JP2002151134A - Flat arranged type electrochemical element unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plane arranged electrochemical element unit enhancing the freedom of design by ensuring gas sealing ability of individual power generating element to prevent mixing of fuel and oxygen, and facilitating connection of electrode layers between adjacent power generating elements. SOLUTION: This flat electrochemical element unit is composed of a plurality of power generating elements 10. The power generating element 10 is formed by stacking a fuel electrode conductive porous plate 11, a fuel electrode layer 12, a proton conductor layer 13, an oxygen electrode layer 14, and an oxygen electrode conductive porous plate 15. The proton conductor layer 13 of each power generating element 10 is arranged on the same plane, and on one side of the proton conductor 13, the fuel electrode layer 12 of adjacent one power generating element 10 and the oxygen electrode layer 14 of the other power generating element 10 are alternately arranged on the same plane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a planar array type electrochemical element unit, and more particularly to a planar array type electrochemical element unit in which a plurality of power generating elements are arranged on the same plane and connected in series.

[0002]

2. Description of the Related Art A power generating element represented by a fuel cell utilizes electric energy among electric energy and heat energy generated by an electrochemical reaction for producing water from hydrogen and oxygen. The solid polymer type uses a solid polymer electrolyte membrane of a proton conductor layer. Both the fuel electrode layer and the cathode oxygen electrode layer are arranged with the proton conductor layer interposed therebetween, and hydrogen gas or the like as fuel is supplied to the fuel electrode layer side, and air or oxygen is supplied to the oxygen electrode layer to supply electricity. Electric power can be extracted by causing a chemical reaction.

Since a single power generating element generates a small amount of power, a plurality of power generating elements are connected in series to obtain a desired power. Here, a planar array-type electrochemical element unit in which a plurality of power generating elements are connected adjacent to each other in a planar manner has a vertical, horizontal, and height like a stack structure in which a plurality of power generating elements are stacked and arranged. In contrast to the structure with some dimensions, the vertical and horizontal dimensions are emphasized, so no space in the height direction is required, miniaturization can be achieved, and This is advantageous in that the degree of freedom of mounting is increased.

For example, in an electrochemical device unit described in Japanese Patent Application Laid-Open No. 4-206162, two insulating plates are arranged in parallel with each other, and an oxygen electrode layer, a proton conductor layer, a fuel A plurality of power generating elements having a laminated structure with the electrode layer are connected in series. Here, a layer of one power generation element adjacent to the plurality of power generation elements and a layer of another power generation element are arranged on substantially the same plane in a layer direction orthogonal to the lamination direction, and specifically, The fuel electrode layer of one power generation element is arranged in the same plane as the fuel electrode layer of the next power generation element, and the proton conductor layer of one power generation element is the same as the proton conductor layer of the next power generation element. The oxygen electrode layers of one power generation element are arranged side by side on the same plane as the oxygen electrode layer of the adjacent power generation element. The fuel electrode layer of one power generation element and the oxygen electrode layer of another power generation element are electrically connected via a connection cable in a state of crossing the plane on which the proton conductor layers are arranged.

[0005]

However, in the conventional planar array type electrochemical element unit, the connecting electrode crosses the fuel electrode layer of one power generating element and the other in a state of crossing the plane where the proton conductor layer is arranged. Is connected to the oxygen electrode layer of the power generating element, and the process becomes complicated in manufacturing the unit. Further, since it is necessary to arrange a connection cable between the power generating elements, it is necessary to secure a predetermined space between the power generating elements, and it has been difficult to reduce the size of the unit.

Therefore, the present invention can increase the degree of freedom in design by ensuring gas sealing properties of individual power generating elements to prevent mixing of fuel and oxygen, and to provide an electrode layer between adjacent power generating elements. It is an object of the present invention to provide a planar array type electrochemical element unit which facilitates connection of the elements.

[0007]

In order to achieve the above object, the present invention relates to an oxygen electrode layer, a proton conductor layer, and a fuel electrode layer having a laminated structure, wherein the oxygen electrode layer, the fuel electrode layer, A plurality of power generating elements in which the proton conductor layer is located are provided, and the layer of one adjacent power generating element and the layer of another power generating element are substantially coplanar in a layer direction orthogonal to the laminating direction. Are arranged in series, and the proton conductor layer of the one power generation element and the proton conductor layer of the other power generation element are arranged on the same plane. On one side of the proton conductor layer,
The fuel electrode layers of the one power generation element and the oxygen electrode layers of the other power generation elements are alternately arranged on substantially the same plane, and on the other side of the proton conductor layer, There is provided a planar array type electrochemical element unit in which the oxygen electrode layers of one power generation element and the fuel electrode layers of the other power generation elements are alternately arranged.

Here, a fuel-permeable fuel electrode conductive porous plate is provided on the fuel electrode layer of at least one of the power generating elements in a state of being electrically connected to the fuel electrode layer. In the oxygen electrode layer of another power generation element disposed adjacent to the power generation element, an oxygen-permeable oxygen electrode conductive porous plate is provided in a state electrically connected to the oxygen electrode layer, The fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are electrically connected at a connecting portion, and the connecting portion is connected to the fuel passing through the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate. It is preferable to form a blocking section for blocking mixing with oxygen permeating the porous porous plate.

