CN1894818A

CN1894818A - Fuel for fuel cell, fuel cell and application thereof

Info

Publication number: CN1894818A
Application number: CNA200480037840XA
Authority: CN
Inventors: 八木稔; 西哲幸
Original assignee: Kurita Water Industries Ltd
Current assignee: Kurita Water Industries Ltd
Priority date: 2003-12-18
Filing date: 2004-12-03
Publication date: 2007-01-10
Anticipated expiration: 2024-12-03
Also published as: CN100521342C

Abstract

A fuel for fuel cell consisting of an organic fuel which is in the form of a solid molecular compound, such as a clathrate compound. This molecular compound can be produced by catalytic reaction between a molecular compound forming compound and an organic fuel and changes a liquid organic fuel to a solid compound, thereby realizing relatively lightweight and stable storage of the organic fuel. Organic fuel can be easily released from the molecular compound by heating, etc. and can be fed to a fuel electrode of the fuel cell. As a result, not only can the handleability of the fuel for fuel cell consisting of an organic fuel be improved but also the problems of corrosion, fuel freezing, crossover, etc. can be solved.

Description

Fuel cell-use fuel, fuel cell and application thereof

Invention field

The present invention's (the 1st mode) is about fuel cell-use fuel and supply method thereof, the problem of the burn into of operability, peripheral equipment that is particularly related to the organic system fuel of methyl alcohol that solution uses etc. in fuel cell seeing through in battery etc. seeks to improve generating efficiency and the fuel cell-use fuel of stable operation and the method that this fuel cell-use fuel is supplied with to fuel cell of fuel cell.

The present invention's (the 2nd mode) is the amount detection method about the fuel material in the fuel cell-use fuel composition, particularly detects the method for residual volume of the fuel material of the methyl alcohol supplied with to fuel cell etc. simply.

The present invention's (the 3rd mode) be about solid electrolyte fuel cell with fuel, solid electrolyte fuel cell and using method thereof, the solid electrolyte fuel cell that sees through that particularly can suppress the fuel in the solid electrolyte fuel cell is with fuel and use the solid electrolyte fuel cell and the using method thereof of this solid electrolyte fuel cell usefulness fuel.

The present invention's (the 4th mode) relates to the method that discharges fuel cell-use fuel from the fuel composition that contains fuel cell-use fuel fairly simplely.

Background technology

Solid macromolecular electrolyte type fuel cell, be that solid electrolyte film with perfluoro sulfonic acid membrane etc. is as electrolyte, engage fuel electrodes and oxidizing agent pole on the two sides of this film and constitute, anode supply with hydrogen, methyl alcohol etc. the liquid organic-fuel, supply with oxygen to negative electrode, the device that generates electricity by electrochemical reaction.

Among fuel cell, in recent years with the direct-type methanol fuel cell be representative, liquid organic-fuel upgrading is not being carried out with regard to the exploitation of the fuel cell directly supplied with to fuel electrodes always actively.The fuel cell that liquid organic-fuel upgrading is just directly supplied with to fuel electrodes not because be structure with the direct fueling utmost point of liquid organic-fuel, does not therefore need the device of modifier and so on.Therefore, there is the formation of battery simple, can will installs the advantage of integral miniaturization simultaneously.With the gaseous fuel of hydrogen, appropriate hydrocarbon gas etc. relatively, the liquid organic-fuel that acts as a fuel has can be easily and the advantage of transportation safely.

In fuel cell, in the electrochemical reaction of each electrode generation, for anode, under the situation of using methyl alcohol, for:

···[1]

In addition, for negative electrode, for:

[2] for this reaction takes place, two electrodes are made of the mixture of carbon particulate that has supported catalyst material and solid macromolecule electrolyte.

In such solid macromolecular electrolyte type fuel cell, under the situation of using methyl alcohol to act as a fuel, the pore of methyl alcohol from electrode that anode (fuel electrodes) is supplied with is by arriving catalyst, because catalyst action makes methyl alcohol be decomposed, and generates electronics and hydrogen ion by the reaction of above-mentioned reaction equation [1].Hydrogen ion from anode electrolyte and two interelectrode solid electrolyte films in by arriving negative electrode (oxidizing agent pole), with the oxygen of supplying with negative electrode and the electron reaction that flows into from external circuit, as above-mentioned reaction equation [2], produce water.On the other hand, the catalyst carrier of electronics from negative electrode that discharges from methyl alcohol passed through and to the external circuit derivation, flowed into negative electrode from external circuit.This result, externally in the circuit, electronics to cathode flow, sends electric power from anode.

This is the direct-type methanol fuel cell of fuel with methyl alcohol, and applicable as portable possibility height with small fuel cell, as portable secondary cell of future generation with computer and portable phone etc., exploitation is being carried out always actively in recent years.

Usually in the fuel cell that uses the liquid organic-fuel, use to comprise the solid polyelectrolyte membrane of solid polymer ion exchanger resin as electrolyte.Here, fuel cell need move to oxidizing agent pole (negative electrode) from fuel electrodes (anode) in this film at the hydrogen ion that anode takes place in order to bring into play function.Known in this hydrionic moves with the motion of water, it is necessary containing certain moisture in this dielectric film.

, in the occasion of using the liquid organic-fuel of the high methyl alcohol of water affinity etc., this liquid organic-fuel spreads in the solid polyelectrolyte membrane that contains moisture, and then arrives oxidizing agent pole, causes that what is called is called as the phenomenon that sees through.See through,, can not be used as fuel effectively, cause that therefore voltage, power output reduce, fuel efficiency reduces because should provide the liquid organic-fuel of electronics oxidized to fuel electrodes originally because of arriving the oxidizing agent pole side.Methanol concentration in the fuel is high more, and methyl alcohol penetrate is remarkable more, therefore in the direct-type methanol fuel cell, is difficult to use the methanol fuel of high concentration.

In order to solve the problem of above-mentioned methyl alcohol penetrate, following various methodologies had been proposed in the past.

[1] method (spy opens flat 11-26005 communique, the spy opens 2002-83612 communique etc.) that improves of the dielectric film between antianode and the negative electrode, its structure.

[2] liquid fuel is used the gasification of gasifier or heater earlier, then the method (for example the spy opens the 2001-93541 communique) of anode supply.

[3] methyl alcohol is replaced with other alcohols (isopropyl alcohols; The spy opens the 2003-217642 communique) or other organic system fuel (cycloalkane; The spy opens the 2003-323896 communique) method.

[4] in the liquid organic-fuel, cooperate carbohydrate, alcohols etc., the method (spy opens the 2004-39293 communique) of utilizing the osmotic pressure in fuel cell to suppress to see through.

, even above-mentioned method in the past can not fully be tackled methyl alcohol penetrate, wish further to improve.

In addition, in the direct-type methanol fuel cell that with methyl alcohol is fuel, also there is the operational problem of following methyl alcohol in methyl alcohol penetrate not only:

(1) stoste of methyl alcohol is equivalent to the violent in toxicity of violent in toxicity regulation law, is equivalent to danger the 4th class etc., needs sufficient attention in operation;

(2) methyl alcohol is liquid, therefore needs to prepare not have the high container of seal of leak of liquid;

Also there is following or the like problem:

(3) when using the methanol aqueous solution of high concentration in order to improve generating efficiency, the electrode of fuel cell is caused damage, corrode peripheral metal material;

(4) as above-mentioned, methanol concentration high methanol more sees through remarkable more; The stoste of methyl alcohol is equivalent to the violent in toxicity of violent in toxicity regulation law, also is equivalent to danger the 4th class, or the like, be in operation, to need the fuel that gives one's full attention to; The problem of high concentration methanol existence corrosion etc.Because above-mentioned or the like reason, when using methyl alcohol to act as a fuel, the aqueous solution of making usually about 10-30 weight % uses, but there is the problem of freezing in the methanol aqueous solution of such low concentration when particularly using in the place of cold.In this case, because can not be used as fuel, use the back that therefore need thaw.In addition, when freezing, also exist to form the problem of the CONCENTRATION DISTRIBUTION of first alcohol and water, in order to eliminate this CONCENTRATION DISTRIBUTION, need the fuel that freeze be thawed fully, vibration container etc. thereafter forms behind the homogeneous solution and uses trivial operations.

Even the organic system fuel of other beyond the methyl alcohol also can cause the problem of above-mentioned (1)-(4), but these problems is still unresolved at present.

In addition, still do not detect at present the method for the residual volume of fuel cell-use fuel simply, for this reason, before fuel cell-use fuel is consumed whole amounts, prepare necessary amount fuel, suitable carry out supply or the like exactly fueling be difficult.

And, also there is following problem at present.

Be used as hydrogen, its dangerous height of methyl alcohol of the fuel of fuel cell, operational problem is a lot.As the method for storing such fuel safely, reported the method that makes fuel become molecular compound (WO2004000857); Polymer is absorbed and make it the method (spy opens the 2004-127659 communique) of gelation.In the past, as these fuel cell-use fuels are formed stable compositions,, generally be the heating fuel composition again from wherein discharging the method for fuel cell-use fuel, fuel is discharged.

; in order to heat the fuel composition that contains fuel cell-use fuel, fuel to be discharged; the device that need be used to heat; in addition; the macro-energy that need be used to heat; therefore in the industrial advantageous method of can not saying so, seek a kind of method that discharges fuel from the fuel composition that contains fuel cell-use fuel more easily always.

Summary of the invention

The object of the invention is as follows:

The purpose of (1) the 1st mode is, the operability that provides a kind of improvement to comprise the fuel cell-use fuel of organic system fuel solves the fuel cell-use fuel and the supply method thereof of the problems such as freezing, see through of burn into fuel simultaneously;

The purpose of (2) the 2nd modes is, a kind of method that can detect the residual volume of fuel cell-use fuel simply is provided;

The purpose of (3) the 3rd modes is, a kind of solid electrolyte fuel cell fuel that sees through that can suppress the fuel in the solid electrolyte fuel cell is provided, and realizes height outputization, the high fuel efficiencyization of fuel cell.The purpose of the 3rd mode also is, a kind of using method and solid electrolyte fuel cell that uses the solid electrolyte fuel cell of such fuel is provided;

The purpose of (4) the 4th modes is, a kind of heater or heat energy of not needing is provided, and easily discharges the method for fuel cell-use fuel from the fuel composition that contains fuel cell-use fuel.

Main idea of the present invention is as follows:

＜1〉fuel cell-use fuel of the 1st mode is characterized in that, the organic system fuel that uses in fuel cell forms the molecular compound of solid, shaped.

The supply method of the fuel cell-use fuel of the 1st mode is characterized in that, discharges organic system fuel from above-mentioned fuel cell-use fuel, supplies with to the fuel electrodes of fuel cell.

＜2〉the amount detection method of the fuel material in the fuel cell-use fuel composition of the 2nd mode, it is characterized in that, it is the method that detects the amount of this fuel material in the fuel composition of the molecular compound contain fuel cell-use fuel material and matching side compound, the index properties by contrasting this molecular compound and/or matching side compound and the index properties of this fuel composition detect the amount of this fuel material.

＜3〉the solid electrolyte fuel cell fuel of the 3rd mode is characterized in that, comprises the liquid organic-fuel and forms the compound of complex or molecular compound with this liquid organic-fuel.

The using method of the solid electrolyte fuel cell of the 3rd mode, it is characterized in that, be possess fuel electrodes, oxidizing agent pole, with the using method of the solid electrolyte fuel cell of the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping, in this using method, supply with above-mentioned solid electrolyte fuel cell fuel to this fuel electrodes.

The solid electrolyte fuel cell of the 3rd mode is characterized in that, possesses fuel electrodes, oxidizing agent pole, with the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping and above-mentioned solid electrolyte fuel cell fuel.

The solid electrolyte fuel cell of the 3rd mode, it is characterized in that, in possessing fuel electrodes, oxidizing agent pole, solid electrolyte fuel cell, possess to this fuel electrodes and supply with the fuel supply system of above-mentioned solid electrolyte fuel cell with fuel with the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping.

＜4〉method from fuel cell-use fuel composition release fuel of the 4th mode, it is characterized in that, be the method that discharges fuel from the fuel composition that contains fuel cell-use fuel, contact with water by making this fuel cell-use fuel composition, in this water, to discharge this fuel.

The simple declaration of accompanying drawing

Fig. 1 is the summary sectional view that is illustrated in the fuel cell system of making among embodiment 5 and the embodiment 11.

Fig. 2 is the summary pie graph that is illustrated in the fuel cell system of making among embodiment 6 and the embodiment 12.

Fig. 3 is the summary pie graph that is illustrated in the fuel cell system of making among embodiment 7 and the embodiment 13.

Fig. 4 is the sectional view of a routine structure of the solid electrolyte fuel cell of pattern ground expression the 3rd mode.

Fig. 5 is the key diagram of the solid electrolyte fuel cell of the 3rd mode with the fuel feed system in the example of fuel.

Fig. 6 is the key diagram of the structure of the solid electrolyte fuel cell among the embodiment 14-16.

Fig. 7 is the summary pie graph that is illustrated in the fuel cell system of making among the embodiment 17.

Embodiment

Below describe preferred version of the present invention in detail.

[1] at first the fuel cell-use fuel and the supply method thereof of the 1st mode described.The fuel cell-use fuel of the 1st mode is characterized in that, the organic system fuel that uses in fuel cell forms the molecular compound of solid, shaped.

The fuel cell-use fuel of the 1st mode, because organic system fuel becomes the molecular compound of solid, shaped, so safety, operability excellence, preservation, transportation etc. are also easy, also do not have the problem of freezing.In addition,, can use high concentration organic system fuel, therefore can improve the electromotive force of fuel cell because can also reduce the problem that burn into sees through.

The supply method of fuel cell-use fuel, be so that organic system fuel discharges from such fuel cell-use fuel, and supply with method into feature to the fuel electrodes of fuel cell, can utilize all excellent fuel cell-use fuel of fail safe, operability to carry out high efficiency fuel supply.

Here, so-called molecular compound, the compound more than 2 kinds that is the compound that can stably exist separately comprises hydrate, solvate, additive compound, inclusion compound etc. by being the compound that combination is carried out in more weak interaction representative, beyond the covalent bond with hydrogen bond, Van der Waals force etc.Such molecular compound can be by forming molecular compound compound and the haptoreaction of organic system fuel form, thereby can make the organic system fuel change of liquid become the compound weight of solid, shaped low weight and stably store organic system fuel.Can organic system fuel easily be discharged from this molecular compound by heating or contact etc., and supply with to the fuel electrodes of fuel cell with water.As this molecular compound, the inclusion compound of organic system fuel that exemplified out by the haptoreaction of host compound and organic system fuel inclusion.

As the organic system fuel of the 1st mode, so long as can be used as fuel cell fuel material just, for example list alcohols, ethers, hydro carbons, acetals etc., but be not limited to these.Organic system fuel is liquid at normal temperatures and pressures generally, specifically lists the alcohols of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol etc.; The ethers of dimethyl ether, ethyl methyl ether, diethyl ether etc.; The hydro carbons of propane, butane etc.; The acetals of dimethoxymethane, trimethoxy-methane etc. etc.These organic system fuel can use a kind separately, also can mix more than 2 kinds and use.

Constitute among the molecular compound of solid, shaped of fuel cell-use fuel, as the host compound of inclusion compound of organic system fuel that formed inclusion, known packets contains organic compound, inorganic compound and organic-inorganic complex chemical compound.As the organic compound of host compound, known unimolecule system, polymolecular system, macromolecular main body etc.

Among the organic system host compound, as unimolecule owner body compound, exemplify out cyclodextrin, crown ether-like, cryptand class, cyclophane class, azepine cyclophane class, calixarene kind, シ Network ロトリベラトリレ Application class, ス Off ェラ Application De class, cyclic oligomer peptide class etc.As polymolecular owner body compound, exemplify out urea class, Thiourea, deoxycholic acid class, perhydrogenate benzophenanthrene class, three-neighbour-チモチ De class, dianthranide class, spiral shell two fluorenes classes, ring phosphonitrile class, single alcohols, glycols, acetylene series alcohols, hydroxy benzophenone ketone, phenol, bisphenols, three phenols, four phenols, Polyphenols, aphthols, dinaphthyl phenols, diphenylmethyl alcohols, carboxylic acyloxy amine, thioamide analog, connection xanthene class, carboxylic acids, imidazoles, hydroquinones etc.As the macromolecular host compound, exemplify out cellulose family, starch based, chitin class, chitosan class, polyvinyl alcohol, with 1,1,2,2-tetraphenyl ethane is for the polyethylene glycol arm type polymer class of nuclear, with α, α, α ', α '-tetraphenyl dimethylbenzene are the polyethylene glycol arm type polymer of nuclear etc.

As the organic system main polymer, also list organic phosphorus compound, organo-silicon compound etc. in addition.

As inorganic owner's body compound, exemplify out titanium oxide, graphite, aluminium oxide, transition metal ジカ Le go ゲ Na イト, lanthanum fluoride, clay mineral (montmorillonite etc.), silver salt, silicate, phosphate, zeolite, silica, porous glass etc.

Organo-metallic compound also has the compound of demonstration as the character of host compound, for example lists organo-aluminum compound, organic titanic compound, organoboron compound, organic zinc compound, organic indium compound, organic gallium compound, organic tellurium compound, organo-tin compound, organic zirconate, organo-magnesium compound etc.Also the slaine of organic carboxyl acid, Organometallic complexes etc. can be used as host compound.Organo-metallic compound owner body compound is not particularly limited to these compounds.

Among these host compounds, preferred inclusion ability is difficult to by the polymolecular owner body compound about the molecular size of guest compound.

As polymolecular owner body compound, specifically list: urea, 1,1,6,6-tetraphenyl own-2,4-diine-1, the 6-glycol, 1,1-two (2, the 4-3,5-dimethylphenyl)-2-propine-1-alcohol, 1,1,4,4-tetraphenyl-2-butine-1, the 4-glycol, 1,1,6,6-four (2, the 4-3,5-dimethylphenyl)-2,4-hexadiine-1, the 6-glycol, 9,10-diphenyl-9,10-dihydroanthracene-9, the 10-glycol, 9, two (the 4-aminomethyl phenyls)-9 of 10-, 10-dihydroanthracene-9,10-glycol, 1,1,2,2-tetraphenyl ethane-1,2-glycol, the 4-metoxyphenol, 2, the 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 4,4 '-sulphonyl bis-phenol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-ethylidene bis-phenol, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, 1,1,2,2-four (3-methyl-4-hydroxy phenyl) ethane, 1,1,2,2-four (3-fluoro-4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-paraxylene, four (p-methoxyphenyl) ethene, 3,6,3 ', 6 '-tetramethoxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrem acyloxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrahydroxy-9,9 '-Lian-9H-xanthene, gallic acid, gallicin, catechuic acid, connection-betanaphthol, α, α, α ', α '-tetraphenyl-1,1 '-biphenyl-2,2 '-dimethanol, the two dicyclohexyl acid amides of diphenic acid, the two dicyclohexyl acid amides of fumaric acid, cholic acid, deoxycholic acid, 1,1,2,2-tetraphenyl ethane, four (to iodine substituted phenyl) ethene, 9,9 '-dianthranide, 1,1,2,2-four (4-carboxyl phenyl) ethane, 1,1,2,2-four (3-carboxyl phenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenyl imidazoles, 1,2,4,5-tetraphenyl imidazoles, 2-phenyl phenanthro-[9,10-d] imidazoles, 2-(adjacent cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(to cyano-phenyl) phenanthro-[9,10-d] imidazoles, quinhydrones, the 2-tertiary butylated hydroquinone, 2, the 5-di-tert-butyl hydroquinone, 2, two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-, or the like.

