JP2002216780A - Electrode member, battery using the same and electrode member producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode member having good electric efficiency, a battery using the same and a method of producing the electrode member having good electric efficiency in simple processes and at a low cost. SOLUTION: The electrode members 13, 14 comprise a porous carbon plate produced by carbonizing a resin material after molded into a predetermined shape.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode member, a battery using the electrode member, and a method for manufacturing the electrode member. Particularly, the electrode member can be manufactured by a simple process and can increase the efficiency of electricity generation. The present invention also relates to a battery using the electrode member and a method for manufacturing the electrode member.

[0002]

2. Description of the Related Art In general, a battery is a source of electric energy using a chemical reaction of a substance. For example, a fuel cell is oxidized by oxidizing chemical energy of a fuel by an electrochemical process. It is a device that directly converts the energy released during the reaction into electrical energy.

Fuel cells have high energy efficiency, are clean and low noise, have few environmental problems, and have good responsiveness to load fluctuations.
Research is being done.

There is also known an air battery in which oxygen in the air is used as a depolarizer (for reducing a decrease in polarization that lowers the battery voltage due to a reaction product). Further, batteries using a fluid such as gas or liquid as an active material are also known.

[0005] In a general fuel cell, a hydrogen gas flow path, a hydrogen electrode plate, an electrolyte layer, an oxygen electrode plate, and an oxygen gas flow path constitute an electromotive section. A shaped electrode plate was used. In the air battery, zinc was used for the cathode, and porous carbon with increased oxygen adsorption was used for the anode.

However, such a conventional battery does not provide a practical electricity generation efficiency. Therefore, in order to obtain an efficient fuel cell and air cell, a technique of forming a hydrogen electrode plate and an oxygen electrode plate from a carbon plate having an uneven structure on one surface is known.

[0007]

However, such a carbon plate having a concavo-convex structure on one side has a problem in that the processing of the concavo-convex structure requires a great deal of labor and a high manufacturing cost. Therefore, for practical use, electricity generation efficiency is good and processing does not take time,
The development of batteries with low manufacturing costs is desired.

An object of the present invention is to provide an electrode member having high electric efficiency and a battery using the electrode member. Another object of the present invention is to provide an electrode member having high electric efficiency,
An object of the present invention is to provide a manufacturing method that can be manufactured with simple steps and at low cost.

[0009]

According to the electrode member of the present invention, a resin material is formed into a predetermined shape in advance of a carbonizing process, and then is formed by performing a carbonizing process. The problem is solved by comprising a quality carbon plate.

[0010] More specifically, it is preferable that the electrode member is formed in one of the following shapes to be processed in advance. That is, the pre-processed shape is formed so as to be a flow path for subjecting the fluid serving as an active material to an electrode reaction, and the pre-processed shape is
On at least one side, the area of the electrode reaction is widened, and the pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for the electrode reaction. That the pre-processed shape is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for the electrode reaction; and the pre-processed shape is at least the electrode reaction One or more recessed active material fluid flow paths formed corresponding to the effective area, and the pre-processed shape is corrugated, at least corresponding to the area effective for the electrode reaction. That the pre-processed shape corresponds to at least a region effective for the electrode reaction, and that the pre-processed shape has concave portions and convex portions. And were formed alternately When one in which it has any one form of.

According to a third aspect of the present invention, there is provided a battery including a pair of electrode plates disposed to face each other, wherein at least one of the electrode plates comprises a porous carbon plate. The problem is solved by forming the electrode plate made of the porous carbon plate into one of the following shapes. That is, the shape is such that the pre-processed shape is formed to be a flow path for subjecting the fluid as an active material to an electrode reaction, and the pre-processed shape is formed on at least one surface of the electrode. That the reaction area is widened, and that the pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for the electrode reaction; The shape to be formed is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for the electrode reaction, and the pre-processed shape is at least a region effective for the electrode reaction. Correspondingly, one or more recessed active material fluid flow paths formed, wherein the pre-processed shape has been subjected to a corrugated process corresponding to at least a region effective for electrode reactions. That there is The shape to be formed is one that has been subjected to concavo-convex processing at least corresponding to a region effective for the electrode reaction, and the pre-processed shape is that concave portions and convex portions are alternately formed. .

Further, the battery is a fuel cell, wherein one of the electrode plates is a fuel electrode plate, and the other is an oxygen electrode plate, and is provided between the fuel electrode plate and the oxygen electrode plate. It is preferable that the fuel cell further includes a formed electrolyte layer, and at least one of the fuel electrode plate and the oxygen electrode plate is formed of a porous carbon plate. When the electrode member made of the carbon plate is used as described above, the thickness of the battery itself can be reduced.

It is preferable that the electrolyte membrane contains a proton conductor capable of conducting a proton under non-humidified conditions. At this time, it is preferable that the proton conductor is formed by introducing a proton dissociable group with a carbonaceous material containing carbon as a main component as a matrix, and the carbonaceous material is preferably a fullerene molecule, The electrolyte membrane may include a binder.

Further, according to the method for manufacturing an electrode member of the ninth aspect, a forming step of forming a carbon plate material so as to form a concave portion on one surface of a desired shape, and the forming step is achieved by the forming step. And a carbonization treatment step of performing a carbonization treatment on the obtained molded product.

[0015] More specifically, the recess is configured to include at least one groove. Preferably, the at least one groove is configured as a meandering groove.

According to a second aspect of the present invention, there is provided a method of manufacturing an electrode member, comprising: forming a carbon plate material so that concave portions and convex portions are alternately formed on one surface of a desired shape. And a carbonization treatment step of carbonizing the molded product obtained in the molding step.

