JP2002216796A - Electrochemical device and proton conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical device for maintaining proton conductivity without lowering electromotive force by preventing the entry of a water from an oxygen electrode side into a proton conductor membrane, and a proton conductor. SOLUTION: The proton conductor to be held between a fuel electrode 2 and an oxygen electrode 3 consists of a first proton conductor 1 having other groups than proton (H+) dissociative hydroxyl groups, disposed on the side of the fuel electrode 2, and a second conductor 7 having proton (H+) dissociative groups, disposed on the side of the oxygen electrode 3, to form a fuel cell. A water produced by the oxygen electrode 3 is shut off by the second proton conductor 7 and prevented from entering into the first proton conductor 1, therefore maintaining electromotive force without impairing the proton conductivity of the first proton conductor 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrochemical device suitable as a fuel cell and a proton (H ⁺ ) conductor used for the same.

[0002]

2. Description of the Related Art In recent years, for example, as a polymer solid electrolyte type fuel cell for driving an automobile, a proton (hydrogen ion) conductive material such as a perfluorosulfonic acid resin (such as Nafion (R) manufactured by Du Pont) has been used. One using a polymer material is known.

[0003] Also, relatively new proton conductors include H ₃ Mo ₁₂ PO ₄₀ .29H ₂ O and Sb ₂ O ₅ .5.4H.
Polymolybdates and oxides having many waters of hydration such as ₂ O are also known.

[0004] When these polymer materials and hydrated compounds are placed in a wet state, they exhibit high proton conductivity near normal temperature.

That is, in the case of a perfluorosulfonic acid resin, for example, protons ionized from the sulfonic acid groups are protonated by bonding (hydrogen bonding) with water taken in a large amount into the polymer matrix. Since water, that is, oxonium ions (H ₃ O ⁺ ) are generated, and protons can smoothly move in the polymer matrix in the form of the oxonium ions, this kind of matrix material can be used at room temperature. A considerably high proton conduction effect can be exhibited.

On the other hand, recently, proton conductors having a completely different conduction mechanism from these have been developed.

That is, it has been found that a composite metal oxide having a perovskite structure, such as Yb-doped SrCeO ₃ , has proton conductivity without using water as a transfer medium. In this composite metal oxide, it is considered that protons are independently channeled between oxygen ions forming the skeleton of the perovskite structure and are conducted.

However, this conductive proton is not always present in the composite metal oxide from the beginning. When the perovskite structure comes into contact with water vapor contained in the surrounding atmosphere gas, the high-temperature water molecules react with oxygen vacancies formed in the perovskite structure by doping, and this reaction causes protons to be produced for the first time. Is thought to occur.

[0009]

However, the following problems have been pointed out with respect to the various proton conductors described above.

[0010] First, the matrix material such as the perfluorosulfonic acid resin needs to be continuously and sufficiently wet during use in order to maintain high proton conductivity.

Therefore, the configuration of a system such as a fuel cell requires a humidifying device and various auxiliary devices, which inevitably increases the size of the device and increases the cost of system construction.

Further, the operating temperature is not wide enough to prevent freezing and boiling of the water contained in the matrix.

In the case of the composite metal oxide having a perovskite structure, it is necessary to maintain the operating temperature at a high temperature of 500 ° C. or higher in order to conduct meaningful proton conduction.

As described above, the conventional proton conductor has a problem in that it has a high dependence on the atmosphere, such as replenishing moisture and requiring steam, and the operating temperature is too high or its range is narrow. Was.

Therefore, the applicant of the present invention can use in a wide temperature range including room temperature, and the lower limit temperature is not particularly high.
In addition, a proton conductor that does not require moisture irrespective of whether or not it is a moving medium, has a small atmosphere dependence, and has a high film strength while maintaining its performance, and further imparts film forming properties, thereby achieving high strength and gas. Japanese Patent Application No. 11-2040 discloses a fuel cell using a proton conductive thin film having a permeation preventing ability.
No. 38 (filed on July 19, 1999; hereinafter referred to as a prior invention).

That is, the fuel cell comprises a fuel cell and an oxygen electrode, and the fuel cell and the oxygen electrode are arranged opposite to each other via a proton conductor membrane. ₃ H, -COOH, -SO ₃ H,-
It uses a proton conductor having a proton dissociating group as represented by OPO (OH) ₂ .

However, as described above, although this fuel cell has excellent performance, among the proton conductors into which a functional group other than the -OH group is introduced, the presence of water may cause the proton conductor to have a certain temperature depending on the temperature conditions. May hydrolyze slowly. For example, when the above functional group is —OSO ₃ H, it is gradually hydrolyzed by water generated from the oxygen electrode to be changed to an acidic hydroxyl group, the proton conductivity is reduced, and as a fuel cell, It has been found that there is still room for improvement, for example, the output may be reduced.

An object of the present invention is to provide an electrochemical device and a proton conductor which can prevent water from entering a proton conductor membrane.

[0019]

That is, the present invention comprises a first electrode, a second electrode, and a proton conductor sandwiched between these two electrodes. The proton conductor is composed of a proton (H).
⁺ ) A group other than a dissociable hydroxyl group is introduced,
A first proton conductor disposed on the pole side, and a second proton conductor having a proton (H ⁺ ) dissociable hydroxyl group introduced therein and disposed on the second pole side; The present invention relates to an electrochemical device (hereinafter, referred to as an electrochemical device of the present invention).

According to the electrochemical device of the present invention, the first
A first proton conductor in which a group other than a proton (H ⁺ ) dissociable hydroxyl group is introduced on the pole side, and a second proton conductor in which a proton (H ⁺ ) dissociable hydroxyl group is introduced on the second pole side Since the body is disposed, when the first electrode is a fuel electrode and the second electrode is an oxygen electrode, a second proton conductor having a hydroxyl group is interposed between the oxygen electrode and the first proton conductor. Therefore, permeation of moisture from the oxygen electrode side is blocked by the second proton conductor, and the ingress of generated water from the oxygen electrode into the first proton conductor can be prevented, so that a decrease in the output of the electrochemical device can be suppressed. Thus, the performance of the above-mentioned prior invention can be further enhanced.

Further, the present invention provides a first proton conductor into which a group other than a proton (H ⁺ ) dissociable hydroxyl group is introduced, and a second proton conductor into which a proton (H ⁺ ) dissociable hydroxyl group is introduced. The present invention relates to a proton conductor having a conductor (hereinafter, referred to as a proton conductor of the present invention).

