KR101163243B1 - Fuel for fuel cell, fuel cell and application thereof - Google Patents

Abstract

A fuel cell fuel in which an organic fuel as a fuel cell fuel is a solid molecular compound such as a clathrate compound. Such a molecular compound can be formed by a contact reaction between a compound forming a molecular compound and an organic fuel, and the organic fuel in a liquid can be converted into a solid compound to store the organic fuel relatively lightly and stably. . From this molecular compound, an organic fuel can be easily discharged by heating or the like and supplied to the fuel electrode of the fuel cell. The handleability of the fuel cell fuel made of the organic fuel can be improved, and problems such as corrosion, freezing of fuel, crossover and the like can be solved.

Description

FUEL FOR FUEL CELL, FUEL CELL AND APPLICATION THEREOF}

The present invention (first aspect) relates to a fuel for a fuel cell and a method of supplying the same, and in particular, problems such as handleability of organic fuels such as methanol used in the fuel cell, corrosion of peripheral devices, crossover in the battery, and the like. The present invention relates to a fuel cell fuel for improving fuel cell power generation efficiency and stable operation, and a method for supplying the fuel cell fuel to the fuel cell.

 The present invention (second aspect) relates to a method for detecting an amount of fuel substance present in a fuel composition for a fuel cell, and more particularly, to a method for easily detecting a residual amount of fuel substance such as methanol supplied to a fuel cell.

 The present invention (third aspect) relates to a fuel for a solid electrolyte fuel cell, a solid electrolyte fuel cell, and a method of using the same, and particularly, a solid electrolyte capable of suppressing crossover of fuel in a solid electrolyte fuel cell. A solid electrolyte fuel cell using the fuel for a fuel cell, the solid electrolyte fuel cell fuel, and a method of using the same.

 The present invention (fourth aspect) relates to a method for releasing fuel for a fuel cell relatively simply from a fuel composition containing a fuel for a fuel cell.

A solid polymer electrolyte fuel cell is composed of a solid electrolyte membrane such as a perfluorosulfonic acid membrane as an electrolyte, and a fuel electrode and an oxidizing electrode are joined to both surfaces of the membrane, and a liquid organic fuel such as hydrogen or methanol is connected to the anode. It is an apparatus which supplies oxygen, respectively, and generate | generates by an electrochemical reaction.

Among fuel cells, in recent years, supplying directly to a fuel electrode without reforming a liquid organic fuel, such as that represented by a direct methanol fuel cell, has been actively developed. The fuel cell which directly supplies the liquid organic fuel to the anode without reforming the liquid organic fuel does not require a device such as a reformer because it is a structure that directly supplies the liquid organic fuel to the anode. Therefore, it has the advantage that the structure of a battery can be made simple and the whole apparatus can be miniaturized. Compared with gaseous fuels, such as hydrogen gas and hydrocarbon gas, the liquid organic fuel of a fuel also has the advantage that it can transport easily and safely.

In a fuel cell, the electrochemical reaction occurring at each electrode is performed at the anode when methanol is used.

_{CH 3 OH + H 2 0 →} 6H + + CO 2 + 6e - [1]

In addition, in the cathode,

^{_{3 / 2O 2 + 6H + +}} 6e - → 3H 2 O [2]

to be. In order to cause this reaction, the positive electrode is composed of a mixture of carbon fine particles on which a catalyst material is supported and a solid polymer electrolyte.

In such a solid polymer electrolyte fuel cell, when methanol is used as the fuel, methanol supplied to the anode (fuel electrode) passes through pores in the electrode to reach the catalyst, and methanol is decomposed by the catalyst. The reaction produces electrons and hydrogen ions. Hydrogen ions pass through the solid electrolyte membrane between the electrolyte in the anode and the positive electrode to reach the cathode (oxidizing electrode), and react with oxygen supplied to the cathode and electrons flowing from an external circuit to form water as in Scheme [2]. On the other hand, electrons emitted from methanol are led to the external circuit through the catalyst carrier in the anode and flow into the cathode from the external circuit. As a result, electrons flow from the anode to the cathode and power is extracted.

 The direct methanol fuel cell using methanol as a fuel has high possibility of being applied as a portable small fuel cell, and has been actively developed as a next-generation secondary battery such as a portable computer or a mobile phone.

 In general, in a fuel cell using a liquid organic fuel, a solid polymer electrolyte membrane made of a solid polymer ion exchange resin is used as the electrolyte. Here, in order for the fuel cell to function, it is necessary for hydrogen ions generated at the anode to move in the membrane from the fuel electrode (anode) to the oxidizer electrode (cathode). It is known that the movement of hydrogen ions is accompanied by the movement of water, and the electrolyte membrane needs to contain a certain amount of water.

However, when a liquid organic fuel such as methanol having a high affinity for water is used, the liquid organic fuel diffuses into a solid polymer electrolyte membrane containing water and further reaches a oxidizing electrode, a phenomenon called so-called crossover. This happens. The crossover causes the liquid organic fuel, which should originally provide electrons, to be oxidized by reaching the oxidizing electrode side, and thus cannot be effectively used as a fuel, resulting in a decrease in voltage, output, and fuel efficiency. . Since methanol crossover becomes more prominent as the methanol concentration in the fuel increases, it is difficult to use a high concentration of methanol fuel in a direct methanol fuel cell.

 Conventionally, the following various methods are proposed in order to solve the problem of the methanol crossover mentioned above.

[1] A method for improving the electrolyte membrane between the anode and the cathode and its structure (Japanese Patent Laid-Open No. 11-26005, Japanese Patent Laid-Open No. 2002-83612, etc.).

[2] A method in which a liquid fuel is first vaporized using a vaporizer or a heater and supplied to the anode (for example, Japanese Patent Laid-Open No. 2001-93541).

[3] A method of converting methanol into another alcohol (isopropanol; Japanese Patent Laid-Open No. 2003-217642) or another organic fuel (cycloparaffins; Japanese Patent Laid-Open No. 2003-323896).

[4] A method of blending sugars, alcohols and the like with a liquid organic fuel and suppressing crossover by using a penetration pressure in a fuel cell (Japanese Patent Laid-Open No. 2004-39293).

However, even in the above conventional method, methanol crossover cannot be sufficiently coped, and further improvement is required.

In addition, in a direct methanol fuel cell using methanol as a fuel, not only methanol crossover,

(1) Methanol is equivalent to the poison of the poison control method, and it is equivalent to the dangerous substance class 4, and sufficient care must be taken for handling;

(2) Since methanol is a liquid, it is necessary to prepare a highly sealed container without liquid leakage;

Problems in handling such as methanol,

(3) The use of a high concentration of aqueous methanol solution to increase power generation efficiency may impair the electrodes of the fuel cell or corrode the surrounding metal materials;

There is also a problem. In addition, there are the following problems.

(4) As described above, methanol crossover becomes more prominent as the methanol concentration increases, and the stock solution of methanol corresponds to the toxic substance of the poison control method, and corresponds to the fourth dangerous substance. In the case of fuel and high concentration methanol, there is a problem of corrosion or the like. When using methanol as a fuel, it is usually used as an aqueous solution of about 10 to 30% by weight. There is a problem of freezing. In this case, since it cannot be used as fuel, it must be used after thawing. In addition, there is a problem that a concentration distribution of methanol and water is generated during freezing. In order to eliminate this concentration distribution, the frozen fuel must be thawed completely and then used after making it into a homogeneous solution by shaking the container. This is troublesome.

 Even with organic fuels other than methanol, the problems of (1) to (4) may occur, but these problems have not been solved conventionally.

 In addition, conventionally, there is no method of simply detecting the remaining amount of fuel for fuel cells, and therefore, it is necessary to prepare the fuel accurately, such as preparing the required amount of fuel before supplying the entire amount of fuel for fuel cell, or supplying appropriately. It was difficult.

Moreover, the following problems also existed conventionally.

Hydrogen and methanol used as fuels for fuel cells have high risk and many handling problems. As a method of safely storing such a fuel, a method of making a fuel a molecular compound (WO2004000857), or a method of absorbing and gelling a polymer (Japanese Patent Laid-Open No. 2004-127659) has been reported. Conventionally, since these fuel cell fuels are made into a stable composition, as a method of releasing the fuel cell fuel, it is common to heat the fuel composition to release the fuel.

However, in order to heat the fuel composition containing the fuel for fuel cell to release the fuel, an apparatus for heating is required, and a large energy for heating is required, which cannot be said to be an industrially advantageous method. There has been a demand for a method for more easily releasing fuel from a fuel composition containing a fuel for fuel cell.

[Object of the present invention]

(1) It is an object of the first aspect to provide a fuel cell fuel and a method of supplying the same, which improves the handleability of a fuel cell fuel made of an organic fuel and solves problems such as corrosion, freezing of fuel, crossover, and the like. do.

(2) It is an object of the second aspect to provide a method capable of easily detecting the remaining amount of fuel for fuel cells.

(3) A third aspect of the present invention is to provide a fuel for a solid electrolyte fuel cell capable of suppressing crossover of fuel in a solid electrolyte fuel cell, thereby achieving high output and high fuel efficiency of the fuel cell. do. A third aspect also aims to provide a method of using a solid electrolyte fuel cell and a solid electrolyte fuel cell using such a fuel.

(4) It is an object of the fourth aspect to provide a method for easily releasing fuel for fuel cells from a fuel composition containing fuel for fuel cells without requiring a heating device or heating energy.

SUMMARY OF THE INVENTION

<1> The fuel for fuel cells of the first aspect is characterized in that the organic fuel used for the fuel cell is a solid molecular compound.

The fuel cell fuel supply method of the first aspect is characterized by releasing an organic fuel from the fuel cell fuel described above and supplying it to the fuel electrode of the fuel cell.

<2> The method for detecting the abundance of fuel substance in the fuel composition for a fuel cell of the second aspect is a method for detecting the abundance of the fuel substance in a fuel composition containing the molecular compound of the fuel substance for fuel cell and a counterpart compound. The abundance of the fuel substance is detected by comparing the index characteristics of the molecular compound and / or the counter compound with the index characteristics of the fuel composition.

<3> The solid electrolyte fuel cell fuel of the third aspect is characterized by comprising a liquid organic fuel and a compound which forms a complex or molecular compound with the liquid organic fuel.

A method of using a solid electrolyte fuel cell according to a third aspect is a method of using a solid electrolyte fuel cell including a fuel electrode, an oxidant electrode, and a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode. It is characterized by supplying the fuel for the solid electrolyte fuel cell described above.

The solid electrolyte fuel cell of the third aspect includes a fuel electrode, an oxidant electrode, a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode, and the fuel for the solid electrolyte fuel cell described above.

The solid electrolyte fuel cell of the third aspect further includes a solid electrolyte fuel cell including a fuel electrode, an oxidant electrode, and a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode, wherein the solid electrolyte type is described in the fuel electrode. And a fuel supply means for supplying fuel for a fuel cell.

<4> A fuel discharge method from a fuel composition for fuel cells according to a fourth aspect is a method of releasing fuel from a fuel composition comprising a fuel cell fuel, wherein the fuel composition is brought into contact with water by bringing the fuel composition into contact with water. It characterized by releasing to.

1 is a schematic cross-sectional view showing a fuel cell system fabricated in Example 5 and Example 11. FIG.

FIG. 2 is a schematic configuration diagram showing a fuel cell system prepared in Example 6 and Example 12. FIG.

FIG. 3 is a schematic configuration diagram showing a fuel cell system fabricated in Example 7 and Example 13. FIG.

4 is a cross-sectional view schematically showing the structure of an example of a solid electrolyte fuel cell of a third aspect.

5 is an explanatory diagram of a fuel supply system in an example of a fuel for a solid electrolyte fuel cell according to a third aspect.

6 is an explanatory diagram of a structure of the solid electrolyte fuel cell in Examples 14 to 16. FIG.

7 is a schematic structural diagram showing a fuel cell system prepared in Example 17. FIG.

EMBODIMENT OF THE INVENTION Below, the preferable aspect of this invention is demonstrated in detail.

[1] First, the fuel cell fuel and its supply method of the first aspect will be described.

The fuel for fuel cells of the first aspect is characterized in that the organic fuel used in the fuel cell is a solid molecular compound.

In the fuel cell fuel of the first aspect, since the organic fuel is a solid molecular compound, it is safe and excellent in handling, easy to store and transport, and there is no problem of freezing. In addition, problems of corrosion and crossover can also be reduced, and it is also possible to use a high concentration organic fuel, so that the electromotive force of the fuel cell can be increased.

The fuel cell fuel supplying method is characterized by releasing an organic fuel from such fuel cell fuel and supplying it to the fuel electrode of the fuel cell. The fuel cell fuel can be efficiently supplied by a fuel cell fuel having excellent safety and handleability.

Here, the molecular compound is a compound in which two or more kinds of compounds which may be stably present alone are bonded by relatively weak interactions other than covalent bonds represented by hydrogen bonds, van der Waals forces, and the like. Addition compounds, clathrate compounds and the like. Such a molecular compound can be formed by a contact reaction between a compound forming a molecular compound and an organic fuel, and the organic fuel in a liquid can be converted into a solid compound to store the organic fuel relatively lightly and stably. . From this molecular compound, an organic fuel can be easily released by heating or contact with water, and can be supplied to the fuel electrode of the fuel cell. As this molecular compound, the clathrate compound which contained the organic fuel by the contact reaction of a host compound and an organic fuel is mentioned.

The organic fuel according to the first aspect may be any fuel that can be used as a fuel of a fuel cell. Examples of the organic fuel include, but are not limited to, alcohols, ethers, hydrocarbons, acetals, and the like. Organic fuels are generally liquid at room temperature and atmospheric pressure, specifically, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, propane, butane and the like. And acetals such as hydrocarbons, dimethoxymethane and trimethoxymethane. These organic fuels may be used individually by 1 type, or may mix and use 2 or more types.

As a host compound which forms the clathrate compound which contained the organic type fuel among the solid molecular compounds which comprise the fuel for fuel cells, what consists of an organic compound, an inorganic compound, and an organic-inorganic composite compound is known. As an organic compound as a host compound, a monomolecular system, a polymolecular system, a high molecular host and the like are known.

 Among the organic host compounds, examples of the monomolecular host compounds include cyclodextrins, crown ethers, kryptands, cyclopanes, azacyclopanes, carlix arenes, cyclotriveratrilenes, spherands, and cyclic oligopeptides. Etc. can be mentioned. Examples of the multimolecular host compounds include urea, thioureas, dioxycholic acids, perhydrotriphenylenes, tri-o-timoteds, biantryls, spirobifluorenes, cyclophosphazenes, monoalcohols, Diols, acetylene alcohols, hydroxybenzophenones, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, b Xanthenes, carboxylic acids, imidazoles, hydroquinones, etc. are mentioned. Examples of the high molecular host compounds include celluloses, all fractions, kitchens, chitosans, polyvinyl alcohols, polyethylene glycol arm polymers having 1,1,2,2-tetrakisphenylethane as a core, and α, α, and α. The polyethyleneglycol arm type polymer etc. which have ', (alpha)'-tetrakisphenyl xylene as a core are mentioned.

Examples of the organic host compound include organophosphorus compounds and organosilicon compounds.

Examples of the inorganic host compound include titanium oxide, graphite, alumina, transition metal decalgogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, porous glass, and the like.