As described above, the resin material is formed into a predetermined shape before the carbonization process, and the shape to be processed in advance is formed so that the fluid as the active material becomes a flow path for the electrode reaction. That the pre-processed shape is
On at least one side, the area of the electrode reaction is widened, and the pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for the electrode reaction. That the pre-processed shape is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for the electrode reaction; and the pre-processed shape is at least the electrode reaction One or more recessed active material fluid flow paths formed corresponding to the effective area, and the pre-processed shape is corrugated, at least corresponding to the area effective for the electrode reaction. That the pre-processed shape corresponds to at least a region effective for the electrode reaction, and that the pre-processed shape has concave portions and convex portions. And were formed alternately Due to the provision of any one of the forms of the, it is possible to improve the contact efficiency between the electrode member, it is possible to obtain a good cell electrical generation efficiency.

The use of an electrolyte membrane containing a proton conductor capable of conducting protons under non-humidified conditions facilitates handling and facilitates various steps such as adhesion and sputtering. For this reason, for example, in order to reduce the poisoning of the catalyst by CO or the like, it is possible to apply a uniform film forming technique by sputtering or the like or a technique of bonding a permselective membrane. When a fullerene derivative bound by a binder is used for the electrolyte membrane, a proton conductor having sufficient strength can be formed because the fullerene derivative is bound by the binder.

In addition, since the forming step of forming the carbon plate material into a predetermined shape is performed before the carbonizing step, the manufacturing can be performed at a low cost by a simple step.

With the above-described structure, when a carbon plate is used in a battery, a fluid serving as an active material serves as a flow path for providing an electrode reaction, and the contact efficiency with the electrode can be improved. Become. Further, the electrode reaction area is applied so as to be widened, and a meandering active material fluid flow path formed corresponding to a region effective for the electrode reaction is formed, and a plurality of grooved active material fluid flow paths are formed. One or more recessed active material fluid flow paths, and the effective contact area increases due to corrugated processing, uneven processing, and alternate formation of concave and convex parts, improving the contact efficiency with electrodes It is possible to do.

[0021]

Embodiments of the present invention will be described below with reference to the drawings. The members, arrangements, and the like described below do not limit the present invention, and can be variously modified within the scope of the present invention.

The battery according to the present embodiment will be described by taking as an example a fuel cell that can be used for various devices such as a mobile body such as an automobile, a portable device, a fixed-type power generation system, and the like.

As shown in FIG. 1, the fuel cell according to the present embodiment is formed as a stack S in which cells C are connected in order to obtain a predetermined output. Hydrogen gas as fuel is supplied from a hydrogen gas cylinder B to each cell C constituting the stack S.

As shown in FIG. 2, the cell C of the present embodiment is configured such that the electrode module is sandwiched between the plates 40a and 40b, and each end is sealed by a sealing member 30. It is formed as.

The electrode module includes an electrolyte membrane 11 serving as an electrolyte layer containing a proton conductor, a frame 20 (conductive) having a predetermined shape for supporting the electrolyte membrane 11, and a gap between the electrolyte membrane 11 and the frame 20. The insulator 12, the hydrogen electrode plate 13 on the fuel side, the oxygen electrode plate 14 on the air side, and the electrode plate 1
A catalyst film (not shown) provided on each of the sheets 3 and 14 and the sheet film 1
7 and 18. The hydrogen electrode plate 13 as the fuel electrode plate on the fuel side and the oxygen electrode plate 14 on the air side constitute a pair of electrode plates.

As shown in FIG. 2, the sheet films 17 and 18 are formed to be smaller than the space surrounded by the frames 20a and 20, and between the sheet films 17 and 18 and the frames 20a and 20, respectively. A space through which hydrogen gas and air pass is formed.

The plate 40b is provided with two holes 41, through which air is supplied to the oxygen electrode plate 14 of the electrode module through the space between the frame 20 and the sheet film 18. It is configured. Oxygen electrode plate 14
In addition to air, oxygen gas, oxygen gas and other gases,
For example, another gas containing oxygen, such as a mixed gas with nitrogen gas or the like, may be supplied.

The oxygen electrode plate 14 according to the present embodiment is formed of a substantially plate-like porous carbon plate. A catalyst film (not shown) is provided, and functions as a catalyst layer, a current collector, and a diffusion layer of the fuel cell. Since the oxygen electrode plate 14 is made of carbon, which is a conductor, it functions as a current collector. However, a current collector made of a metal plate or the like may be separately provided.

The oxygen electrode plate 14 is provided so as to be in contact with the electrolyte membrane 11 when the cell C is assembled. As shown in FIGS. 2 and 3, the oxygen electrode plate 14 has a meandering groove 55 formed on the surface of the oxygen electrode plate 14 on the sheet film 18 side. The groove 55 is formed as a single groove from the groove 55A on one end to the groove 55B on the other end.
Is assembled so that a single groove-shaped space is formed between itself and the sheet film 18. This groove-shaped space serves as a gas flow path.

The grooves 55A, 55B at both ends of the groove 55
2 communicates with the hole 41 via a space between the frame body 20 and the sheet film 18, as shown in FIG. Therefore, the air introduced from the hole 41 flows into the groove 55 from one of the grooves 55A and 55B through the space between the frame 20 and the sheet film 18. After that, it reaches the other groove 55B or 55A through the groove 55, passes through the space between the frame body 20 and the sheet film 18, and is discharged from the hole 41.

With such a structure, the grooves 5 at both ends are formed.
Air can be introduced from one of 5A and 55B and exhausted from the other, and when the cell C is assembled, the groove 55 functions as a gas flow path. The groove 55 may have a rounded shape as shown in FIG. 3B, or may have a polygonal cross section such as a square or a triangle.

