JP2009117282A - Polymer electrolyte fuel cell power generation system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a power generation system capable of obtaining high output, high fuel utilization factor, and having a low load to the environment because of hardly exhausting fuel to the outside of the system in an anion type fuel cell power generation system in which the merit of cost is expected because a catalyst other than platinum is usable. <P>SOLUTION: A fuel cell power generation system is equipped with a polymer electrolyte fuel cell containing an electrolyte membrane-electrode assembly formed by joining an anode to one side of an anion exchange electrolyte membrane through which fuel and water permeate and a cathode to the other side, generating power by supplying fuel to the anode and oxidant gas and water to the cathode; a fuel supply device for supplying fuel to the anode; and an oxidant gas supply device for supplying oxidant gas to the cathode; and a cathode offgas treatment device for removing fuel from cathode offgas exhausted from the cathode of the fuel cell and containing fuel being mixed by permeating through the electrolyte membrane. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a solid polymer electrolyte fuel cell power generation system using a fuel cell using an anion exchange type solid polymer electrolyte.

  The solid polymer fuel cell is a fuel cell using a solid polymer such as an ion exchange resin as an electrolyte. As shown in FIG. 1, the solid polymer fuel cell includes a solid polymer electrolyte membrane 6 in a space in the battery partition wall 1 having a fuel gas flow hole 2 and an oxidant gas flow hole 3 communicating with the outside. The fuel chamber side gas diffusion electrode 4 and the oxidant chamber side gas diffusion electrode 5 are respectively partitioned by a joined body, and a fuel chamber (anode chamber) 7 that communicates with the outside through the fuel gas flow hole 2 and an oxidant It has a basic structure in which an oxidant chamber (cathode chamber) 8 communicating with the outside through the gas flow hole 3 is formed. In FIG. 1, the battery partition wall 1 and the solid polymer electrolyte membrane 6 are separately illustrated for easy understanding of the configuration of each member. However, in actuality, the battery partition 1 and the solid polymer electrolyte membrane 6 are sealed and used with a gasket or the like. .

  Conventionally, in a polymer electrolyte fuel cell, a cation exchange type electrolyte membrane is generally used as the solid electrolyte membrane 6 (hereinafter, a polymer electrolyte fuel cell using a cation exchange type electrolyte membrane is simply referred to as a cation exchange type electrolyte membrane). Also referred to as “cationic fuel cell”), in the cation type fuel cell, the catalyst contained in the electrode and fuel in the fuel chamber side gas diffusion electrode (anode) 4 are brought into contact with each other to generate protons (hydrogen ions). generate. The generated protons conduct in the solid polymer electrolyte membrane 6 and move to the oxidant chamber 8, and react with oxygen in the oxidant gas at the oxidant chamber side gas diffusion electrode (cathode) 5 to generate water. . On the other hand, the electrons generated simultaneously with protons in the fuel chamber side gas diffusion electrode (anode) 4 move to the oxidant chamber side gas diffusion electrode (cathode) 5 through the external load circuit, so that the energy of the reaction is used as electric energy. be able to.

  In general, the fuel includes organic liquid fuels such as methanol, ethanol, isopropanol, 1-propanol, dimethyl ether, formic acid, formalin, ammonia, hydrazine; hydrogen, ammonia, natural gas, naphtha, coal gas, biomass gas, etc. Gaseous fuel that is in a gaseous state during power generation; sodium borohydride or the like is used, and air or oxygen gas is used as the oxidant gas (see Patent Documents 1 and 2).

  On the other hand, it is also possible to use an anion exchange type electrolyte membrane as the solid electrolyte membrane (hereinafter, the polymer electrolyte fuel cell using the anion exchange type electrolyte membrane is also simply referred to as “anion type fuel cell”). . In the anion fuel cell, the catalyst contained in the oxidant chamber side gas diffusion electrode (cathode) 5 is supplied by supplying the above-described fuel to the anode and the oxidant gas and water to the cathode. In this way, hydroxide ions are generated from oxygen and water. The hydroxide ions are conducted through the solid polymer electrolyte membrane 6 formed of the anion exchange type electrolyte membrane, move to the fuel chamber 7, and react with the fuel at the fuel chamber side gas diffusion electrode (anode) 4. Water is generated and electrons serving as an electrical energy source are emitted (see Patent Documents 3 to 5).

JP 2006-4659 A JP 2007-242367 A JP-A-11-135137 Japanese Patent Laid-Open No. 11-273695 JP 2000-331693 A

  As described above, the polymer electrolyte fuel cell is roughly divided into two types of power generation mechanisms, but the proton conduction type cation type fuel cell that can easily increase the conductivity as compared with hydroxide ions. There has been a great deal of consideration about. However, in recent years, depletion of precious metals used as catalysts in cationic fuel cells has become a concern, and anionic fuel cells capable of using catalysts other than precious metals have been attracting attention. That is, in the cation type fuel cell, the reaction field becomes strongly acidic as can be seen from the above-described power generation mechanism, so that only expensive noble metal catalysts such as platinum that does not dissolve even under strong acid conditions can be used as the electrode catalyst. In the anion fuel cell, the ion species moving in the solid polymer electrolyte membrane 6 are hydroxide ions, and the reaction field is a basic atmosphere. Therefore, it is possible to use an easily available and inexpensive transition metal catalyst. It is.

  However, although some pioneering studies related to the principle of power generation have been made for anionic fuel cells, a full-scale study has just begun, and there are examples of reports on anionic fuel cells. Is overwhelmingly less than reported examples of cationic fuel cells. In particular, the power generation system including the fuel and oxidant gas supply system is hardly handled at present.