According to the proton conductor of the present invention, the first proton conductor is disposed on the fuel electrode side, the second proton conductor is disposed on the oxygen electrode side, and the two proton electrodes are sandwiched between the two electrodes. By using the same, it is possible to provide a proton conductor for an electrochemical device, which has the same effect as the above-described electrochemical device of the present invention.

In the present invention, "proton dissociable group"
Means a functional group from which a proton can be released by ionization, and "dissociation of proton (H ⁺ )" means that a proton is separated from the functional group by ionization.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION In the above-described electrochemical device and proton conductor of the present invention, the first proton conductor has XH _x (O
H) _y (X is an arbitrary atom or atomic group, H is a hydrogen atom, O is an oxygen atom, and 1 ≦ x and 0 ≦ y).

In this case, it is preferable that the XH is a group selected from —OSO ₃ H and —OPO (OH) ₂ , wherein x is 1 to 30 and y is 0 to 30. .

Further, the second proton conductor has OH _z (H is a hydrogen atom, O is an oxygen atom, and 1 ≦ z) as the proton dissociating group. It is desirable that z is 1 to 30.

Preferably, the first or second proton conductor has an electron absorbing group containing at least a nitro group, a carbonyl group, a carboxyl group, a nitrile group, a halogenated alkyl group or a halogen atom.

The first or second proton conductor is formed of a spherical carbon cluster molecule Cm (m = 36, 60, 7).
0, 78, 82, 84, etc.) as a base.

[0029] In this case, the ratio of the thickness of the thickness / the second proton conductor of the first proton conductor is 1 to 10 ^5, the thickness of the second proton conductor is 1nm or more, 1 [mu]
m or less.

Thus, it is preferable that the first electrode be a fuel electrode and the second electrode be an oxygen electrode, and that the second proton conductor be in contact with at least the oxygen electrode.

At least one of the first and second poles may be a gas electrode, and at least one of the first and second poles may be an active material electrode.

Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings.

As shown in FIG. 1, the fuel cell according to the present embodiment has negative electrodes (fuel electrode or hydrogen electrode) 2 having terminals 8 and 9 having catalysts 2a and 3a closely contacted or dispersed, respectively, and having opposed terminals 8 and 9. It has a positive electrode (oxygen electrode) 3, a first proton conductor 1 is disposed on the negative electrode 2 side between the two electrodes, and a second proton conductor 1 is disposed on the positive electrode 3 side.
A proton conductor 7 is provided and sandwiched. In the proton conduction of this fuel cell, as shown in FIG. 2 (a schematic diagram in which a part of FIG. 1 is enlarged), the dissociated protons move from the negative electrode 2 side to the positive electrode 3 side in the direction of the arrow.

When this fuel cell is used, hydrogen is supplied from the inlet 12 on the negative electrode 2 side, and is discharged from the outlet 13 (this may not be provided). Fuel (H ₂ ) 1
4 generates protons while passing through the flow path 15, and the protons move together with the protons generated in the first proton conductor 1 through the second proton conductor 7 toward the positive electrode 3, where the protons pass through the inlet 16. It is supplied to the flow path 17 and reacts with oxygen (air) 19 heading to the exhaust port 18, thereby extracting a desired electromotive force.

However, since water is generated at the positive electrode (oxygen electrode) 3 when the conducted protons (H ⁺ ) react with the oxygen 19, depending on the temperature conditions, this water is converted into the first proton having a hydroxyl group. It may penetrate into the body 1, and the functional groups of the first proton conductor 1 may be gradually hydrolyzed and changed into acidic hydroxyl groups, and the proton conductivity may be impaired.

Therefore, as shown in FIG. 1, by providing a membrane of the second proton conductor 7 having a hydroxyl group between the first proton conductor 1 and the oxygen electrode 3, the water generated at the oxygen electrode 3 is reduced. In addition, the infiltration into the first proton conductor 1 can be suppressed by being blocked by the membrane of the second proton conductor 7.

This first proton conductor 1 is preferably made of Cm (XH) _x (OH) _y (m = 36, 60, 70, 7
8, 82, 84..., X = —OSO ₃ H, —OPO
A material represented by (OH) ₂ , x = 1 to 30, y = 0 to 30) is used, but is not limited thereto.

Further, the second proton conductor 7 is preferably _{Cn (OH) z (n =} 36,60,70,78,8
2, 84..., Z = 1 to 30), but the material is not limited thereto.

The proton conductivity is determined by the second proton conductor 7
Since the proton-dissociable group of the first proton conductor 1 is higher than the hydroxyl group of the above, it is desirable that the entire proton conductor is composed of the first proton conductor from the viewpoint of proton conductivity.

However, as described above, the proton-dissociable group of the first proton conductor 1 is hydrolyzed by water, so the membrane of the second proton conductor 7 having a hydroxyl group is placed between the first proton conductor 1 and the oxygen electrode 3. Although it is formed, it is better not to form it too thick in order not to lower the proton conductivity.

More specifically, the thickness of the second proton conductor 7 is 1 nm (corresponding to the thickness of one molecule of fullerenol) or more.
μm or less, more preferably 2 nm or more and 500
nm or less, still more preferably 10 nm or more and 100 n
m or less. If this thickness is greater than 1 μm,
When the relative thickness of the first proton conductor is reduced, the proton (H ⁺ ) conductivity is reduced. On the other hand, when the thickness is less than 1 nm, the penetration of moisture cannot be prevented.

The thickness of the first proton conductor 1 is 1 μm.
m or more and 100 μm or less. That is, if the thickness is larger than this, proton conductivity is rather lowered, which is disadvantageous for thinning. If too thin, the proton (H ⁺ ) conductivity is easily reduced, and the membrane strength becomes insufficient.

Then, the thickness of the first proton conductor / the thickness of the second
The ratio of the thickness of the proton conductor is preferably 1 to 10 ^5. If the thickness ratio is smaller than this range, the proton conductivity is reduced, and if it is too large, the penetration of moisture may not be completely prevented. The thickness ratio is more preferably 2 to 5 × 10 ^{4, and} still more preferably 10 to 10 ⁴ .

The above-mentioned first proton conductor 1 and second proton conductor 7 can be manufactured by using a known method.

Hereinafter, the proton conductor used in the present invention will be described in detail.