The hydrogen electrode plate 13 as the fuel electrode plate of the present embodiment
Consists of a plate-like porous carbon plate. As shown in FIG. 2, the hydrogen electrode plate 13 of this example has substantially flat surfaces on both sides of a plate-like body. However, the hydrogen electrode plate 13 has the same structure as the groove 55 of the oxygen electrode plate 14 shown in FIGS. Alternatively, a groove serving as a gas flow path may be formed on one surface. The cell C is assembled so that a groove-shaped space is formed between the cell C and the sheet film 17 by the groove.

Further, the hydrogen electrode plate 13 may be constituted by a substantially plate-like body formed from a hydrogen storage material.
As the hydrogen storage material, any of titanium-based materials such as Fe-Ti and Ti-Mn, magnesium-based materials such as Mg-Ni, rare earth-based materials such as La-Ni, and hydrogen storage carbonaceous materials such as carbon nanotubes can be used. Good. The hydrogen electrode plate 13 has a catalyst film (not shown), and serves as a catalyst layer, a current collector, and a diffusion layer of the fuel cell, and is supplied with hydrogen gas. In this example, hydrogen gas is introduced, but alcohol such as methanol may be introduced.

The fluid such as hydrogen gas and the above-mentioned gas containing oxygen such as air correspond to the fluid serving as the active material. When the cell C is assembled, the hydrogen electrode plate 13
It is provided so as to be in contact with the electrolyte membrane 11.

The length and width of the hydrogen electrode plate 13 are
It is formed so as to be substantially the same as the oxygen electrode plate 14.

In this embodiment, the groove 55 for forming the gas flow path is formed on the surface of the oxygen electrode plate 14, but both the oxygen electrode plate 14 and the hydrogen electrode plate 13 or only the hydrogen electrode plate 13 is provided. May be provided on the surface of each of the grooves.

Further, both the oxygen electrode plate 14 and the hydrogen electrode plate 13 are made of a porous carbon plate.
Only one of the oxygen electrode plate 14 and the hydrogen electrode plate 13 may be made of a porous carbon plate.

In the present embodiment, the hydrogen electrode plate 1
3. The shape of the oxygen electrode plate 14 is formed from a substantially plate-like body, but is not limited thereto, and may be any other shape such as a cylindrical body, a spherical arc-like body, a boat-like shape, a rectangular parallelepiped having a hollow inside. Is also good. As described above, by adopting another shape, it is possible to form a fuel cell that can be installed at a desired position in various devices.

In the present embodiment, the oxygen electrode plate 14
Forming a groove 55 serving as a flow path on the surface of the electrolyte membrane side of
Although the gas is made to flow easily, the oxygen electrode plate 14
A concave portion 52 and a convex portion 51 may be formed on the surface, respectively, so that the area where the gas comes into contact with the oxygen electrode plate 14 is increased, so that the electrode reaction area may be increased.

In this case, the surface of the oxygen electrode plate 14
As shown in FIGS. 4A and 4B, convex portions 51 and concave portions 52 having a trapezoidal cross section are formed alternately so as to form a staggered lattice shape, and oxygen gas contained in air is reduced to oxygen. The area in contact with electrode plate 14 is formed to be large. In addition, in this specification, "recess" and "convex" shall mean that they are relatively concave or convex, and it does not matter whether they are concave or protrude with respect to the electrode plate surface. .

In FIG. 4, the recess 5 of the oxygen electrode plate 14 is shown.
2. The convex portion 51 is formed in a staggered lattice shape, but is not limited to this, and may have any shape such as a hemispherical hole, a groove extending in a predetermined direction, or the like. Recess,
Protrusions may be formed. For example, as shown in FIG. 5, concave portions 52 and convex portions 51 having a triangular cross section may be provided alternately and continuously. Further, a plurality of concave portions and convex portions may be provided, or only one may be provided. Further, a concave portion and a convex portion may be formed on the surface of the hydrogen electrode plate 13 so that the area where the gas comes into contact with the hydrogen electrode plate 13 may be increased to increase the electrode reaction area.

The sheet films 17 and 18 are provided on the electrode plates 13 and 14
It has a function of maintaining and strengthening, a function of easily sending hydrogen and oxygen to the catalyst in a dispersed manner to easily cause an electrochemical reaction, and a function of removing a product (water).

In the cell C of the present embodiment, the gas supply pipe 3
Nozzle communication pipe (not shown) for fuel gas inside through 1
Hydrogen gas as a fuel is supplied from the frame 20a on which is formed. The hydrogen gas is stored in the hydrogen gas cylinder B, is injected from the gas supply pipe 31 between the hydrogen electrode plate 13 and the plate 40a, and the fuel is supplied to the hydrogen electrode plate 14 of the electrode module. I have.

By stacking a plurality of cells C having the above structure, a stack S capable of supplying electric power required to drive an electric device, for example, a personal computer, is formed. Thus, when a plurality of cells C are stacked,
In order to supply hydrogen to each cell C, each cell C and the hydrogen cylinder are connected by a plurality of gas supply pipes 31.

Next, the electrolyte membrane 11 as an electrolyte layer containing a proton conductor used in the fuel cell according to the present invention will be described. In the present specification, “proton (H ⁺ )
"Dissociation of protons" means that protons (from functional groups)
"Proton dissociable group"
It means "a functional group from which a proton can be eliminated by ionization". The proton conductor of this example is formed by introducing a proton dissociable group using a carbonaceous material containing carbon as a main component as a base material. For example, fullerene molecules are used as the carbonaceous material.