  Accordingly, an object of the present invention is to provide a practical anionic fuel cell power generation system that is expected to have cost merit.

  As a result of studies aimed at the construction of an anionic fuel cell power generation system using an aqueous fuel from the viewpoint of ease of handling and safety, the present inventors have obtained the following knowledge (described later). See reference example).

(1) In an anionic fuel cell using an aqueous fuel, it is advantageous to use a solid electrolyte membrane having water permeability for high output.
(2) Fuel permeation cannot be avoided when a solid electrolyte membrane having water permeability is used.
(3) In the case of an anionic fuel cell, since there are many kinds of catalysts that can be used as electrode materials, it is possible to use a catalyst having low activity against fuel as a catalyst contained in the cathode.
(4) When a catalyst having low activity against fuel is used as the catalyst contained in the cathode, it is possible to prevent a large decrease in battery output even if fuel permeates.
(5) Even in the case of (4) above, a decrease in the fuel utilization rate is inevitable, and the cathode offgas discharged from the cathode of the fuel cell contains fuel, so the cathode offgas remains as it is. When released into the atmosphere, problems such as odor and environmental pollution, as well as corrosion of peripheral equipment, may occur.

  In a direct methanol fuel cell (DMFC), which is a typical cationic fuel cell using an aqueous fuel, it is an important technical problem to keep the fuel permeability of the electrolyte membrane low from the viewpoint of effective use of fuel. In order to solve this problem, it was necessary to reduce the water permeability almost inevitably. For this reason, it is not assumed that a solid electrolyte membrane having high water permeability is used. Therefore, the problems shown in the above (2) and (5) are peculiar to an anionic fuel cell using an aqueous fuel, and can be said to be recognized for the first time by the present inventors.

  In order to construct an anionic fuel cell power generation system based on the knowledge of (1) above, on the premise that a solid electrolyte membrane having water permeability is used, the present inventors (2) and (5) We thought that it was necessary to solve the problem shown in (2), and further examined. As a result, a cathode offgas treatment device that treats the cathode offgas discharged from the cathode of the fuel cell is installed, and the cathode offgas treatment device passes the electrolyte membrane and removes the fuel mixed in the cathode offgas. The inventors have found that the problem (5) can be solved, and that the problem (2) can be solved by reusing the fuel separated from the cathode offgas in the cathode offgas treatment apparatus, and the present invention has been completed.

  That is, the present invention includes an electrolyte membrane-electrode assembly in which an anode is joined to one surface of an anion exchange type electrolyte membrane that allows fuel and water to permeate, and a cathode is joined to the other surface. A solid polymer electrolyte fuel cell that generates electricity by supplying an oxidant gas and water to the cathode, a fuel supply device for supplying fuel to the anode, and an oxidant gas to the cathode A solid polymer electrolyte fuel cell power generation system comprising an oxidant gas supply device for supply, wherein water can be supplied from at least one selected from the fuel supply device and the oxidant gas supply device, A cathode off-gas treatment apparatus for removing the fuel from the cathode off-gas containing the fuel discharged from the cathode of the fuel cell and permeated through the electrolyte membrane; A solid polymer electrolyte fuel cell power generation system, which comprises a.

  As the cathode offgas treatment device, at least one selected from the group consisting of a fuel decomposition and removal device, a fuel adsorption and removal device, and a fuel absorption and removal device is preferably employed. In the solid polymer electrolyte fuel cell power generation system of the present invention, the problem (2) can be solved by reusing the fuel separated from the cathode offgas by the cathode offgas treatment apparatus.

  In the solid polymer electrolyte fuel cell power generation system of the present invention, an anionic fuel cell is used as a fuel cell, and therefore, usable electrode catalysts are not limited to noble metals such as platinum, and transition metal catalysts such as nickel can also be used. It is. For this reason, not only can the manufacturing cost of the fuel cell be greatly reduced, but the catalyst used at the anode and the catalyst used at the cathode can be made different. As a result, it is possible to use a catalyst having low activity with respect to the fuel as the cathode catalyst, and it is possible to obtain a high output even when the fuel cell diaphragm has fuel permeability.

  In addition, since the anion fuel cell used in the solid polymer electrolyte fuel cell power generation system of the present invention uses a solid electrolyte membrane having water permeability, the conductivity of hydroxide ions can be kept high. And high battery output can be obtained. Furthermore, since the solid electrolyte membrane has water permeability, even when an aqueous fuel solution is supplied to the anode chamber, the water component of the aqueous solution permeates to the cathode side, so it is necessary to supply water separately to the cathode chamber. The fuel cell can be made compact. In conventional solid polymer electrolyte fuel cells, it is considered that low fuel permeability is preferable, and a membrane with high water permeability is considered to have high fuel permeability, so it is not suitable for a fuel cell membrane. It was thought. The above-mentioned effects of the present invention can be said to overturn such common sense. The reason why such an undesired effect can be obtained is that the selection range of the catalyst species has been expanded by using an anion exchange resin that has not been attracting much attention as an ion exchange resin. Is.

  Furthermore, the solid polymer electrolyte fuel cell power generation system according to the present invention includes a cathode off-gas treatment device that removes the fuel from the cathode off-gas containing the fuel discharged from the cathode of the fuel cell and permeated through the electrolyte membrane. Further, since the off-gas processed by the cathode off-gas processing apparatus is discharged, it is possible to prevent problems such as odor and environmental pollution caused by fuel, and corrosion of peripheral equipment. Furthermore, since the fuel separated from the off gas by the cathode off gas processing apparatus can be reused, the fuel can be effectively used.