That is, in this proton conductor, the fullerene molecule as a base to which a proton-dissociable group is introduced is not particularly limited as long as it is a spherical cluster molecule, but it is usually C36 or C60 (FIG. 6A). C70 (see FIG. 6)
(See (B)), a fullerene molecule selected from C76, C78, C80, C82, C84 and the like, or a mixture of two or more thereof is preferably used.

These fullerene molecules were discovered in 1985 in a mass spectrometry spectrum of a cluster beam obtained by laser ablation of carbon (Kroto, HW; Hea
th, JR; O'Brien, SC; Curl, RF; Smalley, R.
E. Nature 1985.318,162.). It is only five years later that the manufacturing method is actually established. In 1990, a manufacturing method of a carbon electrode by an arc discharge method was discovered, and since then fullerene has been attracting attention as a carbon-based semiconductor material. Was.

The inventors of the present invention have conducted various studies on the proton conductivity of this fullerene molecule derivative. As a result, the polyhydroxylated fullerene obtained by introducing a hydroxyl group into a carbon atom constituting the fullerene molecule has a room temperature range even in a dry state. It was found that the polymer exhibits high proton conductivity in a wide temperature range, that is, in the freezing point of water and in a temperature range exceeding the boiling point (at least 160 ° C. to −40 ° C.). Then, it was found that this proton conductivity becomes more remarkable when a hydrogen sulfate ester group is introduced into a carbon atom constituting fullerene instead of a hydroxyl group.

More specifically, as shown in FIG. 4, polyhydroxylated fullerene is a general term for a substance having a structure in which a plurality of hydroxyl groups are added to fullerene, and is generally called "fullerenol". Naturally,
Some variations are possible for the number of hydroxyl groups and the arrangement in the molecule. Fullerenol was Chia in 1992
ng et al. first reported a synthetic example (Chiang, L.
Y.; Swirczewski, Jw; Hsu, CS; Chowdhury, SK; Ca
meron, S .; Creegan, KJ Chem. Soc, Chem. Commun. 1
992,1791). Since then, fullerenol, in which a certain amount or more of hydroxyl groups have been introduced, has been particularly noted for its water-soluble properties, and has been studied mainly in the field of biotechnology.

The present inventor has proposed such fullerenol in FIG.
As shown schematically in (A), an aggregate is formed, and an interaction is caused between hydroxyl groups of adjacent fullerenol molecules (in the figure, は indicates a fullerene molecule). It has been found for the first time that the aggregate exhibits high proton conductivity (in other words, dissociation of H ⁺ from the phenolic hydroxyl group of the fullerenol molecule).

The above-mentioned proton conductor can also be achieved by using, for example, a fullerene aggregate having a plurality of —OSO ₃ H groups as the proton conductor in addition to fullerenol. FIG. 5 (B) in which OH groups are replaced with OSO ₃ H groups
Polyhydroxylated fullerenes, i.e., hydrogen sulfated esterified fullerenols, as shown in
994 (Chiang. LY; Wang, L.
Y .; Swirczewski, JW; Soled, S .; Cameron, SJ Or
g. Chem. 1994,59,3960). Some hydrogen sulfate-esterified fullerenes contain only an OSO ₃ H group in one molecule, or a plurality of this group and a plurality of hydroxyl groups can be provided.

When a large number of the above-described fullerene derivatives are aggregated, the proton conductivity of the fullerene derivatives as a bulk is determined because the large amount of protons originally contained in the molecule and the protons derived from the OSO ₃ H groups 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 a substrate of these derivative molecules, has an electrophilic property, which is a significant factor in promoting 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. This is one of the reasons that the above-mentioned proton conductor shows excellent proton conductivity.

Furthermore, 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. This is another reason why the above-described proton conductor exhibits an effective conductivity.

Since most of the above-mentioned proton conductors are composed of fullerene carbon atoms, they are light in weight, difficult to change in quality, and do not contain pollutants.
Further, 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, according to the study of the present inventors, the proton dissociable group does not need to be limited to the above-mentioned hydroxyl group or OSO ₃ H group.

That is, this dissociative group is represented by the formula -XH, and X may be any atom or atomic group having a divalent bond. Furthermore, this group has the formula -OH or -YO
It is represented by H, and Y may be any atom or atomic group having a divalent bond.

Specifically, as the group capable of dissociating the proton, besides the above-mentioned -OH and -OSO ₃ H, -OPO (O
H) ₃ is preferred.

Further, an electron-withdrawing group such as a nitro group, a carbonyl group, a carboxyl group, a nitrile group, a halogenated alkyl group, a halogen atom (fluorine, It is preferable that chlorine or the like has been introduced.
FIG. 5C shows a fullerene molecule in which Z is introduced in addition to -OH. This Z is specifically —NO ₂ , —CN,
_{-F, -C l, -COOR, -CHO} , -COR, -C
F ₃ , —SO ₃ CF ₃ and the like (where R represents an alkyl group). When the electron-withdrawing group coexists in this way,
Due to the electron-withdrawing effect, protons are easily dissociated from the proton-dissociable group.

In the above-mentioned proton conductor, the number of the proton-dissociable groups 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. Is good. 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.

In order to synthesize the fullerene derivative used for the above-mentioned proton conductor, a known treatment such as an acid treatment or hydrolysis is appropriately combined with the fullerene molecule powder, as will be apparent from the examples described later. In this case, a desired proton-dissociable group may be introduced into the constituent carbon atoms of the fullerene molecule.

The powder of the fullerene derivative thus obtained can be pressed into a desired shape, for example, into a pellet. At this time, a binder is not necessary, which is effective in increasing proton conductivity and achieving reduction in weight of the proton conductor.

The above proton conductor can be suitably used for various electrochemical devices. That is, in the basic structure including the first electrode, the second electrode, and the proton conductor sandwiched between these two electrodes, the proton conductor described above can be preferably applied to the proton conductor.

More specifically, an electrochemical device in which the first and / or second electrode is a gas electrode, an electrochemical device in which an active material electrode is used as the first and / or second electrode, etc. On the other hand, the proton conductor described above can be preferably applied.

Hereinafter, an example in which the above proton conductor is applied to a fuel cell will be described.

The proton conduction of the fuel cell is as shown in the schematic diagram of FIG. 7, and the proton conducting portion 1 is sandwiched between a first electrode (for example, hydrogen electrode) 2 and a second electrode (for example, oxygen electrode) 3. The dissociated protons move from the first pole 2 side to the second pole 3 side in the direction of the arrow shown in the figure.