Therefore, the proton conductor used in this embodiment will be described first. As the proton conductor used in this example, polyfullerene hydroxide is a general term for a substance having a structure in which a plurality of hydroxyl groups are added to fullerene, as shown in FIG.
l) ". Not surprisingly, fullerenol was first synthesized by Chiang et al. In 1992 (Chiang, LY; Swirczewski, JW; Hsu,
CS; Chowdhury, SK; Cameron, S.; Creegan,
KJ Chem. Soc, Chem. Commun. 1992, 1791). Since then
Fullerenol having a certain amount of hydroxyl groups introduced therein has been particularly noted for its water-solubility, and has been studied mainly in the field of biotechnology.

The fullerenol is formed into an aggregate as schematically shown in FIG. 7A so that an interaction occurs between hydroxyl groups of adjacent fullerenol molecules (in the figure, ○ indicates a fullerene molecule). . This aggregate has high proton conductivity as a macro-aggregate (in other words, dissociation of H ⁺ from phenolic hydroxyl group of fullerenol molecule)
Demonstrate.

As the proton conductor, in addition to the above fullerenol, for example, an aggregate of fullerene having a plurality of —OSO ₃ H groups may be used as the proton conductor. O
Polyhydroxy fullerenes as shown in FIG. 7 (B), in which the H groups are replaced by OSO ₃ H groups, ie, hydrogen sulfated fullerenol, were also reported by Chiang et al. In 1994 (Chiang, LY; Wang, LY; Swi
rczewski, JW; Soled, S .; Cameron, SJ Org.
Chem. 1994, 59, 3960). Some of the hydrogen sulfate-esterified fullerenes contain only an OSO ₃ H group in one molecule, or may have a plurality of this group and a plurality of hydroxyl groups.

When a large number of the above-described fullerene derivatives are aggregated, the proton conductivity as a bulk shows that the protons originating from a large amount of hydroxyl groups and OSO ₃ H groups originally contained in the molecule are directly involved in the transfer. There is no need to take in hydrogen and protons originating from water vapor molecules and the like, and there is no need to replenish moisture from the outside, in particular, to absorb moisture from outside air, and there is no restriction on the atmosphere. In addition, fullerene, which is the base of these derivative molecules, has an electrophilic property, which promotes ionization of hydrogen ions not only in highly acidic OSO ₃ H groups but also in hydroxyl groups and the like. It is considered to have contributed greatly.

In addition, since a large number of hydroxyl groups and OSO ₃ H groups can be introduced into one fullerene molecule, the number density of protons involved in conduction per conductor volume becomes very large.

Most of the proton conductor of the present embodiment is composed of carbon atoms of fullerene, so that it is light in weight, hardly deteriorates, and contains no pollutants. The production cost of fullerenes is also rapidly decreasing.
In terms of resources, environment and economy, fullerene is considered to be a near ideal carbon-based material above all other materials.

Further, the proton dissociating group need not be limited to the above-mentioned hydroxyl group or OSO ₃ H group. That is, this dissociable group is represented by the formula -XH, and X may be any atom or atomic group having a divalent bonding means. Further, this group is represented by the formula -OH or -YOH, and Y may be any atom or atomic group having a divalent bond.

[0053] Specifically, the proton dissociating groups, the -OH, -COOH besides -OSO ₃ H, -S
Either O ₃ H or —OPO (OH) ₂ is preferable.

Further, in the present embodiment, the carbon atom constituting the fullerene molecule is added with a proton-dissociable group,
It is preferable that an electron-withdrawing group, for example, a nitro group, a carbonyl group, a carboxyl group, a nitrile group, a halogenated alkyl group, a halogen atom (such as fluorine and chlorine) be introduced. FIG. 7C illustrates a fullerene molecule in which Z is introduced in addition to -OH. This Z is, specifically, -N
O ₂ , —CN, —F, —C ₁ , —COOR, —CHO,
—COR, —CF ₃ , —SO ₃ CF ₃ and the like (where R represents an alkyl group). When the electron-withdrawing group is present, protons are easily dissociated from the proton-dissociating group due to the electron-withdrawing effect.

The number of proton-dissociable groups to be introduced into the fullerene molecule may be any number within the range of the number of carbon atoms constituting the fullerene molecule, but is preferably 5 or more. The number of the above groups is preferably not more than half the number of carbon atoms constituting fullerene in order to maintain the π-electron property of fullerene and to exhibit an effective electron-withdrawing property.

For synthesizing the fullerene derivative used for the proton conductor, the powder of the fullerene molecule is subjected to a suitable combination of known treatments such as acid treatment and hydrolysis, for example, so that the desired carbon atoms of the fullerene molecule can be synthesized. May be introduced.

More specifically, the synthesis of polyhydroxylated fullerene is described in the literature (Chiang, LY; Wang, LY).
; Swirczewski, JW; Soled, S.; Cameron, SJ
Org. Chem. 1994, 59, 3960). The powder 2g charged into oleum 30ml of a _{C 70} C ₆ 0 _/ C ₇₀ fullerene mixture containing about 15%, and stirred for 3 days while maintaining the 60 ° C. in a nitrogen atmosphere. The resulting reaction product is dropped little by little into anhydrous diethyl ether cooled in an ice bath, and the precipitate is separated by centrifugation, further three times with diethyl ether, and a 2: 1 mixture of diethyl ether and acetonitrile. After washing twice with liquid, 40
Dry at reduced pressure in ° C. Furthermore, this dried product is
The mixture was placed in ml of ion-exchanged water and stirred at 85 ° C. for 10 hours while bubbling with nitrogen. The reaction product was separated into precipitates by centrifugation, and the precipitates were further washed with pure water several times, centrifuged repeatedly, and then dried at 40 ° C. under reduced pressure. The thus obtained brown powder F
When T-IR measurement was performed, it almost coincided with the IR spectrum of C ₆₀ (OH) ₁₂ shown in the above literature, and this powder was confirmed to be poly (fullerene hydroxide) as a target substance.