It is preferable that the inside of the fuel electrode layer is filled with a hydrogen storage material.

Preferably, the connecting portion is made of a non-porous material through which gas cannot pass.

The fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is preferably made of carbon cloth.

It is preferable that the fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is formed of an acid-resistant metal net.

The fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is preferably made of a foamed metal.

Preferably, the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are arranged on the same plane and are integrated.

Preferably, the connecting portion is made non-porous.

The fuel electrode layer is constituted by a fuel-permeable porous substrate, and the oxygen electrode layer is constituted by an oxygen-permeable porous substrate. The oxygen electrode layer of another power generation element disposed adjacent to the one power generation element is electrically connected at a connection portion, and the connection portion is formed by a fuel that passes through the fuel electrode layer and the oxygen gas. It is preferable to form a blocking portion that blocks mixing with oxygen that passes through the electrode layer.

Preferably, the connecting portion is made of a non-porous material through which gas cannot pass.

Preferably, the fuel electrode layer and the oxygen electrode layer are arranged on the same plane and are integrated.

Preferably, the connecting portion is made non-porous.

The proton conductor layer preferably contains a proton conductor having a carbonaceous material containing carbon as a main component and having a proton-dissociable group introduced therein. Here, “proton dissociation” means that protons (H ⁺ ) are dissociated by ionization, and “proton dissociable group” means a functional group from which protons can be dissociated by ionization.

Further, the proton conductor layer preferably contains a proton conductor made of a perfluorosulfonic acid resin.

Further, the proton conductor layer is preferably formed of an electrolyte membrane which does not require water management.
The electrolyte membrane that does not require water management is more specifically
It refers to an internally humidified solid polymer membrane, a polymer membrane to which a proton conductive inorganic compound is added, and the like.

Further, it is preferable that an insulating plate provided with a fuel supply portion for supplying fuel to the fuel electrode layer is opposed to the fuel electrode layer.

Preferably, the fuel supply section comprises a hydrogen supply path for supplying hydrogen.

It is preferable that the fuel supply section has a hydrogen storage. More specifically, the hydrogen storage body
It is made of carbon-based fullerene, nanotube or nanofiber, or hydrogen storage alloy.

Further, it is preferable that a meandering path for contacting fuel with substantially the entire fuel electrode layer is formed in the insulating plate.

It is preferable that the oxygen electrode layer is provided with an insulating plate having an oxygen entrance path for allowing oxygen to contact the oxygen electrode layer.

It is preferable that the insulating plate has a meandering path for contacting the fuel with substantially the entire oxygen electrode layer.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A planar array type electrochemical element unit 1 according to an embodiment of the present invention will be described with reference to FIG. The planar array type electrochemical element unit 1 has a plurality of power generation elements 10. Each power generating element 10 includes a square-plate-shaped fuel electrode conductive porous plate 11, a fuel electrode layer 12, a proton conductor layer 13, an oxygen electrode layer 14, and an oxygen electrode conductive porous plate 15. The layers are stacked in this order, and the respective planes are connected to each other. Since each layer is square, each power generation element 10
Also have a square shape when viewed from the direction of arrow X. Between the oxygen electrode layer 14 and the fuel electrode layer 12, protons such as hydrogen ions can be conducted through the proton conductor layer 13. Fuel electrode conductive porous plate 1
1. The oxygen electrode conductive porous plate 15 is made of carbon cloth having hydrogen permeability and oxygen permeability. Fuel electrode conductive porous plate 11 and fuel electrode layer 12
Between the oxygen electrode layer 14 and the oxygen electrode conductive porous plate 15
Are electrically connected to each other.

On the opposite side of the fuel electrode conductive porous plate 11 from the side connected to the fuel electrode layer 12, there are two side walls 16B and one bottom surface 16A, and the cross section is substantially U-shaped. An insulating plate 16 having a shape is provided. The insulating plate 16 is made of a resin sheet. The insulating plate 16 is a fuel electrode conductive porous plate 1.
The fuel electrode layer 1 is provided at a position directly facing the fuel electrode layer 1.
2 has an indirectly opposed positional relationship. One end of the ends of the two side walls 16B constituting the insulating plate 16 and not connected to the bottom surface 16A is connected to the fuel electrode conductive porous plate 11.
The surface of the fuel electrode conductive porous plate 11 facing the insulating plate 16 and the two side walls 1 of the insulating plate 16
A space closed to the atmosphere is defined by 6B and the bottom surface 16A, and this space forms a hydrogen supply path. The hydrogen supplied from the hydrogen supply passage is configured to pass through the fuel electrode conductive porous plate 11 and contact the fuel electrode layer 12.

On the opposite side of the oxygen electrode conductive porous plate 15 from the side connected to the oxygen electrode layer 14, there are four side walls 17 extending in the stacking direction of the layers constituting the power generation element 10.
An insulating plate 17 made of A is provided. The outer surface of the insulating plate 17 is in the shape of a quadrangular prism, and its axial direction is oriented in the direction in which the layers forming the power generating element 10 are stacked. An opening is formed at one end of the insulating plate, and the other end is closed by an oxygen electrode conductive porous plate 15. Since an opening is formed at one end of the insulating plate 17,
The space defined by the oxygen electrode conductive porous plate 15 and the four side walls 17A forming the insulating plate 17 communicates with the atmosphere and forms an oxygen entrance path. Therefore,
Oxygen in the atmosphere is configured to be able to contact the oxygen electrode layer 14 via the oxygen electrode conductive porous plate 15 through the oxygen entry path. The insulating plate 17 is formed of a resin sheet.