FIG. 8 shows a specific example of a fuel cell using the above-mentioned proton conductor.

This fuel cell has a negative electrode (fuel electrode or hydrogen electrode) 2 and a positive electrode (oxygen electrode) 3 with terminals 8 and 9 facing each other and having catalysts 2a and 3a adhered or dispersed, respectively.
And the proton conductor portion 1 is sandwiched between these two electrodes. In use, on the negative electrode 2 side, hydrogen is supplied from the inlet 12 and discharged from the outlet 13 (which may not be provided). Protons are generated while the fuel (H2) 14 passes through the flow path 15, and the protons move toward the positive electrode 3 together with the protons generated in the proton conductor portion 1, where they are supplied from the inlet 16 to the flow path 17. Reacts with the oxygen (air) 19 directed to the exhaust port 18 to extract a desired electromotive force.

The fuel cell having such a configuration is characterized in that protons supplied from the negative electrode 2 move toward the positive electrode 3 while the protons are dissociated in the proton conducting portion 1, so that the proton conductivity is high. Therefore, since a humidifying device or the like is not required, the system can be simplified and reduced in weight.

Next, an example in which a binder is used in combination with the above proton conductor will be described. The difference of this example is that the fullerene derivative is used in combination with a polymer material, and other configurations and the basic action of the proton conduction mechanism are the same.

This proton conductor contains the above fullerene derivative (in which a group capable of dissociating a proton is introduced into a carbon atom constituting fullerene) and a polymer material.

As the polymer material, one or more known polymers having a film-forming property are used, and the compounding amount is usually suppressed to 20% by weight or less. 20% by weight
This is because, if it exceeds, the proton conductivity may be reduced.

Since the proton conductor having such a structure also contains a fullerene derivative, it can exhibit substantially the same proton conductivity as described above.

Further, unlike the case of using the fullerene derivative alone, a film-forming property derived from the polymer material is imparted, and the gas permeation preventing ability is higher in strength than the powder compression molded product of the fullerene derivative described above. It can be used as a flexible proton conductive thin film having a thickness of usually 300 μm or less.

The polymer material is not particularly limited as long as it does not inhibit proton conductivity as much as possible (due to reaction with a fullerene derivative or the like) and has a film-forming property. However, usually those having no electron conductivity and good stability are used. Specific examples thereof include polyfluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, and the like.
Particularly preferred polymer materials for this example.

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 a proton conductive thin film having more excellent gas permeation preventing ability can be obtained. In this case, the amount is preferably in the range of 5 to 15% 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.

To obtain the above-mentioned proton conductor thin film,
Known film forming means including extrusion molding may be used.

The above-mentioned proton conductor can be preferably applied to the same electrochemical device as the above-mentioned proton conductor (without binder).

That is, except for the fact that a proton conductor containing a binder is sandwiched between the first electrode and the second electrode, other configurations may be common to the electrochemical device of FIG.

The present invention can be applied to, for example, the fuel cell shown in FIG.
It is also possible to apply to the hydrogen-air battery shown in FIG.
That is, for example, a hydrogen electrode 21 and an air electrode 22 are placed with a thin-film-shaped proton conductor 20 containing a binder (hereinafter the same applies) as a center.
And a Teflon (registered trademark) plate 24a and a Teflon plate 24 provided with a number of holes 25 on the outside thereof.
b, and the whole is fixed by bolts 26a, 26b and nuts 27a, 27b, and a hydrogen electrode lead 28a and an air electrode lead 28b are taken out from each electrode to the outside.

The electrochemical device shown in FIG.
The structure has a structure in which a proton conductor 34 is sandwiched between a negative electrode 31 provided with a negative electrode active material layer 30 on the inner surface and a positive electrode 33 (gas electrode) provided with a gas permeable support 32 on the outer surface. In addition, as the negative electrode active material, a material in which a hydrogen storage alloy is supported on a carbon material such as a hydrogen storage alloy or fullerene is preferable. For the gas permeable support 32, for example, porous carbon paper or the like is used. Preferably, for example, a material in which platinum is supported on carbon powder is applied and formed in a paste form. The gap between the outer end of the negative electrode 31 and the outer end of the positive electrode 33 is closed by a gasket 35. In this electrochemical device, charging can be performed with moisture present on the positive electrode 33 side.

The electrochemical device shown in FIG.
It has a structure in which a thin-film proton conductor 41 is sandwiched between a negative electrode 38 provided with a negative electrode active material layer 37 on the inner surface and a positive electrode 40 provided with a positive electrode active material layer 39 on the inner surface. For example, those containing nickel hydroxide as a main component are used. This electrochemical device was also used for the negative electrode 38.
Of the positive electrode 40 and the outer end of the positive electrode 40 are closed by a gasket 42.

In any of the above-mentioned electrochemical devices, if a binder is used as the proton conductor, the proton conduction effect can be exerted by the same mechanism as that of the electrochemical device shown in FIG. Since the derivative is used in combination with a film-forming polymer material, the derivative can be used in the form of a thin film having improved strength and small gas permeability, and can exhibit good proton conductivity.

Hereinafter, each of the above examples will be specifically described.

<Synthesis of polyhydroxylated fullerene> This synthesis is described in the literature (Chieng, LY; Wang, LY; Swirczewski. JW; S
oled, S .; Cameron, SJOrg. Chem. 1994, 59, 3960). 2 g of a powder of a C ₆₀ / C ₇₀ fullerene mixture containing about 15% of C ₇₀ was poured into 30 ml of fuming sulfuric acid, and stirred for 3 days while maintaining the temperature at 57 ° C. in a nitrogen atmosphere. The obtained reaction product is dropped little by little into anhydrous diethyl ether cooled in an ice bath, the precipitate is separated by centrifugation, further three times with diethyl ether, and a mixture of diethyl ether and acetonitrile in 1: 1. , And dried at 40 ° C. under reduced pressure. Further, the dried product was placed in 60 ml of ion-exchanged water and stirred at 85 ° C. for 10 hours while bubbling with nitrogen. A precipitate was separated from the reaction product by centrifugation, and the precipitate was further washed with pure water several times, and after repeating centrifugation, dried under reduced pressure at 40 ° C. FT-IR measurement of the brown powder obtained in this manner showed an almost identical IR spectrum of C ₆₀ (OH) ₁₂ shown in the above-mentioned literature, and this powder was found to be the target substance polywater. Identified as fullerene oxide.