  Hereinafter, the solid polymer electrolyte fuel cell power generation system 100 of the present invention will be described with reference to FIGS.

  As shown in FIG. 2, the solid polymer electrolyte fuel cell power generation system 100 of the present invention has an anode 112 bonded to one surface of an anion exchange type electrolyte membrane 111 that transmits fuel and water, and the other surface. A solid polymer electrolyte fuel cell 110 comprising an electrolyte membrane-electrode assembly 114 joined with a cathode 113, which generates electricity by supplying fuel to the anode and supplying oxidant gas and water to the cathode; A fuel supply device 120 for supplying fuel to the anode 112; and an oxidant gas supply device 130 for supplying an oxidant gas to the cathode 113, the fuel supply device and the oxidant gas supply device. A solid polymer electrolyte fuel cell power generation system capable of supplying water from at least one selected from: a cathode of the fuel cell; It is discharged, and further comprising a cathode off-gas treatment apparatus 140 for removing the fuel from the cathode off-gas containing a fuel mixed permeate through the electrolyte membrane.

  The solid polymer electrolyte fuel cell 110 used in the present invention is mainly an electrolyte membrane-electrode junction in which an anode 112 is joined to one surface of an anion exchange type electrolyte membrane 111 and a cathode 113 is joined to the other surface. A solid polymer electrolyte fuel cell, ie, an anionic fuel cell, comprising a body electrode (MEA) 114 and generating electricity by supplying fuel to the anode and supplying oxidant gas and water to the cathode It is. The structure of the solid polymer electrolyte fuel cell is not particularly limited as long as it satisfies the above conditions, and may be any of a single cell type, a stack type, a panel type, etc. From the viewpoint that it can be obtained, a stacked structure is preferable.

  For example, as shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2006-4659, the stack type fuel cell includes an MEA in which an anode and a cathode are bonded to both surfaces of a solid polymer electrolyte membrane, a cathode diffusion layer, an anode diffusion layer, a gasket, A single cell is constituted by a separator, and a stack is formed by stacking a plurality of single cells. The cathode diffusion layer and anode diffusion layer play a role in supporting MEA, supplying external air to the electrode, fuel, etc., diffusion of components generated by the electrode, and contact resistance between the electrode and the separator. is there.

  Usually, a fuel supply groove is formed on one side of each separator, an oxidant gas (for example, air) supply groove is formed on the other side, and further, fuel supply holes are formed on the MEA, gasket, and separator which are laminated members. The oxidant gas supply holes are provided, and the fuel supplied from the fuel supply device 120 and the oxidant gas supplied from the oxidant gas supply device 130 pass through these supply holes and supply grooves to the anode and the cathode, respectively. Supplied. In order to generate electric power in an anionic fuel cell, it is necessary to supply fuel to the anode and supply oxidant gas and water to the cathode. As will be described later, the anion exchange type electrolyte membrane 111 used in the MEA of the solid polymer electrolyte fuel cell used in the present invention has a property of permeating water. Therefore, when water is supplied to the anode chamber together with fuel. Even so, water passes through the electrolyte membrane 111 and is supplied to the cathode. Therefore, water may be supplied directly to the cathode chamber, may be supplied to the anode chamber, or may be supplied from both the anode chamber and the cathode chamber. Moreover, when supplying directly to a cathode chamber, it is preferable to mix and supply both beforehand by means, such as humidifying oxidant gas. Note that when the atmosphere is used as the oxidant gas, the atmosphere normally contains moisture, so there is no need for humidification. However, when water is supplied only from the cathode chamber, it depends on the humidity of the atmosphere. Since the supply amount of water changes, it is preferable to humidify in order to obtain a stable output.

  When fuel is supplied to the anode and oxidant gas and water are respectively supplied to the cathode, a potential difference occurs in the MEA, and the fuel cell responds to a power demand from an external load such as a travel motor connected to the output terminal of the fuel cell. Has come to generate electricity. Each unit cell is usually connected to a cell voltage detection monitor that is electrically connected to the control unit and detects its output voltage.

  Hereinafter, the solid polymer electrolyte fuel cell 110, the fuel supply device 120, and the oxidant gas supply device 130 will be described in detail.

1. Solid polymer electrolyte fuel cell 110
The MEA in the solid polymer electrolyte fuel cell 110 used in the present invention needs to use an anion exchange type electrolyte membrane 111 as an electrolyte membrane. By using an anion exchange type electrolyte membrane, an anionic fuel cell is obtained, and a transition metal catalyst such as nickel can be used as an electrode catalyst.

1-1. Anion exchange type electrolyte membrane 111
As the anion exchange type electrolyte membrane 111, an anion exchange resin molded into a membrane shape can be used, but from the viewpoint of membrane strength, a precursor of an ion exchange group on a substrate such as a nonwoven fabric or a microporous membrane. A polymerizable composition comprising a polymerizable monomer having a group to become a crosslinkable polymerizable monomer is contacted, and the polymerizable composition is filled in the voids of the substrate and polymerized, It is preferable to use a precursor produced by converting a precursor group into an ion exchange group and, if necessary, converting a counter ion into a hydroxide ion.