The fuel electrode layer 12 is composed of a combination of Pt-supported carbon and a carbon sheet as a gas diffusion layer, or a porous carbon is provided with a fullerene derivative-based proton conductor, more specifically, The poly (fullerene hydroxide) is impregnated as a proton conductor having a carbonaceous material containing carbon as a main component and a proton dissociable group introduced therein. Fuel electrode layer 12
Is contacted with hydrogen from a hydrogen supply path, and hydrogen ions and electrons are generated from the hydrogen. Since the fullerene derivative-based proton conductor is used as the ion conductor and is impregnated in the fuel electrode layer 12, the ion conduction in the electrode can be kept good even in the non-humidified fuel state.
Further, a fullerene derivative-based proton conductor can be adapted to the platinum catalyst.

The fullerene derivative-based pro
Ton conductor is a fullerene component that forms a spherical cluster molecule.
The child is the mother. Usually, C₃₆, C₆₀, C₇₀, C
₇₆, C₇₈, C₈₀, C₈₂, C₈₄Selected from etc.
However, in the present embodiment, C₆₀And C₇₀Is chosen
You. Proton dissociable groups are present on the constituent carbon atoms of fullerene
Introduced to form fullerene derivative proton conductor
Is done. Furthermore, by introducing an electron withdrawing group,
The proton dissociation of the group is further promoted. Proto
A non-dissociable group is a hydrogen ion (proton
(H⁺)) Means a functional group capable of leaving, and —OH, —O
SO₃H, -COOH, -SO₃H, -OPO (OH)
₂Is preferred, but in the present embodiment, -OH or
Is -OSO ₃H is preferably used. In particular, the proton solution
Polyhydroxylated fullerene having -OH as a releasing group
(Commonly known as fullerenol)
Formed with perfluorosulfonic acid resin used
It has better film-forming properties than the
Humidifier, etc.
Is unnecessary. Further, the operating temperature range is from -40 ° C to 16 ° C.
It has the advantage of being as wide as 0 ° C, etc.
For fuel cells. Also, as an electron withdrawing group
Stands for nitro, carbonyl, carboxyl, nitrile
Group, halogenated alkyl group, halogen atom (fluorine,
One or more of
Has been established.

Similarly to the fuel electrode layer 12, the oxygen electrode layer 14 is formed by combining Pt-supported carbon and a carbon sheet as a gas diffusion layer.
A porous carbon similar to the porous carbon of No. 2 is impregnated with a fullerene derivative-based proton conductor. The oxygen in the air comes into contact with the catalyst in the oxygen electrode layer 14, where the protons generated in the fuel electrode layer 12 and conducted to the oxygen electrode layer 14 through the proton conductor layer 13 and oxygen molecules And water supplied from an external circuit (not shown).

A fullerene derivative-based proton conductor is also used for the proton conductor layer 13 itself. In particular,
The proton conductor layer 13 is formed by impregnating a porous substrate made of polyethylene (PE), polypropylene (PP), or polytetrafluoroethylene (PTFE) with a fullerene derivative-based proton conductor. And form a solid film layer.

The square-shaped power generating elements 10 share one side of the square with each other, that is, one side wall 17A of the insulating plate 17 and one side wall of the insulating plate 16 each having the shape of a quadrangular prism. 16A and are connected. Proton conductor layer 13 of each power generation element 10
Are all arranged on the same plane, and the fuel electrode layer 12 of one power generation element 10 and the oxygen electrode layer 14 of another power generation element 10 adjacent to one power generation element 10 are arranged on the same plane. Have been. That is, the fuel electrode layer 12 and the oxygen electrode layer 14 are alternately arranged on one side with the proton conductor arranged on the same plane as a boundary, and the oxygen electrode layer 14 is also arranged on the other side. The fuel electrode layers 12 and the fuel electrode layers 12 are alternately arranged.

The first, second and third threes connected in series
In one power generating element, between the fuel electrode conductive porous plate 11 of the first power generating element 10 and the oxygen electrode conductive porous plate 15 of the second power generating element A connection portion 18 made of a conductive non-porous material is provided. The connection part 18 electrically connects the fuel electrode conductive porous plate 11 of the first power generation element 10 and the oxygen electrode conductive porous plate 15 of the second power generation element 10. Hydrogen in the fuel electrode conductive porous plate 11 and the oxygen electrode conductive porous plate 15 in the second power generation element 10
It shuts off so that it does not mix with oxygen inside. On the other hand, the fuel electrode layer 12, the proton conductor layer 13, the oxygen electrode layer 14, and the oxygen electrode conductive porous plate 15 of the first power generation element 10
Between the oxygen electrode layer 14, the proton conductor layer 13, the fuel electrode layer 12, and the fuel electrode conductive porous plate 11 of the second power generation element 10. A connecting portion 19 made of a porous material is provided.
The connecting portion 19 is connected to the fuel electrode layer 12 of the first power generation element 10,
Proton conductor layer 13, oxygen electrode layer 14, oxygen electrode conductive porous plate 15 and oxygen electrode layer 1 of second power generation element 10
4. The proton conductor layer 13, the fuel electrode layer 12, and the fuel electrode conductive porous plate 11 are electrically isolated from each other, and the gas in each layer constituting the first power generation element 10 and the second power generation element The gas in each layer constituting 10 is shut off so as not to be mixed.