<Production of Aggregated Pellets of Polyhydroxyfullerene> Next, 90 mg of the powder of the polyhydroxylated fullerene was taken and 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, the polyhydroxylated fullerene powder was excellent in moldability despite not containing any binder resin and the like, and could be easily pelletized. The pellet has a thickness of about 300 microns and is referred to as the pellet of Example 1.

<Synthesis 1 of Polyhydroxylated Fullerene Hydrogen Sulfate (Total Esterification)> This was also performed with reference to the above-mentioned literature. 1 g of polyhydroxylated fullerene powder was dropped into 60 ml of fuming sulfuric acid, and stirred at room temperature under a nitrogen atmosphere for 3 days. The obtained 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 the liquid, it was dried at 40 ° C. under reduced pressure. The powder thus obtained was subjected to TF-IR measurement. The IR spectrum of all the hydroxyl groups converted to hydrogen sulfate was almost the same as that shown in the above-mentioned literature, indicating that the powder was the target substance. Was confirmed.

<Production 1 of Aggregated Pellets of Poly (hydroxylated fullerene hydrogen sulfate)> 70 mg of the 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. This pellet has a thickness of about 300 microns and is referred to as the pellet of Example 2.

[0090] C ₆₀ containing about 15% C ₇₀ <Synthesis 2 of polyhydroxylated fullerene hydrogensulfate ester (partial esterification)>
/ C ₇₀ fullerene mixture powder 2g and fuming sulfuric acid 30ml
While keeping it at 57 ° C in a nitrogen atmosphere.
Stirred for 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 almost coincided with the IR spectrum shown in the above-mentioned literature. It was confirmed that it was the target substance.

<Production 2 of Aggregated Pellets of Hydroxylester Fuller Hydroxide Fullerene> 80 mg of the powder of poly (fullerene hydroxide) partially hydrogenated with hydrogen sulfate was taken, and
Pressing was performed in one direction so as to form a circular pellet having a diameter of 15 mm. The press pressure at this time is about 7 tons / cm
^{Was 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. This pellet has a thickness of about 300 microns and is referred to as the pellet of Example 3.

<Production of Fullerene Aggregated Pellets> For comparison, fullerene powder 90 used as a raw material for synthesis in the above example was used.
mg, and pressed in one direction to form a circular pellet having a diameter of 16 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, the powder was relatively excellent in moldability and could be easily pelletized. This pellet has a thickness of about 300 microns, and is used as the pellet of Comparative Example 1.

<Measurement of Proton Conductivity of Pellets Obtained in Each Example and Comparative Example> In order to measure the conductivity of the pellets of Examples 1 to 3 and Comparative Example 1, first, an aluminum plate having a diameter of 15 mm equal to the pellet was used. An alternating voltage (amplitude: 0.1 V) from 7 MHz to 0.01 Hz was applied to both sides of each pellet, and the complex impedance at each frequency was measured. The measurement was performed under a dry atmosphere.

Regarding the impedance measurement, the proton conducting portion 1 of the proton conductor composed of the pellet electrically forms an equivalent circuit as shown in FIG. Capacitors 6 and 6 'are formed between the first pole 2 and the second pole 3 including the proton conducting portion 1 represented by a circuit. Note that the capacitance 5 represents a delay effect when the proton moves (phase delay at a high frequency), and the resistance 4 represents a parameter of the ease of movement of the proton.

Here, the measured impedance Z is Z = R
The frequency dependence of the proton conducting portion represented by e (Z) + i · Im (Z) and represented by the above equivalent circuit was examined.

FIG. 9B is an equivalent circuit when a normal fullerene molecule having no proton dissociation property is used (comparative example described later).

FIG. 10 shows the impedance measurement results for the pellets in Example 1 and Comparative Example 1.

According to this, in Comparative Example 1, the frequency characteristic of the complex impedance is almost the same as the behavior of the capacitor alone, and the conduction behavior of the charged particles (electrons, ions, etc.) of the aggregate of fullerene itself is completely Not observed. In contrast, in the case of Example 1, it is possible to see a single semicircular arc that is flat but very clear in the high frequency portion. This indicates that some charged particle conduction behavior exists inside the pellet. Furthermore, in the low frequency region, a sharp rise in the imaginary part of the impedance is observed. this is,
It indicates that blocking of charged particles has occurred between the aluminum electrode as the voltage gradually approaches the DC voltage,
Of course, the charged particles on the aluminum electrode side are electrons, so the charged particles inside the pellet are not electrons or holes,
It turns out that it is other charged particles, ie, ions. Due to the configuration of the fullerenol used, this charged particle cannot be considered other than protons.

The conductivity of the charged particles can be obtained from the X-axis intercept of the circular arc seen on the high frequency side. In the pellet of Example 1, it is calculated to be approximately 5 × 10 ⁻⁶ S / cm. Furthermore, when the same measurement was performed for the pellets of Examples 2 and 3, the frequency characteristics of the impedance were similar to those of Example 1 for the overall shape.
However, the conductivity obtained from the X-intercept of the arc is shown in Table 1.
As shown in FIG.

[0100]

Table 1 Table 1 Conductivity of proton conductor pellets when the above binder is not used together (25 ° C)

As described above, when the hydroxyl group is replaced by the OSO ₃ H group, the conductivity in the pellet tends to increase. This is because the OSO ₃ H groups than hydroxyl groups is due to likely occur ionization of hydrogen. Further, the present inventors have found that this type of fullerene derivative aggregate can conduct protons at room temperature in a dry atmosphere, in both cases of a hydroxyl group and an OSO ₃ H group, or in a case where both are mixed. Was completed.

Next, using the pellet of Example 1, the above-described complex impedance measurement was performed in the temperature range of 160 ° C. to −40 ° C., and the temperature dependence of the conductivity obtained from the high-frequency side arc at that time was examined. . FIG. 11 shows the results as an Arrhenius type plot. Thus, 160 ° C.
It can be seen from FIG. 4 that the conductivity changes sharply and linearly at −40 ° C. That is, the figure shows that a single ion conduction mechanism can proceed in this temperature range. That is, the above-described proton conductor can conduct electricity in a wide temperature range including room temperature, particularly in a high temperature of 160 ° C. and a low temperature of −40 ° C.