The production of the polyhydroxylated fullerene aggregated pellets was carried out in the following manner.
g, and pressed in one direction to form a circular pellet having a diameter of 15 mm. The press pressure at this time is about 7
Ton / cm ² . As a result, the polyhydroxylated fullerene powder was excellent in moldability despite not containing any binder resin and the like, and could be easily pelletized. The pellet is about 300 microns thick.

Synthesis 1 of polyhydroxylated fullerene hydrogen sulfate (total esterification) was similarly performed with reference to the above literature. 1mg of polyhydroxylated fullerene powder
Was dropped into 60 ml of fuming sulfuric acid, and the mixture was stirred at room temperature under a nitrogen atmosphere for 3 days. The resulting reaction product is dropped little by little into anhydrous diethyl ether cooled in an ice bath, and the precipitate is separated by centrifugation, and further diluted with diethyl ether.
Times, and 2: 1 of diethyl ether and acetonitrile
After washing twice with the mixed solution, it was dried at 40 ° C. under reduced pressure. The powder thus obtained was subjected to FT-IR measurement. The IR spectrum of the powder, in which all of the hydroxyl groups were converted to hydrogen sulfate, almost coincided with that shown in the above-mentioned literature. Was confirmed.

For the production of aggregated pellets of poly (hydroxy fullerene hydrogen sulfate), 70 mg of powder of poly (hydroxy fullerene hydrogen sulfate) was pressed in one direction so as to form a circular pellet having a diameter of 15 mm. The pressing pressure at this time was about 7 tons / cm ² . As a result, although this powder did not contain any binder resin or the like, it was excellent in moldability and could be easily pelletized. The pellet is about 300 microns thick.

Further, in the synthesis of polyhydroxy fullerene hydrogen sulfate (partial esterification), C ₇₀ was reduced to about 15%
2 g of the powder of the C ₆₀ / C ₇₀ fullerene mixture was poured into 30 ml of fuming sulfuric acid, and the mixture was stirred in a nitrogen atmosphere at 60 ° C. for 3 days. The resulting reaction was dropped little by little into diethyl ether cooled in an ice bath. However, in this case, diethyl ether which had not been subjected to dehydration treatment was used. The obtained precipitate was separated by centrifugation, further washed three times with diethyl ether and twice with a 2: 1 mixture of diethyl ether and acetonitrile, and dried at 40 ° C. under reduced pressure. FT-IR measurement of the thus obtained powder showed that the IR spectrum of the fullerene derivative partially containing a hydroxyl group and an OSO ₃ H group, which was shown in the above literature, almost coincided with the powder. It was confirmed that it was the target substance.

Further, the production of the aggregated pellets of the poly (hydroxysulfuric acid hydrogen sulfate) fullerene hydroxide is carried out by taking 80 mg of the poly (fullerene hydroxide hydrosulfate) partially hydrosulfated, and forming the pellet into a circular pellet having a diameter of 15 mm in one direction. Pressed to. The press pressure at this time is about 7 tons /
cm ² . As a result, although this powder did not contain any binder resin or the like, it was excellent in moldability and could be easily pelletized. The pellet was about 300 microns thick.

In the above embodiment, a membrane made of polyfullerene hydroxide is used as the proton conducting membrane, but the proton conducting membrane is not limited to this. The polyhydroxylated fullerene has a fullerene molecule as a base and a hydroxyl group introduced into its constituent carbon molecules. The base is not limited to the fullerene molecule but may be any carbonaceous material containing carbon as a main component.

The carbonaceous material has a carbon atom
Regardless of the type of carbon-carbon bond, it may include a carbon cluster, which is an aggregate formed by bonding several to several hundreds, and tubular carbonaceous material (commonly called carbon nanotube).

As the former carbon clusters, there are various carbon clusters having a closed surface structure similar to spheres, spheroids, or the like, as shown in FIG. . Also, as shown in FIG.
A carbon cluster in which a part of the spherical structure of those carbon clusters is missing and has an open end in the structure, a carbon cluster having a diamond structure in which most of the carbon atoms are SP3 bonded as shown in FIG. As shown by 11,
A carbon cluster in which these clusters are variously bonded may be included.

The group to be introduced into the parent of this type is not limited to a hydroxyl group, but may be any proton-dissociable group represented by -XH, more preferably -YOH. Where X and Y
Is an arbitrary atom or atomic group having a divalent bond, H is a hydrogen atom, and O is an oxygen atom. In particular,
Besides the -OH, hydrogen sulfate ester group -OSO ₃ H,
Carboxyl group -COOH, other _-SO 3 H, -OPO
(OH) ₂ is preferred.

Here, when the fullerene derivative is used as the proton conductor, it is preferable that the proton conductor is substantially composed of only the fullerene derivative or bound by a binder. Then, an electrolyte membrane may be formed only from the film-form fullerene derivative obtained by press-molding the fullerene derivative, or a fullerene derivative bound by a binder may be used as the proton conductor. When the binder is used as described above, the proton conductor is bound by the binder, and a sufficiently strong proton conductor can be formed.

Here, as the polymer material usable as the binder, one or more known polymers having film-forming properties are used, and the amount of the polymer in the proton conductor is usually Reduce to 40% by weight or less. If it exceeds 40% by weight, the conductivity of hydrogen ions may be reduced.

Since the proton conductor having such a structure also contains the above fullerene derivative as a proton conductor, it can exhibit the same hydrogen ion conductivity as the above-mentioned proton conductor consisting essentially of the fullerene derivative. it can.