Similarly, between the fuel electrode conductive porous plate 11 of the second power generation element 10 and the oxygen electrode conductive porous plate 15 of the third power generation element 10, carbon, a contact-resistant metal or the like is provided. A connection portion 18 made of a conductive non-porous material is provided. The fuel electrode layer 1 of the second power generation element 10
2. Proton conductor layer 13, oxygen electrode layer 14, oxygen electrode conductive porous plate 15, and oxygen electrode layer 14, proton conductor layer 13, fuel electrode layer 12, fuel electrode conductivity of third power generation element 10. A connecting portion 19 made of an insulating non-porous material such as a gas-permeable resin is provided between the porous plate 11 and the porous plate 11.
Is provided.

In the power generating element 10 at one end of the plurality of connected power generating elements 10, a positive electrode terminal 20 made of a good conductive metal is provided so as to protrude outside. Terminal 20 is an oxygen electrode conductive porous plate 1
5 is electrically connected. Power generating element 10 at the other end
Similarly, the negative electrode terminal 21 made of a good conductive metal is electrically connected to the fuel electrode conductive porous plate 11 and provided so as to protrude to the outside.

The connection portions 18, 1 made of a non-porous material are provided between each layer of the first power generation element 10 and each layer of the second power generation element 10 disposed adjacent to the first power generation element 10.
9 is provided, for example, the first power generation element 10
It is possible to block the mixture of oxygen passing through the oxygen electrode layer 14 and hydrogen passing through the fuel electrode layer 12 of the second power generation element 10. Therefore, the fuel electrode layer 12 of the adjacent first power generation element 10 and the oxygen electrode layer 14 of the second power generation element 10 can be arranged on the same plane, and the oxygen electrode layer of the adjacent first power generation element 10 Layer 14 and second power generating element 1
Since the fuel electrode layer 12 and the zero fuel electrode layer 12 can be arranged on the same plane, when a plurality of power generation elements 10 are connected in series, the connection between the power generation elements 10 can be made a small space, and the connection can be made. Can be easier.

Next, a planar array type electrochemical element unit 3 according to a second embodiment will be described with reference to FIG. The power generation element 30 of the planar array type electrochemical element unit 3 according to the second embodiment is different from the first embodiment in that the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are not provided. It is different from the power generating element 10 in the embodiment. The insulating plate 16 and the fuel electrode layer 12 are directly opposed, and the insulating plate 17 and the oxygen electrode layer 14 are provided in direct contact with each other.

Further, the first, second, and third serially connected
In the three power generating elements described above, a conductive non-porous material such as carbon or a contact-resistant metal is provided between the fuel electrode layer 12 of the first power generating element 30 and the oxygen electrode layer 14 of the second power generating element 30. Is provided. The connection portion 18 electrically connects the fuel electrode layer 12 of the first power generation element 10 to the oxygen electrode layer 14 of the second power generation element 10. The hydrogen and the oxygen in the oxygen electrode layer 14 of the second power generation element 10 are blocked so as not to be mixed. On the other hand, between the proton conductor layer 13 and the oxygen electrode layer 14 of the first power generation element 30 and between the proton conductor layer 13 and the fuel electrode layer 12 of the second power generation element 30, a gas-permeable resin or the like is provided. A connection portion 19 made of an insulating non-porous material is provided. Connection part 1
9 electrically disconnects the proton conductor layer 13 and the oxygen electrode layer 14 of the first power generation element 10 from the proton conductor layer 13 and the fuel electrode layer 12 of the second power generation element 10;
Is shut off so that the gas in each layer constituting the power generating element 10 and the gas in each layer constituting the second power generating element 10 do not mix.

Similarly, between the fuel electrode layer 12 of the second power generation element 10 and the oxygen electrode layer 14 of the third power generation element 10, there is provided a conductive non-porous material such as carbon or metal having a contact resistance. Is provided. Also, the second
Conductor layer 13 and oxygen electrode layer 1 of the power generating element 10 of FIG.
A connection section 19 made of an insulating non-porous material such as a gas-permeable resin is provided between the fourth power generation element 10 and the proton conductor layer 13 and the fuel electrode layer 12 of the third power generation element 10. ing.

In the power generating element 30 at one end of the plurality of connected power generating elements 30, a positive electrode terminal 20 made of a good conductive metal is provided so as to protrude outside. The terminal 20 is electrically connected to the oxygen electrode layer 14. Similarly, in the other end of the power generating element 30, the negative electrode terminal 21 made of a good conductive metal is provided so as to be electrically connected to the fuel electrode layer 12 and protrude to the outside.

Since the fuel electrode conductive porous plate and the fuel electrode conductive porous plate need not be provided, the configuration of the planar array type electrochemical element unit 3 can be simplified, and the apparatus can be reduced in size and weight. Can be achieved.