The organometallic compound also exhibits properties as a host compound. For example, an organoaluminum compound, an organic titanium compound, an organoboron compound, an organozinc compound, an organo indium compound, an organ gallium compound, an organo tellurium compound, an organotin compound, or an organo zirconium compound And organic magnesium compounds. It is also possible to use the metal salt of an organic carboxylic acid, an organometallic complex, etc. as a host compound. The organometallic compound-based host compound is not particularly limited to these.

Among these host compounds, multi-molecular host compounds in which the inclusion ability is hardly influenced by the size of the molecule of the guest compound are suitable.

Specific examples of the polymolecular host compound include urea, 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol, and 1,1-bis (2,4-dimethylphenyl) -2. Propyn-1-ol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1,6,6-tetrakis (2,4-dimethylphenyl) -2, 4-hexadiyne-1,6-diol, 9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis (4-methylphenyl) -9,10-dihydro Anthracene-9,10-diol, 1,1,2,2-tetraphenylethane-1,2-diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4'-dihydroxy Benzophenone, 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Sulfonylbisphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-ethylidenebisphenol, 4,4'-thiobis (3-methyl-6-t-butyl Phenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1, To 1,2,2-tetrakis (4-hydroxyphenyl) Lene, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, α , α, α ', α'-tetrakis (4-hydroxyphenyl) -p-xylene, tetrakis (p-methoxyphenyl) ethylene, 3,6,3', 6'-tetramethoxy-9, 9'-non-9H-xanthene, 3,6,3 ', 6'-tetraacetoxy-9,9'-non-9H-xanthene, 3,6,3', 6'-tetrahydroxy- 9,9'-B-9H-Xanthene, Molded Assets, Molded Assets Methyl, Catechin, Bis-β-Naphthol, α, α, α ', α'-Tetraphenyl-1,1'-biphenyl-2,2' Dimethanol, dipentic acid bis dicyclohexylamide, fumaric acid bis dicyclohexylamide, cholic acid, dioxycholic acid, 1,1,2,2-tetraphenylethane, tetrakis (p-iodophenyl) ethylene, 9, 9'-biantryl, 1,1,2,2-tetrakis (4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-carboxyphenyl) ethane, acetylenedicarboxylic acid, 2, 4,5-triphenylimidazole, 1,2,4,5-tetraphenylimidazole, 2-phenylphenanthro [9,10-d] imidazole, 2 -(o-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (m-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (p-cyanophenyl) Phenanthro [9,10-d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4-dimethylphenyl) hydroquinone, and the like. have.

As a host compound, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,2,2- tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2- among the above-mentioned things Phenolic host compounds such as tetrakis (4-hydroxyphenyl) ethylene, diphenic acid bis (dicyclohexylamide), amide host compounds such as bis dicyclohexylamide, and 2- (m-cyanophenyl) phenane Imidazole-based host compounds such as tro [9,10-d] imidazole are advantageous in terms of inclusion ability, and in particular, phenolic host compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane are commercially available. It is advantageous in that it is easy to use.

These host compounds may be used individually by 1 type, and may use 2 or more types together.

These host compounds may be compounds of any shape as long as they form an organic fuel and a solid clathrate compound.

Of the host compounds described above, the organic host compound may be used as an organic-inorganic composite material supported on a porous material. In this case, examples of the porous material supporting the organic host compound include, but are not limited to, interlayer compounds such as clay minerals and montmorillonite, in addition to silicas, zeolites, and activated carbons. The organic-inorganic composite material can be prepared by dissolving the organic host compound described above in a solvent capable of dissolving it, impregnating the solution in a porous substance, and drying the solvent and drying under reduced pressure. Although there is no restriction | limiting in particular as an amount of support of an organic type host compound with respect to a porous material, Usually, it is about 10 to 80 weight% with respect to a porous material.

As a method of synthesizing a clathrate compound of an organic fuel using a host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane, a method of directly contacting and mixing an organic fuel and a host compound may be mentioned. Therefore, the clathrate compound which contained organic fuel can be synthesize | combined easily. The clathrate compound can also be synthesized by recrystallization after dissolving the host compound in an organic fuel by heating or the like.

In the synthesis of the clathrate compound, the temperature at which the organic fuel and the host compound are brought into contact with each other is not particularly limited. Although there is no restriction | limiting in particular also about the pressure condition at this time, It is preferable to carry out in an atmospheric pressure environment. Although there is no restriction | limiting in particular also about the time which makes an organic fuel contact a host compound, It is preferable to set it as about 0.01 to 24 hours from a viewpoint of work efficiency.

The organic fuel to be brought into contact with the host compound is preferably a fuel of high purity, but in the case of using a host compound having selective inclusion ability of the organic fuel, a mixed liquid of the organic fuel and other components may be used.

The clathrate compound thus obtained is also a clathrate compound in which 0.1 to 10 moles of organic fuel molecules are contained with respect to 1 mole of the host compound, although it also varies depending on the kind of the host compound used, the contact conditions with the organic fuel, and the like.

The clathrate compound thus obtained can stably store an organic fuel over a long period of time in a normal temperature and atmospheric pressure environment. Moreover, since the clathrate compound is a solid type that is light in weight and excellent in handleability, the clathrate compound can be easily stored in a container such as glass, metal, or plastic, thereby eliminating the problem of liquid leakage. In addition, since the liquid type organic fuel becomes solid by inclusion, it may be possible to avoid the property of a foreign substance or a dangerous substance. Further, the chemical reactivity of the organic fuel can be reduced, for example, corrosiveness to metals, etc. can also be reduced.

By the method of this invention, there is no restriction | limiting in particular as a method of taking out organic fuel in the state of solid molecular compounds, such as a clathrate compound, It can extract easily by heating this. Specifically, in the case where the solid molecular compound is a clathrate compound, depending on the kind of the host compound used, the solid molecular compound may be heated at about room temperature to about 200 ° C., thereby easily releasing the organic fuel from the clathrate compound for various uses. It is available. In this case, there is no restriction | limiting in particular about a heating method, There exist a thermoelectric element (such as a Peltier element), an inkjet printer head (thermal system, etc.), etc. Moreover, you may use combining a surface acoustic wave element etc.

The organic fuel may be extracted by contacting solid molecular compounds such as clathrate compounds with water, and eluting the organic fuel in the water. In this case, water may be an organic fuel aqueous solution, or an organic fuel aqueous solution having a concentration appropriate to the purpose of use, for example, an organic fuel aqueous solution of about 1 to 64% by weight, may be prepared by elution of an organic fuel from molecular compounds such as clathrate compounds. What is necessary is to supply a fuel cell.

The host compound after releasing the organic fuel from the clathrate compound has selective inclusion with the organic fuel, and can be effectively reused for inclusion of the organic fuel.

According to the first aspect, on the basis of the following effects, it is possible to improve the power generation efficiency of the fuel cell and to ensure stable operation for a long time.

(1) Since liquid leakage can be avoided by changing the liquid organic fuel into a solid phase, there is no need to prepare a highly sealed container without liquid leakage.

(2) Since the organic fuel is made of a solid molecular compound, it is safe and excellent in handling, and it is possible to avoid the safety-related countermeasures such as foreign substances and dangerous substances. The problem of freezing when using an organic fuel aqueous solution can be solved, and stable fuel supply can be performed even in a cold district.

(3) Since the molecular reactivity of the organic fuel reduces the chemical reactivity of the organic fuel, the influence of the organic fuel on the electrode of the fuel cell and the like can be reduced, and corrosion of surrounding metal materials and the like can be reduced.

(4) Crossover in the battery can be improved.

(5) A high concentration of organic fuel can be used in contact with the anode, whereby the electromotive force of the fuel cell can be increased.

The first aspect is useful as a fuel for a fuel cell of a direct methanol fuel cell and a supplying method thereof, which are promising as a solid polymer electrolyte fuel cell, particularly a portable small fuel cell, but are not limited to any of these. Applicable to various fuel cells.

Although a 1st aspect is demonstrated more concretely by giving an Example below, a 1st aspect is not limited to a following example at all, unless the summary is exceeded.

In addition, below, as a host compound which embraces an organic type fuel, 1, 1-bis (4-hydroxyphenyl) cyclohexane (it abbreviates as "BHC" hereafter) or 1,1,6,6- tetraphenyl Hexa-2,4-diyne-1,6-diol (hereinafter abbreviated as "TPHDD") was used, and methanol was used as an organic fuel.

Example 1 (Synthesis Method 1 of Methanol Inclusion Compound)

26.8 g (0.1 mo1) of BHC was dissolved in 50 ml of methanol and recrystallized to obtain a solid methanol clathrate compound having a methanol content of 11% by weight in BHC: methanol = 1: 1 (molar ratio).

Example 2 (Synthesis Method 2 of Methanol Inclusion Compound)

26.8 g (0.1 mol) of BHC and 3.2 g (0.1 mol) of methanol were placed in a beaker, and the mixture was stirred with a stirrer to obtain a solid methanol inclusion compound of BHC: methanol = 1: 1 (molar ratio).

Example 3 (Synthesis Method 3 of Methanol Inclusion Compound)

41.4 g (0.1 mol) of TPHDD was dissolved in 100 ml of methanol and recrystallized to obtain a solid methanol clathrate compound having a methanol content of 13% by weight in TPHDD: methanol = 1: 2 (molar ratio).

Example 4 (Thermal Release Characteristics of Methanol in Methanol Inclusion Compound)

As a result of TG-DTA measurement of the methanol inclusion compound obtained in Example 1 at a temperature increase rate of 10 ° C./min, the inclusion methanol was stably contained up to about 100 ° C., and vaporization release started from 100 ° C.

The clathrate is originally a volatile solvent with a boiling point of about 64 ° C, and the vapor pressure is low, so it vaporizes even below 64 ° C. Thus, the clathrate of the clathrate compound prevents the vaporization of methanol, thereby improving the risk of preservation. It can be seen that. As described above, according to the poison control method, methanol is the object of the polar substance only when it is a stock solution, and when methanol is used as the stock solution, the regulation is regulated. By inclusion, it becomes a solid substance and the vaporization discharge temperature can be controlled as described above. Therefore, it is possible to escape from the object of the dangerous goods fourth class and use it as a highly stable storage method.

The emission temperature of methanol from a methanol clathrate compound by heating can be changed freely by selecting the host compound to be used.

Example 5 (Evaluation of Stability of Electrode of Fuel Cell)

The electrolyte membrane electrode assembly (MEA) to be evaluated was produced as follows. As an electrolyte membrane, Nafion which is an ion exchange membrane of the pafluorosulfonic acid type was used. Pt particles were used for the supported catalyst and supported on acetylene black in order to provide electron conductivity. Pt loading amount was 50 weight% with respect to acetylene black. The Pt supported catalyst and the 5 wt% Nafion solution were mixed and blown onto the electrolyte membrane using a spray brush to attach the electrode layer. The film to which the electrode layer was attached was dried at 90 ° C. for 1 hour in a drier, sandwiched between Teflon plates, and pressed at 130 ° C. and 20 MPa for 30 minutes by a hot press to bond the electrolyte membrane and the electrode.

 As a result of immersing this MEA (1 cm x 1 cm) in an aqueous methanol solution at a concentration of 5, 10, 20, or 50% by weight as in the prior art, and leaving it for one week, the electrode elutes or peels in the methanol aqueous solution at any concentration. This was recognized and the result was that long-term stability was not obtained when using methanol aqueous solution. Therefore, in order to obtain long-term stability, it is necessary to use a lower concentration aqueous methanol solution as a fuel, but in this case, sufficient electromotive force cannot be obtained.

Thus, as shown in Fig. 1, a direct methanol fuel cell system was prepared in which a methanol inclusion compound and water were supplied instead of the aqueous methanol solution, using the above-described electrolyte membrane electrode assembly. 1, 1 is an electrolyte membrane, 2 is an electrode (anode), 3 is an electrode (cathode), 4 is an oxidant flow path, and 5 is a fuel absorber. The tank 6 and the water tank 7 of the clathrate compound were provided in contact with the fuel absorber 5. The heating bodies 6A and 7A are provided in these tanks 6 and 7, respectively, and are comprised so that the water in a tank can be heated, respectively.

In the clathrate compound tank 6, the methanol clathrate compound prepared in Example 1 was placed, heated to 100 ° C. by the heating body 6A, the methanol was released from the clathrate compound, and fed to the fuel absorber 5, and the water tank ( The water in 7) was heated to 100 ° C. by the heating body 7A and supplied to the fuel absorber 5. The supply amount to the fuel absorber 5 is methanol: water = 20:80 (weight ratio), and this ratio is equivalent to supplying 20weight% of aqueous methanol solution.

As a result, there was no adverse effect on the electrode, and it was possible to generate power under optimum conditions without the problem of crossover.

In this direct methanol fuel cell, an electromotive force of 0.22 V can be obtained by a 20 weight% aqueous methanol solution at a current density of 100 mA / cm ² , but as shown in FIG. 1, by using a methanol clathrate compound, 0.48 V EMF could be achieved. When 20% by weight aqueous methanol solution is used, stable operation is difficult due to deterioration of the electrode, crossover, and the like, but when methanol clathrate compound is used, there is no such problem and stable operation can be performed for a long time.

The same applies to the case where the methanol inclusion compound prepared in Example 2 and Example 3 is used.

Example 6 (Evaluation of Stability of Electrode of Fuel Cell)

Using an electrolyte membrane electrode assembly (MEA) prepared in the same manner as in Example 5, as shown in FIG. 2, a direct methanol fuel cell system for supplying an aqueous methanol solution was assembled. In Fig. 2, 1 is an electrolyte membrane, 2 is an electrode (anode), and 3 is an electrode (cathode). The oxidant flow path and the fuel absorber are not shown. 6 is a clathrate compound tank and is equipped with the heating body 6A. 11 is a concentration adjustment tank and 12 is a CO ₂ removal means.

The clathrate compound tank 6 prepared in Example 1 was put into the clathrate compound tank 6, heated to 100 ° C. by the heating body 6A, the methanol was released from the clathrate compound, and supplied to the concentration adjusting tank 11, 20% by weight. Aqueous methanol solution was adjusted and fed to the fuel absorber of the electrolyte membrane electrode assembly.

In the concentration adjusting tank 11, the recovered water used in the anode 2 and lowered in methanol concentration is circulated after treatment with the CO ₂ removal means 12. The water generated in the cathode 3 is also collected in the concentration adjusting tank 11 and used for adjusting the aqueous methanol solution.

As a result, there was no adverse effect on the electrode and there was no problem of crossover, and stable operation could be performed for a long time under optimum conditions.

The same applies to the case where the methanol inclusion compound prepared in Example 2 and Example 3 is used.

Example 7 (Evaluation of Stability of Electrode of Fuel Cell)

Using an electrolyte membrane electrode assembly (MEA) prepared in the same manner as in Example 5, as shown in FIG. 3, a direct methanol fuel cell system for supplying an aqueous methanol solution was assembled. In FIG. 3, 1 is an electrolyte membrane, 2 is an electrode (anode), and 3 is an electrode (cathode). The oxidant flow path and the fuel absorber are not shown. 6 is a clathrate compound tank, and 7 is a water tank.

The clathrate compound tank 6 prepared in Example 1 was placed in the clathrate compound tank 6, and water from the water tank 7 was supplied to the clathrate compound tank 6 to bring the methanol clathrate compound into contact with water, thereby bringing methanol into the water. 20 weight% aqueous methanol solution was adjusted, and it supplied to the fuel absorber of electrolyte membrane electrode assembly.

The water tank 7 may be circulated after treatment with CO ₂ removal means for the recovered water used in the anode 2 and the methanol concentration is lowered. The water generated in the cathode 3 may be collected and supplied to the water tank 7.

