight,
easily transported, can be repeatedly employed at around room temperature without
generating a structural destruction and can be safely handled. Further, the amount
of use of a metallic catalyst such as platinum can be reduced. The carbonaceous
material such as fullerene serving as a starting material can be also produced
at a low cost. Further, there can be realized an excellent practicability that
a problem is not found in view of the procurement of resources nor a problem such
as an environmental destruction is generated during a use.
Additional features and advantages of the present invention are described
in, and will be apparent from, the following Detailed Description of the Invention
and the figures.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a diagram showing a schematic structure of a fuel cell according to
an embodiment of the present invention.
FIG. 2 is a diagram showing a schematic structure of an alkaline storage battery
(secondary battery) according to an embodiment of the present invention.
FIG. 3 is a graph showing the cyclic characteristics of the alkaline storage
battery according to an embodiment of the present invention.
FIG. 4 is a diagram showing a schematic structure of a hydrogen-air fuel cell
according to an embodiment of the present invention.
FIG. 5 is a graph showing the discharge characteristics of the hydrogen-air
fuel cell according to an embodiment of the present invention.
FIG. 6 is a graph showing the discharge characteristics of an another hydrogen-air
fuel cell according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The fuel cell according to an embodiment of the present invention is provided
with a cathode
1 and an anode
2 arranged so as to be opposed to each
other as shown in FIG. 1. Here, as the cathode
1, an oxygen electrode is
used. As the anode
2, a fuel electrode or a hydrogen electrode is used.
The cathode
1 has a cathode lead
3 and a catalyst
5 is dispersed
in the cathode or is adhered to the cathode. The anode
2 also has an anode
lead
6 and a catalyst
7 is dispersed in the anode or is adhered to
the anode. A proton conductor
8 is sandwiched in between the cathode
1
and the anode
2. Hydrogen
12 as fuel is supplied to a passage
13
in the side of the anode
2 through an introducing port
11 from a
hydrogen supply source
10, and discharged from a discharge port
14.
In the side of the cathode
1, air
15 is supplied to a passage
17
from an introducing port
16 and discharged from a discharge port
18.
While the hydrogen
12 serving as the fuel supplied to the passage
13
from the introducing port
11 passes the passage
13, protons are generated
and the generated protons move to the side of the cathode
1 together with
protons generated in the proton conductor
8. As a result, the protons react
with oxygen in the air
15 supplied to the passage
17 from the introducing
port
16 and directed to the discharge port
18 so that a desired electromotive
force is generated.
In the present invention, in an embodiment for the hydrogen supply source
10,
is employed a hydrogen-stored carbonaceous material obtained by heating a carbonaceous
material such as fullerene, carbon nanofiber, carbon nanotube, carbon soot, nanocapsule,
bucky onion and carbon fiber, or the like or combination thereof at more than about
230° C. in the pressure reducing atmosphere and then storing hydrogen.
In the fuel cell according to an embodiment of the present invention, since,
while
the protons are dissociated, the protons supplied from the anode
2 side
move to the cathode
1 side in the proton conductor
8, the conductivity
of the protons is effectively improved. Therefore, since a humidifier which has
been typically required for conducting protons is not needed, a system can be simplified
and lightened in weight.
Without limitation, examples and comparative examples illustrating the effectiveness
of the present invention are described below.
EXAMPLE 1
A carbon nanofiber with one nanotube fiber whose diameter is about 200 mm was
manufactured
by a CVD method and impurities such as a catalyst were completely removed until
purity became 95% or higher before a thermobalance measurement was carried out.
The carbon nanofiber of 15.4 mg thus obtained was accommodated in a sample cup
in a thermobalance, and then, while pressure was reduced by a rotary pump, the
temperature of the carbon nanofiber was raised up to 230° C. at a rate of
60° C. per minute and held at 230° C. for 4 hours to clean the carbon nanofiber.
After the cleaning process was finished, the temperature was lowered to 20°
C. After it was recognized that the temperature of the carbon nanofiber reached
20° C., hydrogen gas was introduced to the measurement vessel to measure the
change of the mass of the carbon nanofiber. Thus, it was found that the hydrogen
of 1.2 wt % was stored.
EXAMPLE 2
After a carbon nanofiber was cleaned in the absolutely same manner as that
of the Example 1 except that the carbon nanofiber was heated up to 400° C.
and held at 400° C. for 3 hours to clean the carbon nanofiber under the pressure
reducing atmosphere, the carbon nanofiber was cooled to 20° C. After it was
recognized that the temperature of the carbon nanofiber reached 20° C., hydrogen
gas was introduced to the measurement vessel to measure the change of the mass
of the carbon nanofiber.
In such a manner, when the amount of stored hydrogen in the carbon nanofiber
was
obtained, it was found that hydrogen of 2.2 wt % was stored in the carbon nanofiber.
EXAMPLE 3
After a carbon nanofiber was cleaned in the absolutely same manner as that
of the Example 1 except that the carbon nanofiber was heated up to 800° C.
and held at 800° C. for 3 hours to clean the carbon nanofiber under the pressure
reducing atmosphere, the carbon nanofiber was cooled to 20° C. After it was
recognized that the temperature of the carbon nanofiber reached 20° C., hydrogen
gas was introduced to the measurement vessel to measure the change of the mass
of the carbon nanofiber.