<Production of polyhydroxylated fullerene pellets A>
Take 70 mg of poly (fullerene hydroxide) powder obtained by the above-mentioned synthesis method, mix this with 10 mg of polyvinylidene fluoride powder, and add 0.5 m of dimethylformamide.
1 was added and stirred well. This mixture was poured into a circular mold having a diameter of 15 mm, and the solvent was evaporated under reduced pressure. Thereafter, pressing was performed to obtain a 15 mm-diameter pellet. The pellet was about 300 microns thick. This is designated as pellet A of Example 4.

<Production of Polyhydroxylated Fullerene Pellets B>
> Similarly, take 70 mg of polyhydroxylated fullerene powder,
This and a dispersion of fine powder of polytetrafluoroethylene (PTFE) (containing 60% of PTFE)
The FE was mixed so that the weight of the FE became 1% of the whole, and kneaded well. This kneaded body was molded to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is designated as pellet 1B of Example 4.

<Synthesis 1 of Polyhydroxylated Fullerene Hydrogen Sulfate (Total Esterification)> This was also performed with reference to the literature described above. 1 g of polyhydroxylated fullerene powder was dropped into 60 ml of fuming sulfuric acid and stirred at room temperature under a nitrogen atmosphere for 3 days. The obtained reaction product was dropped little by little into anhydrous diethyl ether cooled in an ice bath,
The 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. The powder thus obtained was subjected to FT-IR measurement and found to be almost identical to the IR spectrum of all the hydroxyl groups converted to hydrogen sulfate esterified, which was shown in the above-mentioned literature. Was confirmed.

<Preparation 1A of poly (hydroxy fullerene hydrogen sulfate) pellets> 70 mg of the poly (fullerene hydrogen sulfate) powder was mixed with 10 mg of polyvinylidene fluoride powder, and 0.5 ml of dimethylformamide was added. And stirred well. This mixture was poured into a circular mold having a diameter of 15 mm, and the solvent was evaporated under reduced pressure. Thereafter, pressing was performed to obtain a 15 mm-diameter pellet. The pellet was about 300 microns thick. This is designated as pellet 2A of Example 5.

<Production 1B of poly (hydroxy fullerene hydrogen sulfate) pellets> Similarly, 70 mg of the above poly (fullerene hydrogen hydrogen sulfate) powder was taken and dispersed with fine powder of polytetrafluoroethylene (PTFE) (PTFE 60%). Was mixed so that the weight of PTFE was 1% of the whole and kneaded well. This kneaded body was molded to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is designated as pellet 2B of Example 5.

<Synthesis 2 of Poly (hydroxylated fullerene hydrogen sulfate) (partial esterification)> C ₆₀ containing about 15% of C ₇₀
2 g of the / C ₇₀ fullerene mixture was poured into 30 ml of fuming sulfuric acid, and the mixture was stirred in a nitrogen atmosphere at 57 ° C. for 3 days. The resulting reaction was dropped little by little into diethyl ether cooled in an ice bath. However, this diethyl ether used was not dehydrated. 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 almost coincided with the IR spectrum shown in the above-mentioned literature. If it is a target substance,
It could be confirmed.

<Preparation 2A of poly (hydroxy fullerene hydrogen sulfate) pellets> 70 mg of partially hydrosulfated poly (fullerene hydroxide) powder was mixed with 10 mg of polyvinylidene fluoride powder.
0.5 ml of dimethylformamide was added and stirred well. Pour this mixture into a 15 mm diameter circular mold,
The solvent was evaporated under reduced pressure. Thereafter, pressing was performed to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is designated as pellet 3A of Example 6.

<Production 2B of Poly (hydroxylated fullerene hydrogen sulfate) pellets> Similarly, 70 mg of partially hydrogenated fullerene hydrogenated poly (hydroxy fullerene hydroxide) powder was taken, and
This and a dispersion of fine powder of polytetrafluoroethylene (PTFE) (containing 60% of PTFE)
The FE was mixed so that the weight of the FE was 1% of the whole, and kneaded well. This kneaded body was molded to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is designated as pellet 3B of Example 6.

<Production of fullerene pellets> For comparison, fullerene powder 9 used as a synthesis raw material in the above example was used.
0 mg, and powder of polyvinylidene fluoride 10
and 0.5 ml of dimethylformamide, and the mixture was stirred well. This mixture was poured into a circular mold having a diameter of 15 mm, and the solvent was evaporated under reduced pressure. Thereafter, pressing was performed to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is a pellet of Comparative Example 2.

<Production of Polyhydroxylated Fullerene Pellets B>
Similarly, for comparison, 70 mg of the fullerene powder used as a synthesis raw material in the above example was taken, and this was mixed with a fine powder of polytetrafluoroethylene (PTFE) (containing 60% PTFE) so that the weight of PTFE was 1
% And kneaded well. This kneaded body was molded to obtain a pellet having a diameter of 15 mm. The pellet was about 300 microns thick. This is a pellet of Comparative Example 3.

<Measurement of Proton Conductivity in Pellets of Each Example and Comparative Example> In order to measure the conductivity of the pellets of Examples 4 to 6 and Comparative Example 2, first, an aluminum plate having a diameter of 15 mm equal to the pellet was used. , And an alternating voltage (amplitude: 0.1 V) from 7 MHz to 0.01 Hz was applied thereto, and the complex impedance at each frequency was measured. The measurement was performed in a dry atmosphere.

Regarding the impedance measurement, the proton conducting part 1 of the proton conductor composed of the pellet electrically forms an equivalent circuit as shown in FIG. A capacitor 6 is formed between the first pole 2 and the second pole 3 including the conductive portion 1. Note that the capacitance 6 represents a delay effect when the proton moves (phase lag at a high frequency), and the resistance 4 represents a parameter of the ease of movement of the proton. Here, the measured impedance Z is
The frequency dependence of the proton conducting portion represented by Z = Re (Z) + i · Im (Z) and represented by the above equivalent circuit was examined.
FIG. 9B is an equivalent circuit in a case where a normal fullerene molecule having no proton dissociation property is used (a comparative example described later).

FIG. 12 shows the results of impedance measurement of the pellets in Example 4 and Comparative Example 2.