As a result, there was no adverse effect on the electrode and there was no problem of crossover, and stable operation could be performed for a long time under optimum conditions.

The same applies to the case where the methanol inclusion compound prepared in Example 2 and Example 3 is used.

Example 8 (refrigeration test and application test to fuel cell)

For comparison, the methanol clathrate compounds prepared in Examples 1 and 3 and 11 wt% methanol aqueous solution prepared by mixing methanol in pure water were placed in glass bottles, respectively, and left in a freezer at -20 ° C for 24 hours. As a result, although the methanol clathrate compounds of Examples 1 and 2 did not show any changes, the 11 wt% methanol aqueous solution was frozen.

The sample after the above three types of refrigeration tests was heated to 100 ° C. and subjected to a test applied to a fuel cell of the same manner as in Example 5, and as a result, the methanol clathrate compounds of Examples 1 and 2 were heated by heating. Although methanol was released and could be applied immediately, the 11 wt% aqueous methanol solution took time to thaw and could not be applied immediately.

The above results show that the problem of freezing occurs when the organic fuel is used as an aqueous solution, but it can be seen that this problem can be avoided by using a solid molecular compound such as a clathrate compound.

[2] Next, a method for detecting the amount of fuel substance present in the fuel composition for a fuel cell of the second aspect will be described.

A method for detecting the abundance of fuel substance in a fuel composition for a fuel cell of the second aspect is a method for detecting the abundance of the fuel substance in a fuel composition containing a molecular compound of a fuel substance for fuel cell and a counterpart compound. And / or comparing the indicator properties of the counterpart compound with the indicator properties of the fuel composition, thereby detecting the amount of the fuel substance present.

Here, the molecular compound is a compound in which two or more kinds of compounds which may be stably present alone are bonded by relatively weak interactions other than covalent bonds represented by hydrogen bonds, van der Waals forces, and the like. Addition compounds, clathrate compounds and the like. Such molecular compounds can be formed by the contact reaction of a fuel material with a counterpart compound forming a molecular compound, for example, by converting a liquid fuel material into a solid compound, thereby storing fuel material relatively lightly and stably. There are many advantages. From this molecular compound, the fuel substance can be easily discharged and supplied to the fuel electrode of the fuel cell by heating or contact with water.

The form of the fuel cell according to the second aspect is not particularly limited, but is preferably a solid polymer electrolyte fuel cell, including a direct methanol fuel cell and the like.

First, the molecular compound of the fuel material for fuel cell and a counterpart compound contained in the fuel composition for fuel cells which concerns on 2nd aspect is demonstrated.

The fuel material according to the second aspect may be any fuel that can be used as a fuel of a fuel cell. Examples of the fuel material include, but are not limited to, hydrogen, alcohols, ethers, hydrocarbons, acetals, and the like. As the fuel substance, more specifically, alcohols such as hydrogen, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, ethers such as dimethyl ether, methyl ethyl ether and diethyl ether, hydrocarbons such as propane and butane And acetals such as dimethoxymethane and trimethoxymethane. These fuel substances may be used individually by 1 type, and may mix and use 2 or more types.

As a host compound which forms the clathrate compound which contained the fuel substance among the molecular compounds contained in a fuel composition, what consists of an organic compound, an inorganic compound, and an organic-inorganic composite compound is known. In the organic compound as a host compound, a monomolecular system, a polymolecular system, a high molecular host and the like are known.

Examples of the monomolecular host compounds include cyclodextrins, crown ethers, kryptands, cyclopanes, azacyclopanes, calix arenes, cyclotriveratrilenes, spheroids, and cyclic oligopeptides. . Examples of the multimolecular host compounds include urea, thioureas, dioxycholic acids, perhydrotriphenylenes, tri-o-timoteds, biantryls, spirobifluorenes, cyclophosphazenes, monoalcohols, Diols, acetylene alcohols, hydroxybenzophenones, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, b Xanthenes, carboxylic acids, imidazoles, hydroquinones, etc. are mentioned. Examples of the high molecular host compound include celluloses, starches, kitchens, chitosans, polyvinyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2-tetrakisphenylethane as a core, and α, α, and α. The polyethyleneglycol arm type polymer etc. which have ', (alpha)'-tetrakisphenyl xylene as a core are mentioned.

Examples of the organic host compound include organophosphorus compounds and organosilicon compounds.

Examples of the inorganic host compound include titanium oxide, graphite, alumina, transition metal decalgogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, porous glass, and the like.

The organometallic compound also exhibits properties as a host compound. For example, an organoaluminum compound, an organotitanium compound, an organoboron compound, an organozinc compound, an organo indium compound, an organ gallium compound, an organo tellurium compound, an organotin compound, an organo zirconium compound And organic magnesium compounds. It is also possible to use the metal salt of an organic carboxylic acid, an organometallic complex, etc. as a host compound. The organometallic compound-based host compound is not particularly limited to these.

According to the fuel composition according to the second aspect, power generation is performed by supplying the fuel material released from the molecular compound of the fuel material and the counterpart compound to the fuel cell. Since the relative compound and the molecular compound after the fuel substance is released from the molecular compound have different characteristics in color, crystal form, etc., in the second aspect, the amount of fuel substance present in the fuel composition is detected using the change in the indicator property. do. Case where the surface characteristics of the molecular compound of the fuel material and the relative compounds referred to as "S _100", and the surface characteristics of the external compounds as "S _0", the surface characteristics of the fuel composition visible to "S _100", while the fuel composition Fuel material is contained in saturation. If the index characteristic of the fuel composition is "S ₀ ", there is no fuel substance in the fuel composition, and only the relative compound after releasing the fuel substance. If the index characteristic of the fuel composition shows a value between "S ₁₀₀ " and "S ₀ ", the amount of fuel substance according to the index characteristic is present in the fuel composition.

Such index characteristics can be easily quantified by converting them into electrical signals. Although there is no restriction | limiting in particular about the kind of this indicator characteristic, When employing "color" as an indicator characteristic, it is easy to grasp | ascertain the residual of a fuel substance by visual observation of the fuel composition by visual confirmation, and it is advantageous. .

In order to adopt "color" as an index characteristic, as a counterpart compound, when used alone (after releasing a fuel substance from a molecular compound, or not forming a fuel substance and a molecular compound), the molecular compound of a fuel substance It is preferable to use what changes a color in the case of forming.

Thus, as a host compound which changes color, what has a coloring functional group in the above-mentioned host compound is suitable. Specific examples thereof include, but are not limited to, host compounds having a coloring functional group introduced into imidazoles represented by the following general formula (1):

Wherein R ¹ and R ² may be different or the same and each represents a hydrogen atom, a methoxy group, an amino group, a dimethylamino group, a nitro group or a halogen atom, and R ³ represents a nitro group, cyano group, ethoxycarbonyl group or acetyl Group or formyl group, R ⁴ and R ⁵ each represent a hydrogen atom or combine with each other to form a condensed ring, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a methoxy group Or a phenyl group substituted with one or two or more selected from the group consisting of an amino group, a dimethylamino group, a nitro group or a halogen atom.

As imidazole type host compound represented by the said Formula (1), for example, 4, 5-bis (4-methoxyphenyl) -2- (2-nitrophenyl) imidazole, 4, 5-bis (4-methoxyphenyl) ) -2- (3-nitrophenyl) imidazole, 4,5-bis (4-methoxyphenyl) -2- (4-nitrophenyl) imidazole, 4,5-bis (4-aminophenyl) -2 -(2-nitrophenyl) imidazole, 4,5-bis (4-aminophenyl) -2- (3-nitrophenyl) imidazole, 4,5-bis (4-methoxyphenyl) -2- (4 -Nitrophenyl) imidazole, 4,5-bis (4-methoxyphenyl) -2- (2-nitrophenyl) -1-methylimidazole, 4,5-bis (4-methoxyphenyl) -2 -(3-nitrophenyl) -1-methylimidazole, 4,5-bis (4-methoxyphenyl) -2- (4-nitrophenyl) -1-methylimidazole, 2- (2-nitro Phenyl) phenanthro [9,10-d] imidazole, 2- (3-nitrophenyl) phenanthro [9,10-d] imidazole, 2- (4-nitrophenyl) phenanthro [9,10-d ] Imidazole, 1-methyl-2- (2-nitrophenyl) phenanthro [9,10-d] imidazole, 1-methyl-2- (3-nitrophenyl) phenanthro [9,10-d] All , 1-methyl-2- (4-nitrophenyl) phenanthro [9,10-d] imidazole, 1-phenyl-2- (2-nitrophenyl) phenanthro [9,10-d] imidazole, 1 -Phenyl-2- (4-nitrophenyl) phenanthro [9,10-d] imidazole, 1- (4-nitrophenyl) -2- (4-nitrophenyl) phenanthro [9,10-d] imide Dazole, 1- (4-methoxyphenyl) -2- (4-nitrophenyl) phenanthro [9,10-d] imidazole, etc. are mentioned, It is not limited to these.

These host compounds may be used individually by 1 type, and may use 2 or more types together.

These host compounds may be compounds of any shape as long as they form a clathrate compound with a fuel substance.

Of the host compounds described above, the organic host compound may be used as an organic-inorganic composite material supported on an inorganic porous material. In this case, examples of the porous material supporting the organic host compound include, but are not limited to, interlayer compounds such as clay minerals and montmorillonite, in addition to silicas, zeolites, and activated carbons. The organic-inorganic composite material can be prepared by dissolving the organic host compound described above in a solvent capable of dissolving it, impregnating the solution in a porous substance, and drying the solvent and drying under reduced pressure. Although there is no restriction | limiting in particular as an amount of support of an organic type host compound with respect to a porous material, Usually, it is about 10 to 80 weight% with respect to a porous material.

As a method of synthesizing a clathrate compound of a fuel substance using a host compound such as 4,5-bis (4-methoxyphenyl) -2- (3-nitrophenyl) imidazole, the fuel substance and the host compound are directly contacted, The mixing method is mentioned, and the clathrate compound which contained the fuel substance can be synthesize | combined easily by this. The clathrate compound can also be synthesized by recrystallization after dissolving the host compound in a fuel material by heating or the like.

In the synthesis of the clathrate compound, the temperature at which the fuel substance and the host compound are brought into contact with each other is not particularly limited, but the room temperature to about 100 ° C. is preferable. Although there is no restriction | limiting in particular also about the pressure condition at this time, It is preferable to carry out in an atmospheric pressure environment. Although there is no restriction | limiting in particular also about the time which makes a fuel material and a host compound contact, It is preferable to set it as about 0.01 to 24 hours from a viewpoint of work efficiency.

The fuel material to be brought into contact with the host compound is preferably a fuel of high purity, but in the case of using a host compound having selective inclusion ability of the fuel material, a mixed liquid of the fuel material and other components may be used.

The clathrate compound thus obtained is a clathrate compound in which 0.1 to 10 moles of fuel substance molecules are contained with respect to 1 mole of the host compound, although it may vary depending on the kind of the host compound used, the contact conditions with the fuel substance, and the like.

The clathrate compound thus obtained can stably store a fuel substance over a long period of time in a normal temperature and atmospheric pressure environment. Moreover, since the clathrate compound is light in weight and excellent in handleability, and is generally solid, it can be easily stored in a container such as glass, metal, or plastic, thereby eliminating the problem of liquid leakage. In addition, since the gaseous or liquid fuel material is usually made solid by inclusion, it may be possible to avoid the properties as a foreign matter or a dangerous substance. Further, the chemical reactivity of the fuel substance can be reduced, for example, the corrosiveness to metals, etc. can be reduced.

Although there is no restriction | limiting in particular as a method of extracting a fuel substance in the state which consists of molecular compounds, such as a clathrate compound, It can extract easily by heating this. Specifically, in the case where the molecular compound is a clathrate compound, depending on the type of host compound used, the molecular compound may be heated at about room temperature to about 200 ° C., thereby easily releasing the fuel material in the clathrate compound for use in various applications. Can be. In this case, there is no restriction | limiting in particular about a heating method, There exist a thermoelectric element (such as a Peltier element), an inkjet printer head (thermal system, etc.), etc. Moreover, you may use combining a surface acoustic wave element or the like.

It is also possible to extract a fuel substance by making molecular compounds, such as a clathrate compound, contact with water, and eluting a fuel substance in this water. In this case, the water may be an aqueous solution of a fuel substance, or an aqueous fuel substance solution having a concentration appropriate to the purpose of use may be prepared by supplying the fuel cell with elution of the fuel substance from molecular compounds such as clathrate compounds.

The host compound after releasing the fuel material from the clathrate compound has a selective clathability to the fuel material, and can be effectively reused for inclusion of the fuel material.

In the second aspect, for example, the indicator properties of the fuel composition and the indicator compounds after the fuel substance is released from the molecular compound and the fuel compounds and the molecular compounds of the partner compound are grasped in advance, respectively, and the indicator properties of the fuel composition are determined by these indicators. By contrast with the characteristic, the amount of fuel substance in the fuel composition can be easily detected. When color is used as an index characteristic, it is also possible to quantify color using a colorimeter and the like, thereby accurately determining the amount of fuel substance.

According to the second aspect, the amount of the fuel substance present in the fuel composition for fuel cell containing the fuel compound for fuel cell and the molecular compound of the counter compound is determined by the indicator property of the molecular compound and / or counter compound and the indicator property of the fuel composition. By contrast, it can be detected easily.

In particular, by using color as this index characteristic, it becomes possible to visually confirm and to easily confirm the residual amount of fuel substance. In this case, by using the thing which has a coloring functional group as a counterpart compound, a clear difference is made to the color of a molecular compound and the color of a counterpart compound, and it becomes possible to confirm a residual amount more easily.

The second aspect is useful as a method for detecting the remaining amount of fuel for a fuel cell of a direct methanol fuel cell, which is promising as a solid polymer electrolyte fuel cell, in particular, a portable small fuel cell. Applicable to the battery.

The second aspect will be described in more detail with reference to the following Examples, but the second aspect is not limited to the following Examples as long as they do not exceed the gist thereof.

In addition, as a host compound below which a fuel substance is included, 4, 5-bis (4-methoxyphenyl) -2- (3-nitrophenyl) -1H-imidazole (it abbreviates as "BMNI" hereafter). Was used, and methanol was used as the fuel material. The color of the BMNI crystal is yellow.

Example 9

BMNI was dissolved in methanol by heating to recrystallize to obtain a solid methanol clathrate compound of BMNI: methanol = 1: 1 (molar ratio). The color of the obtained methanol inclusion compound was dark red.

When this methanol clathrate compound was put into a container and heated to 100 ° C., methanol was released, and methanol in the crystal gradually decreased as the methanol was released, thereby changing the color of the crystal in the container from dark red to yellow of BMNI.

Therefore, the residual amount of methanol was confirmed by the change of color.

Example 10

The methanol clathrate compound obtained in the same manner as in Example 9 was charged to the column, and water was passed through the column. As a result, methanol was eluted to the water side, and methanol in the crystal gradually decreased with the elution of methanol, thereby reducing the amount of crystal in the column. The color changed from dark red to yellow in BMNI.

Therefore, the residual amount of methanol was confirmed by the change of color.

Example 11

An electrolyte membrane electrode assembly (MEA) was produced as follows. As the electrolyte membrane, Nafion, which is an ion exchange membrane of a pafluorosulfonic acid type, was used. The supported catalyst was supported on acetylene black in order to give electron conductivity by using Pt particles. Pt loading amount was 50 weight% with respect to acetylene black. The Pt supported catalyst and the 5 wt% Nafion solution were mixed and blown onto the electrolyte membrane using a spray brush to attach the electrode layer. After drying at 90 degreeC for 1 hour in the drier, the membrane which affixed the electrode layer was sandwiched between Teflon boards, and it pressed at 130 degreeC and 20 Mpa for 30 minutes with the hot press, and the electrolytic membrane and the electrode were bonded together.