Next, a planar array type electrochemical element unit 5 according to a third embodiment will be described with reference to FIG. In the power generating element 50 of the planar array type electrochemical element unit 5 according to the third embodiment, an insulating plate 51 for storing a hydrogen storage body is provided at a position directly facing the fuel electrode conductive porous plate 11. This is different from the power generating element 10 in the first embodiment in that The insulating plate 51 has a substantially square shape in outer shape, and is provided in a state where the opening of the square shape is closed by the fuel electrode conductive porous plate 11. A space defined by the insulating plate 51 and the fuel electrode conductive porous plate 11 is filled with a hydrogen storage body 52 storing hydrogen. The hydrogen stored in the hydrogen storage body 52 is configured to pass through the fuel electrode conductive porous plate 11 and reach the fuel electrode layer 12.

The hydrogen storage 52 is made of carbon-based fullerene, nanotube, or nanofiber. The hydrogen supplied from the outside of the hydrogen storage body 52 is stored therein,
It functions as a fuel source for supplying hydrogen to the fuel electrode layer 12. Here, storing hydrogen inside does not necessarily mean storing hydrogen molecules as they are, but storing hydrogen supplied from the outside in a predetermined state according to the material constituting the hydrogen storage body 52. Means to do. In addition, supplying hydrogen does not necessarily mean that hydrogen molecules are supplied to the fuel electrode layer 12 as it is, but the hydrogen storage material 52
Means supplying hydrogen to the fuel electrode layer 12 in a predetermined state such that the fuel electrode layer 12 can generate protons as hydrogen ions.

In the planar array type electrochemical element unit 5,
The provision of the hydrogen storage body 52 capable of supplying hydrogen to the fuel electrode layer 12 eliminates the need for a hydrogen supply device or the like for supplying hydrogen from outside the planar array type electrochemical element unit 5, and the planar array type electrochemical element unit 5 is not required. The element unit 5 can be used as a battery that can be used in portable electronic devices and the like.

Next, a planar array type electrochemical device unit 7 according to a fourth embodiment will be described with reference to FIG. In the power generating element 70 of the planar array type electrochemical element unit 7 according to the fourth embodiment, an insulating plate 51 for storing a hydrogen storage body is provided at a position directly facing the fuel electrode layer 12. This is different from the power generating element 30 according to the second embodiment. The insulating plate 51
The outer shape has a substantially square shape, and is provided in a state where the opening of the square shape is closed by the fuel electrode layer 12. A space defined by the insulating plate and the fuel electrode layer 12 is filled with a hydrogen storage body 52 storing hydrogen. The hydrogen stored in the hydrogen storage body 52 can be supplied to the fuel electrode layer 12.

In the planar array type electrochemical element unit 7,
The provision of the hydrogen storage body 52 capable of supplying hydrogen to the fuel electrode layer 12 eliminates the need for a hydrogen supply device or the like for supplying hydrogen from outside the planar array type electrochemical element unit 7, and the planar array type electrochemical element unit 7 is not required. The element unit 7 can be used as a battery that can be used in portable electronic devices and the like.

The electrochemical device and the method of manufacturing the electrochemical device according to the present invention are not limited to the above-described embodiments, and various modifications and improvements can be made within the scope described in the claims. For example, the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are made of carbon cloth, but instead of carbon cloth, they can be in direct contact with an electrode layer having an acidic fullerene derivative-based proton conductor. It may be made of an oxygen and hydrogen permeable substance such as an acid-resistant metal net or foam metal that does not corrode.

In the first and third embodiments, the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are provided separately for each power generating element. On one side of the arranged plane, it may be provided as an integral conductive porous plate common to a plurality or all of the power generating elements. In this case, by making the conductive porous plate non-porous at the position of the connection between the power generating elements, the adjacent fuel electrode conductive porous plate and oxygen electrode conductive porous plate can be distinguished from each other. What is necessary is just to comprise. With this configuration, the planar array type electrochemical element unit can be manufactured more easily.

In the second and fourth embodiments, the fuel electrode layer and the oxygen electrode layer are provided separately for each power generating element, but are separated by the plane on which the proton conductor layer is arranged. On one side, it may be provided as an integral electrode layer common to a plurality or all of the power generating elements. In this case, by making the porous electrode layer non-porous at the position of the connection between the power generating elements, it may be configured to distinguish between the adjacent fuel electrode layer and oxygen electrode layer. With this configuration, the planar array type electrochemical element unit can be manufactured more easily.

The fuel electrode layer 12 and the oxygen electrode layer 14
Although the porous carbon is formed by impregnating the fullerene derivative-based proton conductor, the porous carbon may be formed without impregnation.

Although the insulating plate is made of a resin sheet, it may be made of a block or the like.

As the hydrogen storage material, a hydrogen storage alloy may be used instead of carbon-based fullerene, nanotube or nanofiber.

Further, the space defined by the fuel electrode conductive porous plate or fuel electrode layer and the insulating plate is filled with the hydrogen storage material. Instead, the hydrogen storage material is replaced with the fuel electrode. The hydrogen electrode may be formed by filling the fuel electrode layer with the fuel electrode layer and the hydrogen storage body.