As host compound, among above-mentioned compound, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2, the phenol owner body compound of 2-four (4-hydroxy phenyl) ethene and so on, diphenic acid two (dicyclohexyl acid amides), the acid amides owner body compound of two dicyclohexyl acid amides of fumaric acid and so on, the imidazoles owner body compound of 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles and so on is favourable aspect the inclusion ability, particularly 1, the phenol owner body compound of 1-bis(4-hydroxyphenyl)cyclohexane and so on industrial be favourable aspect wield.

These host compounds can be used alone or two or more kinds may be used.

These host compounds if form the compound of the inclusion compound of solid, shaped with organic system fuel, then can be the compounds of Any shape.

Among the aforementioned body compound, the organic system host compound also can be used as the organic/inorganic composite material that the porous metallic substance is supported.In this case, as the porous metallic substance that supports the organic system host compound, except silica-based, zeolites, active carbon class, also list the intercalation compound of clay mineral class, smectites etc. etc., but be not limited to these.Organic/inorganic composite material can adopt following or the like method manufacturing: above-mentioned organic system host compound is dissolved in the solvent that can dissolve this compound, this solution is infiltrated in the porous metallic substance, again with solvent seasoning, drying under reduced pressure.Be not particularly limited as the loading of organic system host compound, but in normal circumstances, be about 10-80 weight % with respect to the porous metallic substance with respect to the porous metallic substance.

As using 1, the method of the inclusion compound of synthetic organic system fuel such as the host compound of 1-bis(4-hydroxyphenyl)cyclohexane etc., exemplify out the method that organic system fuel is directly contacted, mixes with host compound, the inclusion compound of organic system fuel that can easily synthesize inclusion thus.Heat etc. so that after host compound is dissolved in the organic system fuel, also can synthesize inclusion compound by carrying out crystallization again.

When synthetic inclusion compound, the temperature that organic system fuel is contacted with host compound is not particularly limited, but is preferably about normal temperature-100 ℃.Pressure condition for this moment also is not particularly limited, but preferably carries out under atmospheric pressure environment.Also be not particularly limited for the time that organic system fuel is contacted with host compound, but consider to be preferably about 0.01-24 hour from the aspect of operating efficiency etc.

The organic system fuel that contacts with host compound is preferably highly purified fuel, but has in use under the situation of host compound of ability of selectivity inclusion organic system fuel, also can be the mixing material of organic system fuel and other compositions.

The inclusion compound that obtains like this is also according to the kind of the host compound that uses, different and different with the contact conditions of organic system fuel etc., but normally with respect to 1 mole of host compound inclusion the inclusion compound of 0.1-10 mole organic system fuel molecule.

The inclusion compound that obtains like this can be stored organic system fuel steadily in the long term under the normal temperature and pressure environment.And the solid, shaped that this inclusion compound can form is in light weight, operability is also excellent, therefore can put in the container of glass, metal, plastics etc. storage easily, also eliminated the problem of leak of liquid.In addition, the organic system fuel of liquids in general shape becomes solid, shaped by inclusionization, also can avoid the character as violent in toxicity or danger thus.In addition, can reduce the chemical reactivity that organic system fuel has, can also relax for example to corrosion of metal etc.

The method according to this invention is emitted the method for organic system fuel from the state of the molecular compound of the solid, shaped that forms inclusion compound etc., is not particularly limited, but by it being heated can easily emitting.Particularly, molecular compound in solid, shaped is under the situation of inclusion compound, though also depend on the kind of the host compound of use, be heated to about normal temperature-200 ℃ and get final product, can easily from inclusion compound, discharge organic system fuel thus, be used for various uses.In the case, be not particularly limited, but thermoelectric element (Peltier element etc.), ink jetting head (hot mode etc.) etc. arranged for heating means, in addition, also can the aggregate surface elastic wave device etc. use.

The molecular compound contact water of the solid, shaped by making inclusion compound etc. makes the stripping of organic system fuel in this water, also can emit organic system fuel thus.In this case, water can be the organic system fuel aqueous solution, modulate the organic system fuel aqueous solution of the concentration that is adapted to application target, the organic system fuel aqueous solution about for example 1-64 weight % by molecular compound stripping organic system fuel, and supply with to fuel cell and to get final product from inclusion compound etc.

Host compound after inclusion compound is emitted organic system fuel has the selectivity inclusion ability to this organic system fuel, can be used further to the inclusionization of organic system fuel effectively.

According to the 1st mode, the generating efficiency that can seek fuel cell under following effect improves and operation steady in a long-term.

(1) by making liquid organic system fuel change become solid, shaped, can avoid leak of liquid, therefore do not need to prepare not can leakage the high container of seal.

(2) because organic system fuel forms the molecular compound of solid, shaped, so safety, operability excellence, can avoid with organic system fuel is the relevant counter-measure of fail safe of violent in toxicity, danger etc.The problem of using under the organic system fuel aqueous solution situation of freezing can be solved, also stable fuel supply can be carried out in cold place.

(3) by forming molecular compound, reduce the chemical reactivity of organic system fuel, therefore can reduce of the influence of organic system fuel to the electrode of fuel cell etc., reduce the corrosion of peripheral metal material etc.

(4) can improve seeing through in the battery.

(5) the organic system fuel contact fuel electrodes of high concentration and using can be made, the electromotive force of fuel cell can be improved.

The 1st mode, as solid macromolecular electrolyte type fuel cell, particularly the fuel cell-use fuel and the supply method thereof of direct-type methanol fuel cell likely is useful with small fuel cell as portable, but be not limited to this, applicable to the various fuel cells that use organic system fuel.

Below enumerate embodiment the 1st mode more specifically is described, but the 1st mode, only otherwise exceed its main idea, be not limited to following embodiment.

Below, as the host compound that organic system fuel is carried out inclusion, use 1,1-bis(4-hydroxyphenyl)cyclohexane (following brief note is " BHC ") or 1,1,6, the 6-tetraphenyl oneself-2,4-diine-1,6-glycol (following brief note is " TPHDD ") as organic system fuel, has used methyl alcohol.

Embodiment 1 (synthetic method 1 of methyl alcohol inclusion compound)

BHC 26.8g (0.1mol) heating for dissolving in 50ml methyl alcohol, by carrying out crystallization again, has been obtained BHC: methyl alcohol=1: 1 (mol ratio), methyl alcohol containing ratio are the methyl alcohol inclusion compound of the solid, shaped of 11 weight %.

Embodiment 2 (synthetic method 2 of methyl alcohol inclusion compound)

BHC 26.8g (0.1mol) and methyl alcohol 3.2g (0.1mol) are packed in the beaker, with mixer mixing stirring, obtained BHC: the methyl alcohol inclusion compound of the solid, shaped of methyl alcohol=1: 1 (mol ratio).

Embodiment 3 (synthetic method 3 of methyl alcohol inclusion compound)

TPHDD 41.4g (0.1mol) heating for dissolving in 100ml methyl alcohol, by carrying out crystallization again, has been obtained TPHDD: methyl alcohol=1: 2 (mol ratio), methyl alcohol containing ratio are the methyl alcohol inclusion compound of the solid, shaped of 13 weight %.

Embodiment 4 (heat of the methyl alcohol in the methyl alcohol inclusion compound is emitted characteristic)

The methyl alcohol inclusion compound that obtains in embodiment 1 is carried out the result that TG-DTA measures with the programming rate of 10 ℃/min, and confirmed: the methyl alcohol of institute's inclusion was stabilized the ground inclusion and before being warming up to about 100 ℃, emit since 100 ℃ of gasifications.

The methyl alcohol of institute's inclusion was the about 64 ℃ volatile solvent of boiling point originally, and vapour pressure is also low, even therefore in also gasification below 64 ℃, but by carrying out the inclusionization of inclusion compound in this wise, had prevented the gasification of methyl alcohol as can be known, can improve the danger when preserving.As described above, according to the violent in toxicity regulation law, methyl alcohol only becomes the object of violent in toxicity under the situation of stoste, using under the situation of methyl alcohol with stoste, be subjected to its restriction, but by forming inclusion compound, can get rid of from the object of violent in toxicity.Because become the material of solid, shaped, and can control gasification as described above and emit temperature, therefore also from the object of danger the 4th class, get rid of, the possibility that can be used as safe store method is arranged by inclusionization.

By heating emitting temperature and can change freely when the methyl alcohol inclusion compound is emitted methyl alcohol by selecting used host compound.

Embodiment 5 (estimation of stability of the electrode of fuel cell)

Electrolyte film-electrode joint to be evaluated (MEA) is made as described below.As dielectric film, used the amberplex Nafion of perfluorinated sulfonic acid system.Catalyst-loaded use Pt particle in order to have electronic conductivity, makes it to be supported on the acetylene black.The Pt loading is 50 weight % with respect to acetylene black.Mix the catalyst-loaded and 5 weight %Nafion solution of this Pt, adopt the spraying brush method to spray on the dielectric film, make it to have adhered to electrode layer.The film that has adhered to electrode layer at 90 ℃ down after dry 1 hour, is lived with the teflon plate holder in drying machine, adopts hot press with 130 ℃, 20MPa pressurization 30 minutes, makes dielectric film and electrode engagement.

(1cm * 1cm) resembles and is immersed in the methanol aqueous solution of 5,10,20,50 weight % concentration the prior art with this MEA, place the result in 1 week, all can see electrode stripping or phenomenon of peeling off in methanol aqueous solution under any concentration, the result can not obtain long-term stability when using methanol aqueous solution.Therefore, in order to obtain long-term stability, the methanol aqueous solution of lower concentration need be acted as a fuel, but can not obtain enough electromotive force in the case.

So, use electrolyte film-electrode joint in above-mentioned making, as shown in Figure 1, replace methanol aqueous solution, assembled the direct-type methanol fuel cell system of supplying with methyl alcohol inclusion compound and water.In Fig. 1,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode), and 4 is the oxidant stream, and 5 is the fuel absorber.Be provided with inclusion compound groove 6 and tank 7 contiguously with fuel absorber 5.

In these

grooves

6,7, be provided with calandria 6A, 7A respectively, on constituting, can heat the thing of accommodating in each groove.

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 1, be heated to 100 ℃ by calandria 6A, methyl alcohol is emitted from inclusion compound, and to 5 supplies of fuel absorber, simultaneously, water in the tank 7 is heated to 100 ℃ by calandria 7A, and supplies with to fuel absorber 5.Quantity delivered to fuel absorber 5 is a methyl alcohol: water=20: 80 (weight ratio), this ratio is equal with the methanol aqueous solution of supplying with 20 weight %.

Its result does not have any bad influence to electrode, in addition, does not have the problem that sees through yet, and can generate electricity under optimal conditions.

This direct-type methanol fuel cell is 100mA/cm in current density ²The time, utilize 20 weight % methanol aqueous solutions can obtain the electromotive force of 0.22V, but as shown in Figure 1,, can realize the electromotive force of 0.48V by using the methyl alcohol inclusion compound.Using under the situation of 20 weight % methanol aqueous solutions,, be difficult to stable operation, but under the situation of having used the methyl alcohol inclusion compound, such problem is not existing also, can carry out stable operation for a long time owing to the deterioration of electrode, see through etc.

Used embodiment 2, and embodiment 3 in the methyl alcohol inclusion compound made situation too.

Embodiment 6 (estimation of stability of the electrode of fuel cell)

Use the electrolyte film-electrode joint of making similarly to Example 5 (MEA), assembled the direct-type methanol fuel cell system of supplying with methanol aqueous solution as shown in Figure 2.In Fig. 2,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode).Oxidant stream and fuel absorber have omitted diagram.6 is the inclusion compound groove, possesses calandria 6A.11 are concentration adjustment groove, and 12 is CO ₂Removal device.

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 1, be heated to 100 ℃ by calandria 6A, methyl alcohol is emitted from inclusion compound, adjusting groove 11 to concentration supplies with, adjust the methanol aqueous solution of 20 weight %, and give the fuel absorber of electrolyte film-electrode joint.

Anode 2 use and the recycle-water of methanol concentration step-down by CO ₂Being circulated to concentration after removal device 12 is handled adjusts in the groove 11.Also be recovered in the concentration adjustment groove 11 at the water that negative electrode 3 takes place, and be used for the adjustment of methanol aqueous solution.

Its result does not have any bad influence to electrode, in addition, does not have the problem that sees through yet, and can carry out stable operation under optimal conditions for a long time.

Embodiment 7 (estimation of stability of the electrode of fuel cell)

Use the electrolyte film-electrode joint of making similarly to Example 5 (MEA), assembled the direct-type methanol fuel cell system of supplying with methanol aqueous solution as shown in Figure 3.In Fig. 3,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode).Oxidant stream and fuel absorber have omitted diagram.6 is the inclusion compound groove, and 7 is tank.

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 1, in this inclusion compound groove 6, supply with water from tank 7, the methyl alcohol inclusion compound is contacted with water, in water, emit methyl alcohol thus, adjust the methanol aqueous solution of 20 weight %, and give the fuel absorber of electrolyte film-electrode joint.

Will anode 2 use and the recycle-water of methanol concentration step-down by CO ₂Make it to be circulated in this tank 7 also passable after removal device is handled.Be recovered in the water of negative electrode 3 generations and supply with also passable to tank 7.

Embodiment 8 (refrigeration test and the suitable test in fuel cell)

The methyl alcohol inclusion compound that to make in embodiment 1 and embodiment 3 and the 11 weight % methanol aqueous solutions of modulating in order relatively to mix methyl alcohol in pure water are respectively charged in the vial, place 24 hours at-20 ℃ refrigerating chambers.Its result, the methyl alcohol inclusion compound of

embodiment

1,2 is not all seen variation, but 11 weight % methanol aqueous solutions have freezed.

Sample behind the above-mentioned 3 kinds refrigeration test is heated to 100 ℃, carry out the result of the suitable test in fuel cell similarly to Example 5, the methyl alcohol inclusion compound of

embodiment

1,2 has been emitted methyl alcohol by heating, and can be suitable for immediately, the spended time but 11 weight % methanol aqueous solutions thaw can not be suitable for immediately.

Know from above result, using with aqueous solution form under the situation of organic system fuel, the problem of freezing, but the molecular compound of the solid, shaped by forming inclusion compound etc. can be avoided this problem.

[2] the amount detection method of the fuel material in the fuel cell-use fuel composition of the 2nd mode then is described.

The amount detection method of the fuel material in the fuel cell-use fuel composition of the 2nd mode, it is characterized in that, it is the method that detects the amount of this fuel material in the fuel composition of the molecular compound contain fuel cell-use fuel material and matching side compound, the index properties by contrasting this molecular compound and/or matching side compound and the index properties of this fuel composition detect the amount of this fuel material.

Here, so-called molecular compound, the compound more than 2 kinds that is the compound that can stably exist separately is by with hydrogen bond, Van der Waals force etc. being more weak interaction representative, beyond the covalent bond and the compound of combination comprises hydrate, solvate, additive compound, inclusion compound etc.Such molecular compound can form by the matching side compound of formation molecular compound and the haptoreaction of fuel material, advantage is a lot, for example can make the fuel material of liquid be varied to the compound of solid, shaped, thereby weight is low weight and stably store fuel material, or the like.Can fuel material easily be discharged from this molecular compound by heating or contact etc., and supply with to the fuel electrodes of fuel cell with water.

Form as based on the fuel cell of the 2nd mode is not particularly limited, but solid macromolecular electrolyte type fuel cell preferably wherein, also comprises direct-type methanol fuel cell etc.

At first, to describing based on the contained fuel cell-use fuel material of the fuel cell-use fuel composition of the 2nd mode and the molecular compound of matching side compound.

As fuel material,, for example list hydrogen, alcohols, ethers, hydro carbons, acetals etc., but be not limited to these so long as it is all right to can be used as the material of fuel of fuel cell based on the 2nd mode.The material that acts as a fuel more specifically lists the alcohols of hydrogen, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol etc.; The ethers of dimethyl ether, ethyl methyl ether, diethyl ether etc.; The hydro carbons of propane, butane etc.; The acetals of dimethoxymethane, trimethoxy-methane etc. etc.These fuel materials can use a kind separately, also can mix more than 2 kinds and use.

Among the contained molecular compound of fuel composition, as the host compound of inclusion compound of fuel material that formed inclusion, known packets contains organic compound, inorganic compound and organic-inorganic complex chemical compound.As the organic compound of host compound, known unimolecule system, polymolecular system, macromolecular main body etc.

As unimolecule owner body compound, exemplify out cyclodextrin, crown ether-like, cryptand class, cyclophane class, azepine cyclophane class, calixarene kind, シ Network ロトリベラトリレ Application class, ス Off ェラ Application De class, cyclic oligomer peptide class etc.As polymolecular owner body compound, exemplify out urea class, Thiourea, deoxycholic acid class, perhydrogenate benzophenanthrene class, three-neighbour-チモチ De class, dianthranide class, spiral shell two fluorenes classes, ring phosphonitrile class, single alcohols, glycols, acetylene series alcohols, hydroxy benzophenone ketone, phenol, bisphenols, three phenols, four phenols, Polyphenols, aphthols, dinaphthyl phenols, diphenylmethyl alcohols, carboxylic acyloxy amine, thioamide analog, connection xanthene class, carboxylic acids, imidazoles, hydroquinones etc.As the macromolecular host compound, exemplify out cellulose family, starch based, chitin class, chitosan class, polyvinyl alcohol, with 1,1,2,2-tetraphenyl ethane is for the polyethylene glycol arm type polymer class of nuclear, with α, α, α ', α '-tetraphenyl dimethylbenzene are the polyethylene glycol arm type polymer of nuclear etc.