Using the produced electrolyte membrane electrode assembly, as shown in Fig. 1, a direct methanol fuel cell system for supplying a methanol inclusion compound and water was assembled. In Fig. 1, 1 is an electrolyte membrane, 2 is an electrode (anode), 3 is an electrode (cathode), 4 is an oxidant flow path, and 5 is a fuel absorber. The clathrate compound tank 6 and the water tank 7 were provided in contact with the fuel absorber 5. The heating bodies 6A and 7A are provided in these tanks 6 and 7, respectively, and are comprised so that the water in a tank can be heated, respectively.

In the clathrate compound tank 6, the methanol clathrate compound prepared in Example 9 was placed, heated to 100 ° C. by the heating body 6A, the methanol was released from the clathrate compound, and fed to the fuel absorber 5, and the water tank ( The water in 7) was heated to 100 ° C. by the heating body 7A and supplied to the fuel absorber 5. The supply amount to the fuel absorber 5 is methanol: water = 20:80 (weight ratio), and this ratio is equivalent to supplying 20weight% of aqueous methanol solution.

As a result, an electromotive force of 0.48 V was achieved when the current density was 100 mA / cm ² . Moreover, the residual amount of methanol was fully grasped | ascertained based on the color change of the methanol clathrate compound in clathrate compound tank 6.

Example 12

Using an electrolyte membrane electrode assembly (MEA) prepared in the same manner as in Example 11, as shown in Fig. 2, a direct methanol fuel cell system for supplying an aqueous methanol solution was assembled. In Fig. 2, 1 is an electrolyte membrane, 2 is an electrode (anode), and 3 is an electrode (cathode). The oxidant flow path and the fuel absorber are not shown. 6 is a clathrate compound tank and is equipped with the heating body 6A. 11 is a concentration adjustment tank and 12 is a CO ₂ removal means.

The clathrate compound tank 6 prepared in Example 9 was placed in the clathrate compound tank 6, heated to 100 ° C. by the heating body 6A, methanol was released from the clathrate compound, and supplied to the concentration adjusting tank 11, 20% by weight. Aqueous methanol solution was prepared and fed to the fuel absorber of the electrolyte membrane electrode assembly.

In the concentration adjusting tank 11, the recovered water used in the anode 2 and lowered in methanol concentration is circulated after treatment with the CO ₂ removal means 12. Water generated in the cathode 3 is also collected in the concentration adjusting tank 11 and used for adjusting the methanol aqueous solution.

As a result, it was possible to develop without problems, and the change in the residual amount of methanol was confirmed by gradually changing the color of the clathrate compound from dark red to yellow.

Example 13

Using an electrolyte membrane electrode assembly (MEA) prepared in the same manner as in Example 11, as shown in FIG. 3, a direct methanol fuel cell system for supplying an aqueous methanol solution was assembled. In FIG. 3, 1 is an electrolyte membrane, 2 is an electrode (anode), and 3 is an electrode (cathode). The oxidant flow path and the fuel absorber are not shown. 6 is a clathrate compound tank, and 7 is a water tank.

The clathrate compound tank 6 prepared in Example 9 was placed in the clathrate compound tank 6, and water from the water tank 7 was supplied to the clathrate compound tank 6 to bring the methanol clathrate compound into contact with water, thereby bringing methanol into the water. 20 weight% aqueous methanol solution was prepared, and it supplied to the fuel absorber of electrolyte membrane electrode assembly.

As a result, it was possible to develop without problems, and the change in the residual amount of methanol was confirmed by gradually changing the color of the clathrate compound from dark red to yellow.

[3] Next, a fuel for a solid electrolyte fuel cell, a solid electrolyte fuel cell and a method of using the third aspect will be described.

The fuel for solid electrolyte fuel cells of the third aspect includes a liquid organic fuel and a compound which forms a complex or molecular compound with the liquid organic fuel.

A method of using a solid electrolyte fuel cell according to a third aspect is a method of using a solid electrolyte fuel cell including a fuel electrode, an oxidant electrode, and a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode. It is characterized by supplying the fuel for the solid electrolyte fuel cell described above.

The solid electrolyte fuel cell of the third aspect includes a fuel electrode, an oxidant electrode, a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode, and the fuel for the solid electrolyte fuel cell described above.

The solid electrolyte fuel cell of the third aspect further includes a solid electrolyte fuel cell including a fuel electrode, an oxidant electrode, and a solid electrolyte membrane sandwiched by the fuel electrode and the oxidant electrode, wherein the solid electrolyte type is described in the fuel electrode. And a fuel supply means for supplying fuel for a fuel cell.

As the solid electrolyte membrane used in the solid electrolyte fuel cell, a solid electrolyte membrane having high hydrogen ion conductivity, typically represented by Nafion (registered trademark) or the like, is used. The high hydrogen ion conductivity in such a solid electrolyte membrane is expressed as the solid electrolyte membrane contains water. On the other hand, by containing water, a liquid organic fuel such as methanol can be easily introduced into the water as described above. It melt | dissolves and it moves in a solid electrolyte membrane, and it prompts the expression of the crossover which reaches to an oxidizing electrode.

In the third aspect, a compound (sometimes referred to as "capture compound") that forms a complex with a liquid organic fuel or a molecular compound that cannot penetrate the solid electrolyte membrane is dissolved in the liquid organic fuel supplied to the anode. Let's do it. As a result, a material layer for trapping the liquid organic fuel is formed between the anode and the solid electrolyte membrane, and passage of the liquid organic fuel is suppressed, so that crossover can be reduced.

First, a trapping compound which is characteristic of the fuel for solid electrolyte fuel cells of the third aspect will be described.

In the fuel for the solid electrolyte fuel cell of the third aspect, the trapping compound is not particularly limited as long as it is a compound which forms a complex or molecular compound with the liquid organic fuel, but can be dissolved in the liquid organic fuel and does not penetrate the solid electrolyte membrane. It is a compound which is not a compound, and is a compound other than sulfuric acid, sugars, alcohols, amines, and strong electrolytes from the point of capture effect. It is also important that the metal parts in the fuel cell have less corrosiveness, are electrochemically stable and nonvolatile. Examples of the capturing compound include crown ethers, kryptands, cyclopanes, azacyclopanes, calyx arenes, cyclotriveratrilenes, spheroids, oligopeptides, cyclic oligopeptides, ureas and thioureas. , Dioxycholic acids, perhydrotriphenylenes, tri-o-timoteds, bianthryls, spirobifluorenes, cyclophosphazenes, hydroxybenzophenones, phenols, bisphenols, trisphenols, tetra Key phenols, polyphenols, naphthols, bisnaphthols, carboxylic acid amides, thioamides, bixanthenes, carboxylic acids, hydroquinones and the like can be given as specific examples.

Here, the molecular compound is a compound in which two or more kinds of compounds which may be stably present alone are bonded by relatively weak interactions other than covalent bonds represented by hydrogen bonds, van der Waals forces, and the like. Addition compounds, clathrate compounds and the like.

Even when the capturing compound according to the third aspect is dissolved in a liquid organic fuel, a solvent, or the like, formation of a complex or a molecular compound is likely to occur due to the intermolecular interaction or the like, so that an excess liquid organic fuel is trapped, thereby causing crossover. Can be avoided.

More specifically as the trapping compound, urea, thiourea, dioxycholic acid, cholic acid, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2'-dihydroxybenzo Phenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-methoxyphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonylbisphenol, 2, 2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-ethylidenebisphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol), 1,1 , 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (4-hydroxyphenyl) ethylene, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro- 4-hydroxyphenyl) ethane, α, α, α ', α'-tetrakis (4-hydroxyphenyl) -p-xylene, tetrakis (p-methoxyphenyl) ethylene, 3,6,3', 6'-tetramethoxy-9,9'-bi-9H-xanthene, 3,6,3 ', 6'-tetraacetoxy-9,9'-non-9H-xanthene, 3,6,3 ', 6 '-Tetrahydroxy-9,9'-non-9H-xanthene, malated asset, malated asset methyl, catechin, bis-β-naphthol, diphenic acid bis dicyclohexylamide, fumaric acid bis dicyclohexylamide, 1,1, 2,2-tetraphenylethane, tetrakis (p-iodophenyl) ethylene, 9,9'-bianthryl, 1,1,2,2-tetrakis (4-carboxyphenyl) ethane, 1,1,2 , 2-tetrakis (3-carboxyphenyl) ethane, acetylenedicarboxylic acid, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4-dimethyl Phenyl) hydroquinone etc. are mentioned.

Among these capturing compounds, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis Phenolic compounds such as ethylene, hydroquinones such as hydroquinone, and amides such as bisdicyclohexylamide in (4-hydroxyphenyl) are advantageous in terms of economic efficiency, complex or molecular compound forming ability.

These trapping compounds may be used individually by 1 type, and may use 2 or more types together.

As a liquid organic fuel, the liquid organic fuel which has a C-H bond is used preferably, For example, Alcohol, such as methanol, ethanol, a propanol; Ethers such as dimethyl ether; Cycloparaffins such as cyclohexane; Cycloparaffins having hydrophilic groups such as hydroxyl, carboxyl, amino and amide groups; Mono- or di-substituted cycloparaffins; Etc. can be used. Here, cycloparaffins refer to cycloparaffin and its substituent, and things other than an aromatic compound are used.

The fuel for solid electrolyte fuel cells of the third aspect includes these liquid organic fuels, the aforementioned capturing compounds, and a solvent used as necessary. The capturing compound may be previously dissolved in the liquid organic fuel, or both may be mixed immediately before the fuel electrode such that the liquid organic fuel and the capturing compound are supplied to the fuel electrode of the fuel cell when the fuel cell is operated.

As a solvent, what is necessary is just solubility with respect to a liquid organic fuel and a trapping compound, and water, alcohols, etc. are used normally.

The concentration of the liquid organic fuel in the fuel for solid electrolyte fuel cells of the third aspect is usually used as 5 to 90 wt%. Too low a liquid organic fuel concentration results in poor fuel efficiency, and too high a liquid problem.

In the fuel for solid electrolyte fuel cells of the third aspect, the concentration of the capturing compound is preferably in the range of 0.001 to 1 mol / L. If the concentration of the trapping compound in the fuel for a solid electrolyte fuel cell is too low, the crossover suppression effect by adding the trapping compound cannot be sufficiently obtained, and if it is too high, it is economically disadvantageous.

It is preferable that pH for the solid electrolyte fuel cell fuel of a 3rd aspect is 4-8. By setting the pH value of the fuel for the solid electrolyte fuel cell in the range of 4 to 8, adverse effects on the solid electrolyte membrane and corrosion of the metal member in the fuel cell can be prevented and contribute to stable operation of the fuel cell. Therefore, when pH value is out of this range, you may add pH adjusters, such as an acid or an alkali, as needed.

EMBODIMENT OF THE INVENTION With reference to drawings, the solid electrolyte fuel cell of this invention using the solid electrolyte fuel cell fuel of a 3rd aspect, and its use method are demonstrated.

4 is a cross-sectional view schematically showing the structure of a solid electrolyte fuel cell according to an embodiment.

In FIG. 4, the electrode-electrolyte assembly 21 is composed of a fuel electrode 22, an oxidizer electrode 23, and a solid polymer electrolyte membrane 24. The anode 22 is composed of a base 22A and a catalyst layer 22B. The oxidizing electrode 23 is composed of a base 23A and a catalyst layer 23B. The plurality of electrode-electrolyte assemblies 21 are electrically connected through the fuel electrode side separator 25 and the oxidant electrode side separator 26 to form a fuel cell 30.

In the fuel cell 30 configured as described above, the fuel 27 is supplied to the fuel electrode 22 of each electrode-electrolyte assembly 21 through the fuel electrode side separator 25. An oxidant 28 such as air or oxygen is supplied to the oxidant electrode 23 of each electrode-electrolyte assembly 21 through the oxidant electrode side separator 26.

The solid polymer electrolyte membrane 24 separates the fuel electrode 22 and the oxidant electrode 23 and has a role of transferring hydrogen ions therebetween. For this reason, it is preferable that the solid polymer electrolyte membrane 24 is a membrane with high conductivity of hydrogen ions. It is also desirable to be chemically stable and have high mechanical strength.

As the material constituting the solid polymer electrolyte membrane 24, an organic polymer having a polar group such as a strong acid group such as a sulfone group, a phosphoric acid group, a phosphone group, a phosphine group, or a weak acid group such as a carboxyl group is preferably used. As such an organic polymer, Aromatic containing polymers, such as a sulfonated poly (4-phenoxy benzoyl-1, 4-phenylene) and an alkyl sulfonated polybenzoimidazole; Copolymers such as a polystyrene sulfonic acid copolymer, a polyvinyl sulfonic acid copolymer, a crosslinked alkyl sulfonic acid derivative, a fluorine resin skeleton and a fluorine-containing polymer composed of sulfonic acid; Copolymers obtained by copolymerizing acrylamides such as acrylamide-2-methylpropanesulfonic acid and acrylates such as n-butyl methacrylate; Sulfonic group-containing pafluorocarbon (Nafion (registered trademark, manufactured by DuPont), Asifrex (manufactured by Asahi Kasei Co., Ltd.)); Carboxyl group-containing pafluorocarbon (Premion (registered trademark) S film (made by Asahi Glass Corporation)); Etc. are illustrated. Among these, when aromatic-containing polymers such as sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzoimidazole are selected, permeation of liquid organic fuel can be suppressed and crossover The fall of battery efficiency by this can be suppressed.

As the base 22A of the fuel electrode 22 and the base 23A of the oxidizing electrode 23, both of the fuel electrode 22 and the oxidizing electrode 23 are carbon paper, a molded body of carbon, a sintered body of carbon, a sintered metal, a foamed metal, or the like. Of porous bases can be used. A water repellent such as polytetrafluoroethylene can be used for the water repellent treatment of these bases.

Examples of the catalyst of the anode 22 include platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, lithium, lanthanum, strontium, yttrium, and the like. These catalysts can be used individually or in combination of 2 or more types. As the catalyst of the oxidant electrode 23, the same catalyst as that of the fuel electrode 22 can be used, and the above-described exemplary materials can be used. The catalysts of the fuel electrode 22 and the oxidant electrode 23 may use the same or different catalysts.

Examples of the carbon particles supporting the catalyst include acetylene black (Tenka Black (registered trademark, manufactured by Denki Chemical Co., Ltd.), XC72 (manufactured by Vulcan), etc.), Ketjen Black, carbon nanotubes, carbon nanohorns, and the like. The average particle diameter of the carbon particles is, for example, 0.01 to 0.1 m, preferably 0.02 to 0.06 m.

Although the manufacturing method of the fuel electrode 22 and the oxidizing electrode 23 is not specifically limited, For example, it can manufacture it as follows. First, supporting of the catalysts on the carbon particles of the fuel electrode 22 and the oxidant electrode 23 can be performed by an impregnation method which is generally used. Subsequently, the catalyst-carrying carbon particles and the solid polymer electrolyte particles are dispersed in a solvent to form a paste, and then applied to the bases 22A and 23A and dried to obtain the fuel electrode 22 and the oxidizing electrode 23. Can be.