According to this, in Comparative Example 2, the frequency characteristic of the complex impedance is almost the same as the behavior of the capacitor alone, and the conduction behavior of the charged particles (electrons, ions, etc.) of the aggregate of fullerene itself is completely Not observed. On the other hand, in the case of Example 4, a single semicircular arc which is flat in the high frequency portion but very clear can be seen. This indicates that some charged particle conduction behavior exists inside the pellet. Furthermore, in the low frequency region, a sharp rise in the imaginary part of the impedance is observed. this is,
It indicates that blocking of charged particles has occurred between the aluminum electrode as the voltage gradually approaches the DC voltage,
Of course, the charged particles on the aluminum electrode side are electrons, so the charged particles inside the pellet are not electrons or holes,
It can be seen that they are other charged particles, that is, ions.
Due to the configuration of the fullerenol used, this charged particle cannot be considered other than protons.

[0117] From the arc of X-axis intercept as seen in the high frequency side, it is possible to determine the conductivity of the charged particles in the pellets Example 4, is calculated to be approximately 1 la 10 ^-6 S / cm. Further, the same measurement was performed on the pellets of Examples 5 and 6, and in addition, the pellets of Examples 4, 5 and 6, and the frequency characteristics of the impedance were the same as in Example 4 for the entire shape. However, the conductivity obtained from the X-intercept of the circular arc portion had different values as shown in Table 2.

[0118]

[Table 2] Conductivity (25 ° C.) of proton conductor pellets used in combination with the above binder

[0119] Thus, also conductivity in the pellets When the hydroxyl is replaced by OSO ₃ H groups in the case of B when A is a tendency to increase. This is more of an OS than a hydroxyl group
This is because the O ₃ H group is easier to ionize hydrogen. In both cases of the hydroxyl group and the OSO ₃ H group, or in the case where both are mixed, it is found that the aggregate of this kind of fullerene derivative can conduct proton at room temperature in a dry atmosphere. did it.

Next, using the pellet 1A of Example 4, the above-described complex impedance measurement was performed in a temperature range from 160 ° C. to −40 ° C., and the temperature dependence of the conductivity obtained from the high-frequency side arc at that time was examined. Was. FIG. 13 shows the results as an Arrhenius type plot. According to this, 1
It turns out that it changes very linearly from 60 ° C to -40 ° C. That is, it is understood that a single ion conduction mechanism can proceed in this temperature range. That is, it indicates that a single ion conduction mechanism can proceed in this temperature range. That is, the proton conductor used in combination with the binder has a wide temperature range including room temperature,
Conduction is possible even at a high temperature such as 0 ° C. or a low temperature such as −40 ° C.

[0121]

Embodiments of the present invention will be described below.

According to the above-described embodiment of the present invention, a fuel cell was manufactured as shown in FIG.

Specifically, C ₆₀ (OSO ₃ H) _x (OH)
_Using a complete or partial ester represented by _y (x + y = 12) with polytetrafluoroethylene (PTFE) as a binder, a film of the first proton conductor 1 having a weight ratio of 1: 1 and a thickness of 50 μm was formed.

Next, one side of the first proton conductor membrane 1 has C
_{60 (OH) z (z =} 12) and also PTFE in a weight ratio of 1: 1 with dispersed in DMF (dimethylformamide), was applied by spin coating, the second proton conductor having a thickness of 100nm by evaporation of the DMF The film of No. 7 was formed.

Thereafter, the fuel electrode 2 and the oxygen electrode 3 in which platinum particles serving as a catalyst are dispersed in graphite particles at a weight ratio of 1: 1 are arranged to face each other with a membrane of the second proton conductor 7 interposed therebetween. One fuel cell was constructed. Note that the C
_The electrode in contact with the surface on which the ₆₀ (OH) _z second proton conductor 7 was formed was designated as oxygen electrode 3.

Further, in the fuel cell of FIG. 1, for comparison, a fuel cell of a comparative example was prepared in which both electrodes were arranged without forming the second proton conductor 7 of C ₆₀ (OH) _z .

The output characteristics of the fuel cells of Examples and Comparative Examples when they were continuously operated at a constant current density (500 mW / cm ² ) were measured. FIG. 3 shows the time change of the output voltage obtained as a result. According to this, in the comparative example, the output voltage was reduced after one hour of continuous operation, whereas the output voltage of the fuel cell of the example shown in FIG. 1 was hardly reduced.

That is, according to this embodiment, the second proton conductor 7 having a hydroxyl group is interposed between the first proton conductor 1 made of a complete or partial ester having high proton conductivity and the oxygen electrode 3. As a result, water generated at the oxygen electrode 3 is blocked by the second proton conductor 7 and
It is clear that the desired high electromotive force can be obtained because penetration into the proton conductor 1 is prevented.

The above embodiment can be modified based on the technical idea of the present invention.

For example, in the embodiment, the two-layer proton conductor composed of the first proton conductor 1 and the second proton conductor 7 is formed between the electrodes 2 and 3; however, the present invention is not limited to this. It may have a three-layer structure.

The proton-dissociating group of the first proton conductor 1 may be a proton conductor having a group other than those shown in the examples as long as it is not a hydroxyl group. Such groups include -OPO (OH) ₂ .

The parent of the proton conductor is not limited to the fullerene molecules described above, but may be another substance (for example, an organic polymer).

[0133]

As described above, the present invention relates to an electrochemical device comprising a first electrode, a second electrode, and a proton conductor sandwiched between these two electrodes. A group other than a (H ⁺ ) dissociable hydroxyl group is introduced, and a first proton conductor disposed on the first electrode side and a proton (H ⁺ ) dissociable hydroxyl group are introduced. Since it has the second proton conductor disposed on the two electrode side, when the first electrode is a fuel electrode and the second electrode is an oxygen electrode, between the oxygen electrode and the first proton conductor Since the second proton conductor having a hydroxyl group is interposed, the penetration of moisture from the oxygen electrode side is blocked by the second proton conductor, and the intrusion of generated water from the oxygen electrode into the first proton conductor is prevented. A decrease in the output of the electrochemical device can be suppressed.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a fuel cell according to an embodiment of the present invention.

FIG. 2 is a schematic diagram of the same proton conductor layer.

FIG. 3 shows the same current density (500 mA / c) of the fuel cell.
5 is a graph showing a time change of the output voltage obtained in m ² ).

FIG. 4 is a structural diagram of a polyhydroxylated fullerene which is an example of a fullerene derivative used in the present invention.