According to fuel composition, supply with to fuel cell from the fuel material that the molecular compound of fuel material and matching side compound discharges, thereby generate electricity based on the 2nd mode.Matching side compound and molecular compound after molecular compound discharges fuel material, has different characteristics at aspects such as color, crystalline states, therefore in the 2nd mode, utilize the amount of the fuel material in the change-detection fuel composition of this index properties.Be designated as " S in index properties with the molecular compound of fuel material and matching side compound ₁₀₀", the index properties of matching side compound is designated as " S ₀" situation under, if the index properties of fuel composition shows " S ₁₀₀", then containing with saturation condition in this fuel composition has fuel material.If the index properties of fuel composition is " S ₀", then in fuel composition, there is not fuel material, just emit the matching side compound behind the fuel material.If the index properties of fuel composition demonstrates " S ₁₀₀" and " S ₀" between value, then in fuel composition, have fuel material with the corresponding amount of this index properties.

Such index properties converts quantification easily such as signal of telecommunication to.Kind for this index properties is not particularly limited, but is adopting as index properties under the situation of " color ", by visual fuel composition is done the outward appearance observation, also can easily hold the residual of fuel material, and be favourable.

In order to adopt " color " as index properties, as the matching side compound, preferred use in alone situation (after molecular compound is emitted fuel material or do not form the state of molecular compound) and formed the compound of change color under the situation with the molecular compound of fuel material with fuel material.

As the host compound of such change color, the compound of functional group that has color rendering in above-mentioned host compound is suitable.As its concrete example, list with following general formula (1) expression, in imidazoles, introduced the host compound of the functional group of color rendering, but be not limited to these.

[general formula 1]

(1) in the formula, R ¹, R ²Can difference also can be identical, represent hydrogen atom, methoxyl group, amino, dimethylamino, nitro or halogen atom separately.

R ³Expression nitro, cyano group, ethoxy carbonyl, acetyl group or formoxyl.

R ⁴, R ⁵Represent hydrogen atom respectively or the base of the formation fused rings of representing to mutually combine.

R ⁶The alkyl of expression hydrogen atom, carbon number 1-4, phenyl or with the phenyl of the replacement more than a kind or 2 kinds that is selected from methoxyl group, amino, dimethylamino, nitro or halogen atom.

As imidazoles owner body compound with above-mentioned general formula (1) expression, for example list 4,5-two (4-methoxyphenyl)-2-(2-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone) imidazoles, 4,5-two (4-aminophenyl)-2-(2-nitrobenzophenone) imidazoles, 4,5-two (4-aminophenyl)-2-(3-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(2-nitrobenzophenone)-1-methylimidazole, 4,5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone)-1-methylimidazole, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone)-1-methylimidazole, 2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 2-(3-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(3-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-phenyl-2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-phenyl-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-(4-nitrobenzophenone)-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-(4-methoxyphenyl)-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles etc., but be not limited to these.

These host compounds can be used alone or two or more kinds may be used.

These host compounds if form the compound of inclusion compound with fuel material, then can be the compounds of Any shape.

Among the aforementioned body compound, the organic system host compound can be used as also that to be supported on inorganic be the organic/inorganic composite material that forms on the porous metallic substance.In this case, as the porous metallic substance that supports the organic system host compound, except silica type, zeolites, active carbon class, also list the intercalation compound of clay mineral class, smectites etc. etc., but be not limited to these.Organic/inorganic composite material can adopt following or the like method manufacturing: above-mentioned organic system host compound is dissolved in the solvent that can dissolve this compound, this solution is infiltrated in the porous metallic substance, again with solvent seasoning, drying under reduced pressure.Be not particularly limited as the loading of organic system host compound, but in normal circumstances, be about 10-80 weight % with respect to the porous metallic substance with respect to the porous metallic substance.

As using 4, the method of the inclusion compound of the host compound synthetic fuel material of 5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone) imidazoles etc., exemplify out the method that fuel material is directly contacted, mixes with host compound, the inclusion compound of fuel material that can easily synthesize inclusion thus.Heat etc. so that after host compound is dissolved in the fuel material, also can synthesize inclusion compound by carrying out crystallization again.

When synthetic inclusion compound, the temperature that fuel material is contacted with host compound is not particularly limited, but is preferably about normal temperature-100 ℃.Pressure condition for this moment also is not particularly limited, but preferably carries out under atmospheric pressure environment.Also be not particularly limited for the time that fuel material is contacted with host compound, but consider to be preferably about 0.01-24 hour from the aspect of operating efficiency etc.

The fuel material that contacts with host compound is preferably highly purified fuel, but has in use under the situation of host compound of ability of selectivity inclusion fuel material, also can be the mixing material of fuel material and other compositions.

The inclusion compound that obtains like this is also according to the kind of the host compound that uses, different and different with the contact conditions of fuel material etc., but normally with respect to 1 mole of host compound inclusion the inclusion compound of 0.1-10 mole fuel material molecule.

The inclusion compound that obtains like this can be stored fuel material steadily in the long term under the normal temperature and pressure environment.And this inclusion compound is in light weight, and operability is also excellent, is generally solid, shaped, therefore can put in the container of glass, metal, plastics etc. storage easily, has also eliminated the problem of leak of liquid.In addition, the fuel material of gaseous state or liquid condition becomes solid, shaped by inclusionization usually, also can avoid the character as violent in toxicity, danger thus.In addition, can reduce the chemical reactivity that fuel material has, can also relax for example to corrosion of metal etc.

Method as emit fuel material from the state of the molecular compound that forms inclusion compound etc. is not particularly limited, but by it being heated can easily emitting.Particularly, be under the situation of inclusion compound at molecular compound, though also depend on the kind of the host compound of use, be heated to about normal temperature-200 ℃ and get final product, can easily from inclusion compound, discharge fuel material thus, be used for various uses.In the case, be not particularly limited, but thermoelectric element (Peltier element etc.), ink jetting head (hot mode etc.) etc. arranged for heating means, in addition, also can the aggregate surface elastic wave device etc. use.

By making the molecular compound contact water of inclusion compound etc., make the fuel material stripping in this water, also can emit fuel material thus.In this case, water can be the aqueous solution of fuel material, modulates the fuel material aqueous solution of the concentration that is adapted to application target by the molecular compound stripping fuel material from inclusion compound etc., and supplies with to fuel cell and to get final product.

Host compound after inclusion compound is emitted fuel material has the selectivity inclusion ability to this fuel material, can be used further to the inclusionization of fuel material effectively.

In the 2nd mode, for example hold the index properties of color etc. respectively in advance for the molecular compound of the matching side compound after molecular compound is emitted fuel material and fuel material and matching side compound, by the index properties of fuel composition and their index properties are compared, can easily detect the fuel material amount in the fuel composition.Adopting under the situation of color as index properties, use colorimeter etc. also can be obtained the fuel material amount thus exactly with color quantificationization.

According to the 2nd mode, the index properties by contrasting this molecular compound and/or matching side compound and the index properties of this fuel composition can easily detect the amount of this fuel material in the fuel cell-use fuel composition of the molecular compound that contains fuel cell-use fuel material and matching side compound.

Particularly by using color as this index properties, by the visual residual volume that also can easily confirm fuel material.In this case, by with the compound of functional group with color rendering as the matching side compound, the color of the color of molecular compound and matching side compound has clear and definite difference, can carry out the affirmation of residual volume more easily.

The 2nd mode, as solid macromolecular electrolyte type fuel cell, particularly the detection method of the residual volume of the fuel cell-use fuel of direct-type methanol fuel cell likely is useful with small fuel cell as portable, but be not limited to this, applicable to various fuel cells.

Below enumerate embodiment the 2nd mode more specifically is described, but the 2nd mode, only otherwise exceed its main idea, be not limited to following embodiment.

Below,, use 4 as the host compound that fuel material is carried out inclusion, 5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone)-1H-imidazoles (following brief note is " BMNI "), the material that acts as a fuel has used methyl alcohol.The crystal color of BMNI is yellow.

Embodiment 9

The BMNI heating for dissolving in methyl alcohol, by carrying out crystallization again, has been obtained BMNI: the methyl alcohol inclusion compound of the solid, shaped of methyl alcohol=1: 1 (mol ratio).The color of the methyl alcohol inclusion compound that obtains is a peony.

This methyl alcohol inclusion compound is packed in the container, be heated to 100 ℃, the result discharges methyl alcohol, is accompanied by the release of methyl alcohol, and the methyl alcohol in the crystal slowly reduces, and the color of the crystal in the container becomes the yellow of BMNI from peony thus.

Therefore can confirm the residual volume of methyl alcohol according to change in color.

Embodiment 10

In the methyl alcohol inclusion compound fitted into column that obtains similarly to Example 9, water flowing in this post, methyl alcohol is accompanied by the stripping of methyl alcohol to the stripping of water side as a result, methyl alcohol in the crystal reduces at leisure, and the color of the crystal in the post becomes the yellow of BMNI from peony thus.

Embodiment 11

Made electrolyte film-electrode joint (MEA) as described below.As dielectric film, used the amberplex Nafion of perfluorinated sulfonic acid system.Catalyst-loaded use Pt particle in order to have electronic conductivity, makes it to be supported on the acetylene black.The Pt loading is 50 weight % with respect to acetylene black.Mix the catalyst-loaded and 5 weight %Nafion solution of this Pt, adopt the spraying brush method to spray on the dielectric film, make it to have adhered to electrode layer.The film that has adhered to electrode layer at 90 ℃ down after dry 1 hour, is lived with the teflon plate holder in drying machine, adopts hot press with 130 ℃, 20MPa pressurization 30 minutes, makes dielectric film and electrode engagement.

The electrolyte film-electrode joint of use as shown in Figure 1, has been assembled the direct-type methanol fuel cell system of supplying with methyl alcohol inclusion compound and water.In Fig. 1,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode), and 4 is the oxidant stream, and 5 is the fuel absorber.Be provided with inclusion compound groove 6 and tank 7 contiguously with fuel absorber 5.In these

grooves

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 9, be heated to 100 ℃ by calandria 6A, methyl alcohol is emitted from inclusion compound, and to 5 supplies of fuel absorber, simultaneously, water in the tank 7 is heated to 100 ℃ by calandria 7A, and supplies with to fuel absorber 5.Quantity delivered to fuel absorber 5 is a methyl alcohol: water=20: 80 (weight ratio), this ratio is equal with the methanol aqueous solution of supplying with 20 weight %.

Its result is 100mA/cm in current density ²The time, can realize the electromotive force of 0.48V.In addition, based on the change color of the methyl alcohol inclusion compound in the inclusion compound groove 6, can hold the residual volume of methyl alcohol fully.

Embodiment 12

Use the electrolyte film-electrode joint of making similarly to Example 11 (MEA), assembled the direct-type methanol fuel cell system of supplying with methanol aqueous solution as shown in Figure 2.In Fig. 2,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode).Oxidant stream and fuel absorber have omitted diagram.6 is the inclusion compound groove, possesses calandria 6A.11 are concentration adjustment groove, and 12 is CO ₂Removal device.

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 9, be heated to 100 ℃ by calandria 6A, methyl alcohol is emitted from inclusion compound, and adjust groove 11 to concentration and supply with, modulate the methanol aqueous solution of 20 weight %, and give the fuel absorber of electrolyte film-electrode joint.

Its result, but the generating of no problem ground, in addition, the color of inclusion compound slowly is varied to yellow from peony, can confirm the variation of methyl alcohol residual volume thus.

Embodiment 13

Use the electrolyte film-electrode joint of making similarly to Example 11 (MEA), assembled the direct-type methanol fuel cell system of supplying with methanol aqueous solution as shown in Figure 3.In Fig. 3,1 is dielectric film, and 2 is electrode (anode), and 3 is electrode (negative electrode).Oxidant stream and fuel absorber have omitted diagram.6 is the inclusion compound groove, and 7 is tank.

In inclusion compound groove 6, be enclosed in the methyl alcohol inclusion compound of making among the embodiment 9, in this inclusion compound groove 6, supply with water from tank 7, the methyl alcohol inclusion compound is contacted with water, in water, emit methyl alcohol thus, modulate the methanol aqueous solution of 20 weight %, and give the fuel absorber of electrolyte film-electrode joint.

[3] solid electrolyte fuel cell of following the 3rd mode describes with fuel, solid electrolyte fuel cell and using method thereof.

The solid electrolyte fuel cell fuel of the 3rd mode is characterized in that, comprises the liquid organic-fuel and forms the compound of complex or molecular compound with this liquid organic-fuel.

The solid electrolyte fuel cell of the 3rd mode, it is characterized in that, in possessing fuel electrodes, oxidizing agent pole, solid electrolyte fuel cell, also possess to this fuel electrodes and supply with the fuel supply system of above-mentioned solid electrolyte fuel cell with fuel with the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping.

The solid electrolyte film that solid electrolyte fuel cell is used generally uses with Nafion (registered trade mark) etc. to be solid electrolyte film representative, that have high hydrogen.High hydrogen in such solid electrolyte film contains moisture by this solid electrolyte film and manifests, but then, by containing this moisture, as described above, the liquid organic-fuel of methyl alcohol and so on easily is dissolved in the water, and in solid electrolyte film, move, thereby arrive to oxidizing agent pole, what promotion saw through manifests.

In the 3rd mode, make in the liquid organic-fuel that fuel electrodes is supplied with dissolving not see through and form the compound (following often be called " seizure property compound ") of complex or molecular compound from solid electrolyte film with the liquid organic-fuel.Become the state that between fuel electrodes and solid electrolyte film, forms the material layer of catching the liquid organic-fuel thus, suppressed passing through of liquid organic-fuel, therefore can reduce seeing through.

At first, to describing as the solid electrolyte fuel cell of the 3rd mode seizure compound with the feature of fuel.

Use in the fuel at the solid electrolyte fuel cell of the 3rd mode, seizure property compound, so long as form the compound of complex or molecular compound with regard to qualification especially with the liquid organic-fuel, but be the compound that is dissolvable in water the liquid organic-fuel, does not see through from solid electrolyte film, and being the compound that does not belong to sulfuric acid, carbohydrate, alcohols, amine and strong electrolyte class, is effective catching on the effect.In addition, the corrosivity to the metallic parts in the fuel cell is little, the electrochemistry aspect is stable and for non-volatile also be important.As seizure property compound, list crown ether-like as concrete example, the cryptand class, the cyclophane class, azepine cyclophane class, calixarene kind, シ Network ロトリベラトリレ Application class, ス Off ェラ Application De class, the oligopeptide class, cyclic oligomer peptide class, the urea class, Thiourea, the deoxycholic acid class, perhydrogenate benzophenanthrene class, three-neighbour-チモチ De class, the dianthranide class, spiral shell two fluorenes classes, ring phosphonitrile class, the hydroxy benzophenone ketone, phenol, bisphenols, three phenols, four phenols, Polyphenols, aphthols, the dinaphthyl phenols, the carboxylic acyloxy amine, thioamide analog, connection xanthene class, carboxylic acids, hydroquinones etc.

Here, so-called molecular compound, the compound more than 2 kinds that is the compound that can stably exist separately comprises hydrate, solvate, additive compound, inclusion compound etc. by being the compound that combination is carried out in more weak interaction representative, beyond the covalent bond with hydrogen bond, Van der Waals force etc.

Seizure compound based on the 3rd mode, even under the state in being dissolved in liquid organic-fuel and even solvent etc., also easily cause the formation of complex or molecular compound by its intermolecular interaction etc., by catching superfluous liquid organic-fuel, can avoid seeing through thus.

As seizure property compound; more specifically list urea; thiocarbamide; deoxycholic acid; cholic acid; 2; the 4-dihydroxy benaophenonel; 4; 4 '-dihydroxy benaophenonel; 2; 2 '-dihydroxy benaophenonel; 2,2 ', 4; 4 '-tetrahydroxybenzophenone; the 4-metoxyphenol; 1; the 1-bis(4-hydroxyphenyl)cyclohexane; 4,4 '-sulphonyl bis-phenol; 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol); 4; 4 '-sulfonyl bis-phenol; 2; 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol); 4,4 '-ethylidene bis-phenol; 4,4 '-thiobis (3 methy 6 tert butyl phenol); 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1,1,2; 2-four (4-hydroxy phenyl) ethane; 1; 1,2,2-four (4-hydroxy phenyl) ethene; 1; 1; 2,2-four (3-methyl-4-hydroxy phenyl) ethane; 1,1; 2; 2-four (3-fluoro-4-hydroxy phenyl) ethane; α, α, α '; α '-four (4-hydroxy phenyl)-paraxylene; four (p-methoxyphenyl) ethene; 3; 6,3 ', 6 '-tetramethoxy-9; 9 '-Lian-9H-xanthene; 3; 6,3 ', 6 '-tetrem acyloxy-9; 9 '-Lian-9H-xanthene; 3; 6,3 ', 6 '-tetrahydroxy-9; 9 '-Lian-9H-xanthene; gallic acid; gallicin; catechuic acid; connection-betanaphthol; the two dicyclohexyl acid amides of diphenic acid; the two dicyclohexyl acid amides of fumaric acid; 1; 1,2,2-tetraphenyl ethane; four (to iodine substituted phenyl) ethene; 9; 9 '-dianthranide; 1; 1,2,2-four (4-carboxyl phenyl) ethane; 1; 1; 2,2-four (3-carboxyl phenyl) ethane; acetylenedicarboxylic acid; quinhydrones; the 2-tertiary butylated hydroquinone; 2, the 5-di-tert-butyl hydroquinone; 2; two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-; or the like.

Among such seizure compound, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2, the amide-type of the hydroquinones of the phenol system compound of 2-four (4-hydroxy phenyl) ethene and so on, quinhydrones and so on, the two dicyclohexyl acid amides of fumaric acid and so on is being favourable aspect economy, complex or the molecular compound formation ability.

These seizure property compounds can be used alone or two or more kinds may be used.

As the liquid organic-fuel, the preferred liquid organic-fuel with c h bond that uses for example can use: the alcohols of methyl alcohol, ethanol, propyl alcohol etc.; The ethers of dimethyl ether etc.; The cycloalkane of cyclohexane etc.; Cycloalkane with hydrophilic group of hydroxyl, carboxyl, amino, amide groups etc.; One of cycloalkane replaces body or two and replaces body; Or the like.Here, cycloalkane is meant cycloalkane and replacement body thereof, beyond the use aromatic compound.

The solid electrolyte fuel cell fuel of the 3rd mode is to comprise these liquid organic-fuels, above-mentioned seizure compound, and the fuel of the solvent that uses as required.Seizure property compound can be dissolved in the liquid organic-fuel in advance, also can be by mixing both to the mode of the fuel electrodes feed fluid organic-fuel of fuel cell and seizure property compound during at fuel cell operation before reaching fuel electrodes.

As solvent,, make water, alcohols etc. usually so long as liquid organic-fuel and seizure property compound are had deliquescent solvent just.