The average particle diameter of the carbon particles is, for example, 0.01 to 0.1 µm as described above. The average particle diameter of a catalyst particle shall be 1-10 nm, for example. The average particle diameter of the solid polymer electrolyte particles is, for example, 0.05 to 1 m. Carbon particles and solid polymer electrolyte particles are used, for example, in a weight ratio of 2: 1 to 40: 1. The weight ratio of water and solute in the paste is, for example, about 1: 2 to 10: 1.

There is no restriction | limiting in particular about the coating method of the paste to a base, For example, methods, such as brushing, spray application, and screen printing, can be used. The paste is applied to a thickness of about 1 μm to 2 mm. After the paste is applied, the fuel electrode 22 or the oxidizer electrode 23 is produced by heating at a heating temperature and a heating time according to the fluorine resin or the like of the solid polymer electrolyte to be used. Although heating temperature and heating time are suitably selected according to the material to be used, For example, it can be set as heating temperature of 100-250 degreeC, and heating time of 30 second-30 minutes.

The solid polymer electrolyte membrane 24 can be produced by employing an appropriate method depending on the material used. For example, when the solid polymer electrolyte membrane 24 is made of an organic polymer material, the liquid obtained by dissolving or dispersing the organic polymer material in a solvent can be obtained by casting the liquid on a peelable sheet such as polytetrafluoroethylene and drying it. have.

The solid polymer electrolyte membrane 24 produced as described above is sandwiched between the fuel electrode 22 and the oxidizing electrode 23 and hot pressed to obtain the electrode-electrolyte assembly 21. At this time, the surface on which the catalyst of both electrodes is installed and the solid polymer electrolyte membrane 24 are in contact with each other. The conditions of the hot press are selected depending on the material. When the solid polymer electrolyte membrane 24 or the electrolyte membrane on the surface of the electrode is composed of an organic polymer, the temperature of the hot press can be a temperature exceeding the softening temperature or the glass potential temperature of these polymers. Specifically, the conditions of a hot press employ | adopt the conditions of temperature 100-250 degreeC, pressure 5-100 kgf / cm <^2> (0.49-9.8 MPa), and time 10 second-300 second.

In the solid electrolyte fuel cell of the third aspect and a method of using the same, the fuel for the solid electrolyte fuel cell described above is supplied to the fuel electrode 22 of the solid electrolyte fuel cell configured as described above. As a result, a layer of a material for trapping the liquid organic fuel by the capturing compound is formed between the fuel 27 in the fuel electrode 22 and the solid polymer electrolyte membrane 24. Since passing through the electrolyte membrane 24 is suppressed, crossover can be reduced.

In the third aspect, the fuel for the solid electrolyte fuel cell of the third aspect is supplied to the fuel electrode of the solid electrolyte fuel cell as described above, but at this time, the liquid organic fuel that has not reacted at the fuel electrode is recovered and used again. It is preferable for the improvement of the utilization efficiency.

This form will be described below with reference to FIG. 5.

In FIG. 5, since the details of the fuel cell 30 are the same as in FIG. 4, they are omitted. In this embodiment, the fuel supply part 41 which supplies fuel to the fuel electrode of the fuel cell 30, the fuel recovery part 42 which collect | recovers the spent fuel discharged from the fuel electrode of the fuel cell 30, and the recovered use A fuel including a concentration detector 43 for measuring the concentration of the liquid organic fuel and the capturing compound in the finished fuel, and a concentration adjusting unit 44 for adjusting the concentration of the liquid organic fuel and the capturing compound in the used liquid fuel. A supply system 40 is provided. The fuel containing the capturing compound is circulated and used in the direction of the arrow in the figure by a liquid transport mechanism (not shown).

The fuel is supplied from the fuel supply part 41 to the fuel electrode of the fuel cell 30, passes through the fuel electrode, and is recovered by the fuel recovery part 42. Substances generated by electrode reaction in the anode, such as carbon dioxide, are separated in the fuel recovery section 42. The recovered fuel is then sent to the concentration detecting unit 43, whereby the concentrations of the liquid organic fuel and the capturing compound are measured. Based on this measurement result, the concentration of the liquid organic fuel and the capturing compound are appropriately adjusted in the concentration adjusting unit 44 to be regenerated as fuel. The regenerated fuel is transported to the fuel supply part 41 and sent to the fuel electrode of the fuel cell 30.

By having such a fuel supply system, a fuel cell which can utilize fuel efficiently can be realized.

According to the third aspect, the crossover of the liquid organic fuel in the solid electrolyte fuel cell can be suppressed, so that high output power and high fuel efficiency of the solid electrolyte fuel cell can be realized.

The solid electrolyte fuel cell of the third aspect using the solid electrolyte fuel cell fuel of the third aspect has high output and good battery efficiency because crossover of the liquid organic fuel is suppressed.

The solid electrolyte fuel cell according to the third aspect includes a fuel electrode, an oxidizing electrode, and a solid electrolyte membrane sandwiched by the fuel electrode and the oxidizing electrode, and employs a configuration in which a liquid organic fuel is directly supplied to the fuel electrode. It is a fuel cell. Conventional direct fuel cells have a high battery efficiency and can be space-saving because the reformer is unnecessary, while crossover of liquid organic fuels such as methanol becomes a problem. According to the third aspect, it is possible to stably realize good battery efficiency over a long period of time while eliminating this crossover problem.

Recovery means for recovering the spent fuel discharged from the anode, concentration adjusting means for adjusting the concentration of the liquid fuel and the capturing compound in the recovered used fuel, and transporting means for transporting the fuel whose concentration has been adjusted to the supply means; According to the solid electrolyte fuel cell of the third aspect further provided, since it is possible to reuse the liquid organic fuel not consumed in the fuel electrode, the liquid organic fuel can be used with high efficiency without waste.

Although a 3rd aspect is more concretely demonstrated to an Example and a comparative example below, a 3rd aspect is not limited to a following example unless the summary is exceeded.

Example 14

A fuel for a solid electrolyte fuel cell according to the present embodiment will be described with reference to FIG. 6.

First, 10 g of acetylene black (Denka Black (registered trademark); manufactured by Denki Chemical Co., Ltd.) in 500 g of dinitrodiamine platinum nitric acid solution containing 3% by weight of platinum serving as a catalyst in the fuel electrode 22 and the oxidizing electrode 23; ) Was mixed and stirred, and then 60 mL of 98% ethanol was added as a reducing agent. The solution was stirred and mixed at about 95 ° C. for 8 hours to support platinum fine particles on acetylene black particles. This solution was filtered and dried to obtain platinum-carrying carbon particles. The amount of platinum supported was about 50% by weight based on the weight of acetylene black.

Subsequently, 200 mg of platinum-supported carbon particles and 3.5 mL of a 5% Nafion (registered trademark) solution (alcohol solution, manufactured by Aldorrich Chemical Co., Ltd.) were mixed and stirred to adsorb Nafion (registered trademark) on the surface of platinum and carbon particles. I was. The obtained dispersion liquid was made into paste form by disperse | distributing with an ultrasonic disperser at 50 degreeC for 3 hours. This paste was apply | coated on the carbon paper (TGP-H-120 by Toray) by 2 mg / cm <^2> by screen printing, and it dried at 120 degreeC, and obtained the electrode.

As the solid polymer electrolyte membrane 24, Dupont's Nafion 117 (registered trademark, membrane thickness of 150 µm) was used. With respect to the solid polymer electrolyte membrane 24, the electrode obtained above was thermally compressed at 120 ° C., and the solid polymer electrolyte membrane 24 was sandwiched between the fuel electrode 22 and the oxidizing electrode 23 to obtain a temperature of 150 ° C. and a pressure. The electrode-electrolyte assembly 21 was produced by hot pressing at 10 kgf / cm ² (0.98 MPa) for 10 seconds.

In order to supply fuel to the fuel electrode 22, a fuel flow path 51 made of tetrafluoroethylene resin was provided on the fuel electrode 22. The fuel tank 52 and the waste liquid tank 53 were provided in this fuel flow path 51. The fuel tank 52 is provided with a pump, and as shown by the arrow in the figure, it is set as the structure which can supply a fuel to the fuel electrode 22 continuously.

In addition, in order to supply an oxidizing agent to the oxidizing electrode 23, an oxidizing agent flow path 54 made of tetrafluoroethylene resin was provided on the oxidizing electrode 23. An oxygen compressor 55 and an exhaust port 56 are provided in this oxidant flow path 54, and as shown by the arrow in the figure, it was set as the structure which can supply oxygen to an oxidizer electrode 23 continuously.

The fuel tank 52 was injected with a fuel in which 1,1-bis (4-hydroxyphenyl) cyclohexane was dissolved in a 10% by weight aqueous methanol solution. The concentration of 1,1-bis (4-hydroxyphenyl) cyclohexane in this fuel was 0.01 mol / L. This fuel was supplied to the anode 22 at 2 mL / min. About the oxidizing electrode 23, the oxygen compressor 55 supplied 1.1 atmospheres (0.11 MPa) and 25 degreeC oxygen.

Operating under these conditions, the current voltage characteristics of the unit cell were measured, and the results are shown in Table 1.

Example 15

In Example 14, the fuel cell was operated in the same manner as the fuel to be injected into the fuel tank 52, except that a fuel obtained by dissolving hydroquinone in a 10% by weight aqueous methanol solution was used. The measured results are shown in Table 1. The hydroquinone concentration of this fuel was 0.01 mol / L.

Example 16

In Example 14, the fuel cell was operated in the same manner as the fuel to be injected into the fuel tank 52, except that a fuel in which bisdicyclohexylamide was dissolved in a 10% by weight aqueous methanol solution was used. Table 1 shows the results of measuring the current voltage characteristics. The bisdicyclohexylamide concentration of this fuel was 0.01 mol / L.

Comparative Example 1

In Example 14, the fuel cell was operated in the same manner except that 10 wt% methanol aqueous solution was used as the fuel to be injected into the fuel tank 22, and the results of measuring the current voltage characteristics of the unit cells are shown in Table 1. .

Trapping compound Opening voltage
(V) Short circuit current
(mA / cm ² ) Power
(mW / cm ² ) Example 14 1,1-bis (4-hydroxyphenyl) cyclohexane 0.65 270 48 Example 15 Hydroquinone 0.66 340 55 Example 16 Bisdicyclohexylamide 0.65 280 49 Comparative Example 1 - 0.60 210 35

From Table 1, it is clear that the unit cell in Examples 14-16 is excellent also in any of an open voltage, a short circuit current, and a maximum power compared with the unit cell of the comparative example 1.

[4] Next, a fuel discharge method from the fuel composition for a fuel cell of the fourth aspect will be described.

A method for releasing fuel from a fuel composition for fuel cell of the fourth aspect is a method for releasing fuel from a fuel composition comprising fuel for fuel cell, wherein the fuel composition is discharged into the water by contacting the fuel composition with water. It is characterized by.

Although it does not specifically limit as a form of the fuel cell which concerns on 4th aspect, Preferably it is a solid polymer electrolyte fuel cell, Among these, a direct methanol fuel cell etc. are contained.

The fuel for the fuel cell according to the fourth aspect may be any fuel that can be used as a fuel of the fuel cell. Examples of the fuel for the fuel cell include, but are not limited to, hydrogen, alcohols, ethers, hydrocarbons, acetals, and the like. As the fuel substance, more specifically, alcohols such as hydrogen, methanol, ethanol, n-propanol, isopropanol and ethylene glycol, ethers such as dimethyl ether, methyl ethyl ether and diethyl ether, hydrocarbons such as propane and butane and dimeth Acetals, such as a methoxymethane and a trimethoxymethane, are mentioned. These fuel cell fuels may be used individually by 1 type, or may mix and use 2 or more types.

As a form of the fuel composition for fuel cells which concerns on a 4th aspect, although [1] the fuel cell fuel is made into the molecular compound, [2] the fuel cell fuel is absorbed in the polymer, etc., It is limited to these. no.

First, the fuel compositions of the above-mentioned [1] and [2] as fuel compositions containing the fuel for fuel cells according to the fourth aspect will be described.

[1] molecular compounds, fuel and counterpart compounds for fuel cells

Here, the molecular compound is a compound in which two or more kinds of compounds which may be stably present alone are bonded by relatively weak interactions other than covalent bonds represented by hydrogen bonds, van der Waals forces, and the like. Addition compounds, clathrate compounds and the like. Such a molecular compound can be formed by a contact reaction between a counterpart compound forming a molecular compound and a fuel cell fuel, for example, by converting a gas or liquid fuel cell fuel into a solid compound, which is relatively light and stable. Fuel for fuel cells can be stored.

As a molecular compound which concerns on 4th aspect, the clathrate compound which contained the fuel cell fuel by the contact reaction of a host compound and the fuel cell fuel is mentioned, for example.

As a host compound which forms the clathrate compound which contained the fuel for fuel cells, what consists of an organic compound, an inorganic compound, and an organic-inorganic composite compound is known. In the organic compound as a host compound, a monomolecular system, a polymolecular system, a high molecular host and the like are known.

Examples of the monomolecular host compounds include cyclodextrins, crown ethers, kryptands, cyclopanes, azacyclopanes, calix arenes, cyclotriveratrilenes, spheroids, and cyclic oligopeptides. . Examples of the multimolecular host compounds include urea, thioureas, dioxycholic acids, perhydrotriphenylenes, tri-o-timoteds, biantryls, spirobifluorenes, cyclophosphazenes, monoalcohols, Diols, acetylene alcohols, hydroxybenzophenones, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, b Xanthenes, carboxylic acids, imidazoles, hydroquinones, etc. are mentioned. Examples of the high molecular host compound include celluloses, starches, kitchens, chitosans, polyvinyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2-tetrakisphenylethane as a core, and α, α, and α. The polyethyleneglycol arm type polymer etc. which have ', (alpha)'-tetrakisphenyl xylene as a core are mentioned.

Examples of the organic host compound include organophosphorus compounds and organosilicon compounds.

Examples of the inorganic host compound include titanium oxide, graphite, alumina, transition metal decalgogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, porous glass, and the like.

The organometallic compound also exhibits properties as a host compound. For example, an organoaluminum compound, an organotitanium compound, an organoboron compound, an organozinc compound, an organo indium compound, an organ gallium compound, an organo tellurium compound, an organotin compound, an organo zirconium compound And organic magnesium compounds. It is also possible to use the metal salt of an organic carboxylic acid, an organometallic complex, etc. as a host compound. The organometallic compound-based host compound is not particularly limited to these.

Among these host compounds, multi-molecular host compounds in which the inclusion ability is hardly influenced by the size of the molecule of the guest compound are suitable.