The insulating plates 16 and 17 may be formed with a meandering path for bringing fuel and oxygen into contact with substantially the entire fuel electrode layer and oxygen electrode layer.

In the electrochemical device according to the present embodiment, the proton conductor layer is formed by impregnating the porous substrate with the fullerene derivative-based proton conductor, but the present invention is not limited to this. Instead of the proton conductor layer, a film type obtained by blending a resin binder or the like with any proton conductor not limited to the fullerene derivative-based material may be used. In addition, an electrolyte membrane that does not require water management, more specifically, a so-called internal structure in which a very small amount of ultrafine platinum catalyst and ultrafine oxide particles such as TiO ₂ and SiO ₂ are highly dispersed in the proton conductor layer. and humidified solid polymer membrane, phosphate - silicate (P ₂ O ₅ -SiO ₂₎ based proton conductive inorganic compound polymer film may be used with the addition of glass. By using these, as in the case of the electrochemical device according to the present embodiment, it is not necessary to include moisture in the fuel with a humidifier or the like.

In the flat array type electrochemical element units according to the first and second embodiments described above, hydrogen gas is supplied as a fuel. However, alcohol such as methanol or other fossil fuels or the like is used as a liquid or a liquid. It is also possible to adopt a direct type in which the gas is supplied in a gaseous state, and obtain a proton from a fuel material by a catalyst at a fuel electrode. In this case, a fuel source capable of storing alcohol, fossil fuel, or the like may be used instead of the hydrogen storage body provided in the electrochemical device according to the present embodiment.

Although the proton conductor is composed of a fullerene derivative-based proton conductor, it may be composed of a proton conductor composed of an organic material such as a perfluorosulfonic acid resin. However, when a perfluorosulfonic acid resin is used, it is necessary to make the fuel contain moisture by a humidifier or the like.

Further, in the present embodiment, poly (fullerene hydroxide) (commonly called fullerenol) is used as a proton conductor constituting an ion exchange membrane capable of conducting proton in a non-humidified state, but the present invention is not limited to this. It is not something to be done. The polyhydroxylated fullerene has a fullerene molecule as a base as shown in FIG. 5 and a hydroxyl group introduced into its constituent carbon atoms. However, the base is not limited to the fullerene molecule but may be a carbonaceous material mainly composed of carbon. Should be fine. This carbonaceous material includes carbon clusters, which are aggregates formed by bonding several to hundreds of carbon atoms regardless of the type of carbon-carbon bond, and tubular carbonaceous materials (commonly known as carbon Nanotubes). The former carbon cluster includes various carbon clusters having a closed surface structure similar to spheres or spheroids (FIG. 6), which are composed of a large number of carbon atoms (FIG. 6), and a part of those spherical structures. Is missing and a carbon cluster having an open end in the structure (FIG. 7), a carbon cluster having a diamond structure in which most of the carbon atoms are sp ³ bonded (FIG. 8), and these clusters are variously bonded. Carbon clusters (FIG. 9) may be included.

The group to be introduced into the host of this type is not limited to a hydroxyl group, but may be any proton-dissociable group represented by -XH, more preferably -YOH. Here, X and Y are arbitrary atoms or atomic groups having a divalent bond, H is a hydrogen atom, and O is an oxygen atom. Specifically, in addition to the -OH, a hydrogen sulfate ester group -OSO ₃
H, carboxyl group -COOH, and other sulfone group -SO
It is preferably any of ₃ H and a phosphate group -OPO (OH) ₂ .

In any of the above modifications, humidification is not required for proton conduction, and the effect of the present invention remains unchanged.

[0065]

According to the first aspect of the present invention, the fuel electrode layer of one power generation element and the fuel electrode layer of another power generation element are arranged on substantially the same plane on one side of the proton conductor layer. Oxygen electrode layers are alternately arranged, and on the other side of the proton conductor layer, oxygen electrode layers of one power generation element and fuel electrode layers of another power generation element are alternately arranged on substantially the same plane. Therefore, connection between the power generating elements can be facilitated. Further, the space required for connection between the power generating elements can be minimized, the size of the planar array type electrochemical element unit can be reduced, and the degree of freedom for connecting a plurality of power generating elements in series can be increased. can do.

According to the planar array type electrochemical element unit of the present invention, the fuel electrode conductive porous plate of one power generating element and the oxygen electrode conductive porous plate of another power generating element are connected to each other. Since the connection portion is configured to block mixing of fuel permeating the fuel electrode conductive porous plate and oxygen permeating the oxygen electrode conductive porous plate,
Adjacent power generating elements can be easily electrically connected to each other in a state where oxygen and hydrogen are prevented from being mixed in adjacent power generating elements.

According to the third aspect of the present invention, since the inside of the fuel electrode layer is filled with the hydrogen absorbing material, the hydrogen as the fuel is supplied from outside the flat type electrochemical element unit. Need not be supplied, and the planar array type electrochemical element unit can be used as a battery used in a portable electronic device.

According to the planar array type electrochemical element unit of the fifth, sixth and seventh aspects, the fuel electrode conductive porous plate which does not corrode even when directly in contact with the electrode layer having the acidic proton conductor is provided. An oxygen electrode conductive porous plate can be used.