The solid electrolyte fuel cell of the 3rd mode uses with concentration 5-90 weight % usually with the liquid organic-fuel in the fuel.Cross when low when liquid organic-fuel concentration, fuel efficiency is poor, when liquid organic-fuel excessive concentration, has problems aspect fail safe.

Solid electrolyte fuel cell in the 3rd mode is used in the fuel, and above-mentioned seizure compound concentrations is preferably the scope of 0.001-1mol/L.Cross when low with the seizure compound concentration in the fuel when solid electrolyte fuel cell, can not fully obtain catching the effect that inhibition that the property compound brings sees through by adding, when seizure property compound concentration is too high, unfavorable economically.

The solid electrolyte fuel cell of the 3rd mode is preferably 4-8 with the pH value of fuel.Is the scope of 4-8 by making solid electrolyte fuel cell with the pH value of fuel, can prevent the bad influence to solid electrolyte film, the corrosion of the metallic member in the fuel cell, helps the stable operation of fuel cell.Therefore, under departing from the situation of this scope, the pH value also can add the pH conditioning agent of acid or alkali etc. as required.

Followingly the solid electrolyte fuel cell that uses the 3rd mode solid electrolyte fuel cell of the present invention and the using method thereof with fuel described with reference to accompanying drawing.

Fig. 4 is the sectional view of pattern ground expression based on the structure of the solid electrolyte fuel cell of embodiment.

In Fig. 4, electrode-electric is separated matter conjugant 21 and is made of fuel electrodes 22, oxidizing agent pole 23 and solid polyelectrolyte membrane 24.Fuel electrodes 22 is made of matrix 22A and catalyst layer 22B.Oxidizing agent pole 23 is made of matrix 23A and catalyst layer 23B.It is that intermediary is electrically connected then with fuel electrodes side dividing plate 25 and oxidation utmost point side dividing plate 26 that a plurality of electrode-electrics are separated matter conjugant 21, constitutes fuel cell 30.

In the fuel cell 30 that constitutes like this, separate fuel electrodes 22 fuelings 27 of matter conjugant 21 to each electrode-electric by fuel electrodes side dividing plate 25.Separate the oxidant 28 of oxidizing agent pole 23 air supplies of matter conjugant 21 or oxygen etc. to each electrode-electric by oxidation utmost point side dividing plate 26.

Solid polyelectrolyte membrane 24 separates fuel electrodes 22 and oxidizing agent pole 23, has the effect that between moves hydrogen ion simultaneously.For this reason, the high film of the preferably hydrionic conductivity of solid polyelectrolyte membrane 24.In addition, chemically stable, mechanical strength is high for well.

As the material that constitutes solid polyelectrolyte membrane 24, the organic polymer of the polar group of the preferred weak acid base that uses strong acid with sulfonic group, phosphate, phosphonate group, phosphinic acids base etc., carboxyl etc. etc.Organic polymer as such exemplifies out: sulfonation gathers the aromatic polymer that contains of (4-phenoxy group benzoyl-1,4-phenylene), alkyl sulfonated polyphenyl and imidazoles etc.; Polystyrene sulfonate copolymer, polyvinyl sulfonic acid copolymer, crosslinked alkyl sulfonic acid derivative, comprise the copolymer of the fluoro containing polymers etc. of fluororesin skeleton and sulfonic acid; The copolymer that makes the acrylic ester copolymerization of the acrylic amide of acrylamide-2-methyl propane sulfonic acid and so on and n-BMA and so on and obtain; Contain sulfonic perfluocarbon (Nafion (registered trade mark, デュ Port Application corporate system), アシプレッ Network ス (Asahi Chemical Industry's corporate system); Contain carboxyl perfluocarbon (Off レミオ Application (registered trade mark) S film (Asahi Glass corporate system)); Or the like.Wherein, under the situation that contains aromatic polymer of selecting sulfonation poly-(4-phenoxy group benzoyl-1,4-phenylene), alkyl sulfonated polyphenyl and imidazoles etc., can suppress seeing through of liquid organic-fuel, can suppress by the reduction that sees through the battery efficiency that causes.

Act as a fuel the matrix 22A of the utmost point 22 and the matrix 23A of oxidizing agent pole 23, fuel electrodes 22, oxidizing agent pole 23 all can use the porousness matrix of carbon paper, carbon formed body, carbon sintered body, sintering metal, foam metal etc.When these matrixes are carried out hydrophobic treatment, can use the water-repelling agent of polytetrafluoroethylene etc.

The act as a fuel catalyst of the utmost point 22 exemplifies out platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, lithium, lanthanum, strontium, yttrium etc.These catalyst can be used alone or in combination of two or more kinds.As the catalyst of oxidizing agent pole 23, also can use the catalyst same with the catalyst of fuel electrodes 22, can use the above-mentioned material that exemplifies.The catalyst of fuel electrodes 22 and oxidizing agent pole 23 can use identical catalyst also can use different catalyst.

As catalyst-loaded carbon granule, exemplify out that acetylene black (デ Application カ Block ラッ Network (registered trade mark, Denki Kagaku Kogyo kabushiki's system), XC72 (Vulcan corporate system) etc.), ケッチェ Application are black, carbon nano-tube, carbon nanometer loudspeaker etc.The average grain diameter of carbon granule for example is 0.01-0.1 μ m, is preferably 0.02-0.06 μ m.

The manufacture method of fuel electrodes 22 and oxidizing agent pole 23 is not particularly limited, and for example can make as described below.At first, catalyst the supporting on carbon granule of fuel electrodes 22 and oxidizing agent pole 23 can adopt general employed method of impregnation to carry out.Then, make the carbon granule that supported catalyst and solid macromolecule electrolyte Dispersion of Particles in solvent, form paste after, it is last and carry out drying that it is coated on

matrix

22A, 23A, can obtain fuel electrodes 22 and oxidizing agent pole 23 thus.

The average grain diameter of carbon granule for example is 0.01-0.1 μ m as described above.The average grain diameter of catalyst granules for example is 1-10nm.The average grain diameter of solid macromolecule electrolyte particle for example is 0.05-1 μ m.Carbon granule and solid macromolecule electrolyte particle are that 2: 1～40: 1 scope is used in weight ratio for example.In addition, the part by weight of water in the cream and solute is as being about 1: 2～10: 1.

Be not particularly limited for method, for example can use brushings, spraying, reach the method for silk screen printing etc. to matrix coating cream.Cream is applied with the thickness of about 1 μ m-2mm.After the coating cream, with the corresponding heating-up temperature and heating heating time such as fluororesin of the solid macromolecule electrolyte that uses, thereby make fuel electrodes 22 or oxidizing agent pole 23.Heating-up temperature and heating time are selected according to the material that uses is suitable, and for example heating-up temperature can be 100-250 ℃, can be 30 second-30 minute heating time.

Solid polyelectrolyte membrane 24 can adopt suitable method to make according to the material that uses.For example constituting under the situation of solid polyelectrolyte membrane 24 with high-molecular organic material, high-molecular organic material is dissolved or dispersed in the solvent, the liquid curtain coating that obtains like this makes it drying and can obtain thus on the fissility sheet of polytetrafluoroethylene etc. etc.

Clamp the solid polyelectrolyte membrane of making as described above 24 with fuel electrodes 22 and oxidizing agent pole 23, carry out hot pressing, obtain electrode-electric and separate matter conjugant 21.At this moment, the face that is provided with catalyst of two electrodes contacts with solid polyelectrolyte membrane 24.The condition of hot pressing is selected according to material.Under the situation of the dielectric film that constitutes solid polyelectrolyte membrane 24, electrode surface with organic polymer, the temperature of hot pressing can be the temperature above these high molecular softening temperatures or glass transformation temperature.The condition of hot pressing specifically adopts such condition: temperature 100-250 ℃, pressure 5-100kgf/cm ²(0.49-9.8MPa), time 10-300 second.

In the solid electrolyte fuel cell and using method thereof of the 3rd mode, supply with above-mentioned solid electrolyte fuel cell fuel to the fuel electrodes 22 of the solid electrolyte fuel cell of such formation.Thus, form the layer of the material that forms by seizure property compound seizure liquid organic-fuel between fuel 27 in fuel electrodes 22 and the solid polyelectrolyte membrane 24, suppressed superfluous liquid organic-fuel thus and passed through, therefore can reduce seeing through from solid polyelectrolyte membrane 24.

In the 3rd mode, supply with the solid electrolyte fuel cell fuel of the 3rd mode in this wise to the fuel electrodes of solid electrolyte fuel cell, but this moment,, preferably be recovered in unreacted liquid organic-fuel and utilization once again in the fuel electrodes in order to improve the utilization ratio of fuel.

Below describe with reference to Fig. 5 about such scheme.

In Fig. 5, the details of fuel cell 30 is the same with Fig. 4, therefore omits.In the present embodiment, possess fuel feeding system 40, this fuel feeding system 40 comprises: to the fuel supplying part 41 of the fuel electrodes fueling of fuel cell 30, reclaim fuel recovery portion 42, the liquid organic-fuel that is used for measuring the used fuel that is reclaimed and the seizure property compound concentrations of the used fuel of discharging from the fuel electrodes of fuel cell 30 concentration 43, be used for adjusting the concentration adjustment part 44 of the liquid organic-fuel of used liquid fuel and seizure property compound concentrations.The fuel that contains seizure property compound utilizes not shown liquid transporting body to move along the direction of arrow among the figure, is recycled.

Fuel is supplied with to the fuel electrodes of fuel cell 30 by fuel supplying part 41, after fuel electrodes, is reclaimed by fuel recovery portion 42.Carbon dioxide etc., the material that is produced by the electrode reaction in the fuel electrodes are separated in fuel recovery portion 42.Then, the fuel that is reclaimed is sent to concentration 43, measures liquid organic-fuel and seizure property compound concentrations.Based on this measurement result, 44 suitably adjust liquid organic-fuel and seizure property compound concentrations in the concentration adjustment part, and regeneration becomes fuel.Zai Sheng fuel is transported to fuel supplying part 41 like this, is sent to the fuel electrodes of fuel cell 30 then.

By possessing such fuel feeding system, can realize to utilize expeditiously the fuel cell of fuel.

According to the 3rd mode, can suppress the seeing through of liquid organic-fuel in the solid electrolyte fuel cell, therefore can realize the height outputization and the high fuel efficiencyization of solid electrolyte fuel cell.

Use the solid electrolyte fuel cell of the solid electrolyte fuel cell of the 3rd mode, suppressed seeing through of liquid organic-fuel with the 3rd mode of fuel, so the power output height, battery efficiency is good.

Based on the solid electrolyte fuel cell of the 3rd mode be possess fuel electrodes, oxidizing agent pole, and with the solid electrolyte film of fuel electrodes and oxidizing agent pole clamping, and adopted formation, the so-called directly fuel cell of type to the direct feed fluid organic-fuel of its fuel electrodes.The fuel cell of existing direct type is not because the battery efficiency height, need modifier, so advantage that can obtain to seek to save space or the like, but then, seeing through of the liquid organic-fuel of methyl alcohol etc. becomes problem, but according to the 3rd mode, such problem that sees through can be eliminated, good battery efficiency can be realized steadily in the long term simultaneously.

The solid electrolyte fuel cell of the 3rd mode of the conveying device of carrying to feedway according to the retracting device that further has the used fuel that recovery discharges from fuel electrodes, the concentration regulator of adjusting liquid fuel the used fuel that is reclaimed and seizure property compound concentrations, the fuel that will adjust concentration, can utilize in fuel electrodes the liquid organic-fuel that does not consume again, therefore can not have waste, use the liquid organic-fuel expeditiously.

Below enumerate embodiment and comparative example the 3rd mode more specifically is described, but the 3rd mode, only otherwise exceed its main idea, be not limited to following embodiment.

Embodiment 14

With reference to the solid electrolyte fuel cell fuel of Fig. 6 explanation based on present embodiment.

At first, in fuel electrodes 22 and oxidizing agent pole 23, in the dinitro diamines platinum salpeter solution 500g of the platinum that will become catalyst that contains 3 weight %, mix acetylene black 10g (デ Application カ Block ラッ Network (registered trade mark); Denki Kagaku Kogyo kabushiki's system), after the stirring, add 98% ethanol 60mL as reducing agent.This solution was mixed 8 hours under about 95 ℃, make acetylene black particles supported platinum particulate.This solution is filtered, and drying has obtained supporting the carbon granule of platinum.The loading of platinum is about 50 weight % with respect to the weight of acetylene black.

Then, mix and stir carbon granule 200mg and 5%Nafion (registered trade mark) solution (alcoholic solution, the ア Le De リッチケミカ Le corporate system) 3.5mL that supports platinum, made platinum and carbon granule surface adsorption Nafion (registered trade mark).The dispersion liquid that obtains was disperseed 3 hours with ultrasonic disperser under 50 ℃, form paste thus.Adopt silk screen print method with 2mg/cm ²This cream is coated on carbon paper (eastern beautiful corporate system: TGP-H-120), make it dry under 120 ℃, obtained electrode.

As solid polyelectrolyte membrane 24, used the Nafion117 (registered trade mark, thickness are 150 μ m) of デュ Port Application corporate system.For this solid polyelectrolyte membrane 24, at the above-mentioned electrode that obtains, clamp solid polyelectrolyte membrane 24 120 ℃ of following thermo-compressed, at 150 ℃ of temperature, pressure 10kgf/cm with fuel electrodes 22 and oxidizing agent pole 23 ²(0.98MPa), hot pressing under the condition in 10 seconds, made electrode-electric thus and separated matter conjugant 21.

For to fuel electrodes 22 fuelings, on fuel electrodes 22, be provided with the fuel stream 51 of polyflon system.Be provided with tanks 52 and waste liquid tank 53 at this fuel on stream 51.In tanks 52, possess pump, shown in the arrow among the figure, form can be constantly to the structure of fuel electrodes 22 fuelings.

In addition, in order to supply with oxidant, on oxidizing agent pole 23, be provided with the oxidant stream 54 of polyflon system to oxidizing agent pole 23.Be provided with oxygen compressor 55 and exhaust outlet 56 at this oxidant on stream 54, shown in the arrow among the figure, form the structure that constantly to supply with oxygen to oxidizing agent pole 23.

Injected at 10 weight % methanol aqueous solutions to tanks 52 and to have dissolved 1, the fuel that the 1-bis(4-hydroxyphenyl)cyclohexane forms.1 of this fuel, the concentration of 1-bis(4-hydroxyphenyl)cyclohexane are 0.01mol/L.This fuel is supplied with to fuel electrodes 22 with 2mL/min.Utilize oxygen compressor 55 pairs of oxidizing agent poles 23 to supply with 1.1 atmospheric pressure (0.11MPa), 25 ℃ oxygen.

Under such condition, move, the current-voltage characteristic of determination unit battery, table 1 shows the result.

Embodiment 15

In embodiment 14, as the fuel that injects to tanks 52, use the fuel that the dissolving quinhydrones forms in 10 weight % methanol aqueous solutions, fuel cell operation similarly in addition, the current-voltage characteristic of determination unit battery, it the results are shown in the table 1.The quinhydrones concentration of this fuel is 0.01mol/L.

Embodiment 16

In embodiment 14, as the fuel that injects to tanks 52, use the fuel that the two dicyclohexyl acid amides of dissolving fumaric acid form in 10 weight % methanol aqueous solutions, in addition fuel cell operation similarly, the current-voltage characteristic of determination unit battery, it the results are shown in the table 1.The two dicyclohexyl amide concentration of the fumaric acid of this fuel are 0.01mol/L.

Comparative example 1

In embodiment 14, the fuel as injecting to tanks 22 has used 10 weight % methanol aqueous solutions, fuel cell operation similarly in addition, and the current-voltage characteristic of determination unit battery, it the results are shown in the table 1.

Table 1

	Seizure property compound	Open voltage (V)	Short circuit current (mA/cm ²)	Maximum power (mW/cm ²)
	Seizure property compound	Open voltage (V)	Short circuit current (mA/cm ²)	Maximum power (mW/cm ²)	Embodiment 14	1, the 1-bis(4-hydroxyphenyl)cyclohexane	0.65	270	48
Embodiment 15	Quinhydrones	0.66	340	55	Embodiment 14	1, the 1-bis(4-hydroxyphenyl)cyclohexane	0.65	270	48
Embodiment 15	Quinhydrones	0.66	340	55	Embodiment 16	The two dicyclohexyl acid amides of fumaric acid	0.65	280	49
Comparative example 1	-	0.60	210	35	Embodiment 16	The two dicyclohexyl acid amides of fumaric acid	0.65	280	49

Clear and definite from table 1: the element cell of element cell the embodiment 14-16 and comparative example 1 is relatively opened all excellences of voltage, short circuit current, maximum power.

What [4] the 4th mode is described then discharges the method for fuel from the fuel cell-use fuel composition.

The method from fuel cell-use fuel composition release fuel of the 4th mode, it is characterized in that, be the method that discharges fuel from the fuel composition that contains fuel cell-use fuel, contact with water, in this water, discharge this fuel by making this fuel cell-use fuel composition.

As scheme, do not limit especially, but solid macromolecular electrolyte type fuel cell preferably wherein, also comprises the direct-type methanol fuel cell based on the fuel cell of the 4th mode.

As fuel cell-use fuel based on the 4th mode, so long as can be used as fuel cell fuel material just, for example list hydrogen, alcohols, ethers, hydro carbons, acetals etc., but be not limited to these.The material that acts as a fuel more specifically lists the alcohols of hydrogen, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol etc.; The ethers of dimethyl ether, ethyl methyl ether, diethyl ether etc.; The hydro carbons of propane, butane etc.; Acetals such as dimethoxymethane, trimethoxy-methane or the like.These fuel cell-use fuels can use a kind separately, also can mix more than 2 kinds and use.

As the form based on the fuel cell-use fuel composition of the 4th mode, list: [1] forms such fuel cell-use fuel the form of molecular compound; [2] make polymer absorb the form of fuel cell-use fuel; Or the like, but be not limited to these forms.

At first, as the fuel composition that comprises fuel cell-use fuel, the fuel composition of representational above-mentioned [1], [2] is described based on the 4th mode.

[1] molecular compound of fuel cell-use fuel and matching side compound

Here, so-called molecular compound, the compound more than 2 kinds that is the compound that can stably exist separately comprises hydrate, solvate, additive compound, inclusion compound etc. by being the compound that combination is carried out in more weak interaction representative, beyond the covalent bond with hydrogen bond, Van der Waals force etc.Such molecular compound can be by forming molecular compound the matching side compound and the haptoreaction of fuel cell-use fuel form, thereby it is low weight and stably store fuel cell-use fuel for example can to make the fuel cell-use fuel of gas or liquid be varied to the compound weight of solid, shaped.

As molecular compound based on the 4th mode, the inclusion compound of for example having enumerated by the haptoreaction of host compound and fuel cell-use fuel the fuel cell-use fuel inclusion.