Specific examples of the polymolecular host compound include urea, 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol, and 1,1-bis (2,4-dimethylphenyl) -2. Propyn-1-ol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1,6,6-tetrakis (2,4-dimethylphenyl) -2, 4-hexadiyne-1,6-diol, 9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis (4-methylphenyl) -9,10-dihydro Anthracene-9,10-diol, 1,1,2,2-tetraphenylethane-1,2-diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4'-dihydroxy Benzophenone, 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Sulfonylbisphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-ethylidenebisphenol, 4,4'-thiobis (3-methyl-6-t-butyl Phenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1, To 1,2,2-tetrakis (4-hydroxyphenyl) Lene, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, α , α, α ', α'-tetrakis (4-hydroxyphenyl) -p-xylene, tetrakis (p-methoxyphenyl) ethylene, 3,6,3', 6'-tetramethoxy-9, 9'-non-9H-xanthene, 3,6,3 ', 6'-tetraacetoxy-9,9'-non-9H-xanthene, 3,6,3', 6'-tetrahydroxy- 9,9'-B-9H-Xanthene, Molded Assets, Molded Assets Methyl, Catechin, Bis-β-Naphthol, α, α, α ', α'-Tetraphenyl-1,1'-biphenyl-2,2' Dimethanol, dipentic acid bis dicyclohexylamide, fumaric acid bis dicyclohexylamide, cholic acid, dioxycholic acid, 1,1,2,2-tetraphenylethane, tetrakis (p-iodinephenyl) ethylene, 9,9 '-Biantryl, 1,1,2,2-tetrakis (4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-carboxyphenyl) ethane, acetylenedicarboxylic acid, 2,4 , 5-triphenylimidazole, 1,2,4,5-tetraphenylimidazole, 2-phenylphenanthro [9,10-d] imidazole, 2- (o-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (m-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (p-cyanophenyl) phenan Tro [9,10-d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4-dimethylphenyl) hydroquinone, etc. are mentioned. .

As a host compound, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,2,2- tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2- among the above-mentioned things Phenolic host compounds such as tetrakis (4-hydroxyphenyl) ethylene, diphenic acid bis (dicyclohexylamide), amide host compounds such as bis dicyclohexylamide, and 2- (m-cyanophenyl) phenane Imidazole-based host compounds such as tro [9,10-d] imidazole are advantageous in terms of inclusion ability, and in particular, phenolic host compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane are commercially available. It is advantageous in that it is easy to use.

These host compounds may be used individually by 1 type, and may use 2 or more types together.

These host compounds may be compounds of any shape as long as they form a solid clathrate compound with fuel for fuel cells.

Of the host compounds described above, the organic host compound may be used as an organic-inorganic composite material supported on an inorganic porous material. In this case, examples of the porous material supporting the organic host compound include, but are not limited to, interlayer compounds such as clay minerals and montmorillonite, in addition to silicas, zeolites, and activated carbons. The organic-inorganic composite material can be prepared by dissolving the organic host compound described above in a solvent capable of dissolving it, impregnating the solution in a porous material, and drying the solvent and drying under reduced pressure. The amount of the organic host compound supported on the porous material is not particularly limited, but is usually about 10 to 80% by weight based on the porous material.

As a method of synthesizing the clathrate compound of the fuel cell fuel using a host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane, a method of directly contacting and mixing the fuel cell fuel and the host compound may be mentioned. Therefore, the clathrate compound which contained the fuel for fuel cell can be synthesize | combined easily. A clathrate compound can be synthesize | combined also by melt | dissolving a host compound in fuel for fuel cells, etc., and recrystallizing. If the fuel for a fuel cell is a gas or a liquid, the fuel may be brought into contact with the host compound in a pressurized state.

In the synthesis of the clathrate compound, the temperature at which the fuel for fuel cell and the host compound are brought into contact with each other is not particularly limited. There is no restriction | limiting in particular also about the pressure condition at this time. Although there is no restriction | limiting in particular also about the time which makes the fuel cell fuel and a host compound contact, It is preferable to set it as about 0.01 to 24 hours from a viewpoint of work efficiency.

The fuel cell fuel to be brought into contact with the host compound is preferably a high purity fuel. However, when a host compound having selective inclusion ability of the fuel cell fuel is used, a mixed liquid of the fuel cell fuel and other components may be used.

The clathrate compound thus obtained is also a clathrate compound in which 0.1 to 10 moles of the fuel cell fuel molecule is contained with respect to 1 mole of the host compound, although it varies depending on the type of the host compound used, the contact conditions with the fuel for fuel cell, and the like.

The clathrate compound thus obtained can stably store fuel for fuel cells over a long period of time in a normal temperature and atmospheric pressure environment. In addition, since the clathrate compound is lightweight, has excellent handleability, and can be made into a solid form, it can be easily stored in a container such as glass, metal, or plastic, and the problem of liquid leakage is also eliminated. In addition, since the fuel for gaseous or liquid fuel cells becomes solid by inclusion, it may be possible to avoid the properties as a foreign substance or a dangerous substance. Furthermore, the chemical reactivity of the fuel for fuel cells can be reduced, for example, the corrosiveness to metals, etc. can be reduced.

From such a clathrate compound, the host compound after releasing the fuel cell fuel by the method described later has a selective clathability to the fuel for the fuel cell, and can be effectively reused for inclusion of the fuel cell fuel.

[2] fuel compositions in which fuel for fuel cells is absorbed into polymers

This fuel composition is obtained by absorbing (impregnating) a liquid fuel cell fuel (hereinafter referred to as "liquid fuel") in a crosslinked product (A) of the following polymer compound (1):

Polymer compound (1): A polymer compound obtained by polymerizing or copolymerizing a structural unit having a carboxyl group and / or a sulfonic acid group (hereinafter referred to as an “acidic group-containing structural unit (a)”) in a molecule, wherein the acidic group-containing structural unit (a A polymer compound in which 30 to 100 mol% of the carboxyl group and / or the proton of the sulfonic acid group is substituted with an onium cation of the polymer compound (2) having a content of 20 to 100% by weight.

On the other hand, as will be described later, in the fourth aspect, the polymer compound (1) is not limited to one produced by replacing a predetermined amount of protons of the carboxyl group and / or sulfonic acid group of the polymer compound (2) with an onium cation. The polymer compound (1) may be produced by polymerizing or copolymerizing the protons of the carboxyl group and / or sulfonic acid group of the acidic group-containing structural unit (a) with an onium cation in advance. Similarly, the crosslinked product (A) of the high molecular compound (1) is not necessarily crosslinked with the polymer compound (1) prepared in advance, and the high molecular compound (2) as long as it can obtain a crosslinked product of the high molecular compound (1) Alternatively, crosslinking may be performed in the step of producing the polymer compound (1). In addition, introduction and crosslinking of an onium cation may be performed in two or more steps.

As an acidic group containing structural unit (a) which comprises the said high molecular compound (2),

Monomers having a carboxyl group such as (meth) acrylic acid, etaacrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, and anhydrides thereof

Monomers having sulfonic acid groups, such as aliphatic vinylsulfonic acid [vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, etc.], (meth) acrylate type sulfonic acids [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, etc.] And (meth) acrylamide type sulfonic acids [[acrylamide-2-methylpropanesulfonic acid, etc.]

Can be mentioned. The preferable carbon number of the acidic group-containing structural unit (a) is 3 to 30.

In the high molecular compound (2), one type of these acidic group-containing structural units (a) may be included alone, or two or more types may be included. The high molecular compound (2) may contain structural units copolymerizable with acidic group containing structural unit (a) other than the said acidic group containing structural unit (a) (henceforth "other structural unit (b)").

As another structural unit (b), for example

Alkyl (meth) acrylates (1 to 30 carbon atoms); Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, phenyl (meth) acrylate, octylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.

Oxyalkyl (meth) acrylates (C1-4); Specifically, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic acid mono (polyethylene glycol) ester (PEG number average molecular weight: 100-4,000), (meth) acrylic acid mono (polypropylene glycol) Ester (PPG number average molecular weight: 100-4,000), (meth) acrylic acid monomethoxy polyethylene glycol (PEG number average molecular weight: 100-4,000), (meth) acrylic acid monomethoxy propylene glycol (PPG number average molecular weight: 100-4,000 )Etc

(Meth) acrylamides; Specifically, (meth) acrylamide, (di) methyl (meth) acrylamide, (di) ethyl (meth) acrylamide, (di) propyl (meth) acrylamide, etc.

Allyl ethers; Specifically, methyl allyl ether, ethyl allyl ether, propyl allyl ether, glycerol monoallyl ether, trimethylolpropanetriallyl ether, pentaerythritol monoallyl ether, etc.

C4-C20 alpha-olefins; Specifically, isobutylene, 1-hexene, 1-octene, isooctene, 1-nonene, 1-decene, 1-dodecene and the like

Aromatic vinyl compounds having 8 to 20 carbon atoms; Specifically, styrene, t-butyl styrene, octyl styrene, etc.

Other vinyl compounds; Specifically, N-vinylacetamide, vinyl caproate, vinyl laurate, vinyl stearate, etc.

Amino group-containing monomers; Specifically, dialkyl (alkyl carbon number: 1 to 5) aminoethyl (meth) acrylate, meta (acryloyl) oxyethyl trialkyl (alkyl carbon number: 1 to 5) ammonium crawlide, bromide or sulfate

Alkali metal salts, primary to tertiary amine salts or alkanolamine salts of the monomers having the carboxyl group and sulfonic acid group;

Can be mentioned. Also about these other structural units (b), 1 type may be contained independently in the high molecular compound (2), and 2 or more types may be included.

The content of the acidic group-containing structural unit (a) in the high molecular compound (2) is usually 20 to 100% by weight, preferably 40 to 100% by weight, more preferably 60 to 100% by weight. If the content of the acidic group-containing structural unit (a) in the high molecular compound (2) is less than 20%, even if the protons of the carboxyl group or sulfonic acid group are replaced with onium cations described later, the amount of absorption of the liquid fuel to be stored decreases, or In small amounts, the liquid fuel may not be gelled.

When the high molecular compound (2) contains another structural unit (b), (meth) acrylic acid alkyl esters and oxyalkyl (meth) from the above-described structural units in view of the polymerizability of the monomer, the stability of the produced polymer, and the like. ) Acrylates, allyl ethers, α-olefins and aromatic vinyl compounds are preferable.

For efficient absorption and gelation of liquid fuel, the liquid fuel and the liquid fuel having a difference in SP value of 5 or less in the structural unit (b) selected in accordance with the SP value (solvability parameter) of the liquid fuel are the absorption amount or gelation power. Since it is easy to rise, it is preferable, and it is more preferable to select that the difference of the SP value of the liquid fuel made into absorption object, and the SP value of another structural unit (b) is three or less.

The manufacturing method of the high molecular compound (2) may be a method of finally obtaining the high molecular compound (2) containing a predetermined amount of the acidic group-containing structural unit (a), and there is no particular limitation. The high molecular compound (2) is a method of polymerizing an acidic group-containing structural unit (a) in a predetermined amount, for example, a monomer that can be easily changed into a carboxyl group or a sulfonic acid group such as esterified or amidated of the carboxyl group or sulfonic acid group-containing monomer. It can also manufacture by superposing | polymerizing and introduce | transducing the structural unit of a predetermined amount of a carboxyl group and a sulfonic acid group in a molecule | numerator using methods, such as hydrolysis. Moreover, it can also manufacture by the carboxyl group represented by carboxymethylcellulose, the sulfonic-acid group containing polysaccharide polymer, the method of graft copolymerization of this polysaccharide, and another monomer.

The high molecular compound (1) substitutes 30-100 mol% of the proton of the carboxyl group and / or sulfonic acid group of this high molecular compound (2) with an onium cation.

Here, the onium cation is selected from the group of cations consisting of quaternary ammonium cation (I), tertiary phosphonium cation (II), quaternary phosphonium cation (III) and tertiary oxonium cation (IV). 1 type, or 2 or more types are mentioned.

As quaternary ammonium cation (I), following (I-1)-(I-11) is mentioned.

(I-1) aliphatic quaternary ammonium having an alkyl and / or alkenyl group having 4 to 30 or more carbon atoms; Specifically, tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethylpropylammonium, tetrapropylammonium, butyltrimethylammonium, tetrabutylammonium, etc.

(I-2) aromatic quaternary ammonium having 6 to 30 or more carbon atoms; Specifically, trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium, etc.

(I-3) alicyclic quaternary ammonium having 3 to 30 or more carbon atoms; Specifically, N, N-dimethylpyrodinium, N-ethyl-N-methylpyrrolidinium, N, Ndimethylmorpholinium, N, Ndiethylmorpholinium, N, Ndimethylpiperidinium, N, N -Diethylpiperidinium, etc.

(I-4) imidazolinium having 3 to 30 or more carbon atoms; Specifically 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,2- Dimethyl-3,4-diethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1,2,3,4-tetraethyl Midazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 4-formyl-1,2,3-trimethylimidazolinium 3-hydroxyethyl-1,2,3-trimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium and the like

(I-5) imidazolium having 3 to 30 or more carbon atoms; Specifically, 1,3-dimethylimidazolium, 1-ethyl-3-butylimidazolium, 1-butyl-3-ethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1, 2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3-triethylimidazolium, 1,2,3 , 4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 4-cyano-1,2,3-trimethylimidazolium , 3-cyanomethyl-1,2-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-form Milmethyl-1,2-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium, N, N'-dimethylbenzoimidazolium, N, N'-diethylbenzoimidazolium, N-butyl-N'-ethylbenzoimidazolium, etc.

(I-6) tetrahydropyrimidinium having 4 to 30 or more carbon atoms; Specifically 1,3-dimethyltetrahydropyridinium, 1,2,3-trimethyltetrahydropyridinium, 1,2,3,4-tetramethyltetrahydropyridinium, 8-butyl-1,8-diazabi Cyclo [5,4,0] -7-undecnium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonene, 3-cyanomethyl-1,2-dimethyltetra Hydropyrimidinium, 3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium, 4-butylcarboxymethyl-1,2,3-trimethyl-tetrahydropyrimidinium, 3-methoxymethyl-1,2 -Dimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium, etc.

(I-7) dihydropyrimidinium having 4 to 30 or more carbon atoms; Specifically, 1,3-dimethyl-2,4-or-2,6-dihydropyrimidinium [These are denoted as 1,3-dimethyl-2,4, (6) -dihydropyrimidinium. Using the same expression], 1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-2,4, (6) -dihydro Pyrimidinium, 1,2,3,5-tetramethyl-2,4, (6) -dihydropymidinium, 8-methyl-1,8-diazacyclo [5,4,0] -7, 9 (10) -undecanedienium, 2-cyanomethyl-1,3-dimethyl-2,4, (6) -dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-2,4 , (6) -dihydropyrimidinium, 4-butylcarboxymethyl-1,2,3-trimethyl-2,4, (6) -dihydropyrimidinium, 4-formyl-1,2,3- Trimethyl-2,4, (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-2,4, (6) -dihydropyrimidinium, etc.

(I-8) guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; Specifically, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-dimethylamino-1-methyl-3,4 -Diethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-di Ethylimidazolinium, 1,5,6,7-tetrahydro1,2-dimethyl-2H-pyrimid [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H -Pyrimid [1,2a] imidazolinium, 2-dimethylamino-3-butylcarboxymethyl-1-butylimidazolinium, 2-dimethylamino-3-methoxymethyl-1-butylimidazolinium 2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium and the like

(I-9) guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; Specifically, 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4- Ethylimidazolium, 2-diethylamino-1,3,4-triethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 1,5,6,7-tetrahydro-1, 2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimid [1,2a] imidazolium, 2-dimethylamino-3- Cyanomethyl-1-butylimidazolium, 2-dimethylamino-4-butylcarboxymethyl-1,3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-butylimidazolium, 2 -Dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium, etc.

(I-10) guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms; Specifically, 2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyl Tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyltetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-imide [1 , 2a] pyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-pyrimid [1,2a] pyrimidinium, 2-dimethylamino-3-cyano Methyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyri Midinium, 2-dimethylamino-3-methoxymethyl-1-butyltetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4- Hydroxymethyl-1,3-dimethyltetrahydropyrimidinium, etc.