FIG. 5 is a schematic diagram showing an example of a fullerene derivative.

FIG. 6 is a structural diagram of the same fullerene molecule.

FIG. 7 is a schematic diagram showing an example of a proton conductor.

FIG. 8 is a configuration diagram of the fuel cell showing the embodiment.

FIG. 9 is a diagram showing an equivalent circuit.

FIG. 10 is a view showing a measurement result of a complex impedance of the pellet.

FIG. 11 is a diagram showing the temperature dependence of the proton conductivity of the pellet.

FIG. 12 is a view showing a measurement result of a complex impedance of another pellet.

FIG. 13 is a diagram showing the temperature dependence of the proton conductivity of the pellet.

FIG. 14 is a configuration diagram of a hydrogen-air battery according to another embodiment of the present invention.

FIG. 15 is a schematic configuration diagram of an electrochemical device showing another embodiment of the present invention.

FIG. 16 is a schematic configuration diagram of an electrochemical device showing still another embodiment of the present invention.

[Explanation of symbols]

1 ... first proton conductor, proton conducting part, 2 ... first
Electrodes, 2a: catalyst, 3: second electrode, 3a: catalyst, 7: second proton conductor, 20: proton conductor, 21: hydrogen electrode,
22: air electrode, 24a: Teflon plate, 24b: Teflon plate provided with holes, 30: negative electrode active material, 31: negative electrode, 32 ...
Gas permeable support, 33: positive electrode (gas electrode), 34: proton conductor, 35: gasket, 37: negative electrode active material, 3
8 negative electrode, 39 positive electrode active material, 40 positive electrode, 41 proton conductor, 42 gasket

Claims (26)

[Claims] 1. A proton conductor comprising a first electrode, a second electrode, and a proton conductor sandwiched between these two electrodes. The proton conductor introduces a group other than a proton (H ⁺ ) -dissociable hydroxyl group. A first proton conductor disposed on the first pole side and a proton (H ⁺ ) dissociable hydroxyl group introduced thereinto, and a second proton conductor disposed on the second pole side. An electrochemical device having a body. 2. The method according to claim 1, wherein the first proton conductor has a proton dissociating group of XH _x (OH) _y (X is an arbitrary atom or atomic group, H is a hydrogen atom, O is an oxygen atom, The electrochemical device according to claim 1, wherein 1 ≦ x and 0 ≦ y. 3. The method according to claim 1, wherein said XH is -OSO ₃ H, and -OP
The electrochemical device according to claim 2, which is a group selected from any of O (OH) ₂ . 4. The electrochemical device according to claim 2, wherein x is 1 to 30 and y is 0 to 30. 5. The method according to claim 5, wherein the second proton conductor has OH _z (H is a hydrogen atom, O
Is an oxygen atom, and 1 ≦ z. The electrochemical device according to claim 1, comprising: 6. The electrochemical device according to claim 5, wherein z is 1 to 30. 7. The method according to claim 1, wherein the first or second proton conductor has an electron absorbing group containing at least a nitro group, a carbonyl group, a carboxyl group, a nitrile group, a halogenated alkyl group or a halogen atom. Electrochemical device. 8. The method according to claim 1, wherein the first or second proton conductor is a spherical carbon cluster molecule Cm (m = 36, 60, 70, 7).
8. The electrochemical device according to claim 1, wherein a fullerene molecule represented by 8, 8, 84, or the like) is used as a base. 9. The electrochemical device according to claim 1, wherein the ratio of the thickness of the first proton conductor / the thickness of the second proton conductor is 1 to 10 ⁵ . 10. The thickness of the second proton conductor is 1n.
The electrochemical device according to claim 9, wherein the diameter is not less than m and not more than 1 μm. 11. The fuel cell according to claim 1, wherein the first electrode is a fuel electrode and the second electrode is an oxygen electrode, and the second proton conductor is in contact with at least the oxygen electrode. Electrochemical device. 12. The electrochemical device according to claim 1, wherein at least one of the first electrode and the second electrode is a gas electrode. 13. The electrochemical device according to claim 1, wherein at least one of the first pole and the second pole is an active material electrode. 14. A proton (H ⁺⁾ first proton conductor obtained by introducing a group other than dissociative hydroxyl, a proton (H ⁺⁾ second proton conductor obtained by introducing a dissociable hydroxyl group Proton conductor that has. 15. The method according to claim 15, wherein the first proton conductor contains, as the proton dissociating group, XH _x (OH) _y (X is an arbitrary atom or atomic group, H is a hydrogen atom, O is an oxygen atom, , 1 ≦ x, 0 ≦ y).
5. The proton conductor according to 4. 16. The method according to claim 16, wherein XH is -OSO ₃ H and -OP.
The proton conductor according to claim 15, which is a group selected from any of O (OH) ₂ . 17. The x is 1 to 30, and the y is 0 to 30.
The proton conductor according to claim 15, which is: 18. The method according to claim 18, wherein the second proton conductor contains OH _z (H is a hydrogen atom,
O is an oxygen atom, and 1 ≦ z. 15. The proton conductor according to claim 14, wherein 19. The method according to claim 18, wherein z is 1 to 30.
3. The proton conductor according to item 1. 20. The first or second proton conductor,
At least a nitro group, a carbonyl group, a carboxyl group,
15. The proton conductor according to claim 14, having an electron absorbing group containing a nitrile group, a halogenated alkyl group, or a halogen atom. 21. The first or second proton conductor,
Spherical carbon cluster molecule Cm (m = 36, 60, 70,
15. The proton conductor according to claim 14, wherein a fullerene molecule represented by (78, 82, 84, etc.) is used as a base. 22. The proton conductor according to claim 14, wherein the ratio of the thickness of the first proton conductor / the thickness of the second proton conductor is 1 to 10 ⁵ . 23. The thickness of the second proton conductor is 1n.
23. The proton conductor according to claim 22, which is at least m and at most 1 m. 24. The proton conductor according to claim 14, wherein the proton conductor is used in a fuel cell in which a first electrode is a fuel electrode and a second electrode is an oxygen electrode, and the second proton conductor is in contact with at least the oxygen electrode. 25. The first of which at least one is a gas electrode
15. The proton conductor according to claim 14, which is sandwiched between a pole and a second pole. 26. The proton conductor according to claim 14, wherein at least one of the proton conductors is sandwiched between a first pole and a second pole which are active material electrodes.