Further, unlike the case of using the fullerene derivative alone, a film-forming property derived from a polymer material is imparted, and the flexibility and the strength are higher and the gas permeation preventing ability is higher than that of the powder compression molded product of the fullerene derivative. It can be used as a suitable ion conductive thin film (thickness is usually 300 μm or less).

The polymer material is not particularly limited as long as it does not inhibit the conductivity of hydrogen ions as much as possible (by reaction with the fullerene derivative) and has a film-forming property. Usually, those having good stability without electron conductivity are used. Specific examples thereof include polyfluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, and the like.
It is a preferred polymer material.

First, polyfluoroethylene is preferable because a thin film having higher strength can be easily formed with a smaller amount of compounding than other polymer materials. In this case, the compounding amount can be as small as 3% by weight or less, preferably 0.5 to 1.5% by weight, and the thickness of the thin film can be normally reduced to 100 μm to 1 μm.

The reason why polyvinylidene fluoride or polyvinyl alcohol is preferable is that an ion conductive thin film having more excellent gas permeation preventing ability can be obtained. In this case, the compounding amount is preferably in the range of 5 to 40% by weight.

When the amount of polyfluoroethylene, polyvinylidene fluoride or polyvinyl alcohol falls below the lower limit of each of the above ranges, film formation may be adversely affected.

In order to obtain a thin film of a proton conductor in which each fullerene derivative of the present embodiment is bound by a binder, a known film forming method such as pressure forming or extrusion forming may be used.

Further, the proton conductor is selected from the group consisting of polyvinyl chloride, vinyl chloride copolymer, polyethylene, polypropylene, polycarbonate, polyethylene oxide, polyphenylene oxide, perfluorosulfonic acid resin and derivatives thereof. It is also possible to form by containing at least one kind of resin and the above-mentioned fullerene derivative.

In this case, the content of the resin is preferably 50% by weight or less, and if the content exceeds 50% by weight, the proton conductivity may be reduced.

When the proton conductor contains the resin as described above, it is possible to realize a thin film having higher moldability and higher strength. Therefore, it can be used as a thin film which is excellent in film strength and gas permeation preventing ability, and has good acid resistance and heat resistance.

The polyvinyl chloride and the polyvinyl chloride copolymer are excellent in acid resistance and heat resistance, and are desirable resins. Here, the vinyl chloride-based copolymer is a copolymer of vinyl chloride and a copolymerizable monomer, such as a vinyl chloride-vinylidene chloride copolymer and a vinyl chloride-vinyl acetate copolymer.

The polyethylene, the polypropylene,
The polyethylene oxide and the polyphenylene oxide are resins having good acid resistance.

The polycarbonate is a transparent non-crystalline resin, has excellent heat resistance and low-temperature characteristics, and can be used in a wide temperature range. Also, it has excellent impact resistance.

Since the perfluorosulfonic acid resin is a resin having excellent acid resistance and heat resistance and good weather resistance, it does not cause a significant change in its properties even under severe temperature or long-term light exposure.

When the proton conductor contains the resin as described above, even if the acidity of the proton conductor is significantly increased due to the dissociation of protons (H ⁺ ), the proton conductor hardly undergoes oxidative deterioration and has excellent durability. Therefore, it can be suitably used as a proton conductive thin film, and can exhibit high conductivity over a wide temperature range including room temperature.

Further, a proton (hydrogen ion) highly conductive glass prepared by a sol-gel method may be used. This highly conductive glass is, for example, phosphoric acid-silicate (P ₂ O)
_5- SiO ₂ ) -based glass, which can be prepared as a glass by hydrolyzing a metal alkoxide raw material to produce a gel and heating at 500 to 800 ° C. This glass has micropores of about 2 nanometers, in which moisture is adsorbed and the movement of protons is promoted.

Further, an organic-inorganic hybrid ion exchange membrane may be used. This is a composite membrane in which polyethylene oxide (PEO), polypropylene oxide (PPO), polytetramethylene oxide (PTMO), etc. and silica are bonded at the molecular level, and monodotesyl phosphate (MDP), 1,2-tungsten It is obtained by doping phosphoric acid (PWA) or the like as a proton conductive donor.

Further, a self-humidifying electrolyte membrane may be used. As shown in FIG. 12, for example, this film has a very small amount of ultrafine platinum catalyst and oxide (TiO ₂ .SiO ₂ ) in the film.
Ultra-fine terminals are highly dispersed. Water is generated on a platinum catalyst by reversing the crossover of hydrogen and oxygen, and the generated water is adsorbed and retained on the oxide ultrafine particles, thereby humidifying the membrane from the inside and keeping the water content high. It is. Pt in which ultrafine platinum particles (0.09 mg / cm ² ) having a very small particle size of 1 to ² nm and ultrafine particles of TiO _{2 having} a particle size of 5 nm (3% of the weight of dry Nafion) are highly dispersed.
With -TiO ₂ dispersion film in the electrolyte, completely even when the external non-humidified, extremely stable and high performance (0.4-0.6
A battery operation of about 0.6 W / cm ² at V becomes possible. In any of the above modifications, humidification is not required for proton conduction.

As described above, when the electrolyte membrane 11 containing a proton conductor capable of conducting proton under non-humidified conditions is used as the electrolyte membrane, the humidification of hydrogen gas is not required.
Since there is no need to provide a humidifier and no installation space for the humidifier, there is no need to make the separator a complicated shape, and the fuel cell can have a compact configuration.

Next, an embodiment of a method for manufacturing a porous carbon plate for a fuel cell will be described with reference to FIG. The porous carbon plate for a fuel cell can be used for the oxygen electrode plate 14 already described.