According to the flat array type electrochemical element unit of the present invention, the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are arranged on the same plane and are integral with each other. The manufacture of the arrayed electrochemical element unit can be further simplified.

According to the planar array type electrochemical element unit of the ninth aspect, the manufacture of the planar array type electrochemical element unit is further simplified, and oxygen and hydrogen are mixed in adjacent power generating elements. Can be prevented.

According to the planar array type electrochemical element unit of the tenth and eleventh aspects, the fuel electrode layer of one power generation element and the oxygen electrode layer of the other power generation element are electrically connected at the connection portion. , The connection portion, the fuel permeating the fuel electrode layer,
Since it is configured to block mixing with oxygen passing through the oxygen electrode layer, adjacent power generating elements can be easily electrically connected to each other in a state where oxygen and hydrogen are prevented from being mixed in adjacent power generating elements. And the planar array type electrochemical element unit can be made thinner and lighter.

According to the twelfth aspect of the present invention, the fuel electrode layer and the oxygen electrode layer are arranged on the same plane and are integrated. It can be more simplified.

According to the planar array type electrochemical element unit, the manufacturing of the planar array type electrochemical element unit is further simplified, and oxygen and hydrogen are mixed in adjacent power generating elements. Can be prevented.

According to the planar array type electrochemical element unit of the present invention, it is possible to provide a planar array type electrochemical element unit which performs good proton conduction even in a non-humidified state of fuel.

According to the flat array type electrochemical element unit of the present invention, a flat array type electrochemical element unit which can conduct good proton conduction in a fuel humidified state can be obtained.

According to the planar array type electrochemical element unit of the present invention, the planar array type electrochemical element unit can be insulated from the outside, and
Fuel can be easily supplied to the fuel electrode layer from outside the planar array type electrochemical element unit.

According to the planar array type electrochemical device unit of the present invention, the planar array type electrochemical device unit can be insulated from the outside, and can be insulated from the outside of the planar array type electrochemical device unit. There is no need to supply hydrogen as a fuel, and the planar array type electrochemical element unit can be used as a battery used in portable electronic devices.

According to the planar array type electrochemical element unit according to the twentieth and twenty-second aspects, since the meandering path is formed, the fuel and oxygen can be brought into contact with substantially the entire fuel electrode layer and oxygen electrode layer. it can.

According to the planar array type electrochemical device unit of the present invention, oxygen in the atmosphere is removed from the outside of the planar array type electrochemical device unit while the planar array type electrochemical device unit is insulated from the outside. It can be brought into contact with the electrode layer, and handling of the planar array type electrochemical element unit can be facilitated.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a planar array type electrochemical element unit according to a first embodiment of the present invention, and FIG. 1 (b) is a cross-sectional view showing a state in which layers of a power generating element are stacked; FIG. 3B is a cross-sectional view along the line aa in FIG. 3B, and FIG.
Sectional drawing along the -c line.

FIGS. 2A and 2B are cross-sectional views showing a planar array type electrochemical element unit according to a second embodiment of the present invention, wherein FIG. 2B is a cross-sectional view showing a state in which layers of a power generating element are stacked, and FIG. FIG. 3B is a cross-sectional view along the line aa in FIG. 3B, and FIG.
Sectional drawing along the -c line.

FIG. 3 is a cross-sectional view showing a planar array type electrochemical element unit according to a third embodiment of the present invention, wherein (b) is a cross-sectional view showing a state in which layers of a power generation element are stacked, and (a). FIG. 3B is a cross-sectional view along the line aa in FIG. 3B, and FIG.
Sectional drawing along the -c line.

FIG. 4 is a cross-sectional view showing a planar array type electrochemical element unit according to a fourth embodiment of the present invention, and FIG. 4 (b) is a cross-sectional view showing a state in which layers of a power generating element are stacked; FIG. 3B is a cross-sectional view along the line aa in FIG. 3B, and FIG.
Sectional drawing along the -c line.

FIG. 5 is a molecular structure diagram showing fullerene constituting a proton conductor used in the electrochemical device according to the embodiment of the present invention.

FIG. 6 is a molecule showing various carbon clusters having a spherical surface or a long sphere, or a closed surface structure similar to these, constituting a proton conductor used in a modification of the electrochemical device according to the embodiment of the present invention. Structural drawing.

FIG. 7 is a molecular structural diagram showing a carbon cluster having a part of a spherical structure missing and having an open end in the structure, which constitutes a proton conductor used in a modification of the electrochemical device according to the embodiment of the present invention. .

FIG. 8 is a molecular structure diagram showing a carbon cluster having a diamond structure in which most of the carbon atoms constitute an sp ³ bond, which constitutes a proton conductor used in a modification of the electrochemical device according to the embodiment of the present invention.