As the formed inclusion host compound of inclusion compound of fuel cell-use fuel, known organic compound, inorganic compound and organic-inorganic complex chemical compound.In organic compound as host compound, known unimolecule system, polymolecular system, macromolecular main body etc.

As unimolecule owner body compound, exemplify out cyclodextrin, crown ether-like, cryptand class, cyclophane class, azepine cyclophane class, calixarene kind, シ Network ロトリベラトリレ Application class, ス Off ェラ Application De class, cyclic oligomer peptide class etc.As polymolecular owner body compound, exemplify out urea class, Thiourea, deoxycholic acid class, perhydrogenate benzophenanthrene class, three-neighbour-チモチ De class, dianthranide class, spiral shell two fluorenes classes, ring phosphonitrile class, single alcohols, glycols, acetylene series alcohols, hydroxy benzophenone ketone, phenol, bisphenols, three phenols, four phenols, Polyphenols, aphthols, dinaphthyl phenols, diphenylmethyl alcohols, carboxylic acyloxy amine, thioamide analog, connection xanthene class, carboxylic acids, imidazoles, hydroquinones etc.As the macromolecular host compound, exemplify out cellulose family, starch based, chitosan kind, chitosan class, polyvinyl alcohol, with 1,1,2,2-tetraphenyl ethane is for the polyethylene glycol arm type polymer class of nuclear, with α, α, α ', α '-tetraphenyl dimethylbenzene are the polyethylene glycol arm type polymer of nuclear etc.

As polymolecular owner body compound, specifically list: urea, 1,1,6,6-tetraphenyl own-2,4-diine-1, the 6-glycol, 1,1-two (2, the 4-3,5-dimethylphenyl)-2-propine-1-alcohol, 1,1,4,4-tetraphenyl-2-butine-1, the 4-glycol, 1,1,6,6-four (2, the 4-3,5-dimethylphenyl)-2,4-hexadiine-1, the 6-glycol, 9,10-diphenyl-9,10-dihydroanthracene-9, the 10-glycol, 9, two (the 4-aminomethyl phenyls)-9 of 10-, 10-dihydroanthracene-9,10-glycol, 1,1,2,2-tetraphenyl ethane-1,2-glycol, the 4-metoxyphenol, 2, the 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 4,4 '-sulphonyl bis-phenol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-ethylidene bis-phenol, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, 1,1,2,2-four (3-methyl-4-hydroxy phenyl) ethane, 1,1,2,2-four (3-fluoro-4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-paraxylene, four (p-methoxyphenyl) ethene, 3,6,3 ', 6 '-tetramethoxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrem acyloxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrahydroxy-9,9 '-Lian-9H-xanthene, gallic acid, gallicin, catechuic acid, two-betanaphthol, α, α, α ', α '-tetraphenyl-1,1 '-biphenyl-2,2 '-dimethanol, the two dicyclohexyl acid amides of diphenic acid, the two dicyclohexyl acid amides of fumaric acid, cholic acid, deoxycholic acid, 1,1,2,2-tetraphenyl ethane, four (to iodine substituted phenyl) ethene, 9,9 '-dianthranide, 1,1,2,2-four (4-carboxyl phenyl) ethane, 1,1,2,2-four (3-carboxyl phenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenyl imidazoles, 1,2,4,5-tetraphenyl imidazoles, 2-phenyl phenanthro-[9,10-d] imidazoles, 2-(adjacent cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(to cyano-phenyl) phenanthro-[9,10-d] imidazoles, quinhydrones, the 2-tertiary butylated hydroquinone, 2, the 5-di-tert-butyl hydroquinone, 2, two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-, or the like.

These host compounds can be used alone or two or more kinds may be used.

These host compounds if form the compound of the inclusion compound of solid, shaped with fuel cell-use fuel, then can be the compounds of Any shape.

Among the aforementioned body compound, the organic system host compound also can be used as the organic/inorganic composite material that inorganic porous metallic substance is supported.In this case, as the porous metallic substance that supports the organic system host compound, except silica type, zeolites, active carbon class, also list the intercalation compound of clay mineral class, smectites etc. etc., but be not limited to these.Organic/inorganic composite material can adopt following or the like method manufacturing: above-mentioned organic system host compound is dissolved in the solvent that can dissolve this compound, this solution is infiltrated in the porous metallic substance, again with solvent seasoning, drying under reduced pressure.Be not particularly limited as the loading of organic system host compound, but in normal circumstances, be about 10-80 weight % with respect to the porous metallic substance with respect to the porous metallic substance.

As using 1, the method of the inclusion compound of fuel such as the host compound synthetic fuel battery of 1-bis(4-hydroxyphenyl)cyclohexane etc., exemplify out the method that fuel cell-use fuel is directly contacted, mixes with host compound, the inclusion compound of fuel cell-use fuel that can easily synthesize inclusion thus.Heat etc. so that after host compound is dissolved in the fuel cell-use fuel, also can synthesize inclusion compound by carrying out crystallization again.Fuel cell-use fuel is the occasion of gas or liquid, contacts with host compound under pressurized state by making this fuel, also can form inclusion compound.

When synthetic inclusion compound, the temperature that fuel cell-use fuel is contacted with host compound is not particularly limited, but is preferably about normal temperature-100 ℃.Pressure condition for this moment also is not particularly limited.Also be not particularly limited for the time that fuel cell-use fuel is contacted with host compound, but consider to be preferably about 0.01-24 hour from the aspect of operating efficiency etc.

The fuel cell-use fuel that contacts with host compound is preferably highly purified fuel, but under use has situation to the host compound of the selectivity inclusion ability of fuel cell-use fuel, also can be the mixing material of fuel cell-use fuel and other compositions.

The inclusion compound that obtains like this is also according to the kind of the host compound that uses, different and different with the contact conditions of fuel cell-use fuel etc., but normally with respect to 1 mole of host compound inclusion the inclusion compound of 0.1-10 mole fuel cell-use fuel molecule.

The inclusion compound that obtains like this can be stored fuel cell-use fuel steadily in the long term under the normal temperature and pressure environment.And the solid, shaped that this inclusion compound can form is in light weight, operability is also excellent, therefore can put in the container of glass, metal, plastics etc. storage easily, also eliminated the problem of leak of liquid.In addition, gaseous state or liquid fuel cell-use fuel become solid, shaped by inclusionization usually, also can avoid the character as violent in toxicity, danger thus.In addition, can reduce the chemical reactivity that fuel cell-use fuel has, can also relax for example to corrosion of metal etc.

Adopt method described later to discharge host compound behind the fuel cell-use fuel, have selection inclusion ability, can be used further to the inclusionization of fuel cell-use fuel effectively this fuel cell-use fuel from such inclusion compound.

[2] make polymer absorb the fuel composition that fuel cell-use fuel forms

This fuel composition is to make the crosslinked body (A) of following macromolecular compound (1) absorb the composition that (infiltration) liquid fuel cell-use fuel (hereinafter referred to as " liquid fuel ") forms.

Macromolecular compound (1): have in the macromolecular compound that (hereinafter referred to as " contain acidic groups constitute unit (a) ") polymerization of carboxyl and/or sulfonic formation unit or copolymerization form the macromolecular compound that this carboxyl of the macromolecular compound (2) that this content that contains that acidic groups constitutes unit (a) is 20-100 weight % and/or the 30-100 mole % of this sulfonic proton form with the replacement of  cation in the molecule.

In addition, as described later, in the 4th mode, macromolecular compound (1) is not limited to the macromolecular compound made from the proton of the carboxyl of  cation replacement macromolecular compound (2) and/or sulfonic ormal weight, macromolecular compound (1) also can be: replace with the  cation in advance and contain after the carboxyl and/or sulfonic proton that acidic groups constitutes unit (a), the macromolecular compound that its polymerization or copolymerization are made.Equally, the crosslinked body (A) of macromolecular compound (1) not necessarily is limited to the crosslinked crosslinked body of making in advance that forms of macromolecular compound (1), if can obtain the crosslinked body of macromolecular compound (1), then also can be to carry out the crosslinked crosslinked body that forms in the fabrication stage of macromolecular compound (2) or macromolecular compound (1).In addition, cationic introducing of  and crosslinked can carrying out via the step more than 2.

Constitute unit (a) as the acidic groups that contains that constitutes above-mentioned macromolecular compound (2), list: have the monomer of carboxyl, for example (methyl) acrylic acid, ethylacrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, and these sour acid anhydrides etc.; Has sulfonic monomer, for example aliphatic ethylene base sulfonic acid [vinyl sulfonic acid, allyl sulphonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid etc.], (methyl) acrylic ester type sulfonic acid [(methyl) acrylic acid sulphur ethyl ester, (methyl) acrylic acid sulphur propyl ester etc.], and (methyl) acid/acrylic amide type sulfonic acid [acrylamide-2-methyl propane sulfonic acid etc.].The preferred carbon number that contains acidic groups formation unit (a) is 3-30.

In macromolecular compound (2), these contain acidic groups formation unit (a) can contain a kind separately, also can contain more than 2 kinds.In macromolecular compound (2), also can contain above-mentioned contain acidic groups constitute unit (a) in addition, can with contain the formation unit (hereinafter referred to as " other constitute unit (b) ") that acidic groups constitutes unit (a) copolymerization.

Constitute unit (b) as other, for example can enumerate:

(methyl) acrylic acid alkyl (carbon number 1-30) ester class specifically lists (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) stearyl acrylate ester, (methyl) phenyl acrylate, (methyl) acrylic acid octyl octylphenyl, (methyl) cyclohexyl acrylate etc.;

(methyl) acrylic acid hydroxy alkyl (carbon number 1-4) ester class, specifically list (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid hydroxy propyl ester, (methyl) acrylic acid list (polyethylene glycol) ester (PEG number-average molecular weight: 100-4,000), (methyl) acrylic acid list (polypropylene glycol) ester (PPG number-average molecular weight: 100-4,000), (methyl) acrylic acid mono methoxy polyethylene glycol ester (PEG number-average molecular weight: 100-4,000), (methyl) acrylic acid mono methoxy propylene glycol ester (PPG number-average molecular weight: 100-4,000) etc.;

(methyl) acrylic amide specifically lists (methyl) acrylamide, (two) methyl (methyl) acrylamide, (two) ethyl (methyl) acrylamide, (two) propyl group (methyl) acrylamide etc.;

Allyl ether series specifically lists methallyl ether, ethyl allyl ether, propyl group allyl ether, glycerol mono allyl ether, trimethylolpropane tris allyl ether, pentaerythritol monoallyl ether etc.;

The alpha-olefines of carbon number 4-20 specifically lists isobutene, 1-hexene, 1-octene, isooctene, 1-nonene, 1-decene, 1-dodecylene etc.;

The aromatic ethenyl compound class of carbon number 8-20 specifically lists styrene, t-butyl styrene, octyl group styrene etc.;

Other vinyl compound specifically lists N-vinyl acetamide, vinyl caproate, vinyl laurate, stearic acid vinyl ester etc.;

Contain amino monomers, specifically list the dialkyl group (carbon number of alkyl: 1-5) amino-ethyl (methyl) acrylate, methyl (acryloyl group) ethoxy trialkyl (alkyl carbon number: 1-5) ammonium chloride, methyl (acryloyl group) ethoxy trialkyl (alkyl carbon number: 1-5) ammonium bromide or methyl (acryloyl group) ethoxy trialkyl (alkyl carbon number: 1-5) ammonium sulfate etc.;

Above-mentioned alkali metal salt, primary～tertiary ammonium salt or alkanol amine salt etc. with carboxyl, sulfonic monomer.These other formation unit (b) can contain a kind separately in macromolecular compound (2), also can contain more than 2 kinds.

The content that contains acidic groups formation unit (a) in the macromolecular compound (2) is generally 20-100 weight %, is preferably 40-100 weight %, more preferably 60-100 weight %.When in the macromolecular compound (2) contain content that acidic groups constitutes unit (a) less than 20 weight % the time, promptly use  cation described later to replace carboxyl, sulfonic proton, the uptake that becomes the liquid fuel of storage object also reduces, in addition, when being a small amount of, often can not be with the liquid fuel gelation.

Contain under other situations that constitute unit (b) at macromolecular compound (2), among the above-mentioned formation unit that exemplifies, from the viewpoint of the stability of the polymer of the polymerism of monomer, generation etc., preferred (methyl) alkyl-acrylates, (methyl) acrylic acid hydroxyalkyl acrylate class, allyl ether series, alpha-olefines, aromatic ethenyl compound class.

For absorption liquid fluid fuel expeditiously or with its gelation, selecting liquid fuel and other differences that constitute the SP value of unit (b) according to the SP (solubility parameter) of this liquid fuel is that liquid fuel below 5 is for well, reason is like this, uptake, gelation power easily improve, and further preferred selection is below 3 as SP value and other differences that constitutes the SP value of unit (b) of the liquid fuel that absorbs object.

The manufacture method of macromolecular compound (2), so long as finally obtain containing ormal weight contain acidic groups constitute unit (a) macromolecular compound (2) method just, be not particularly limited.Macromolecular compound (2), except the method that contains acidic groups formation unit (a) of polymerization ormal weight, for example also can adopt following method to make: to adopt the method that can easily become the sulfonic monomer polymerization of carboxyl, hydrolysis etc. with the above-mentioned carboxylate that contains carboxyl or sulfonic monomer, amidate etc. and so on, in molecule, introduce the sulfonic formation of the carboxyl unit of ormal weight, can make therefrom.In addition, also can adopt following method or the like to make: contain carboxyl or the sulfonic polysaccharide macromolecule and this polysaccharide and other monomer that will be representative with the carboxymethyl cellulose carry out graft copolymerization.

Macromolecular compound (1) is to replace the proton of the carboxyl of such macromolecular compound (2) and/or sulfonic 30-100 mole % and the macromolecular compound that obtains with the  cation.

Here, as the  cation, list from comprising quaternary ammonium cation (I), uncle  cation (II), season  cation (III), and more than a kind or 2 kinds of cation group selection of uncle's oxygen  cation (IV).

As quaternary ammonium cation (I), list following (I-1)～(I-11).

(I-1) have the above alkyl of carbon number 4-30 or this numerical value and/or the fatty family quaternary ammonium of thiazolinyl, specifically list tetramethyl-ammonium, ethyl trimethyl ammonium, diethyl-dimethyl ammonium, triethyl group ammonium methyl, tetraethyl ammonium, trimethyl propyl ammonium, tetrapropyl ammonium, butyl trimethyl ammonium, TBuA etc.;

(I-2) the above aromatic series quaternary ammonium of carbon number 6-30 or this numerical value specifically lists trimethylphenyl ammonium, dimethyl ethyl phenyl ammonium, triethyl group phenyl ammonium etc.;

(I-3) the above ester ring type quaternary ammonium of carbon number 3-30 or this numerical value specifically lists N, N-dimethyl ピロジニウ system, N-ethyl-N-crassitude , N, N-thebaine , N, N-diethyl morpholine , N, N-lupetidine , N, N-diethyl piperidines  etc.;

(I-4) the above imidazoline  of carbon number 3-30 or this numerical value specifically lists 1,2,3-tri-methylimidazolium quinoline , 1,2,3,4-tetramethyl imidazoline , 1,3,4-trimethyl-2-ethyl imidazol(e) quinoline , 1,2-dimethyl-3,4-diethyl imidazoline , 1,2-dimethyl-3-ethyl imidazol(e) quinoline , 1-ethyl-3-methylimidazole quinoline , 1,2,3,4-tetraethyl imidazoline , 1,2,3-triethyl group imidazoline , 4-cyano group-1,2,3-tri-methylimidazolium quinoline , 2-cyano methyl-1,3-methylimidazole quinoline , 4-acetyl group-1,2,3-tri-methylimidazolium quinoline , 4-methyl carboxymethyl-1,2,3-tri-methylimidazolium quinoline , 4-formoxyl-1,2,3-tri-methylimidazolium quinoline , 3-hydroxyethyl-1,2,3-tri-methylimidazolium quinoline , 3-hydroxyethyl-1,2-methylimidazole quinoline  etc.;

(I-5) the above imidazoles  of carbon number 3-30 or this numerical value, specifically list 1,3-methylimidazole , 1-ethyl-3-methylimidazole , 1-methyl-3-ethyl imidazol(e) , 1,2,3,4-tetramethyl imidazoles , 1,2-dimethyl-3-ethyl imidazol(e) , 1-ethyl-3-methylimidazole , 1-methyl-3-ethyl imidazol(e) , 1,2,3-triethyl group imidazoles , 1,2,3,4-tetraethyl imidazoles , 1,3-dimethyl-2-phenylimidazole , 1,3-dimethyl-2-benzyl imidazole , 4-cyano group-1,2,3-tri-methylimidazolium , 3-cyano methyl-1,2-methylimidazole , 4-acetyl group-1,2,3-tri-methylimidazolium , 4-methoxyl group-1,2,3-tri-methylimidazolium , 3-formoxyl methyl isophthalic acid, 2-methylimidazole , 2-hydroxyethyl-1,3-methylimidazole , N, N '-dimethylbenzimidazole , N, N '-diethyl benzo imidazoles , N-methyl-N '-ethyl benzo imidazole  etc.;

(I-6) the above tetrahydropyrimidine  of carbon number 4-30 or this numerical value, specifically list 1,3-dimethyl tetrahydro pyridine , 1,2,3-trimethyl tetrahydropyridine , 1,2,3,4-tetramethyl tetrahydropyridine , the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-hendecene , the 5-methyl isophthalic acid, 5-diazabicyclo [4,3,0]-5-nonene , 3-cyano methyl-1,2-dimethyl tetrahydro pyrimidine , 3-acetyl group methyl isophthalic acid, 2-dimethyl tetrahydro pyrimidine , 4-methyl carboxymethyl-1,2,3-trimethyl-tetrahydropyrimidine , 3-methoxy-1,2-dimethyl tetrahydro pyrimidine , 4-hydroxymethyl-1,3-dimethyl tetrahydro pyrimidine  or the like;

(I-7) the above dihydro-pyrimidin  of carbon number 4-30 or this numerical value specifically lists 1,3-dimethyl-2,4-or 2, [with their souvenirs is 1 to 6-dihydro-pyrimidin , 3-dimethyl-2,4, (6)-dihydro-pyrimidin , below adopt same expression], 1,2,3-trimethyl-2,4, (6)-dihydro-pyrimidin , 1,2,3,4-tetramethyl-2,4, (6)-dihydro-pyrimidin , 1,2,3,5-tetramethyl-2,4, (6)-dihydro-pyrimidin , the 8-methyl isophthalic acid, 8-diazacyclo [5,4,0]-7,9 (10)-11 carbon diene , 2-cyano methyl-1,3-dimethyl-2,4, (6)-dihydro-pyrimidin , 3-acetonyl-1,2-dimethyl-2,4, (6)-dihydro-pyrimidin , 4-methyl carboxymethyl-1,2,3-trimethyl-2,4, (6)-dihydro-pyrimidin , 4-formoxyl-1,2,3-trimethyl-2,4, (6)-dihydro-pyrimidin , 3-hydroxyethyl-1,2-dimethyl-2,4, (6)-dihydro-pyrimidin  or the like;