In the method for manufacturing a porous carbon plate for a fuel cell according to the present embodiment, a forming step is carried out on a belt conveyor 61 and then a carbonizing step is carried out. The molding is performed using a carbon plate mold 62. First, the carbon plate mold 62 is moved to the belt conveyor 6.
Fix to 1. At this time, the belt conveyor 61 and the molding die 62 may be formed integrally.

Next, a molding step of charging the carbon plate material into the molding die 62 and molding the carbon plate material into a substantially plate-like body having a recess on at least one surface is performed. In the molding step, first, the carbon plate material is supplied by a material supply device 63 onto a molding die 62 fixed on a belt conveyor to form a layer of a mixture. Mold 62 of this example
Is a mold capable of forming a staggered pattern of irregularities shown in FIG.

Next, the molding die 62 is moved to the belt conveyor 61.
Is moved to a position of a second belt 64 disposed at a position at a constant height, and the carbon plate material is formed to a predetermined thickness by being sandwiched between the second belt 64 and a forming die 62.

Thereafter, the carbon plate material is subjected to a carbonizing process. In the carbonizing process, the carbon plate material transferred from the second belt 64 is placed in a firing furnace 65, and the carbon plate material is fired to perform a carbonizing process. The firing is performed at a temperature of 2000 ° C. or higher in an atmosphere of an inert gas such as an argon gas. Thereby, carbonization and porosity are simultaneously performed. Through the above steps, a porous carbon plate 66 is obtained.

The porous carbon plate 66 can be used as an oxygen electrode plate. Further, it may be used for a fuel electrode plate such as a hydrogen electrode plate and the like.

As the carbon plate material, a mixture of graphite powder, a powdery thermosetting resin, and a fibrous material is used. As the graphite powder, a graphite powder generally used for a carbon molded article for a fuel cell is used. As the thermosetting resin, phenol resin, polyimide, petroleum pitch, furfuryl alcohol, or the like is used. As the fibrous material, carbon fibers such as polyacrylonitrile are used. In addition, a material generally used for a carbon molded article for a fuel cell may be used.

In the present embodiment, as described above, before the carbonizing step of carbonizing and making porous, the carbon plate material is preliminarily formed into a shape having irregularities on one surface. The manufacturing process of the porous carbon plate 66 is simplified, and a high-quality porous carbon plate with less cracking and peeling can be obtained.

As described above, the shape of the electrode member is processed in advance. For example, the shape processing is performed such that a fluid serving as an active material is formed to be a flow path for providing an electrode reaction. On at least one side, the area of the electrode reaction is applied so as to be expanded, or at least a meandering active material fluid flow path corresponding to the area effective for the electrode reaction, or at least corresponding to the area effective for the electrode reaction A plurality of groove-shaped active material fluid flow paths, or at least one concave active material fluid flow path corresponding to an area effective for electrode reaction, or at least an area effective for electrode reaction In this case, a corrugated surface is formed, or at least a concave and convex portion is formed corresponding to a region effective for an electrode reaction, or concave portions and convex portions are alternately formed.

The battery has a pair of electrode plates disposed to face each other, at least one of the electrode plates is formed of a porous carbon plate, and the electrode plate formed of the porous carbon plate is formed of the above-described electrode member. In a predetermined shape. Examples of the battery using the electrode member include a fuel cell, an air battery, and a battery using a fluid as an active material.

[0098]

According to the present invention, since the forming step of forming the carbon plate material into a predetermined shape is performed before the carbonizing step of the resin material, the processing is easy by a simple step.
It can be manufactured at low cost.

Further, the shape in which the electrode member is pre-processed is formed so as to be a flow path for supplying a fluid as an active material to an electrode reaction.
On at least one side, the area of the electrode reaction is widened, and the pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for the electrode reaction. That the pre-processed shape is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for the electrode reaction; and the pre-processed shape is at least the electrode reaction One or more recessed active material fluid flow paths formed corresponding to the effective area, and the pre-processed shape is corrugated, at least corresponding to the area effective for the electrode reaction. That the pre-processed shape corresponds to at least a region effective for the electrode reaction, and that the pre-processed shape has concave portions and convex portions. And were formed alternately By using the carbon plate in a battery, a fluid serving as an active material becomes a flow path for performing an electrode reaction when the carbon plate is used in a battery, and the contact efficiency with the electrode is improved. Can be improved.

Further, a meandering active material fluid flow path is formed in such a manner that the area of the electrode reaction is widened and corresponding to a region effective for the electrode reaction. Path and one or more concave active material fluid flow paths, and the effective contact area increases due to the corrugated processing / irregular processing / concave and convex portions formed alternately, and the contact with the electrodes Efficiency can be improved.

When an electrolyte membrane containing a proton conductor capable of conducting proton under non-humidified conditions is used, handling is easy and various processes such as adhesion and sputtering are facilitated. For this reason, for example, in order to reduce the poisoning of the catalyst by CO or the like, it is possible to apply a uniform film forming technique by sputtering or the like or a technique of bonding a permselective membrane. When a fullerene derivative bound by a binder is used for the electrolyte membrane, a proton conductor having sufficient strength can be formed because the fullerene derivative is bound by the binder.

As described above, according to the present invention, the contact efficiency with the electrode member can be improved, and not only can a battery with high electricity generation efficiency be obtained, but also the carbon plate of the present invention can be obtained. Using an electrode member consisting of
The battery itself can be made thinner. In addition, since the forming step of forming the carbon plate material into a predetermined shape is performed before the carbonizing step, the carbon plate material can be manufactured by a simple step.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an entire fuel cell according to an example of an embodiment of the present invention.