1-1-1. As the base material , polymer porous membranes such as woven fabrics and nonwoven fabrics made of polyolefin, polyfluoroolefin, hydrolysis-resistant polyimide, etc. can be used. It is preferable to use a polymer porous film of 50 μm. When the thickness of the porous film is less than 3 μm, the durability may decrease due to long-term use, and when it exceeds 50 μm, the membrane resistance tends to increase and the battery output tends to decrease. The film thickness is particularly preferably 5 to 15 μm from the viewpoint of the durability of the diaphragm and the battery output. In addition, the average pore diameter of the porous membrane is generally 0.005 to 5.0 μm and 0.01 to 1.0 μm considering the small membrane resistance and mechanical strength of the obtained anion exchange membrane. More preferably, it is most preferably 0.015 to 0.4 μm. The porosity of the porous membrane is generally 20 to 95%, more preferably 30 to 80%, and most preferably 30 to 50% for the same reason as the average pore diameter. preferable.

1-1-2. Anion exchange resin As the anion exchange resin filled in the voids of the porous membrane, the viewpoint of easy control of hydroxide ion conductivity, fuel and water permeability, ease of production and production cost From this viewpoint, a crosslinked hydrocarbon-based anion exchange resin having a functional group containing a quaternary nitrogen atom as an anion exchange group is preferably used. Here, the crosslinked hydrocarbon system means that a portion excluding an ion exchange group composed of a functional group containing a quaternary nitrogen atom is composed of a crosslinked hydrocarbon polymer. The hydrogen-based polymer means a polymer in which most of the main chain and side chain bonds constituting the polymer are constituted by carbon-carbon bonds. In the hydrocarbon polymer, oxygen, nitrogen, silicon, sulfur, boron, phosphorus, etc. due to ether bond, ester bond, amide bond, siloxane bond, etc. between the carbon-carbon bonds constituting the main chain and the side chain. A small amount of other atoms may be present. In addition, the atoms bonded to the main chain and the side chain need not all be hydrogen atoms, and if the amount is small, other atoms such as chlorine, bromine, fluorine, iodine, etc., or substituents containing other atoms It may be replaced. The amount of these elements other than carbon and hydrogen is 40 mol% or less, preferably 10 mol% or less, based on all elements constituting the resin excluding the anion exchange group.

  Examples of such anion exchange resins include those obtained by introducing a quaternary ammonium base into a (chloromethyl) styrene / divinylbenzene copolymer, and those obtained by introducing a quaternary pyridinium base into a 4-vinylpyridine / divinylbenzene copolymer. And anion exchange resins as disclosed in JP-A-2003-155361.

  In order to fill the voids of the porous membrane with the anion exchange resin, a polymerizable composition containing a polymerizable monomer having an anion exchange group or an active group that can be exchanged for an anion exchange group is formed with the porous membrane. After contacting and filling the voids of the porous membrane, polymerization curing and crosslinking may be performed, and then the active groups may be converted into anion exchange groups as necessary.

  For example, when filling the voids of the porous membrane with the suitable anion exchange resin, a polymerizable monomer having a halogenoalkyl group, a crosslinkable polymerizable monomer, and an effective amount of polymerization start The polymerizable composition containing the agent is brought into contact with the porous membrane, and the polymerizable composition is filled in the voids of the porous membrane, followed by polymerization curing and crosslinking, and then the halogenoalkyl group is converted to quaternary ammonium. What is necessary is just to convert into a base. Instead of a polymerizable monomer having a halogenoalkyl group, a polymerizable monomer having a functional group capable of introducing a halogenoalkyl group such as styrene is used, and a halogenoalkyl group is introduced after polymerization (crosslinking). The halogenoalkyl group may then be converted to a quaternary ammonium base. Furthermore, in place of the polymerizable monomer having a halogenoalkyl group, a polymerizable monomer into which a quaternary ammonium base has been introduced in advance may be used.

  However, the first method, that is, a method using a polymerizable monomer having a halogenoalkyl group, is adopted from the viewpoint of easily obtaining an anion exchange resin having a high ion exchange capacity and easy control of denseness. It is preferable to do. In this case, when an anion exchange resin having a higher density is to be obtained, it is preferable to add a compound having an epoxy group to the polymerizable composition. When a compound having an epoxy group is not blended, the denseness of the ion exchange resin may be reduced due to the influence of chlorine gas or hydrogen chloride gas which is a by-product derived from a halogenoalkyl group during polymerization. In the case where a compound having the above is blended, the above-mentioned by-product is supplemented by the epoxy group, so that a reduction in denseness can be prevented.

1-1-3. Anion-exchange resin raw material In the said method, as a polymerizable monomer which has a halogenoalkyl group, a well-known thing can be used without a restriction | limiting. Examples of the halogenoalkyl group include chloromethyl group, bromomethyl group, iodomethyl group, chloroethyl group, bromoethyl group, iodoethyl group, chloropropyl group, bromopropyl group, iodopropyl group, chlorobutyl group, bromobutyl group, iodobutyl group, chloropentyl group, Examples include a bromopentyl group, an iodopentyl group, a chlorohexyl group, a bromohexyl group, and an iodohexyl group. Specific examples of the polymerizable monomer having a halogenoalkyl group include chloromethyl styrene, bromomethyl styrene, iodomethyl styrene, chloroethyl styrene, bromoethyl styrene, iodoethyl styrene, chloropropyl styrene, bromopropyl styrene, iodo. Examples include propyl styrene, chlorobutyl styrene, bromobutyl styrene, iodobutyl styrene, chloropentyl styrene, bromopentyl styrene, iodopentyl styrene, chlorohexyl styrene, bromohexyl styrene, and iodohexyl styrene, of which chloromethyl styrene and bromomethyl Styrene, iodomethyl styrene, chloroethyl styrene, bromoethyl styrene, iodoethyl styrene, chloropropyl styrene, bromopropyl Styrene, iodopropyl styrene, chloro-butyl styrene, bromobutyl styrene, to use iodine-butylstyrene, particularly preferred.