(I-8) has the guanidine  of the above imidazoline  skeleton of carbon number 3-30 or this numerical value, specifically list 2-dimethylamino-1,3,4-tri-methylimidazolium quinoline , 2-diethylamino-1,3,4-tri-methylimidazolium quinoline , 2-dimethylamino-1-methyl-3,4-diethyl imidazoline , 2-dimethylamino-1,3-methylimidazole quinoline , 2-diethylamino-1,3-methylimidazole quinoline , 2-diethylamino-1,3-diethyl imidazoline , 1,5,6,7-tetrahydrochysene-1,2-dimethyl-2H-pyrimido [1,2a] imidazoline , 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazoline , 2-dimethylamino-3-methyl carboxymethyl-1-methylimidazole quinoline , 2-dimethylamino-3-methoxy-1-methylimidazole quinoline , 2-dimethylamino-3-ethoxy-1-methylimidazole quinoline , 2-dimethylamino-4-methylol-1,3-methylimidazole quinoline  or the like;

(I-9) has the guanidine  of the above imidazoles  skeleton of carbon number 3-30 or this numerical value, specifically list 2-dimethylamino-1,3,4-tri-methylimidazolium , 2-diethylamino-1,3,4-tri-methylimidazolium , 2-diethylamino-1,3-dimethyl-4-ethyl imidazol(e) , 2-diethylamino-1,3,4-triethyl group imidazoles , 2-dimethylamino-1,3-methylimidazole , 1,5,6,7-tetrahydrochysene-1,2-dimethyl-2H-imido [1,2a] imidazoles , 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazoles , 2-dimethylamino-3-cyano methyl-1-methylimidazole , 2-dimethylamino-4-methyl carboxymethyl-1,3-methylimidazole , 2-dimethylamino-3-methoxy-1-methylimidazole , 2-dimethylamino-3-formoxyl methyl isophthalic acid-methylimidazole , 2-dimethylamino-4-methylol-1,3-methylimidazole  or the like;

(I-10) has the guanidine  of the above tetrahydropyrimidine  skeleton of carbon number 4-30 or this numerical value, specifically list 2-dimethylamino-1,3,4-trimethyl tetrahydropyrimidine , 2-diethylamino-1,3,4-trimethyl tetrahydropyrimidine , 2-dimethylamino-1,3-dimethyl tetrahydro pyrimidine , 2-diethylamino-1,3-dimethyl tetrahydro pyrimidine , 1,3,4,6,7,8-six hydrogen-1,2-dimethyl-2H-imido [1,2a] pyrimidine , 1,3,4,6,7,8-six hydrogen-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidine , 2-dimethylamino-3-cyano methyl-1-methyl tetrahydropyrimidine , 2-dimethylamino-4-acetyl group-1,3-dimethyl tetrahydro pyrimidine , 2-dimethylamino-4-methyl carboxymethyl-1,3-dimethyl tetrahydro pyrimidine , 2-dimethylamino-3-methoxy-1-methyl tetrahydropyrimidine , 2-dimethylamino-3-ethoxy-1-methyl tetrahydropyrimidine , 2-dimethylamino-4-methylol-1,3-dimethyl tetrahydro pyrimidine  or the like;

(I-11) has the guanidine  of the above dihydro-pyrimidin  skeleton of carbon number 4-30 or this numerical value; specifically list 2-dimethylamino-1; 3; 4-trimethyl-2; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3; 4-trimethyl-2; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3; 4-triethyl group-2; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3-dimethyl-2; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-1-ethyl-3-methyl-2,4 (6)-dihydro-pyrimidin ; 1,6; 7; 8-tetrahydrochysene-1,2-dimethyl-2H-imido [1,2a] pyrimidine ; 1; 6-dihydro-1; 2-dimethyl-2H-pyrimido [1,2a] pyrimidine ; 2-dimethylamino-4-cyano group-1,3-dimethyl-2; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-acetyl group methyl isophthalic acid-methyl-2; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-methyl carboxymethyl-1-methyl-2,4 (6)-dihydro-pyrimidin ; 2-dimethylamino-4-formoxyl-1,3-dimethyl-2; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-formoxyl methyl isophthalic acid-methyl-2,4 (6)-dihydro-pyrimidin  or the like.

As uncle  cation (II), list following (II-1)～(II-3).

(II-1) have the above alkyl of carbon number 1-30 or this numerical value and/or the fatty family uncle  of thiazolinyl, specifically list trimethyl , triethyl group , ethyl dimethyl , diethylmethyl  or the like;

(II-2) the above fragrant family uncle  of carbon number 6-30 or this numerical value specifically lists phenyl dimethyl , phenylethyl methyl , phenyl methyl benzyl  or the like;

(II-3) the above ester ring type uncle  of carbon number 3-30 or this numerical value specifically lists methyl チオラニウ system, phenyl チオラニウ system, methyl チアニウ system or the like.

As season  cation (III), list following (III-1)～(III-3).

(III-1) have the above alkyl of carbon number 1-30 or this numerical value and/or the fatty family season  of thiazolinyl, specifically list tetramethyl , tetraethyl , tetrapropyl , tetrabutyl , methyl triethyl group , methyl tripropyl , methyl tributyl , dimethyl diethyl , dimethyl dibutyl , trimethyl ethyl , trimethyl propyl group , trimethyl butyl  or the like;

(III-2) the above fragrant family season  of carbon number 6-30 or this numerical value specifically lists trityl group , diphenyl dimethyl , triphenyl benzyl  or the like;

(III-3) the above ester ring type season  of carbon number 3-30 or this numerical value, specifically list 1,1-dimethyl ホスホラニウ system, 1-methyl isophthalic acid-ethyl ホスホラニウ system, 1,1-diethyl ホスホラニウ system, 1,1-diethyl ホスホリ Na ニウ system, 1,1-five ethylidene ホスホリ Na ニウ system or the like.

As season oxygen  cation (IV), list following (IV-1)～(IV-3).

(IV-1) have the above alkyl of carbon number 1-30 or this numerical value and/or the fatty family uncle oxygen  of thiazolinyl, specifically list trimethyl oxygen , triethyl group oxygen , ethyl dimethyl oxygen , diethylmethyl oxygen  or the like;

(IV-2) the above fragrant family uncle oxygen  of carbon number 6-30 or this numerical value specifically lists phenyl dimethyl oxygen , phenylethyl methyl oxygen , phenyl methyl benzyl oxygen  or the like;

(IV-3) the above ester ring type uncle oxygen  of carbon number 3-30 or this numerical value specifically lists methyl オキソラニウ system, phenyl オキソラニウ system, methyl オキサニウ system or the like.

Among these materials, preferred  cation is quaternary ammonium cation (I), and further preferably above-mentioned (I-1), (I-4) reach (I-5), particularly preferably is (I-4) and reaches (I-5).

These  cations can be used alone or two or more kinds may be used.

As adopting above-mentioned  cation to replace the carboxyl of macromolecular compound (2) and/or the method for sulfonic proton, so long as this proton of ormal weight can be replaced to the cationic method of , it then can be any method, for example, with the cationic hydroxide salt of above-mentioned  (for example tetraethyl ammonium hydroxide etc.), monomethyl carbonated salt (for example 1,2,3,4-tri-methylimidazolium quinoline  monomethyl carbonate etc.) add in the macromolecular compound (2), dewater as required, decarbonate, separating methanol, can easily replace thus.In addition, also can similarly replace in the stage of the monomer that constitutes macromolecular compound (2).

Make the method for macromolecular compound (1) as carrying out the cationic replacement of , for example can enumerate: with the  cation replace above-mentioned contain the carboxyl and/or sulfonic proton that acidic groups constitutes unit (a) after, the method for carrying out polymerization or copolymerization; Replace the carboxyl of macromolecular compound (2) and/or the method for sulfonic proton with the  cation; Or the like, but if can obtain having introduced the method for the cationic macromolecular compound of  (1) of ormal weight, then the  cation is to containing acidic groups and constitute the carboxyl of unit (a) and/or the replacement of sulfonic proton can being carried out in any stage.

Be generally 30-100 mole % with the carboxyl of  cation replacement macromolecular compound (2) and/or the ratio (hereinafter referred to as "  cation replacement rate ") of sulfonic proton, be preferably 50-100 mole %, more preferably 70-100 mole %.When  cation replacement rate during less than 30 moles of %, carboxyl, sulfonic group and the  of macromolecular compound (1) be cationic to be dissociated lowly, and often swelling power, gelation power are low.

In arbitrary operation of the manufacturing process of the manufacturing process of above-mentioned macromolecular compound (2) or macromolecular compound (1) or operation thereafter, carry out crosslinkedly, form the crosslinked body (A) of macromolecular compound (1).As crosslinked method can be known method, for example can enumerate the method for following (1)-(5).

(1) with the copolymerization crosslinking agent carry out crosslinked

Enable with as the raw material of macromolecular compound (2) contain acidic groups constitute unit (a) and/or contain  cation that acidic groups constitutes unit (a) replace body and use as required other constitute copolymerization crosslinking agent and the material composition copolymerization (following they are generically and collectively referred to as " material composition ") copolymerization or that in molecule, have two keys more than 2 more than a kind or 2 kinds of unit (b), carry out macromolecular compound (2) synthesize before or carry out crosslinked method when synthetic.As the copolymerization crosslinking agent, for example list polynary vinyl-type crosslinking agent, the N of divinylbenzene etc., polynary (methyl) acrylic ester type crosslinking agent of the polynary allyl ether type crosslinking agent of (methyl) acid/acrylic amide type crosslinking agent of N '-methylene diacrylamine etc., pentaerythritol triallyl ether etc., trimethylolpropane triacrylate etc. etc.

(2) with reactant cross-linker carry out crosslinked

Use in molecule, have more than 2 can with the reactant cross-linker of the functional group of reaction such as the functional group of material composition, carry out macromolecular compound (2) synthetic before or carry out crosslinked method when synthetic.As reactant cross-linker, for example list 4, the multivalent metal salt type crosslinking agent of the halogenated epoxy type crosslinking agent of the polyamine of the polyalcohol type crosslinking agent of the polynary epoxy type crosslinking agent of the multicomponent isocyanate type crosslinking agent of 4 '-methyl diphenylene diisocyanate etc., polyglycerol polyglycidyl ether etc., glycerine etc., hexa, polymine etc., imines type crosslinking agent, chloropropylene oxide etc., aluminum sulfate etc. etc.

(3) with the polymerisation reactivity crosslinking agent carry out crosslinked

Use can with the material composition copolymerization or in molecule, have have in two keys and the molecule can with the polymerisation reactivity crosslinking agent of the functional group of reaction such as the functional group of material composition, carry out macromolecular compound (2) synthetic before or carry out crosslinked method when synthetic.As the polymerisation reactivity crosslinking agent, for example list the pi-allyl epoxy type crosslinking agent etc. of (methyl) glycidyl acrylate type crosslinking agent, allyl glycidyl ether etc. of glycidyl methacrylate etc.

(4) by radiation exposure carry out crosslinked

Radioactive ray to macromolecular compound (1) irradiation ultraviolet radiation, electron beam, gamma-rays etc., macromolecular compound (1) is carried out crosslinked method or to material composition irradiation ultraviolet radiation, electron beam, gamma-rays etc., when carrying out macromolecular compound (2) synthetic, carry out polymerization and crosslinked method simultaneously.

(5) by heating carry out crosslinked

Macromolecular compound (2) or macromolecular compound (1) are heated to more than 100 ℃, at the intermolecular heat cross-linking that carries out of macromolecular compound (2) or macromolecular compound (1), the free radical that for example utilizes heating to produce carries out the crosslinked method between crosslinked, functional group between carbon etc.

Among these cross-linking methods, preferable methods is different and different according to purposes, the form of final products, consider from comprehensive aspect, be (1) with the copolymerization crosslinking agent carry out crosslinked, (2) with reactant cross-linker carry out crosslinked reach (4) by radiation exposure carry out crosslinked.

Among above-mentioned copolymerization crosslinking agent, preferred cross-linking agents is polynary (methyl) acid/acrylic amide type crosslinking agent, allyl ether type crosslinking agent, polynary (methyl) acrylic ester type crosslinking agent, further preferably allyl ether type crosslinking agent.Among above-mentioned reactant cross-linker, preferred cross-linking agents is multicomponent isocyanate type crosslinking agent and polynary epoxy type crosslinking agent, further preferably has the multicomponent isocyanate type crosslinking agent or the polynary epoxy type crosslinking agent of the functional group more than 3 in molecule.

About the degree of cross linking, can select according to application target is suitable, but under the situation of using the copolymerization crosslinking agent, its addition is preferably 0.001-10 weight %, more preferably 0.01-5 weight % with respect to whole material composition weight.

Under the situation of using reactant cross-linker, preferably addition is also different according to what kind of shape crosslinked body (A) is formed for its addition, but be 0.001-10 weight % preferably with respect to whole material compositions, in order to make the incorporate good gel that contains liquid fuel described later, be 0.01-50 weight % especially preferably with respect to whole material compositions.

Material composition, promptly contain acidic groups and constitute unit (a) and/or contain that  cation that acidic groups constitutes unit (a) replaces body and other polymerizations that constitute unit (b) of using as required also can be known method, for example can enumerate: the solution polymerization process that in the solvent of the polymer of above-mentioned each monomer of dissolving and generation, carries out, do not use solvent and the mass polymerization of polymerization, emulsion polymerization etc.Solution polymerization process preferably wherein.

The solvent that under the situation of polymerisation in solution, uses, the selection that can suit according to the dissolubility of the monomer that uses, polymer for example can list aromatic hydrocarbon based etc. the organic solvent, water of the ethers, toluene, dimethylbenzene etc. of the carboxylic acid esters, oxolane, dimethoxy-ethane etc. of the ketone, ethyl acetate etc. of the lactone, acetone, methylethylketone etc. of the lactone, epsilon-caprolactams etc. of the carbonates, gamma-butyrolacton etc. of the alcohols, ethylene carbonate, propylene carbonate, dimethyl carbonate etc. of methyl alcohol, ethanol etc. etc.These solvents can use a kind separately, also can mix more than 2 kinds and use.

Polymerization concentration during polymerisation in solution also is not particularly limited, and distinguishes difference according to the purposes difference of purpose, but is preferably 1-80 weight %, more preferably 5-60 weight %.

Polymerization initiator can be common polymerization initiator, can exemplify out azo series initiators, peroxide series initiators, redox initiator.As the azo series initiators, list azodiisobutyronitrile, azo dicyanogen methyl isophorone valeric acid, azo two (2, the 4-methyl pentane nitrile), two (2-amidine propane) dihydrochlorides of azo, azo two { 2-methyl-N-(2-ethoxy) プロロピオ Application acid amides } etc.As the peroxide series initiators, list benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, succinic acid peroxide, two (2-ethoxyethyl group) peroxy dicarbonate, hydrogen peroxide etc.As redox initiator, list the combination of above-mentioned peroxide series initiators and reducing agent (ascorbic acid, persulfate) etc.

As other polymerization, the radioactive ray that can exemplify out the method, irradiating gamma-ray, electron beam etc. of interpolation light enhanced sensitivity initator [benzophenone etc.] and irradiation ultraviolet radiation etc. carry out method of polymerization etc.

The addition of the initator when using polymerization initiator is not particularly limited, but with respect to the total weight of the material composition that uses, is preferably 0.0001-5 weight %, more preferably 0.001-2 weight %.

Polymerization temperature is also different and all ground is different according to the boiling point of the solvent of the decomposition temperature of target molecular weight, initator, use etc., but is preferably-20 ℃ to 200 ℃, more preferably 0～100 ℃.

Crosslinked body (A) like this has the ability of absorption liquid fluid fuel, and the absorption liquid fluid fuel forms stable fuel composition.

The liquid fuel uptake of crosslinked body (A) is according to as differences such as the composition of the kind of the fuel of object, crosslinked body (A) or gel strengths and change allly.Crosslinked body (A) for example is preferably designed for the crosslinked body of 10～1000g methyl alcohol/g (A) to the uptake of methyl alcohol, further is preferably designed for 50～900g/g.If this uptake is more than the 10g/g, it is abundant then to protect liquid measure, storage efficient excellence.When being 1000g/g when following, there is not the weak excessively problem of gel strength of the fuel composition that keeps liquid fuel.

To form under the granular situation based on the crosslinked body (A) of the 4th mode, its particle diameter is represented with volume average particle size, is preferably 0.1-5,000 μ m, more preferably 50～2,000 μ m.In addition, preferably the particle less than 0.1 μ m is below the 10 weight % of integral body, and the part that surpasses 5,000 μ m is below the 10 weight % of integral body, and further preferred both are below 5%.

The mensuration of particle diameter, can adopt Luo Taipu testing sieve bobbing machine and JIS Z8801-2000 standard screen, and the 6th edition (マッ Network グロ one ヒ Le Block ッ Network カ Application パニ one of employing ペリ one ズケミカ Le エ Application ジニア, one ズ Ha Application De Block ッ Network, 1984,21 pages) method of record carries out the mensuration of the following particle diameter (adopt this method).

As the method that crosslinked body (A) is formed granular form, as long as finally become graininess, just be not particularly limited, for example list the method that following (i)-(iv) waits.

(i) use solvent with the copolymerization of above-mentioned copolymerization crosslinking agent as required, make the crosslinked body (A) of macromolecular compound (1), adopt the method for drying etc. to heat up in a steamer as required and desolvate, use known breaking method to pulverize, thereby form granular method.

(ii) use solvent to carry out polymerization as required, make macromolecular compound (1), the method that then adopts above-mentioned reactant cross-linker or irradiation etc. with macromolecular compound (1) crosslinked after, adopting the method for drying etc. to heat up in a steamer as required desolvates, use known breaking method to pulverize, thereby form granular method.

(iii) in the presence of above-mentioned copolymerization crosslinking agent, using solvent will contain acidic groups as required constitutes unit (a), as required other and constitutes unit (b) and carry out after copolymerization, crosslinked, the producing high-molecular, add above-mentioned  cationic compound, the proton of acidic group is replaced to after the  cation of ormal weight, adopting the method for drying etc. to heat up in a steamer as required desolvates, use known breaking method to pulverize, thereby form granular method.