FIG. 2 is an explanatory diagram showing a specific configuration of a fuel cell according to one embodiment of the present invention.

FIG. 3A is a view showing one surface (a surface on a sheet film side) of an electrode plate according to one embodiment of the present invention,
3B is a cross-sectional view when the oxygen electrode plate and the hydrogen electrode plate are opposed to each other, and FIG. 3C is a view taken along line WW of FIG. 3A.

FIG. 4A is a diagram showing one surface (a surface on a sheet film side) of an electrode plate according to another embodiment of the present invention,
(B) is sectional drawing of an electrode plate.

5A is a diagram showing one surface (a surface on a sheet film side) of an electrode plate according to still another embodiment of the present invention, and FIG. 5B is a cross-sectional view of the electrode plate. is there.

FIG. 6 is a structural diagram of an example of a polyhydroxylated fullerene having a group capable of dissociating protons with a fullerene molecule as a main component.

FIG. 7 is a schematic diagram showing an example in which a fullerene molecule is a main component and a group that dissociates a proton is provided.

FIG. 8 is an explanatory diagram showing an example of a carbon cluster.

FIG. 9 is an explanatory diagram showing an example of a carbon cluster having an open end.

FIG. 10 is an explanatory diagram showing an example of a carbon cluster having a diamond structure.

FIG. 11 is an explanatory diagram showing an example of a carbon cluster in which various clusters are bonded.

FIG. 12 is an explanatory diagram of a self-humidifying electrolyte membrane.

FIG. 13 is an explanatory view of a method for producing a porous carbon plate for a fuel cell.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Electrolyte film 12 Insulator 13 Hydrogen electrode plate 14 Oxygen electrode plate 17 and 18 Sheet film 20 Frame 30 Seal member 31 Gas supply pipe 40 Plate 41 Hole 51 Convex part 52 Concave part 53 Convex part 54 Concave part 55 Concave part 55 Groove 56, 57 Opening 58 , 59 holes 61 belt conveyor 62 carbon plate forming die 63 material supply device 64 second belt 65 firing furnace 66 porous carbon plate B hydrogen gas cylinder C cell S stack

Claims (12)

[Claims] 1. An electrode member comprising a porous carbon plate produced by forming a resin material into a predetermined shape in advance of a carbonization treatment and then performing a carbonization treatment. 2. The electrode member according to claim 1, wherein said pre-processed shape is formed as any one of the following 1 to 8. 1. The shape to be processed in advance is formed so as to be a flow path for subjecting a fluid as an active material to an electrode reaction. 2. The pre-processed shape is on at least one side,
The electrode reaction area was widened. 3. The pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for an electrode reaction. 4. The pre-processed shape is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for an electrode reaction. 5. The pre-processed shape is one or more concave active material fluid flow paths formed corresponding to at least a region effective for an electrode reaction. 6. The pre-processed shape has been subjected to a corrugated process at least corresponding to a region effective for an electrode reaction. 7. The pre-processed shape has been subjected to a concavo-convex processing at least corresponding to a region effective for an electrode reaction. 8. The pre-processed shape is such that concave portions and convex portions are formed alternately. 3. A battery comprising a pair of electrode plates disposed opposite to each other, wherein at least one of the electrode plates comprises a porous carbon plate, and the electrode plate comprising the porous carbon plate comprises: 9. A battery formed as any one of the shapes 1 to 8. 1. The shape to be processed in advance is formed so as to be a flow path for subjecting a fluid as an active material to an electrode reaction. 2. The pre-processed shape is on at least one side,
The electrode reaction area was widened. 3. The pre-processed shape is a meandering active material fluid flow path formed corresponding to at least a region effective for an electrode reaction. 4. The pre-processed shape is a plurality of groove-shaped active material fluid flow paths formed corresponding to at least a region effective for an electrode reaction. 5. The pre-processed shape is one or more concave active material fluid flow paths formed corresponding to at least a region effective for an electrode reaction. 6. The pre-processed shape has been subjected to a corrugated process at least corresponding to a region effective for an electrode reaction. 7. The pre-processed shape has been subjected to a concavo-convex processing at least corresponding to a region effective for an electrode reaction. 8. The pre-processed shape is such that concave portions and convex portions are formed alternately. 4. The fuel cell according to claim 1, wherein the one electrode plate is a fuel electrode plate, and the other electrode plate is an oxygen electrode plate, between the fuel electrode plate and the oxygen electrode plate. The battery according to claim 3, further comprising an electrolyte layer formed, wherein at least one of the fuel electrode plate and the oxygen electrode plate comprises a porous carbon plate. 5. The battery according to claim 4, wherein the electrolyte membrane includes a proton conductor capable of conducting proton under non-humidified conditions. 6. The battery according to claim 5, wherein the proton conductor is formed by introducing a proton-dissociable group using a carbonaceous material containing carbon as a main component as a matrix. 7. The fuel cell according to claim 6, wherein the carbonaceous material is a fullerene molecule. 8. The fuel cell according to claim 4, wherein the electrolyte membrane contains a binder. 9. A method for manufacturing an electrode member, comprising: a forming step of forming a carbon plate material so as to form a concave portion on one surface of a desired shape; and a carbonizing treatment on the formed product obtained in the forming step. And a carbonization treatment step of performing the following. 10. The method according to claim 9, wherein the recess comprises at least one groove. 11. The method according to claim 10, wherein the at least one groove is a meandering groove. 12. A method for manufacturing an electrode member, comprising: a molding step of molding a carbon plate material so as to alternately form a concave portion and a convex portion on one surface of a desired shape; A carbonization treatment step of subjecting the formed product to a carbonization treatment.