(I-11) guanidium having a dihydropyrimidinium skeleton having 4 to 30 or more carbon atoms; Specifically, 2-dimethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-2,4 (6)- Dihydropyrimidinium, 2-diethylamino-1,3,4-triethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-2,4 ( 6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-2,4 (6) -dihydropyrimidinium, 1,6,7,8-tetrahydro-1,2- Dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-pyrimid [1,2a] pyrimidinium, 2-dimethylamino-4-cyano -1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-butyl-2,4 (6) -dihydropyrimidinium, 2-dimethyl Amino-3-methylcarboxymethyl-1-butyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-2,4 (6) -dihydro Pyrimidinium, 2-dimethylamino-3-formylmethyl-1-butyl-2,4 (6) -dihydropyrimidinium, etc.

As tertiary phosphonium cation (II), following (II-1)-(II-3) is mentioned.

(II-1) aliphatic tertiary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; Specifically, trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium, etc.

(II-2) aromatic tertiary phosphonium having 6 to 30 or more carbon atoms; Specifically, phenyl dimethyl sulfonium, phenyl ethyl methyl sulfonium, phenyl methyl benzyl sulfonium, etc.

(II-3) alicyclic tertiary phosphonium having 3 to 30 or more carbon atoms; Specifically, methylthioranium, phenylthioranium, methyl thinium, etc.

As quaternary phosphonium cation (III), following (III-1)-(III-3) is mentioned.

(III-1) aliphatic quaternary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; Specifically, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyltripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldibutyl Phosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.

(III-2) aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; Specifically, triphenylmethyl phosphonium, diphenyl dimethyl phosphonium, triphenyl benzyl phosphonium, etc.

(III-3) alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms; Specifically, 1,1-dimethylphosphoranium, 1-methyl-1-ethylphosphoranium, 1,1-diethylphosphoranium, 1,1-diethylphosphorinium, 1,1-pentaethyleneforce Porinium, etc.

As quaternary oxonium cation (IV), following (IV-1)-(IV-3) is mentioned.

(IV-1) aliphatic tertiary oxonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; Specifically, trimethyl oxonium, triethyl oxonium, ethyl dimethyl oxonium, diethyl methyl oxonium, etc.

(IV-2) aromatic tertiary oxonium having 6 to 30 or more carbon atoms; Specifically, phenyl dimethyl oxonium, phenyl ethyl methyl oxonium, phenyl methyl benzyl oxonium, etc.

(IV-3) alicyclic tertiary oxonium having 3 to 30 or more carbon atoms; Specifically, methyloxoranium, phenyloxoranium, methyloxanium, etc.

Of these, preferred onium cations are quaternary ammonium cations (I), more preferably the above (I-1), (I-4) and (I-5), particularly preferred are (I-4) and ( I-5).

These onium cations may be used individually by 1 type, and may use 2 or more types together.

As a method for substituting the protons of the carboxyl group and / or sulfonic acid group of the high molecular compound (2) with the onium cation, any method may be used as long as it can replace a predetermined amount of the protons with the onium cation. Hydroxide salts (e.g., tetraethylammonium hydroxide, etc.) and monomethyl carbonate salts (e.g., 1,2,3,4-trimethylimidazolinium monomethyl carbonate, etc.) are added to the polymer compound (2). Therefore, it can be easily substituted by dehydration, decarbonation, and demethanol as needed. Moreover, you may substitute similarly in the step of the monomer which comprises the high molecular compound (2).

As a method of preparing the polymer compound (1) by substitution with an onium cation, for example, a method of polymerizing or copolymerizing the protons of the carboxyl group and / or sulfonic acid group of the acidic group-containing structural unit (a) with an onium cation and then And a method in which the protons of the carboxyl group and / or sulfonic acid group of the high molecular compound (2) are substituted with an onium cation, and the like, and if the high molecular compound (1) having a predetermined amount of onium cation introduced therein can be obtained, Substitution of the carboxyl group and / or sulfonic acid group of the containing structural unit (a) with the onium cation may be performed at any stage.

The ratio of replacing the protons of the carboxyl group and / or sulfonic acid group of the high molecular compound (2) with an onium cation (hereinafter referred to as "onium cation substitution rate") is usually 30 to 100 mol%, preferably 50 to 100 mol%, More preferably, it is 70-100 mol%. When onium cation substitution rate is less than 30 mol%, dissociation of the carboxyl group, sulfonic acid group, and onium cation of the high molecular compound (1) may be too low, and swelling power or gelation power may be low.

The crosslinking is carried out at any of the above-described manufacturing steps of the polymer compound (2), the manufacturing step of the polymer compound (1), or a subsequent step to obtain a crosslinked product (A) of the polymer compound (1). As a method of bridge | crosslinking, what is necessary is just a well-known method, For example, the method of following (1)-(5) is mentioned.

(1) crosslinking with a copolymerizable crosslinking agent;

One or two of the onium cation substituents of the acidic group-containing structural unit (a) and / or the acidic group-containing structural unit (a) which are raw materials of the high molecular compound (2), and other structural units (b) used as necessary. A copolymerizable crosslinking agent copolymerizable with the above (hereinafter, collectively referred to as "raw material component") or having two or more double bonds in a molecule is copolymerized with the raw material component, before or during synthesis of the high molecular compound (2). How to crosslink in. As a copolymerizable crosslinking agent, For example, polyvalent vinyl type crosslinking agents, such as divinylbenzene, (meth) acrylamide type crosslinking agents, such as N, N'-butylene bisacrylamide, polyvalent allylether crosslinking agents, such as pentaerythritol triallyl ether, and trimethyl Polyvalent (meth) acrylic acid ester crosslinking agents, such as an all propane triacrylate, etc. are mentioned.

(2) crosslinking with a reactive crosslinking agent;

A method of crosslinking before or during the synthesis of the high molecular compound (2) using a reactive crosslinking agent having two or more functional groups in a molecule capable of reacting with a functional group or the like of a raw material component. As a reactive crosslinking agent, For example, polyvalent isocyanate type crosslinking agents, such as 4,4'- diphenylmethane diisocyanate, polyvalent epoxy type crosslinking agents, such as polyglycerol polyglycidyl ether, polyhydric alcohol type crosslinking agents, such as glycerin, hexamethylenetetramine and polyethylene Polyvalent amines such as imines, imine crosslinking agents, haloepoxy crosslinking agents such as epichlorohydrin, and polyvalent metal salt crosslinking agents such as aluminum sulfate.

(3) crosslinking with a polymerization reactive crosslinking agent;

Crosslinking before or during synthesis of the polymer compound (2) using a polymerization-reactive crosslinking agent copolymerizable with the raw material component or having a double bond in the molecule and having a functional group capable of reacting with the functional group of the raw material component, etc. in the molecule. How to. As a polymerization reactive crosslinking agent, glycidyl (meth) acrylate type crosslinking agents, such as glycidyl methacrylate, allyl epoxy crosslinking agents, such as allyl glycidyl ether, etc. are mentioned, for example.

(4) crosslinking by irradiation;

When the polymer compound (1) is irradiated with radiation such as ultraviolet rays, electron beams, gamma rays, or the like to crosslink the polymer compound (1), or the raw material components are irradiated with ultraviolet rays, electron beams, gamma rays or the like to synthesize the polymer compound (2). A method of simultaneously performing polymerization and crosslinking;

(5) crosslinking by heating;

The polymer compound (2) or the polymer compound (1) is heated to 100 ° C. or higher, and thermal crosslinking between molecules of the polymer compound (2) or the polymer compound (1), for example, between carbons due to the generation of radicals by heating. Bridge | crosslinking, the method of bridge | crosslinking between functional groups, etc.

Among these crosslinking methods, preferred methods are, depending on the use and form of the final product, in general, (1) crosslinking with a copolymerizable crosslinking agent, (2) crosslinking with a reactive crosslinking agent, and (4) crosslinking with radiation.

Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide crosslinking agents, allyl ether crosslinking agents, and polyvalent (meth) acrylic acid ester crosslinking agents, and more preferably allylether crosslinking agents. Preferred among the reactive crosslinking agents are polyisocyanate crosslinking agents and polyvalent epoxy crosslinking agents, more preferably polyvalent isocyanate crosslinking agents or polyvalent epoxy crosslinking agents having three or more functional groups in the molecule.

Although the crosslinking degree can be suitably selected according to a use purpose, when using a copolymerizable crosslinking agent, 0.001-10 weight% is preferable with respect to the total raw material component weight, and, as for the addition amount, 0.01-5 weight% is more preferable. .

In the case of using a reactive crosslinking agent, the amount of addition varies depending on the shape of the crosslinked body (A), but the amount of addition is preferably 0.001 to 10% by weight based on the total raw material components, and the integral fuel containing the liquid fuel described later. In order to produce a good gel, 0.01-50 weight% is especially preferable with respect to all the raw material components.

The polymerization method of the raw material component, ie, the onium cation substituent of the acidic group-containing structural unit (a) and / or the acidic group-containing structural unit (a), and other structural units (b) used as necessary may be a known method. The solution polymerization method in the solvent which each said monomer and the polymer to produce | generate dissolve, the block polymerization method which superposes | polymerizes without using a solvent, an emulsion polymerization method, etc. can be illustrated. Among these, the solution polymerization method is preferable.

The solvent used in the case of solution polymerization can be appropriately selected depending on the solubility of the monomer and polymer to be used, but for example, carbon such as alcohols such as methanol and ethanol, ethylene carbonate, propylene carbonate and dimethyl carbonate Lactones such as nates, γ-butyrolactone, lactones such as ε-caprolactam, ketones such as acetone and methyl ethyl ketone, carboxylic acid esters such as ethyl acetate, tetrahydrofuran and dimethoxyethane Organic solvents, such as aromatic hydrocarbons, such as ether, toluene, and xylene, water, etc. are mentioned. These solvent may be used individually by 1 type, and may mix and use 2 or more types.

The polymerization concentration in solution polymerization is also not particularly limited and varies in various ways depending on the intended use, but is preferably 1 to 80% by weight, more preferably 5 to 60% by weight.

The polymerization initiator may be a conventional one, and examples thereof include azo initiators, peroxide initiators, and redox initiators. Examples of azo initiators include azobisisobutyronitrile, azobiscyanovaleric acid, azobis (2,4-dimethylvaleronitrile), azobis (2-amidinopropane) dihydrochloride and azobis {2- Methyl-N- (2-hydroxyethyl) propionamide} etc. are mentioned. Examples of the peroxide initiator include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, succinate peroxide, di (2-ethoxyethyl) peroxydicarbonate, hydrogen peroxide and the like. As a redox initiator, the combination of the said peroxide initiator and a reducing agent (ascorbic acid or persulfate), etc. are mentioned.

As another polymerization method, the method of irradiating an ultraviolet-ray etc. by adding a photosensitization initiator [benzophenone etc.], the method of irradiating a superposition | polymerization by irradiating radiation, such as a gamma ray or an electron beam, can be illustrated.

Although the addition amount of the initiator in the case of using a polymerization initiator is not specifically limited, 0.0001-5 weight% is preferable with respect to the total weight of the raw material component to be used, and 0.001-2 weight% is more preferable.

The polymerization temperature also varies depending on the target molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent to be used, etc., but is preferably -20 to 200 ° C, more preferably 0 to 100 ° C.

This crosslinked body (A) has the ability to absorb the liquid fuel, thereby absorbing the liquid fuel to form a stable fuel composition.

The liquid fuel absorption amount of the crosslinked product (A) varies in accordance with the kind of the target fuel, the composition of the crosslinked product (A), the gel strength, and the like. It is preferable to design a crosslinked body (A) by 10-1,000 g-methanol / g-crosslinked body (A), for example, and it is more preferable to design it as 50-900 g / g. If this absorption amount is 10 g / g or more, the amount of liquid retention will be sufficient and it will be excellent in storage efficiency. If it is 1,000 g / g or less, there is no problem that the gel strength of the fuel composition in which the liquid fuel is held is too weak.

When making the crosslinked body (A) which concerns on a 4th aspect into a particle shape, the particle diameter is 0.1-5,000 micrometers in volume average particle diameter, More preferably, it is 50-2,000 micrometers. Moreover, 10 weight% or less of the whole and the part over 5,000 micrometers are less than 0.1 micrometer are preferable, and 10 weight% or less of the whole is preferable, and 5% or less is more preferable, respectively.

The particle diameter was measured by a method described in Ferris Chemicals 6th Handbook (MacGlohill, North, Company, 1984, p. 21), using a low-top test sieve shaker and JIS Z8801-2000 standard sieve. (Hereinafter, the particle diameter is measured by this method).

As a method of making a crosslinked body (A) into a particulate form, if it finally becomes a particulate form, there will be no limitation in particular, For example, methods, such as following (i)-(i), are mentioned.

(i); If necessary, a solvent is used to copolymerize the copolymerizable crosslinking agent to prepare a crosslinked product (A) of the polymer compound (1), and if necessary, the solvent is distilled off by drying or the like, using a known grinding method. Grinding to granules.

(Ii); If necessary, polymerization is carried out using a solvent to prepare a high molecular compound (1), and then the high molecular compound (1) is crosslinked by a means such as the reactive crosslinking agent or irradiation, and then the solvent is dried by a method such as drying if necessary. A method of distilling and pulverizing using a known grinding method to form a particulate.

(Iii); The acidic group-containing structural unit (a) and, if necessary, the other structural unit (b) are copolymerized with a solvent and polymerized by crosslinking, if necessary, in the presence of the copolymerizable crosslinking agent, and then the onium cation compound is added. A method of dissolving a proton of an acid group by a predetermined amount onium cation, then distilling a solvent by methods, such as drying, if necessary, and grind | pulverizing using a well-known grinding | pulverization method to make it a granular form.

(Iii); The acidic group-containing structural unit (a) and, if necessary, the other structural unit (b) are copolymerized with a solvent as necessary in the presence of the copolymerizable crosslinking agent to form an uncrosslinked polymer, and then the onium cationic compound and the reactive crosslinking agent By irradiating with radiation, the proton of an acidic radical is substituted, and a polymer is bridge | crosslinked, a solvent is distilled off by the method of drying etc. as needed, and it grind | pulverizes using a well-known grinding | pulverization method, and is made into a particulate form.

In the said method, drying performed as needed in the process of making the shape of a crosslinked body (A) into a particle shape should just be a well-known drying method, For example, aeration drying (for example, a pure air dryer), air drying (band type dryer, etc.), Drying under reduced pressure (pressure reduction dryer etc.), contact drying (drum dryer etc.), etc. are mentioned.

The drying temperature in the case of drying is not particularly limited as long as deterioration such as a polymer or excessive crosslinking does not occur, but it is preferably 0 to 200 ° C, more preferably 50 to 150 ° C.

The grinding | pulverization method in the case of making the shape of a crosslinked body (A) into a particle shape may be a well-known method, for example, a high-speed rotary grinder, such as impact grinding (pin mill, cutter mill, ball mill grinder, ACM pulverizer, etc.). Etc.), air grinding (jet grinder etc.), freeze grinding, etc. are mentioned.

The fuel composition composed of the crosslinked product (A) and the fuel can be processed into various forms depending on the purpose thereof, and the shape thereof is not particularly limited, but examples of the preferred form include particulate, sheet and monogel formation. .

Hereinafter, although the preparation method of a preferable aspect is demonstrated, since the preparation method, a preferable method, etc. differ slightly according to the form of a fuel composition, each is demonstrated.

The particulate fuel composition may be one in which the particulate crosslinked product (A) has absorbed the liquid fuel, or may have been made into particulate after absorbing the liquid fuel. The method of making a particle shape may be the same as the method of manufacturing said particle | grain crosslinked body (A), and the value similar to the volume average particle diameter etc. is preferable.