In such a manner, when the amount of stored hydrogen in the carbon nanofiber
was
obtained, it was found that hydrogen of 2.1 wt % was stored in the carbon nanofiber.
EXAMPLE 4
After a carbon nanofiber was cleaned in the absolutely same manner as that
of the Example 1 except that the carbon nanofiber was heated up to 1400° C.
and held at 1400° C. for 3 hours to clean the carbon nanofiber under the pressure
reducing atmosphere, the carbon nanofiber was cooled to 20° C. After it was
recognized that the temperature of the carbon nanofiber reached 20° C., hydrogen
gas was introduced to the measurement vessel to measure the change of the mass
of the carbon nanofiber.
In such a manner, when the amount of stored hydrogen in the carbon nanofiber
was
obtained, it was found that hydrogen of 0.4 wt % was stored in the carbon nanofiber.
COMPARATIVE EXAMPLE 1
A carbon nanofiber was manufactured in the same manner as that of the Example
1
and impurities such as a catalyst were completely removed until purity became 95%
or higher before a thermobalance measurement was carried out.
The carbon nanofiber of 15.4 mg thus obtained was accommodated in a sample cup
in a thermobalance, and then, initially, the contents in a measurement vessel were
completely replaced by using nitrogen gas.
Then, hydrogen gas of 1 atmospheric pressure was introduced into the measurement
vessel at a flow velocity of 100 cc per minute and held for 3 hours.
Subsequently, nitrogen gas was introduced again into the measurement
vessel to measure the change of the mass of the carbon nanofiber.
As a result, the change of the mass was not recognized. Thus, it was found that
hydrogen was not stored.
COMPARATIVE EXAMPLE 2
After a carbon nanofiber was manufactured in the effectively same manner as
that of the Example 1 and impurities such as a catalyst were effectively removed
until purity became 95% or higher before a thermobalance measurement was carried out.
The carbon nanofiber of 15.4 mg thus obtained was accommodated in a sample cup
in a thermobalance, then, while the pressure was reduced by a rotary pump, the
carbon nanofiber was heated up to 200° C. at a rate of 60° C. per minute
and held at 200° C. for 4 hours to clean the carbon nanofiber.
After the cleaning operation, the carbon nanofiber was cooled to 20° C.
After it was recognized that the temperature of the carbon nanofiber reached 20°
C., hydrogen gas was introduced to the measurement vessel to measure the change
of the mass of the carbon nanofiber. Thus, it was recognized that the hydrogen
of 0.2 wt % was stored in the carbon nanofiber.
It was understood from the Examples 1 to 4 made pursuant to an embodiment of
the
present invention and the Comparative Examples 1 and 2 that while the carbon nanofiber
subjected to no processing had no hydrogen storage capacity and the carbon nanofiber
cleaned at the temperature of 200° C. in the pressure reducing atmosphere
had only a hydrogen storage capacity of 0.2 wt %, the hydrogen storage capacity
of the carbon nanofiber cleaned by the carbon monoxide gas of 1 atmospheric pressure
under from 230° C. to 1400° C. was improved, and the above described
effect was effectively enhanced especially at from 400° C. to 800° C.
EXAMPLE 5
An alkaline storage battery was manufactured in the following manner.
<Manufacture of Cathode>
Carboxymethyl cellulose of 3 wt % was added to spherical nickel hydroxide
of 10 g with the average particle size of 30 mm and cobalt hydroxide of Ig and
the mixture was kneaded with water to prepare paste. A porous nickel foam with
the porosity of 95% was filled with the paste, and the porous nickel foam filled
with the paste was dried and pressed, and then punched to manufacture a cathode
having the diameter of 20 mm and the thickness of 0.7 mm.
<Manufacture of Anode>
Carboxymethyl cellulose of 5% and water were added to the hydrogen-stored
carbonaceous material which prepared in accordance with the Example 2 to prepare
kneaded paste. The porous nickel foam with the porosity of 95% was filled with
the paste, the porous nickel foam filled with the paste was dried and pressed,
and then punched to manufacture an anode with the diameter of 20 mm and the thickness
of 0.5 mm.
<Alkaline Storage Battery>
Then, an alkaline storage battery (secondary battery) schematically shown in
FIG. 2 was manufactured by using the cathode and the anode manufactured as described
above and potassium hydroxide solution of 7N as electrolyte solution.
The alkaline storage battery includes a cathode 1, an anode 2 and
electrolyte solution 21 contained therebetween in a battery vessel 20.
A cathode lead 3 and an anode lead 6 are taken outside the battery
vessel 20 from the respective electrodes.
<Charge and Discharge Performance>
For the alkaline storage battery manufactured as described above, the charge
and discharge test was carried out with 0.1 C, the upper limit of 1.4V and the
lower limit of 0.8 V. The cyclic characteristics at that time are shown in FIG. 3.