  The crosslinkable polymerizable monomer is not particularly limited, and examples thereof include divinylbenzenes, divinylsulfone, butadiene, chloroprene, divinylbiphenyl, trivinylbenzenes, divinylnaphthalene, diallylamine, and divinylpyridines. A divinyl compound is used. The crosslinkable polymerizable monomer is usually used in an amount of 1 to 20 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the polymerizable monomer having a halogenoalkyl group. By controlling the crosslinkable polymerizable monomer, the degree of crosslinking can be controlled, and the permeability of fuel and water can be controlled.

  As the compound having an epoxy group (epoxy compound), a known compound having one or more epoxy groups in the molecule can be used without limitation. Specific examples include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, derivatives thereof, terpene oxide, styrene oxide and derivatives thereof, epoxidized α-olefin, and epoxidized polymer. Such an epoxy compound can be obtained by the method described in JP-A No. 11-158486, or is commercially available (for example, ADEKA “ADEKA SIZER”, Kao “KABOX”, Kyoeisha Chemical “Epolite”, Daicel Chemical “Cyclo” "Mer" "Daimak", Nagase ChemteX "Denacol"). The epoxy compound is preferably used in an amount of 1 to 12 parts by weight, particularly 3 to 8 parts by weight, based on 100 parts by weight of the polymerizable monomer having a halogenoalkyl group.

  A conventionally well-known thing is used without a restriction | limiting especially as a polymerization initiator. Specific examples of such polymerization initiators include octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy Organic peroxides such as laurate, t-hexyl peroxybenzoate, and di-t-butyl peroxide are used. The blending ratio of these polymerization initiators can be selected from a wide range as long as it is an effective amount necessary for carrying out the polymerization reaction, but in general, with respect to 100 parts by mass of the polymerizable monomer having a halogenoalkyl group. 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass.

  In addition, other components can also be suitably mix | blended with the said polymeric composition in the range which does not impair an effect. In particular, in addition to the polymerizable monomer having a halogenoalkyl group or a crosslinkable polymerizable monomer, if necessary, other monomers or plasticizers copolymerizable with these monomers are added. You may do it. Examples of such other monomers include styrene, acrylonitrile, methylstyrene, acrolein, methyl vinyl ketone, and vinyl biphenyl. The blending ratio is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer having a halogenoalkyl group.

  Further, as the plasticizers, dibutyl phthalate, dioctyl phthalate, dimethyl isophthalate, dibutyl adipate, triethyl citrate, acetyl tributyl citrate, dibutyl sebacate and the like are used. The blending ratio is preferably 50 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer having a halogenoalkyl group.

1-1-4. Anion exchange resin filling method The porous membrane can be filled with the polymerizable composition by immersing the porous membrane in the polymerizable composition, or by applying the polymerizable composition to the porous membrane. Spraying methods can be used. In order to reliably and uniformly fill the pores inside the porous membrane, it is preferable to perform a pressure reduction operation or ultrasonic irradiation while the porous membrane is immersed in the polymerizable composition.

  As a method for polymerizing the monomer composition filled in the voids of the porous membrane, generally, a method in which the membrane is sandwiched between films of polyester or the like and heated from room temperature under pressure is preferable. Such polymerization conditions depend on the type of polymerization initiator involved, the composition of the monomer composition, and the like, and are not particularly limited and may be appropriately selected.

  The film-like material obtained after the polymerization is derived from the polymerizable monomer having a halogenoalkyl group and converts the halogenoalkyl group contained in the resin into a quaternary ammonium base. The quaternization method may follow a regular method. For example, a halogenoalkyl group can be easily converted to a quaternary ammonium group by immersing the film-like material obtained after polymerization in a solution containing a tertiary amine such as trimethylamine, triethylamine, or dimethylaminoethanol at 5 to 50 ° C. for 10 hours or more. Can be converted.

In this way, a composite membrane (anion exchange resin membrane) in which the void portion of the porous membrane is filled with the quaternary ammonium salt type hydrocarbon anion exchange resin can be obtained. The obtained composite membrane is washed, cut or the like as necessary, and used directly as a diaphragm for a liquid fuel cell according to a conventional method. Incidentally, the composite film, 0.2~3mmol · ^{g -1,} preferably has an anion exchange capacity of 0.5 to 2.5 mmol · ^{g -1,} also conductivity of hydroxide ions by drying It is preferable to prepare such that the water content at 25 ° C. is 7% or more, and preferably about 10 to 90% so that the property is not easily lowered.

1-1-5. Water permeability and fuel permeability The anion exchange type electrolyte membrane 111 used in the present invention needs to have water permeability. By having water permeability, it is possible to increase the conductivity of hydroxide ions and obtain a high battery output. Further, when the fuel is supplied to the anode as an aqueous solution, the water component of the aqueous solution is transmitted to the cathode side, so that it is not necessary to separately supply water to the cathode, and the fuel cell can be made compact. Become. Such an anion exchange type electrolyte membrane 111 preferably has a water permeability of 500 g · m ⁻² · hr ⁻¹ or more, particularly 1000 g · m ⁻² · hr ⁻¹ or more. Here, the water permeability can be measured as follows. That is, a fuel cell membrane is sandwiched between fuel cells (electrolyte membrane area 5 cm ² ) installed in a constant temperature bath at 25 ° C., water is supplied by a liquid chromatography supply pump, and argon gas is supplied to the opposite side of the membrane. 300 ml · min. ^-1 to supply. And it can measure by measuring the water concentration in the argon gas collected with the gas collection container by gas chromatography. If the water permeability is too high, the oxidant gas is difficult to come into contact with the cathode due to the permeated water, so the water permeability is 10,000 g · m ⁻² · hr ⁻¹ or less, particularly 7,000 g · It is preferable that it is below m ^<-2> * hr ^{< -1} . The water permeability can be adjusted by controlling the degree of crosslinking of the ion exchange resin and the thickness of the electrolyte membrane.