When making a fuel composition into a sheet form, the method of following (v)-(i) is mentioned as the sheeting method, for example.

(v); A particulate crosslinked product (A) is sandwiched between a nonwoven fabric, paper, or the like to form a sandwich sheet, and then the liquid fuel is absorbed.

(Iii); After impregnating and / or coating the uncrosslinked polymer compound (1) with one or two or more substrates consisting of nonwoven fabric, woven fabric, paper, and film, crosslinking by the crosslinking agent, crosslinking by the radiation, and heating A method of crosslinking a polymer compound (1) using one or two or more crosslinking means selected from the group consisting of crosslinking, and distilling off the solvent as necessary to form a sheet to absorb the liquid fuel.

(Iii); 20-100 weight% of the acidic group containing structural unit (a) which substituted 30-100 mol% proton by the said onium cation, 0-80 weight% of other structural units (b), and the mixed solution which consists of the said crosslinking agents, After impregnating and / or coating a substrate made of one or two or more of nonwoven fabric, woven fabric, paper, and film, the substrate is selected from the group of crosslinking by irradiation with a polymerization initiator and / or radiation, and crosslinking by heating. A method of polymerizing using one or two or more crosslinking means and sheeting by distilling off the solvent, if necessary, and then absorbing the liquid fuel.

Among these methods, from the viewpoint of ease of thickness adjustment of the created sheet, absorption rate of the created sheet, and the like, (i) or (iii) is preferable. 1-50,000 micrometers is preferable, as for the thickness of the fuel composition sheet in the case of making a shape into a sheet form, 5-30,000 are more preferable, 10-10,000 micrometers is especially preferable. If the thickness of the sheet is 1 µm or more, the basis weight of the crosslinked product (A) does not become too small, and if the thickness is 50,000 µm or less, the thickness of the sheet does not become too thick. The sheet length and width can be appropriately selected according to the size to be used, and there is no particular limitation, but the preferred length is 0.01 to 10,000 m and the preferred width is 0.1 to 300 cm.

The basis weight of the crosslinked product (A) in the fuel composition sheet is not particularly limited, but the basis weight is 10 to 3, when the absorption and retention capability of the target liquid fuel and the thickness are not too thick. OOO g / m ² is preferable and 20-1, OO g / m ² is more preferable.

In a 4th aspect, base materials, such as a nonwoven fabric, a woven fabric, a paper, and a film, used as needed in order to make a form into a sheet form should just be a well-known thing, For example, the synthetic fiber whose basis weight is about 10-500 g / m <^2> and Non-woven or woven fabric made of natural fibers, paper (quality paper, thin paper, Japanese paper, etc.), a film made of synthetic resin, two or more substrates thereof, and composites thereof can be exemplified.

Among these substrates, preferred are nonwoven fabrics or composites of nonwoven fabrics and plastic films or metal films, and particularly preferred are composites of nonwoven fabrics, nonwoven fabrics and plastic films.

Although there is no restriction | limiting in particular about the thickness of these base materials, Usually, it is 1-50,000 micrometers, Preferably it is 10-20,000 micrometers. If the thickness is less than 1 μm, impregnation and coating of a predetermined amount of the polymer compound (1) is difficult. If the thickness is more than 50,000 μm, the sheet is too thick, and when the fuel composition containing the fuel cell fuel is used, the total volume becomes large. It becomes hard to use.

The coating method and impregnation method of the polymeric compound (1) to a base material may be a well-known method, For example, what is necessary is just to apply methods, such as normal coating and padding. After coating or padding treatment, the solvent used for polymerization, dilution, viscosity adjustment, or the like may be removed by drying or the like as necessary.

The fuel absorption amount (fuel content) in the sheet-like fuel composition is not particularly limited as long as it is an amount capable of sufficiently securing the supply amount of the fuel, but preferably from 0.1 to 500 g-fuel / cm ² -sheet, preferably from 1 to 400 It is more preferable that it is g / cm <^2> . If the amount of absorption is 0.1 g / cm ² or more, a sufficient amount of the liquid fuel can be absorbed. If the amount of absorption is 500 g / cm ² or less, the sheet absorbing the liquid fuel does not become too thick.

The fuel composition according to the fourth aspect may be an integral gelled fuel composition comprising a crosslinked body (A) and a liquid fuel. The ratio of the crosslinked product (A) / fuel in the unitary gelled fuel composition is preferably 0.1 to 99/1 to 99.9% by weight, more preferably 0.5 to 50/50 to 99.5% by weight, particularly preferably. Preferably it is 1-30 / 70-99 weight%, Most preferably, it is 1-20 / 80-99 weight%. If the ratio of the crosslinked product (A) is 0.1% by weight or more, the gel strength of the resulting fuel-containing gel is not weak or cannot be gelled in the entirety, while the content of the crosslinked product (A) is 99% by weight or less. Since there are too many, the amount of fuel required is too small, and there is no problem that the supply amount of fuel cannot be sufficiently secured.

As a preparation method of an integral gelation type fuel composition, For example, (iv) the method of adding a predetermined amount of fuel to the particle | grain crosslinked body (A) mentioned above; (Iv) Although the method of adding a fuel to the sheet | seat containing a crosslinked body (A) may be sufficient, it is preferable that these fuel containing gels were created by the method mentioned to the following (x), (xi), etc., for example.

(x); A method in which the polymer compound (1) is dissolved in a liquid fuel and the polymer compound (1) is integrated into a gel by crosslinking by any of the crosslinking means of crosslinking by the crosslinking agent, crosslinking by irradiation, and crosslinking by heating.

(xi); In the liquid fuel, 20 to 100% by weight of the acidic group-containing structural unit (a) in which 30 to 100 mol% of the proton is substituted with the onium cation and 0 to 80% by weight of the other structural unit (b), if necessary, A method of forming an integrated gel by polymerizing in the presence of a copolymerizable crosslinking agent.

The form of the integrated gel fuel composition which consists of a crosslinked body (A) and a liquid fuel can be selected suitably, As a shape, shapes, such as a sheet form, a block form, a spherical form, a columnar form, can be illustrated, for example. Among these, a preferable shape is sheet form, block form, or columnar form.

1-50,000 micrometers is preferable and, as for the thickness of the gel in the case of using a sheet-like gel, 10-20,000 micrometers is more preferable. What is necessary is just to select the width | variety and length of a sheet-shaped gel suitably according to the purpose of use, a place, and a use.

The method for producing an integral gelling fuel composition having a desired shape is not particularly limited, and the polymer compound (1) or the method of gelling in a container or a cell according to the shape to be created, or on a release paper, a film, a nonwoven fabric, or the like, for example. The method of making a gel by making a mixture of a raw material component etc. and a liquid fuel into a sheet form by lamination or coating etc. can be illustrated.

In addition, other types of gelling agents (fatty acid soap, dibenzal sorbitol, hydroxypropyl cellulose, benzylidene sorbitol, carboxyvinyl polymer, polyethylene glycol, polyoxyalkylene, sorbitol, nitrocellulose, methyl, etc.) Cellulose, ethyl cellulose, acetylbutyl cellulose, polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylic resin, acetal resin, polycarbonate, nylon, phenolic resin, phenoxy resin, glassia resin, alkyd resin, polyester, epoxy Chemical conversion of resins, diallyl resins, polyalomas, etc.) and adsorbents (dextrin, dextran, silica gel, silica, alumina, molecular sieve, kaolin, diatomaceous earth, carbon black, activated carbon, etc.), thickeners, binders, fuels Even if one or two or more kinds selected from the group consisting of non-fluidizing substances are blended good. These are not particularly limited as long as they can exhibit respective functions, and may be either solid or liquid. In addition, these may be combined at any stage of preparing the fuel composition.

[3] release of fuel for fuel cell from fuel composition

In a fourth aspect, the fuel cell fuel is discharged from a fuel composition such as the fuel composition containing the molecular compound of the fuel cell fuel [1] described above, or the fuel composition in which the fuel cell fuel is absorbed in a polymer. In this case, the fuel composition is brought into contact with water to elute the fuel for fuel cell in the fuel composition toward water to extract the fuel.

In this case, water may be an aqueous solution of the fuel for fuel cell. In addition, in the contact between the fuel composition and water, heating is not particularly necessary and may be room temperature, but may be heated to about 50 to 150 ° C.

There is no restriction | limiting in particular as a method of making a fuel composition and water contact, For example, the method which fills a fuel composition in the container which has water inlet and outlet, and which can pass water inside, and passes water through this container is mentioned. Moreover, the method of injecting a fuel composition into a tank and releasing a fuel may be sufficient.

What is necessary is just to prepare the fuel discharge | released in water from a fuel composition suitably, and to supply fuel fuel aqueous solution of the density | concentration according to a use purpose, for example, about 1 to 64 weight% of fuel aqueous solution.

According to the fourth aspect, for example, the fuel for fuel cell is extracted from a fuel composition including the fuel cell fuel without requiring a heating device or heating energy in a very simple way such as passing water through a container filled with the fuel composition. It can be easily released.

Therefore, after the fuel cell fuel, which is difficult to handle, is safely and stably stored as a fuel composition containing the fuel cell fuel, the fuel cell fuel can be easily and inexpensively extracted from the fuel composition. It is advantageous.

On the other hand, in the fuel for fuel cells, the stock solution of methanol is equivalent to the poison of the poison control method, and it is equivalent to the dangerous substance class 4, and care must be taken with sufficient care, and in high concentration methanol, there are problems such as corrosion, etc. When methanol is used as a fuel, it is usually used as an aqueous solution of about 10 to 30% by weight. In the fourth aspect, the fuel composition is brought into contact with water and the fuel in the fuel composition is released into water, whereby the fuel can be supplied to the fuel cell as an aqueous solution of a suitable concentration, and in this respect, the discharge method of the fourth aspect It is very advantageous industrially.

The fourth aspect is useful as a fuel release method from a fuel composition for a direct methanol fuel cell, which is promising as a solid polymer electrolyte fuel cell, in particular, a portable small fuel cell, but is not limited to this, but is a fuel for various fuel cells. It is applicable to the release of the fuel from the fuel composition containing the.

Although a 4th aspect is more concretely demonstrated to a manufacture example and an Example below, a 4th aspect is not limited to a following example at all, unless the summary is exceeded.

Preparation Example 1

BHC: Methanol = 1: 1 (26.8 g (0.1 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter abbreviated as "BHC") was dissolved in 50 ml of methanol and recrystallized. Molar ratio) to obtain a solid methanol clathrate compound having a methanol content of 11% by weight.

Production Example 2

41.4 g (0.1 mol) of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (hereinafter abbreviated as "TPHDD") is dissolved in 100 ml of methanol and recrystallized by , TPHDD: methanol = 1: 2 (molar ratio) yielded a solid methanol clathrate compound having a methanol content of 13% by weight.

Production Example 3

39.8 g (0.1 mol) of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (hereinafter abbreviated as "THPE") was dissolved by heating in 100 ml of methanol and recrystallized to obtain THPE: methanol = A solid methanol clathrate compound having a methanol content of 14 wt% was obtained in a ratio of 1: 2 (molar ratio).

Production Example 4

360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether, and 1140 g of water were placed in a 2-liter adiabatic polymerization tank. After cooling the temperature of the monomer solution to 0 ° C. and letting the solution flow through nitrogen to lower the dissolved oxygen, 0.36 g of 2,2′-azobis (2-amidinopropane) hydrochloride and 35 wt% hydrogen peroxide as the polymerization initiator. 3.1 g of water and 0.38 g of L-ascorbic acid were added to start the polymerization. After the polymerization, the resultant hydrogel was subdivided into a gel using a meat chopper, and then 60, of methyl carbonate (molecular weight: 203) of 1,2,3,4-tetramethylimidazolinium cation was added to the gel. 1353 g (4 mol) of% methanol solution (manufactured by Sanyo Chemical Co., Ltd.) was added, and it was observed that decarbonic acid and demethanol were generated. In the gel to which the imidazolinium cation was added, a hot air at 100 ° C. was dumped into the gel using a band dryer (aeration dryer, manufactured by Inoue Kinzoku Co., Ltd.), and water and incidental methanol used as a solvent were distilled away. Dried up. The dried product was pulverized using a cutter mill to prepare a particulate crosslinked product having an average particle diameter of 400 µm, and 100 g of methanol was absorbed into this 20 g to obtain a gel fuel composition.

Example 17

First, an electrolyte membrane electrode assembly (MEA) was produced in the following manner. As an electrolyte membrane, Nafion which is an ion exchange membrane of the pafluorosulfonic acid type was used. Pt particles were used for the supported catalyst and supported on acetylene black in order to provide electron conductivity. Pt loading amount was 50 weight% with respect to acetylene black. The Pt supported catalyst and the 5 wt% Nafion solution were mixed and blown onto the electrolyte membrane using a spray brush to attach the electrode layer. The film to which the electrode layer was attached was dried at 90 ° C. for 1 hour in a drier, sandwiched between teflon plates, and pressed at 130 ° C. and 20 MPa for 30 minutes by a hot press to bond the electrolyte membrane and the electrode.

Using the produced electrolyte membrane electrode assembly (MEA), as shown in Fig. 7, a direct methanol fuel cell system for supplying an aqueous methanol solution was assembled. In Fig. 7, 61 is an electrolyte membrane, 62 is an electrode (anode), 63 is an electrode (cathode), 64 is a fuel composition tank, and 65 is a water tank.

The methanol clathrate compound prepared in Production Example 1 was placed in the fuel composition tank 64, and the methanol clathrate compound was brought into contact with water by supplying water from the water tank 65 to the fuel composition tank 64. 20 weight% aqueous methanol solution was prepared, and it supplied to the fuel absorber of electrolyte membrane electrode assembly. On the other hand, the water tank 65 may be circulated after treatment with CO ₂ removal means for the recovered water used in the anode 62 and the methanol concentration is lowered. Water generated in the cathode 63 may be recovered and supplied to the water tank 65.

As a result, it was possible to stably supply an aqueous methanol solution to the fuel cell, thereby generating power by stable operation for a long time.

The same applies to the case where the methanol inclusion compound prepared in Production Examples 2 and 3 or the gel fuel composition prepared in Production Example 4 was used as the fuel composition.

From the above results, it can be seen that by contacting the fuel composition with water, it is possible to easily release the fuel for fuel cell in water and stably supply the fuel to the fuel cell.

Claims (63)

As a fuel for fuel cells which becomes a solid molecular compound by the organic fuel used for a fuel cell being a clathrate compound formed with the said organic fuel and a host compound, The fuel cell is a direct methanol fuel cell, the organic fuel is methanol, The host compound is 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis ( Selected from the group consisting of 4-hydroxyphenyl) ethylene, diphenic acid bis (dicyclohexylamide), bis dicyclohexylamide and 2- (m-cyanophenyl) phenanthro [9,10-d] imidazole A fuel cell fuel, characterized in that one or two or more. The fuel cell fuel according to claim 1, wherein the fuel cell is a portable small fuel cell. The fuel cell fuel according to claim 1 or 2, wherein the host compound is supported on a porous material. A method for supplying fuel for a fuel cell, wherein the organic fuel is discharged from the fuel for fuel cell according to claim 1 or 2 and supplied to the fuel electrode of the fuel cell. The fuel cell fuel supply method according to claim 4, wherein the organic fuel is released by heating the fuel cell fuel. The fuel cell fuel supply method according to claim 4, wherein the organic fuel is released into water by bringing the fuel cell fuel into contact with water. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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