(iv) in the presence of above-mentioned copolymerization crosslinking agent, use solvent will contain that acidic groups constitutes unit (a), as required other constitute unit (b) and carry out copolymerization as required, form after the uncrosslinked macromolecule, adopt above-mentioned  cationic compound and reactant cross-linker or carry out radiation exposure, when the proton of acidic group is replaced, macromolecule is crosslinked, adopting the method for drying etc. to heat up in a steamer as required desolvates, use known breaking method to pulverize, thereby form granular method.

In above-mentioned method, form the drying of carrying out as required in the granular process in shape with crosslinked body (A), can be known drying means, for example can list ventilation dry (circulated air drying machine etc.), ventilative dry (band drier etc.), drying under reduced pressure (drying under reduced pressure machine etc.), contact drying (drum dryer etc.) etc.

Baking temperature when carrying out drying only otherwise cause the deterioration of polymer etc., excessive crosslinkedly just be not particularly limited, is preferably 0～200 ℃, more preferably 50-150 ℃.

The shape of crosslinked body (A) is formed under the granular situation, breaking method also can be a known method, for example can list the method that impact comminution (the high speed rotating type pulverizer of pin mill, cutter mill, ball milling type pulverizer, ACM flour mill etc. etc.), air are pulverized (jet mill etc.), freezed to pulverize etc.

The fuel composition that comprises crosslinked body (A) and fuel can be processed into all forms according to its purpose, its shape is not particularly limited, but can enumerates the form of graininess, sheet, one gelation as preferred form.

The following creating method of the preferred form of explanation, but therefore also some difference such as different its creating methods of the form of based on fuel composition etc., preferable methods describes its each.

Granular fuel composition both can be the fuel composition that granular crosslinked body (A) absorption liquid fluid fuel forms, and also can be to form granular fuel composition behind the absorption liquid fluid fuel.Making granular method can be identical with the method for making above-mentioned granular crosslinked body (A), and its volume average particle size etc. also is preferably same value.

Fuel composition is being formed under the situation of sheet, as its sheet method, for example can enumerate following (v)～(method vii).

(v) between nonwoven fabrics, paper etc., sandwich granular crosslinked body (A), form interlayer sheet, make it the method for absorption liquid fluid fuel thereafter;

(vi) after the ground that constitutes more than a kind or 2 kinds by nonwoven fabrics, woven cloths, paper, film infiltrates and/or applies the uncrosslinked body of macromolecular compound (1), the cross-linking method more than a kind or 2 kinds of employing selection from crosslinked, the heating of crosslinked, the above-mentioned radiation exposure of above-mentioned crosslinking agent crosslinked makes macromolecular compound (1) crosslinked, simultaneously heat up in a steamer as required to desolvate and carried out making it the method for absorption liquid fluid fuel after the sheetization.

(vii) to by nonwoven fabrics, woven cloths, paper, the ground that constitutes more than a kind or the 2 kinds infiltration of film and/or apply comprise with above-mentioned  cation replaced 30-100 mole % proton contain acidic groups formation unit (a) 20-100 weight %, other constitute unit (b) 0-80 weight %, after the mixed solution of above-mentioned crosslinking agent, employing is crosslinked from irradiations such as polymerization initiator and/or radioactive ray, the crosslinked middle cross-linking method of selecting more than a kind or 2 kinds of heating carries out polymerization on this ground, heat up in a steamer as required and desolvate, carried out thus making it the method for absorption liquid fluid fuel after the sheetization.

Among these methods, from the viewpoint of the infiltration rate of the adjustment easness of the thickness of the sheet that makes, the sheet that makes etc., preferred (vi) or (vii).The thickness that shape is formed the fuel composition sheet under the situation of sheet is preferably 1-50,000 μ m, and 5-30 more preferably, 000 μ m is preferably 10-10 especially, 000 μ m.When the thickness of sheet is 1 μ m when above, the order amount of paying of crosslinked body (A) can be not very few, and when being 50,000 μ m when following, the thickness of sheet can be not blocked up.About length, the width of sheet, can suit to select according to the size of using, be not particularly limited, but preferred length is 0.01-10,000m, preferred width is 0.1-300cm.

The order amount of paying about the crosslinked body (A) in the fuel composition sheet is not particularly limited, but be considered as the liquid fuel of object the absorption liquid-keeping property, to also have thickness not want blocked up etc., the order amount of paying is preferably 10-3,000g/m ², 20-1 more preferably, 000g/m ²

In the 4th mode, be sheet in order to make form, the ground of the nonwoven fabrics of Shi Yonging, woven cloths, paper, film etc. can be known as required, for example can enumerate the order amount of paying is 10-500g/m ²About the nonwoven fabrics that comprises synthetic fibers and/or natural fiber or woven cloths, paper (changing slurry paper, tissue paper and paper etc. entirely), comprise film and their ground more than 2 kinds and their complex of synthetic resin.

Among these grounds, the complex of nonwoven fabrics or nonwoven fabrics and plastic film or metal film preferably particularly preferably is the complex of nonwoven fabrics, nonwoven fabrics and plastic film.

Thickness for these grounds is not particularly limited, and is generally 1-50, and 000 μ m is preferably 10-20,000 μ m.When thickness during less than 1 μ m, be difficult to infiltrate, apply the above-mentioned macromolecular compound (1) of ormal weight, when thickness surpassed 50,000 μ m, sheet was blocked up, and when forming the fuel composition that contains fuel cell-use fuel, it is big that whole volume becomes, and is difficult to use.

Painting method, the infiltration method of macromolecular compound (1) on ground can be known method, and the method for for example be suitable for common coating, padding etc. gets final product.Apply, pad after the processing, can adopt the method for drying etc. to heat up in a steamer the solvent that uses for polymerization, dilution, adjustment viscosity etc. as required.

Fuel uptake in the sheet fuel composition (fuel amount) if can guarantee fully that the amount of the quantity delivered of fuel then is not particularly limited, is preferably 0.1-500g fuel/cm ²Sheet, more preferably 1-400g/cm ²When uptake is 0.1g/cm ²When above, can absorb the liquid fuel of q.s, when uptake is 500g/cm ²When following, the sheet of absorption liquid fluid fuel can be not blocked up.

Based on the fuel composition of the 4th mode, also can be the one gelation type fuel composition that comprises crosslinked body (A) and liquid fuel.The ratio of crosslinked body (the A)/fuel in this one gelation type fuel composition, be preferably 0.1～99/1～99.9 weight %, more preferably 0.5～50/50～99.5 weight % are preferably 1～30/70～99 weight % especially, most preferably are 1～20/80～99 weight %.When the ratio of crosslinked body (A) is that 0.1 weight % is when above, the gel strength that contains Fuel gel that can not occur generating is weak, can not be with the situation of whole gelation, on the other hand, when being that 99 weight % are when following, following unfavorable condition can not appear: because the amount of crosslinked body (A) is too much, therefore the addition of necessary fuel is very few, can not fully guarantee the quantity delivered of fuel.

Creating method as one gelation type fuel composition for example can be (viii) to add the method for the fuel of ormal weight to above-mentioned granular crosslinked body (A); (ix) add the method for fuel to the sheet that contains crosslinked body (A), but preferably these to contain Fuel gel be to make with the method that following (x), (xi) etc. list.

(x) macromolecular compound (1) is dissolved in the liquid fuel, adopts any cross-linking method cross-linked polymer compound (1) of crosslinked, the heat cross-linking of crosslinked, the radiation exposure be selected from above-mentioned crosslinking agent, thus the method for the gel of forming as one;

(xi) in the presence of above-mentioned copolymerization crosslinking agent in the liquid fuel within to the proton that replaced 30-100 mole % with above-mentioned  cation contain acidic groups constitute unit (a) 20-100 weight %, and as required other constitute unit (b) 0-80 weight % and carry out polymerization, the method for forming as one gel thus.

The form that comprises the integrated gel-type fuel composition of crosslinked body (A) and liquid fuel can suit to select, and as shape, for example can exemplify out sheet, bulk, spherical, cylindric etc. shape.Preferred shape is sheet, bulk or cylindric among these shapes.

The thickness of making the gel under the situation of slabbing gel is preferably 1-50,000 μ m, 10-20 more preferably, 000 μ m.About width, the length of sheet gel, wait suitable the selection to get final product according to its application target, place, purposes.

The method that makes the one gelation type fuel composition of desirable shape also is not particularly limited, and for example can enumerate: in the suitable method of closing in the shapes of containers that will make, making it gelation in the box; Employing method stacked or that apply the mixture or the like of above-mentioned macromolecular compound (1) or material composition etc. and liquid fuel on processing release paper, film, nonwoven fabrics etc. forms sheet, makes the method for gel; Or the like.

In addition, also can in the fuel composition of this scheme, cooperate the gelating agent (fatty acid soaps that is selected from other as required; dibenzyl sorbitol; hydroxypropyl cellulose; the benzal D-sorbite; carboxyl vinyl polymer; polyethylene glycol; polyoxyalkylene; D-sorbite; NC Nitroncellulose; methylcellulose; ethyl cellulose; the acetyl group butyl cellulose; polyethylene; polypropylene; polystyrene; ABS resin; the AB resin; acrylic resin; acetal resin; Merlon; nylon; phenol resin; phenoxy resin; carbamide resin; alkyd resins; polyester; epoxy resin; diallyl phthalate resin; polyallmer etc.); adsorbent (dextrin; glucan; silica gel; silicon dioxide; aluminium oxide; molecular sieve; kaolin; diatomite; carbon black; active carbon etc.); tackifier; binding agent; to fuel carry out chemical conversion make it in the material of non-currentization more than a kind or 2 kinds.These materials then are not particularly limited if can bring into play separately function, no matter be that solid or liquid can.In addition, these materials can cooperate in the stage arbitrarily that makes fuel composition.

[3] discharge the method for fuel cell-use fuel from fuel composition

In the 4th mode, when the fuel composition that absorbs fuel composition that fuel cell-use fuel forms or the like at the fuel composition of the molecular compound that comprises fuel cell-use fuel from above-mentioned [1] or [2] polymer discharges fuel cell-use fuel, by this fuel composition is contacted with water, make fuel cell-use fuel in the fuel composition to the stripping of water side, thereby discharge fuel.

In this case, water can be the aqueous solution of fuel cell-use fuel.In addition, when fuel composition contacts with water, not to be necessary heating especially, can be normal temperature, but also can be heated to about 50-150 ℃.

Be not particularly limited as the method that fuel composition is contacted with water, for example list: the introducing port with water and outlet, can be in the container of inner water flowing the filling fuel composition, in this container, feed the method for water then.In addition, also can be in tank, to drop into fuel composition, the method that fuel is emitted.

Be discharged into fuel the water from fuel composition, the fuel aqueous solution of the concentration that modulation and application target adapt to, the fuel aqueous solution about for example 1-64 weight % are supplied with to fuel cell then and are got final product.

According to the 4th mode, for example adopt in the container of having filled fuel composition the very easy method that feeds water etc., do not need heater, heat energy just can easily discharge fuel cell-use fuel from the fuel composition that comprises fuel cell-use fuel.

Therefore, the fuel cell-use fuel of operating difficulties is formed the fuel composition that comprises fuel cell-use fuel, can store safely and stably, and, can obtain fuel cell-use fuel easily and at an easy rate from this fuel composition, industrial be very favourable.

In addition, among the fuel cell-use fuel, the stoste of methyl alcohol is equivalent to the violent in toxicity of violent in toxicity regulation law, also be equivalent to dangerous position 4 classes or the like, need in the operation to give one's full attention to, and also there is the problem of corrosion etc. in high concentration methanol, owing to above-mentioned or the like reason, when methyl alcohol being acted as a fuel use, the aqueous solution of making usually about 10-30 weight % uses.In the 4th mode, fuel composition is contacted with water, thereby the fuel in the fuel composition is discharged in the water, fuel can be made the aqueous solution of debita spissitudo thus, and to the fuel cell supply, at that point, the method for releasing of the 4th mode is industrial also very favourable.

The 4th mode, as being useful from solid macromolecular electrolyte type fuel cell, the method that particularly discharges fuel as the portable fuel composition that direct-type methanol fuel cell likely is used with small fuel cell, but be not limited to this, applicable to emitting fuel from the various fuel compositions that contains fuel cell-use fuel.

Below enumerate Production Example and embodiment the 4th mode more specifically is described, but the 4th mode, only otherwise exceed its main idea, be not limited to following embodiment.

Production Example 1

With 1,1-bis(4-hydroxyphenyl)cyclohexane (following brief note is " BHC ") 26.8g (0.1mol) heating for dissolving is in methyl alcohol 50ml, by carrying out crystallization again, obtained BHC: methyl alcohol=1: 1 (mol ratio), methyl alcohol containing ratio are the methyl alcohol inclusion compound of the solid, shaped of 11 weight %.

Production Example 2

With 1,1,6,6-tetraphenyl own-2,4-diine-1,6-glycol (following brief note is " TPHDD ") 41.4g (0.1mol) heating for dissolving is in methyl alcohol 100ml, and by carrying out crystallization again, obtained TPHDD: methyl alcohol=1: 2 (mol ratio), methyl alcohol containing ratio are the methyl alcohol inclusion compound of the solid, shaped of 13 weight %.

Production Example 3

With 1,1,2,2-four (4-hydroxy phenyl) ethane (following brief note is " THPE ") 39.8g (0.1mol) heating for dissolving is in methyl alcohol 100ml, by carrying out crystallization again, obtained THPE: methyl alcohol=1: 2 (mol ratio), methyl alcohol containing ratio are the methyl alcohol inclusion compound of the solid, shaped of 14 weight %.

Production Example 4

Acrylic acid 360g (5 moles) and pentaerythritol triallyl ether 1.08g and water 1140g are packed in 2 liters the adiabatic polymerisation groove.The temperature of monomer solution is cooled to 0 ℃, logical nitrogen in solution makes after the dissolved oxygen reduction, adds polymerization initiator 2, two (2-amidine propane) the hydrochloride 0.36g of 2 '-azo and 35 weight % aqueous hydrogen peroxide solution 3.1g and L-ascorbic acid 0.38g, the beginning polymerization.After the polymerization, use mincer with after the aqueous gel sectionalization that generates, in this gel, add 1,2,3, (molecular weight: 60% methanol solution 203) (Sanyo changes into industrial group's system) 1353g (4 moles) observes decarbonate and separating methanol has taken place the cationic methylcarbonate of 4-tetramethyl imidazoline .Use band drier (ventilative drying machine, aboveground metal company system) to the methyl alcohol that has added the penetrating 100 ℃ hot blast of the cationic gel of above-mentioned imidazoline , heated up in a steamer the water that is used as solvent and by-product and carry out drying.Use cutter mill that dry thing is pulverized, make the crosslinked body of graininess of average grain diameter 400 μ m, make to absorb 100g methyl alcohol among this crosslinked body 20g, obtained the gel fuel composition.

Embodiment 17

Made electrolyte film-electrode joint (MEA) at first, as described below.As dielectric film, used the amberplex Nafion of perfluorinated sulfonic acid system.Catalyst-loaded use Pt particle in order to have electronic conductivity, makes it to be supported on the acetylene black.The Pt loading is 50 weight % with respect to acetylene black.Mix the catalyst-loaded and 5 weight %Nafion solution of this Pt, adopt the spraying brush method to spray on the dielectric film, make dielectric film adhere to electrode layer.The film that has adhered to electrode layer at 90 ℃ down after dry 1 hour, is lived with the teflon plate holder in drying machine, adopts hot press with 130 ℃, 20MPa pressurization 30 minutes, makes dielectric film and electrode engagement.

The electrolyte film-electrode joint of use (MEA) as shown in Figure 7, has been assembled the direct-type methanol fuel cell system of supplying with methanol aqueous solution.In Fig. 7,61 is dielectric film, and 62 is electrode (anode), and 63 is electrode (negative electrode), and 64 is the fuel composition groove, and 65 is tank.

In fuel composition groove 64, be enclosed in the methyl alcohol inclusion compound of making in the Production Example 1, to the water of these fuel composition groove 64 supplies from tank 65, the methyl alcohol inclusion compound is contacted with water, methyl alcohol is discharged in the water, modulate the methanol aqueous solution of 20 weight %, and give the fuel absorber of electrolyte film-electrode joint.In addition, anode 62 use and the recycle-water of methanol concentration step-down by CO ₂Be circulated in this tank 65 also passable after removal device is handled.The water that negative electrode 63 generates reclaims and supply with tank 65 also can.

Its result can stably supply with methanol aqueous solution to fuel cell, can move steadily in the long term and generate electricity.

Methyl alcohol inclusion compound that use is made in Production Example 2,3 or the gel fuel composition of in Production Example 4, making act as a fuel composition situation too.

Know from above result, contact with water, fuel cell-use fuel easily is discharged in the water by making fuel composition, can be to fuel cell fueling stably.

Claims

1. a fuel cell-use fuel is characterized in that, the organic system fuel that uses in fuel cell forms the molecular compound of solid, shaped.

2. fuel cell-use fuel according to claim 1 is characterized in that, this fuel cell is a solid macromolecular electrolyte type fuel cell.

3. fuel cell-use fuel according to claim 2 is characterized in that, this fuel cell is the direct-type methanol fuel cell.

4. fuel cell-use fuel according to claim 1 is characterized in that, this fuel cell is the portable small fuel cell of using.

5. fuel cell-use fuel according to claim 1 is characterized in that, this organic system fuel is to be selected from more than a kind or 2 kinds of alcohols, ethers, hydro carbons and acetals.

6. fuel cell-use fuel according to claim 5, it is characterized in that organic system fuel is to be selected from more than a kind or 2 kinds of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol, dimethyl ether, ethyl methyl ether, diethyl ether, propane, butane, dimethoxymethane and trimethoxy-methane.

7. fuel cell-use fuel according to claim 1 is characterized in that, the molecular compound of this solid, shaped inclusion compound that this organic system fuel and host compound form of serving as reasons.

8. fuel cell-use fuel according to claim 7 is characterized in that this host compound is supported on the porous metallic substance.

9. fuel cell-use fuel according to claim 7 is characterized in that, this host compound is to be selected from more than a kind or 2 kinds of organic compound, inorganic compound and organic-inorganic complex chemical compound.

10. fuel cell-use fuel according to claim 7 is characterized in that, this host compound is to be selected from unimolecule system, polymolecular system and more than a kind or 2 kinds of macromolecular host compound.