  When the anion exchange type electrolyte membrane has water permeability, the fuel also permeates the anion exchange type electrolyte membrane. From the viewpoint of effective use of fuel and reaction inhibition at the cathode, it is preferable that the fuel does not permeate the anion exchange type electrolyte membrane, but a technique for selectively permeating only water is not known at present, When an anion exchange type electrolyte membrane having water permeability is used, fuel permeation cannot be completely prevented. Therefore, the anion exchange electrolyte membrane 111 used in the present invention has a property of permeating not only water but also fuel. Although the fuel permeability of the anion exchange type electrolyte membrane used in the present invention cannot be generally defined by the type of fuel, it is usually 30% by mass of a fuel aqueous solution instead of water in the water permeability measurement method. The fuel permeability is about 1/20 to 1 times the water permeability.

1-2. Electrolyte membrane-electrode assembly 114
In the electrolyte membrane-electrode assembly (MEA) 114 in the solid polymer electrolyte fuel cell 110 used in the present invention, the anode 112 is joined to one surface of the anion exchange type electrolyte membrane 111 and the cathode is joined to the other surface. 113 is joined. These anode and cathode are usually bonded to both surfaces of the anion exchange electrolyte membrane 111 as follows. That is, if necessary, a binder or dispersion medium is added to the electrode catalyst to form a paste-like composition, which is roll-molded as it is or coated on a support layer material such as carbon paper and then heat-treated to form a layered composition. A method for obtaining a product, applying an ion conductivity-imparting agent to the surface to be a joint surface, and then drying as necessary, followed by thermocompression bonding with the fuel cell membrane of the present invention; If necessary, a binder or dispersion medium is added to form a paste-like composition, which is applied onto a support layer material such as carbon paper, or applied to a blank and applied to the fuel cell membrane of the present invention. It can be suitably manufactured by a method such as transferring or directly applying on the membrane for fuel cell of the present invention and then drying, followed by thermocompression bonding with the solid polymer electrolyte membrane. Also, as disclosed in JP-A-2003-86193, a molding comprising a composition containing two or more organic compounds that can be cross-linked to form an ion exchange resin by contact with each other, and an electrode catalyst After obtaining the body, the two or more organic compounds contained in the molded body may be cross-linked to form a gas diffusion electrode, which may be bonded to both surfaces of the fuel cell membrane of the present invention.

  Examples of the ion conductivity-imparting agent include hydrocarbon polymer elastomers having an anion exchange group in the molecule and hardly soluble in water and methanol, as disclosed in JP-A-2002-367626. Alternatively, an ion conductivity-imparting agent for a gas diffusion electrode of a polymer fuel cell, characterized by comprising a solution or a suspension thereof, is preferably used.

1-2-1. As the electrocatalyst electrode catalyst, platinum, gold, silver, palladium, iridium, rhodium, ruthenium, tin, iron that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen, which are used as electrode catalysts in conventional gas diffusion electrodes Metal particles such as cobalt, nickel, molybdenum, tungsten, vanadium, or alloys thereof can be used without limitation, but a transition metal catalyst is preferably used from the viewpoint of cost. These catalysts may be used after being supported on a conductive agent in advance. The conductive agent is not particularly limited as long as it is an electronic conductive material. For example, carbon black such as furnace black and acetylene black, activated carbon, graphite and the like are generally used alone or in combination. is there.

  In the electrolyte membrane-electrode assembly used in the present invention, fuel and water are supplied to the anode chamber, and the water supplied to the anode chamber is supplied to the cathode through the electrolyte membrane-electrode assembly. In order to prevent a decrease in output due to the fuel that permeates together with water, an electrode catalyst that is active with respect to the fuel is used as the electrode catalyst included in the anode, and the electrode catalyst included in the cathode is used with respect to the fuel. It is preferable to use an electrode catalyst whose activity is lower than that of the electrode catalyst contained in the anode. Here, the activity of the electrode catalyst contained in the cathode with respect to the fuel is preferably 1/10 or less, particularly preferably 1/100 or less, and preferably 1/1000 or less of the activity of the electrode catalyst contained in the anode with respect to the fuel. Most preferred. Such a catalyst can be easily selected by performing a simple activity test for each type of fuel used.

2. Fuel Supply Device 120 and Fuel Supply Method to Anode In the solid polymer electrolyte fuel cell power generation system of the present invention, the fuel supply device 120 includes a fuel tank 121, a fuel supply line (pipe) 122, and a fuel transfer mechanism 123. As the fuel tank 121 and the fuel transfer mechanism 123, those which can be used in the cation type fuel cell can be used without particular limitation depending on the type of fuel used. The same fuel as that used in the cation type fuel cell can be used as the fuel, but it is preferable to use a water-soluble fuel in the form of an aqueous solution from the viewpoint of safety and ease of handling. Examples of such water-soluble fuels include methanol, ethanol, isopropanol, 1-propanol, ammonia, hydrazine, and mixtures thereof.