As apparent from FIG. 3, although it could not be said that a cycle life was
not
sufficient from the viewpoint of structure of the battery, a basic charge and discharge
performance could be recognized.
EXAMPLE 6
A hydrogen-air fuel cell was manufactured in the following manner.
<Manufacture of Air Electrode>
The hydrogen-stored carbonaceous material was prepared in accordance with the
Example 2. The hydrogen-stored carbonaceous material and polymer electrolyte alcoholic
solution composed of perfluorosulfonic acid were dispersed in n-butyl acetate to
prepare catalyst layer slurry.
On the other hand, a carbon nonwoven fabric with the thickness of 250 mm was
immersed
in the emulsion of fluorine water repellent, dried and then heated at 400°
C., so that the carbon nonwoven fabric was subjected to a water repellent process.
Subsequently, the carbon nonwoven fabric was cut to the size of 4 cm×4 cm
and the catalyst layer slurry prepared as described above was applied to one surface thereof.
<Adhesion of Air Electrode to Polymer Electrolyte Film>
A polymer electrolyte film composed of perfluorosulfonic acid with the thickness
of 50 mm was adhered to the surface of the carbon nonwoven fabric to which the
catalyst layer was applied, and then, the film adhered to the nonwoven fabric was dried.
<Manufacture of Hydrogen Electrode>
Carboxymethyl cellulose of 5% and water were added to the same hydrogen-stored
carbonaceous material as that used for manufacturing the air electrode to prepare
paste. A porous nickel foam with the porosity of 95% was filled with the paste,
dried and pressed and the dried and pressed porous nickel foam was cut to the size
of 4 cm×4 cm to manufacture a hydrogen electrode with the thickness of 0.5 mm.
<Manufacture of Hydrogen-Air Fuel Cell>
The hydrogen electrode was superposed on the adhered body of the air electrode
and the perfluorosulfonic acid polymer electrolyte film obtained as described above
by holding the polymer electrolyte film therebetween. Both the surfaces thereof
were firmly held by Teflon plates with the thickness of 3 mm and fixed by bolts.
Many holes with diameter of 1.5 mm are previously opened on the Teflon plate arranged
in the air electrode side so that air can be smoothly supplied to an electrode.
The schematic structure of the hydrogen-air fuel cell thus assembled is shown
in FIG. 4.
As shown in FIG. 4, in the hydrogen-air fuel cell thus manufactured, a hydrogen
electrode 31 and an air electrode 32 are arranged so as to be opposed
to each other by locating a polymer electrolyte film 30 between the hydrogen
electrode and the air electrode. The outer side of these members is held by a Teflon
plate 33 and a Teflon plate 35 provided with many air holes 34
and all the body is fixed by means of bolts 36 and 36. A hydrogen
electrode lead 37 and an air electrode lead 38 are respectively taken
out from the respective electrodes.
<Discharge Characteristics of Hydrogen-Air Fuel Cell>
Then, the discharge characteristics of the hydrogen-air fuel cell was examined.
Initially, electric current was supplied in a charging direction with
the current density of 1 mA/cm
2 to store hydrogen in the hydrogen electrode.
Then, a discharging operation was carried out with the current density of 1 mA/cm
2.
As a result, the discharge characteristics as shown in FIG. 5 could be obtained
and a function as the hydrogen-air fuel cell was recognized.
Further, before the fuel cell was assembled, hydrogen was previously stored
in the hydrogen electrode under the pressure of 100 kg/cm
2. The hydrogen
electrode thus hydrogen storage was superposed on the adhered body of the air electrode
and the perfluorosulfonic acid polymer electrolyte film obtained as described above
to assemble the hydrogen-air fuel cell. When the discharge characteristic of the
obtained fuel cell was measured with the current density of 1 mA/cm
2,
the discharge characteristic as shown in FIG. 6 was obtained and a function as
the hydrogen-air fuel cell could be also recognized in this case.
It is to be understood that the present invention is not limited to the above
described embodiments and Examples and an can include any number of suitable modifications.
For example, in the above described embodiments, although the fuel cell using the
hydrogen-storing carbonaceous material and the hydrogen-stored carbonaceous material
was described, the hydrogen-storing carbonaceous material and the hydrogen-stored
carbonaceous material according to the present invention are not limited to the
fuel cell but also may be widely applied to uses for hydrogen storage as well as
other batteries such as an alkaline storage battery, a hydrogen-air fuel cell,
or the like.
According to the present invention, there can be provided a hydrogen-storing
carbonaceous material which can efficiently store a large amount of hydrogen, is
light-weight, can be repeatedly used in a safe manner and may not possibly generate
problems in view of resources and an environment and a method for producing it,
a hydrogen-stored carbonaceous material and a method for producing it, a battery
using a hydrogen-stored carbonaceous material and a fuel cell using a hydrogen-stored
carbonaceous material.
It should be understood that various changes and modifications to the presently
preferred embodiments described herein will be apparent to those skilled in the
art. Such changes and modifications can be made without departing from the spirit
and scope of the present invention and without diminishing its intended advantages.
It is therefore intended that such changes and modifications be covered by the
appended claims.
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