11. fuel cell-use fuel according to claim 10, it is characterized in that, host compound is to be selected from more than a kind or 2 kinds of following compound: urea, 1,1,6,6-tetraphenyl own-2,4-diine-1, the 6-glycol, 1,1-two (2, the 4-3,5-dimethylphenyl)-2-propine-1-alcohol, 1,1,4,4-tetraphenyl-2-butine-1, the 4-glycol, 1,1,6,6-four (2, the 4-3,5-dimethylphenyl)-2,4-hexadiine-1, the 6-glycol, 9,10-diphenyl-9,10-dihydroanthracene-9, the 10-glycol, 9, two (the 4-aminomethyl phenyls)-9 of 10-, 10-dihydroanthracene-9, the 10-glycol, 1,1,2,2-tetraphenyl ethane-1, the 2-glycol, the 4-metoxyphenol, 2, the 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 4,4 '-sulphonyl bis-phenol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-ethylidene bis-phenol, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, 1,1,2,2-four (3-methyl-4-hydroxy phenyl) ethane, 1,1,2,2-four (3-fluoro-4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-to ditolyl, four (p-methoxyphenyl) ethene, 3,6,3 ', 6 '-tetramethoxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrem acyloxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrahydroxy-9,9 '-Lian-9H-xanthene, gallic acid, gallicin, the acid of the youngster bitter edible plant, connection-betanaphthol, α, α, α ', α '-tetraphenyl-1,1 '-biphenyl-2,2 '-dimethanol, the two dicyclohexyl acid amides of diphenic acid, the two dicyclohexyl acid amides of fumaric acid, cholic acid, deoxycholic acid, 1,1,2,2-tetraphenyl ethane, four (to iodine substituted phenyl) ethene, 9,9 '-dianthranide, 1,1,2,2-four (4-carboxyl phenyl) ethane, 1,1,2,2-four (3-carboxyl phenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenyl imidazoles, 1,2,4,5-tetraphenyl imidazoles, 2-phenyl phenanthro-[9,10-d] imidazoles, 2-(adjacent cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(to cyano-phenyl) phenanthro-[9,10-d] imidazoles, quinhydrones, the 2-tertiary butylated hydroquinone, 2, the 5-di-tert-butyl hydroquinone, and 2, two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-.

12. fuel cell-use fuel according to claim 10 is characterized in that, host compound is to be selected from phenol owner body compound, acid amides owner body compound and more than a kind or 2 kinds of imidazoles owner body compound.

13. fuel cell-use fuel according to claim 12, it is characterized in that, host compound is to be selected from more than a kind or 2 kinds of following compound: 1, and 1-bis(4-hydroxyphenyl)cyclohexane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, diphenic acid two (dicyclohexyl acid amides), the two dicyclohexyl acid amides of fumaric acid and 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles.

14. the supply method of a fuel cell-use fuel is characterized in that, accessory rights requires 1 described fuel cell-use fuel to discharge above-mentioned organic system fuel, and supplies with to the fuel electrodes of fuel cell.

15. the supply method of fuel cell-use fuel according to claim 14 is characterized in that, by heating this fuel cell-use fuel, above-mentioned organic system fuel is discharged.

16. the supply method of fuel cell-use fuel according to claim 14 is characterized in that, contacts with water by making this fuel cell-use fuel, and above-mentioned organic system fuel is discharged in this water.

17. the amount detection method of the fuel material in the fuel cell-use fuel composition, it is characterized in that, it is the method that detects the amount of this fuel material in the fuel cell-use fuel composition of the molecular compound contain fuel cell-use fuel material and matching side compound, wherein, detect the amount of this fuel material by the index properties of this molecular compound of contrast and/or matching side compound and the index properties of this fuel composition.

18. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 17 is characterized in that, this index properties is a color.

19. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 17 is characterized in that this matching side compound has the functional group of color rendering.

20. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 17 is characterized in that, this fuel cell is a solid macromolecular electrolyte type fuel cell.

21. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 20 is characterized in that, this fuel cell is the direct-type methanol fuel cell.

22. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 17 is characterized in that, this fuel cell is the portable small fuel cell of using.

23. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 17 is characterized in that, this fuel material is to be selected from more than a kind or 2 kinds of hydrogen, alcohols, ethers, hydro carbons and acetals.

24. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 23, it is characterized in that this fuel material is to be selected from more than a kind or 2 kinds of hydrogen, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol, dimethyl ether, ethyl methyl ether, diethyl ether, propane, butane, dimethoxymethane and trimethoxy-methane.

25. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 23 is characterized in that, this molecular compound inclusion compound that this fuel material and host compound form of serving as reasons.

26. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 25 is characterized in that this host compound is supported on the porous metallic substance.

27. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 25 is characterized in that, this host compound is to be selected from more than a kind or 2 kinds of organic compound, inorganic compound and organic-inorganic complex chemical compound.

28. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 25 is characterized in that, this host compound is to be selected from unimolecule system, polymolecular system and more than a kind or 2 kinds of macromolecular host compound.

29. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 25, it is characterized in that, the host compound of the functional group of color rendering is represented, introduced to this host compound with following general formula (1) in imidazoles

[general formula 1]

(1) in the formula, R ¹, R ²Can difference also can be identical, represent hydrogen atom, methoxyl group, amino, dimethylamino, nitro or halogen atom separately; R ³Expression nitro, cyano group, ethoxy carbonyl, acetyl group or formoxyl; R ⁴, R ⁵Represent hydrogen atom respectively or the base of the formation fused rings of representing to mutually combine; R ⁶The alkyl of expression hydrogen atom, carbon number 1-4, phenyl or with the phenyl of the replacement more than a kind or 2 kinds that is selected from methoxyl group, amino, dimethylamino, nitro or halogen atom.

30. the amount detection method of the fuel material in the fuel cell-use fuel composition according to claim 29, it is characterized in that, imidazoles owner body compound with above-mentioned general formula (1) expression is to be selected from more than a kind or 2 kinds of following compound: 4,5-two (4-methoxyphenyl)-2-(2-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone) imidazoles, 4,5-two (4-aminophenyl)-2-(2-nitrobenzophenone) imidazoles, 4,5-two (4-aminophenyl)-2-(3-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone) imidazoles, 4,5-two (4-methoxyphenyl)-2-(2-nitrobenzophenone)-1-methylimidazole, 4,5-two (4-methoxyphenyl)-2-(3-nitrobenzophenone)-1-methylimidazole, 4,5-two (4-methoxyphenyl)-2-(4-nitrobenzophenone)-1-methylimidazole, 2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 2-(3-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(3-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-methyl-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-phenyl-2-(2-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-phenyl-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles, 1-(4-nitrobenzophenone)-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles and 1-(4-methoxyphenyl)-2-(4-nitrobenzophenone) phenanthro-[9,10-d] imidazoles.

31. a solid electrolyte fuel cell fuel is characterized in that, comprises the liquid organic-fuel and forms the compound of complex or molecular compound with this liquid organic-fuel.

32. solid electrolyte fuel cell fuel according to claim 31, it is characterized in that, with the compound of aforesaid liquid organic-fuel formation complex or molecular compound, be at least a kind of compound selecting the compound beyond sulfuric acid, carbohydrate, alcohols, amine and strong electrolyte class.

33. solid electrolyte fuel cell fuel according to claim 32, it is characterized in that, with the compound of aforesaid liquid organic-fuel formation complex or molecular compound, be from crown ether-like, the cryptand class, the cyclophane class, azepine cyclophane class, calixarene kind, シ Network ロトリベラトリレ Application class, ス Off ェラ Application De class, the oligopeptide class, cyclic oligomer peptide class, the urea class, Thiourea, the deoxycholic acid class, perhydrogenate benzophenanthrene class, three-neighbour-チモチ De class, the dianthranide class, spiral shell two fluorenes classes, ring phosphonitrile class, the hydroxy benzophenone ketone, phenol, bisphenols, three phenols, four phenols, Polyphenols, aphthols, the dinaphthyl phenols, the carboxylic acyloxy amine, thioamide analog, connection xanthene class, at least a kind of compound selecting in carboxylic acids and the hydroquinones.

34. solid electrolyte fuel cell fuel according to claim 33, it is characterized in that, compound with aforesaid liquid organic-fuel formation complex or molecular compound, be from urea, thiocarbamide, deoxycholic acid, cholic acid, 2, the 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, the 4-metoxyphenol, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 4,4 '-sulphonyl bis-phenol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-ethylidene bis-phenol, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, 1,1,2,2-four (3-methyl-4-hydroxy phenyl) ethane, 1,1,2,2-four (3-fluoro-4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-paraxylene, four (p-methoxyphenyl) ethene, 3,6,3 ', 6 '-tetramethoxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrem acyloxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrahydroxy-9,9 '-Lian-9H-xanthene, gallic acid, gallicin, catechuic acid, two-betanaphthol, the two dicyclohexyl acid amides of diphenic acid, the two dicyclohexyl acid amides of fumaric acid, 1,1,2,2-tetraphenyl ethane, four (to iodine substituted phenyl) ethene, 9,9 '-dianthranide, 1,1,2,2-four (4-carboxyl phenyl) ethane, 1,1,2,2-four (3-carboxyl phenyl) ethane, acetylenedicarboxylic acid, quinhydrones, the 2-tertiary butylated hydroquinone, 2,5-di-tert-butyl hydroquinone and 2, select in two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-more than a kind or 2 kinds.

35. solid electrolyte fuel cell fuel according to claim 33, it is characterized in that, form the compound of complex or molecular compound with the aforesaid liquid organic-fuel, be from phenol system compound, hydroquinones and amide-type, select more than a kind or 2 kinds.

36. solid electrolyte fuel cell fuel according to claim 35, it is characterized in that, with the compound of aforesaid liquid organic-fuel formation complex or molecular compound, be from 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2, select in the two dicyclohexyl acid amides of 2-four (4-hydroxy phenyl) ethene, quinhydrones and fumaric acid more than a kind or 2 kinds.

37. solid electrolyte fuel cell fuel according to claim 31, it is characterized in that, the aforesaid liquid organic-fuel be from alcohols, ethers, cycloalkane, have hydrophilic group cycloalkane, and cycloalkane replace select the body more than a kind or 2 kinds.

38. according to the described solid electrolyte fuel cell fuel of claim 37, it is characterized in that, the aforesaid liquid organic-fuel be from one of methyl alcohol, ethanol, propyl alcohol, dimethyl ether, cyclohexane, cycloalkane, cycloalkane with hydroxyl, carboxyl, amino or amide groups replace two of body and cycloalkane replace select the bodies more than a kind or 2 kinds.

39. solid electrolyte fuel cell fuel according to claim 31 is characterized in that, as solvent, comprises water and/or alcohols, this solid electrolyte fuel cell is 5-90 weight % with the concentration of the liquid organic-fuel in the fuel.

40. solid electrolyte fuel cell fuel according to claim 31, it is characterized in that this solid electrolyte fuel cell is 0.001-1mol/L with the compound concentrations with aforesaid liquid organic-fuel formation complex or molecular compound in the fuel.

41. solid electrolyte fuel cell fuel according to claim 31 is characterized in that, the pH value is 4-8.

42. the using method of a solid electrolyte fuel cell, it is characterized in that, be possess fuel electrodes, oxidizing agent pole, with the using method of the solid electrolyte fuel cell of the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping, in this using method, supply with the described solid electrolyte fuel cell fuel of claim 31 to above-mentioned fuel electrodes.

43. a solid electrolyte fuel cell is characterized in that, possesses fuel electrodes, oxidizing agent pole, with the solid electrolyte film and the described solid electrolyte fuel cell fuel of claim 31 of this fuel electrodes and oxidizing agent pole clamping.

44. solid electrolyte fuel cell, it is characterized in that, in possessing fuel electrodes, oxidizing agent pole, solid electrolyte fuel cell, possess to above-mentioned fuel electrodes and supply with the fuel supply system of the described solid electrolyte fuel cell of claim 31 with fuel with the solid electrolyte film of this fuel electrodes and oxidizing agent pole clamping.

45. according to the described solid electrolyte fuel cell of claim 44, it is characterized in that also further possessing: reclaim the fuel of discharging from above-mentioned fuel electrodes retracting device, adjust the fuel that reclaims by this retracting device the aforesaid liquid organic-fuel and with this liquid organic-fuel forms complex or molecular compound compound concentrations concentration regulator and will adjust the conveying device of the fuel of concentration with above-mentioned concentration regulator to above-mentioned feedway conveying.

46. method that discharges fuel from the fuel cell-use fuel composition, it is characterized in that, be the method that discharges fuel from the fuel composition that contains fuel cell-use fuel, wherein, in this water, discharge this fuel by this fuel cell-use fuel composition is contacted with water.

47., it is characterized in that this fuel cell is a polymer electrolyte fuel cell according to the described method of claim 46 from fuel cell-use fuel composition release fuel.

48., it is characterized in that this fuel cell is the direct-type methanol fuel cell according to the described method of claim 47 from fuel cell-use fuel composition release fuel.

49., it is characterized in that this fuel cell is the portable small fuel cell of using according to the described method of claim 46 from fuel cell-use fuel composition release fuel.

50., it is characterized in that this fuel cell-use fuel is to be selected from more than a kind or 2 kinds of hydrogen, alcohols, ethers, hydro carbons and acetals according to the described method of claim 46 from fuel cell-use fuel composition release fuel.

51. according to the described method that discharges fuel from the fuel cell-use fuel composition of claim 50, it is characterized in that this fuel cell-use fuel is to be selected from more than a kind or 2 kinds of hydrogen, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethylene glycol, dimethyl ether, ethyl methyl ether, diethyl ether, propane, butane, dimethoxymethane and trimethoxy-methane.

52., it is characterized in that this fuel cell-use fuel composition comprises the molecular compound of fuel cell-use fuel and matching side compound according to the described method of claim 46 from fuel cell-use fuel composition release fuel.

53. discharge the method for fuel from the fuel cell-use fuel composition, it is characterized in that the molecular compound of this fuel cell-use fuel inclusion compound that this fuel cell-use fuel and host compound form of serving as reasons according to claim 52 is described.

54., it is characterized in that this host compound is being supported by the porous metallic substance according to the described method of claim 53 from fuel cell-use fuel composition release fuel.

55., it is characterized in that this host compound is to be selected from more than a kind or 2 kinds of organic compound, inorganic compound and organic-inorganic complex chemical compound according to the described method of claim 53 from fuel cell-use fuel composition release fuel.

56., it is characterized in that this host compound is to be selected from unimolecule system, polymolecular system and more than a kind or 2 kinds of macromolecular host compound according to the described method of claim 53 from fuel cell-use fuel composition release fuel.

57. according to the described method that discharges fuel from the fuel cell-use fuel composition of claim 56, it is characterized in that, this host compound is to be selected from more than a kind or 2 kinds of following compound: urea, 1,1,6,6-tetraphenyl own-2,4-diine-1, the 6-glycol, 1,1-two (2, the 4-3,5-dimethylphenyl)-2-propine-1-alcohol, 1,1,4,4-tetraphenyl-2-butine-1, the 4-glycol, 1,1,6,6-four (2, the 4-3,5-dimethylphenyl)-2,4-hexadiine-1, the 6-glycol, 9,10-diphenyl-9,10-dihydroanthracene-9, the 10-glycol, 9, two (the 4-aminomethyl phenyls)-9 of 10-, 10-dihydroanthracene-9, the 10-glycol, 1,1,2,2-tetraphenyl ethane-1, the 2-glycol, the 4-metoxyphenol, 2, the 4-dihydroxy benaophenonel, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 4,4 '-sulphonyl bis-phenol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 4,4 '-ethylidene bis-phenol, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, 1,1,2,2-four (3-methyl-4-hydroxy phenyl) ethane, 1,1,2,2-four (3-fluoro-4-hydroxy phenyl) ethane, α, α, α ', α '-four (4-hydroxy phenyl)-paraxylene, four (p-methoxyphenyl) ethene, 3,6,3 ', 6 '-tetramethoxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrem acyloxy-9,9 '-Lian-9H-xanthene, 3,6,3 ', 6 '-tetrahydroxy-9,9 '-Lian-9H-xanthene, gallic acid, gallicin, catechuic acid, connection-betanaphthol, α, α, α ', α '-tetraphenyl-1,1 '-biphenyl-2,2 '-dimethanol, the two dicyclohexyl acid amides of diphenic acid, the two dicyclohexyl acid amides of fumaric acid, cholic acid, deoxycholic acid, 1,1,2,2-tetraphenyl ethane, four (to iodine substituted phenyl) ethene, 9,9 '-dianthranide, 1,1,2,2-four (4-carboxyl phenyl) ethane, 1,1,2,2-four (3-carboxyl phenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenyl imidazoles, 1,2,4,5-tetraphenyl imidazoles, 2-phenyl phenanthro-[9,10-d] imidazoles, 2-(adjacent cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles, 2-(to cyano-phenyl) phenanthro-[9,10-d] imidazoles, quinhydrones, the 2-tertiary butylated hydroquinone, 2, the 5-di-tert-butyl hydroquinone, and 2, two (2, the 4-3,5-dimethylphenyl) quinhydrones of 5-.

58., it is characterized in that this host compound is to be selected from phenol owner body compound, acid amides owner body compound, more than a kind or 2 kinds of imidazoles owner body compound according to the described method of claim 56 from fuel cell-use fuel composition release fuel.

59. according to the described method that discharges fuel from the fuel cell-use fuel composition of claim 58, it is characterized in that, this host compound is to be selected from more than a kind or 2 kinds of following compound: 1, and 1-bis(4-hydroxyphenyl)cyclohexane, 1,1,2,2-four (4-hydroxy phenyl) ethane, 1,1,2,2-four (4-hydroxy phenyl) ethene, diphenic acid two (dicyclohexyl acid amides), the two dicyclohexyl acid amides of fumaric acid and 2-(cyano-phenyl) phenanthro-[9,10-d] imidazoles.

60. according to the described method of claim 46, it is characterized in that this fuel cell-use fuel composition comprises the crosslinked body (A) and the fuel cell-use fuel of following macromolecular compound (1) from fuel cell-use fuel composition release fuel,

Macromolecular compound (1): in molecule, have in the macromolecular compound that (hereinafter referred to as " contain acidic groups constitute unit (a) ") polymerization of carboxyl and/or sulfonic formation unit or copolymerization form the macromolecular compound that this carboxyl of the macromolecular compound (2) that this content that contains that acidic groups constitutes unit (a) is 20-100 weight % and/or the 30-100 mole % of this sulfonic proton form with the replacement of  cation.

61., it is characterized in that this  cation is a quaternary ammonium cation according to the described method of claim 60 from fuel cell-use fuel composition release fuel.

62., it is characterized in that this quaternary ammonium cation is cationic more than a kind or 2 kinds for being selected from fatty family ammonium cation, imidazoles  cation and imidazoline  according to the described method of claim 61 from fuel cell-use fuel composition release fuel.

63. according to the described method that discharges fuel from the fuel cell-use fuel composition of claim 60, it is characterized in that, the contained above-mentioned content that contains acidic groups formation unit (a) of this macromolecular compound (2) is 40-100 weight %, and this macromolecular compound (1) is to replace the macromolecular compound that the 50-100 mole % of the carboxyl of this macromolecular compound (2) and/or sulfonic proton forms with the  cation.