  When water-soluble fuel is used as an aqueous solution, the fuel tank 121 preferably has a concentration adjusting mechanism 124. As shown in FIG. 3, the concentration adjusting mechanism includes a raw fuel tank 125a for storing a fuel not diluted with water or a high-concentration aqueous fuel solution (hereinafter also referred to as raw fuel), and the raw fuel from the raw fuel tank to the fuel tank. A pipe 125b and a transfer mechanism 125c for transferring the fuel, a raw fuel transfer amount adjusting means 125d for controlling the amount of raw fuel transferred from the raw fuel tank to the fuel tank, a water tank 126a for storing water, and from the water tank to the fuel tank A pipe 126b and a transfer mechanism 126c for transferring water, and a water transfer amount adjusting means 126d for controlling the amount of water transferred from the water tank to the fuel tank are included. As the transfer mechanism (125c, 126c) for transferring the raw fuel and water, a diaphragm, plunger type, and other type liquid feed pumps are preferably used. When the raw fuel is gas or liquefied gas, the raw fuel tank may be a pressure-resistant container that can be sealed with a valve or the like, and the inside of the container may be pressurized to transfer the raw fuel by a pressure difference. Various flow rate regulators are preferably used as the raw fuel transfer amount adjusting means 125d and the water transfer amount adjusting means 126d. In order to prevent the outside air temperature from dropping and water freezing when the fuel cell is not in operation, a predetermined amount of alcohol that can also be used as fuel is mixed in advance with water stored in the water tank to be used. It is preferable to keep it.

  When water-soluble fuel is used as an aqueous solution, the fuel transfer mechanism 123 is usually a diaphragm, plunger type, or other type liquid feed pump. It is preferable that fuel transfer amount adjusting means 123 a such as a flow controller is installed downstream of the fuel transfer mechanism 123. The fuel stored in the fuel tank is supplied to the anode 112 of the fuel cell 110 directly or through the fuel supply line 122 by a liquid feed pump. When reforming fuel, for example, as disclosed in JP-A-10-223249, gas and fuel are evaporated by evaporating fuel and water in an evaporating section 127b heated by a burner 127a as shown in FIG. In order to remove the carbon monoxide by-produced in the reforming reaction as necessary, the gas is sent to the reforming unit 127c, where the reforming reaction is performed by catalytic action, and the gas is changed to a hydrogen gas-rich fuel. , Such as a CO selective oxidation device 127d, is supplied to the anode 112 of the fuel cell 110. In FIG. 4, the oxidant gas supply system on the cathode side is omitted for simplification.

  The fuel supplied to the anode 112 in this way is used for the electrochemical reaction. The remaining fuel that is not used at this time is discharged through an anode off gas (or liquid) discharge line 128 as anode off gas or anode off liquid. The discharged anode off gas or anode off liquid is circulated as necessary according to the type of off gas (or off liquid). When alcohol such as methanol is used as a fuel by electrode reaction, carbon dioxide is produced as a by-product. When fuel is hydrazine, nitrogen is produced as a by-product. It is preferable to appropriately separate and discharge the gas. The fuel is reused by returning off-gas (or off-liquid) to the fuel tank or fuel supply line, but when reforming the fuel, it is used as fuel for the burner as shown in FIG. May be. In this case, separation of the byproduct gas is not particularly necessary.

3. Oxidant Gas Supply Device 130 and Oxidant Gas Supply Method to Cathode In the solid polymer electrolyte fuel cell power generation system of the present invention, an oxidant gas for supplying an oxidant gas to the solid polymer electrolyte fuel cell 110 The supply device 130 includes an oxidant gas supply source 131 composed of an oxidant gas tank or air, an oxidant gas supply line (pipe) 132, and an oxidant gas transfer mechanism 133. When an oxidant gas other than air, such as pure oxygen gas, is used as the oxidant gas, the oxidant gas is stored in an oxidant gas tank including a pressure vessel such as a gas cylinder (gas cylinder). However, air is generally used as the oxidant gas from the viewpoint of cost and the like. In this case, outside air is taken in and compressed by a compressor which is the oxidant gas transfer mechanism 133, and the oxidant supply line 132 is used. And supplied to the cathode 113 of the solid polymer electrolyte fuel cell 110. The compressor is electrically connected to a solid polymer electrolyte fuel cell and a power source (for example, a capacitor or a secondary battery) mounted separately from the fuel cell. When the amount of power generated by the fuel cell is small, power is supplied from the power source to operate. It is preferable to install a flow rate regulator 133a downstream of the oxidant gas transfer mechanism 133. The oxidant gas supply device 130 may be provided with a humidifier, and air from the compressor may be supplied as humidified air to the cathode. Further, when the oxidant gas supply source 131 is a gas cylinder (gas cylinder), the oxidant gas transfer mechanism 133 serves as a pressure regulating valve.

  In this way, the oxidant gas supplied from the oxidant supply source 131 to the cathode 113 through the oxidant supply line 132 is subjected to the electrochemical reaction. The remaining oxidant gas that is not used at this time is discharged through the cathode offgas discharge line 134 as cathode offgas. At this time, the cathode off gas contains fuel that has permeated the anion exchange electrolyte membrane 111 from the anode side. In addition, when the water supplied to the cathode is not completely consumed at the cathode, the cathode off gas contains water.