FIG. 9 is a molecular structure diagram showing a carbon cluster in which a plurality of clusters are variously combined, constituting a proton conductor used in a modification of the electrochemical device according to the embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Planar arrangement type electrochemical element unit 3 Planar arrangement type electrochemical element unit 5 Planar arrangement type electrochemical element unit 7 Planar arrangement type electrochemical element unit 10 Power generation element 11 Fuel electrode conductive porous plate 12 Fuel electrode layer 13 Proton conduction Body layer 14 Oxygen electrode layer 15 Oxygen electrode conductive porous plate 16 Insulating plate 17 Insulating plate 18 Connecting portion 19 Connecting portion 30 Power generating element 50 Power generating element 51 Insulating plate 52 Hydrogen storage element 70 Power generating element

Claims (22)

[Claims] An oxygen electrode layer, a proton conductor layer, and a fuel electrode layer form a laminated structure, and a plurality of power generating elements in which the proton conductor layer is located between the oxygen electrode layer and the fuel electrode layer are provided. Adjacent one layer of the power generation element and another layer of the power generation element are arranged in series on a substantially same plane in a layer direction orthogonal to the laminating direction and are connected in series, and the protons of the one power generation element are connected in series. In a planar array type electrochemical element unit in which a conductor layer and the proton conductor layer of the other power generation element are arranged on the same plane, one side of the proton conductor layer is substantially coplanar with the proton conductor layer. The fuel electrode layer of one power generation element and the oxygen electrode layer of the other power generation element are alternately arranged, and the other side of the proton conductor layer is substantially coplanar with the one power generation element. The oxygen electrode layer and the fuel electrode layer of the other power generation element are alternately arranged A planar array type electrochemical element unit characterized in that: 2. The fuel electrode layer of at least one of the power generating elements is provided with a fuel-permeable fuel electrode conductive porous plate in a state of being electrically connected to the fuel electrode layer. An oxygen-permeable oxygen electrode conductive porous plate is provided on the oxygen electrode layer of another power generation element disposed adjacent to the power generation element in a state where the porous plate is electrically connected to the oxygen electrode layer. The electrode conductive porous plate and the oxygen electrode conductive porous plate are electrically connected at a connection portion, and the connection portion is connected to the fuel that passes through the fuel electrode conductive porous plate and the oxygen electrode conductivity. 2. The flat array type electrochemical element unit according to claim 1, wherein a blocking portion for blocking mixing with oxygen permeating through the porous plate is formed. 3. The planar array type electrochemical element unit according to claim 2, wherein the inside of the fuel electrode layer is filled with a hydrogen storage material. 4. The connecting part is made of a non-porous material through which gas cannot pass.
The planar array type electrochemical element unit according to the above. 5. The flat array type electrochemical element unit according to claim 2, wherein the fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is made of carbon cloth. 6. The planar array type electrochemical element according to claim 2, wherein the fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is formed of an acid-resistant metal net. unit. 7. The flat array type electrochemical element unit according to claim 2, wherein the fuel electrode conductive porous plate or the oxygen electrode conductive porous plate is made of a foamed metal. 8. The planar array type electrochemical device according to claim 2, wherein the fuel electrode conductive porous plate and the oxygen electrode conductive porous plate are arranged on the same plane and are integrated. Element unit. 9. The planar array type electrochemical element unit according to claim 8, wherein said connecting portion is made non-porous. 10. The fuel electrode layer is composed of a fuel-permeable porous substrate, the oxygen electrode layer is composed of an oxygen-permeable porous substrate, and at least one of the fuel electrode layers of the power generating element; The oxygen electrode layer of another power generation element disposed adjacent to the one power generation element is electrically connected at a connection portion, and the connection portion is formed by a fuel that passes through the fuel electrode layer and the oxygen gas. 2. The planar array type electrochemical element unit according to claim 1, wherein a blocking portion for blocking mixing with oxygen passing through the electrode layer is formed. 11. The flat array type electrochemical element unit according to claim 10, wherein said connecting portion is made of a non-porous material through which gas cannot pass. 12. The flat array type electrochemical element unit according to claim 10, wherein said fuel electrode layer and said oxygen electrode layer are arranged on the same plane and are integrated. 13. The flat array type electrochemical element unit according to claim 12, wherein said connecting portion is made non-porous. 14. The fuel according to claim 1, wherein the proton conductor layer contains a carbonaceous material containing carbon as a main component and a proton conductor into which a proton dissociating group is introduced. battery. 15. The fuel cell according to claim 1, wherein the proton conductor layer includes a proton conductor made of a perfluorosulfonic acid resin. 16. The flat array type electrochemical element unit according to claim 1, wherein said proton conductor layer is constituted by an electrolyte membrane which does not require water management. 17. The fuel electrode layer according to claim 1, wherein an insulating plate provided with a fuel supply section for supplying fuel to the fuel electrode layer is disposed to face the fuel electrode layer. Planar array type electrochemical element unit. 18. The flat array type electrochemical element unit according to claim 17, wherein said fuel supply section comprises a hydrogen supply path for supplying hydrogen. 19. The flat array type electrochemical element unit according to claim 17, wherein the fuel supply section has a hydrogen storage body. 20. The planar array type electrochemical element unit according to claim 17, wherein a meandering path for contacting the fuel with substantially the entire fuel electrode layer is formed in the insulating plate. . 21. The oxygen electrode layer is provided with an insulating plate having an oxygen entrance path for allowing oxygen to contact the oxygen electrode layer.
The planar array type electrochemical element unit according to the above. 22. The planar array type electrochemical element unit according to claim 21, wherein a meandering path for making fuel contact with substantially the entire oxygen electrode layer is formed in the insulating plate. .