4). Cathode off-gas treatment device 140 and recovered fuel reuse method Cathode off-gas containing fuel discharged through the cathode off-gas discharge line 134 is guided to the cathode off-gas treatment device 140 installed downstream of the line, and mixed into the cathode off-gas here. The removed fuel is removed from the cathode offgas. The cathode offgas treatment device 140 may be any device having such a function, but is at least one selected from the group consisting of a fuel decomposition / removal device 140a, a fuel adsorption / removal device 140b, and a fuel absorption / removal device 140c. It is preferable that The fuel decomposition / removal device 140a means a device that oxidizes or reduces fuel to convert it into a less harmful substance, and specifically, a reaction device or a combustion device filled with a catalyst that promotes such a reaction. Can be mentioned. For example, when reforming fuel using a burner as described above, as shown in FIG. 4, this burner is used as a fuel decomposition / removal device, and combustion is performed with the burner (not fuel cell fuel). The cathode offgas discharge line 134 may be connected to a line for supplying fuel to be used, and the fuel mixed in the cathode offgas may be burned.

  The fuel adsorption / removal device 140b adsorbs and removes fuel contained in an adsorbent having a property of adsorbing fuel materials such as activated carbon, activated alumina, silica gel, and zeolite, and cathode offgas containing fuel. Means a device to do. The fuel adsorption / removal device includes a container filled with an adsorbent, and the fuel is adsorbed and removed by passing a cathode off gas through the container. By making the container into a detachable cartridge type, the adsorbent whose adsorption capacity has decreased after a predetermined period of time can be easily replaced with a new one. The adsorbent in the removed cartridge can be reused by performing a separate regeneration process. When the cathode off gas contains water (water vapor), a dehydrator is provided upstream of the adsorption / removal device in order to prevent the adsorption life from being shortened due to water adsorption, or a container filled with the adsorbent is used. It is preferable to provide a drainage mechanism or to provide a mechanism that prevents the water from adsorbing by heating the container or selectively desorbing the adsorbed water. When the cathode offgas treatment device 140 includes such an adsorption / removal device 140b for fuel, the cathode offgas that has passed through the adsorption / removal device 140b can be directly released into the atmosphere. For this reason, even if the cathode offgas treatment device 140 includes a fuel decomposition / removal device 140a and / or a fuel absorption / removal device 140c, as shown in FIG. It is preferable to install an adsorption removal device 140b.

  Further, the fuel absorption and removal device 140c uses a liquid that dissolves the fuel substance well as an absorbent, and contacts the absorbent with a cathode offgas containing fuel to absorb the fuel contained in the absorbent (physical). Means a device that is removed by absorption or chemical absorption). In general, a liquid that is a good solvent for the fuel substance is used as the absorbent, but when water is used as the fuel and the absorbed fuel is reused, water, the same substance as the fuel, or Preference is given to using mixtures of these. A known gas-liquid contact device can be used as the fuel absorption / removal device, but a device in which the off-gas and the absorbent are brought into contact with each other by blowing the cathode off-gas into the tank into which the absorbent has been introduced is preferably used. At this time, it is preferable to make the cathode offgas blown into the absorbent finer by stirring the absorbent to increase the gas-liquid contact area. Further, absorption may be performed in multiple stages in order to increase the absorption efficiency. When water is used as the absorbent, the water that has absorbed the fuel contained in the cathode offgas is sent to the fuel supply device 120 using a liquid feed pump or the like and reused again as fuel for the fuel cell.

  In order to prevent the outside air temperature from dropping and water freezing when the fuel cell is not in operation, a predetermined amount of alcohol that can also be used as fuel is mixed in advance with water stored in the water tank to be used. It is preferable to keep it.

  In FIG. 5, an aqueous solution of a water-soluble fuel is supplied from the fuel supply device 120, and the cathode off-gas treatment device 140 is a fuel absorption / removal device 140c using water as an absorbent. 1 shows a block diagram of a solid polymer electrolyte fuel cell power generation system of the present invention that reuses fuel separated from cathode offgas by supplying it to a fuel supply device 120. FIG. The system includes the above-described concentration adjusting mechanism 124, the raw fuel tank 125a, the piping 125b for transferring the raw fuel from the raw fuel tank to the fuel tank, the transfer mechanism 125c, and the raw fuel tank to the fuel tank. A raw fuel transfer amount adjusting means 125d for controlling the amount of raw fuel to be transferred is provided. The fuel absorption / removal device 140c also serves as a water tank (126a in FIG. 3), and water or alcohol as necessary is added as an absorbent 150 in advance from an absorbent supply means (not shown). A predetermined amount of water is stored. By doing so, it is not necessary to separately provide the water tank 126a and the water transfer mechanism 126c, and the system can be made compact. In this system, when the battery is in operation, the anode removal liquid (or anode offgas) is introduced into the absorption removal device 140c, and the remaining fuel that is not used in the anode is temporarily stored here, and the absorption removal device 140c. Cathode off-gas is blown into the absorbent stored inside, and the fuel contained in the cathode off-gas is absorbed by the absorbent and removed. At this time, the absorption efficiency of the fuel can be increased by circulating the absorbent or the like to keep the inside agitated. Then, the cathode off-gas from which the fuel has been removed is discharged out of the absorption removal device 140c, and is released into the atmosphere through the adsorption removal device 140b installed as necessary. The adsorption removal device 140b is not necessarily required and can be omitted. However, even if the absorption removal device 140c cannot completely remove the fuel by installing it, the remaining fuel is almost completely removed here. It becomes possible to do. On the other hand, the remaining fuel not used in the anode and the fuel contained in the cathode off-gas are sent to the fuel supply device 120 in a form dissolved in the absorbent using a liquid transfer means such as a liquid feed pump, and again the fuel. Used as.

  In this system, a dehydrating device can be installed instead of the adsorption removing device 140b, or a dehydrating device can be installed between the absorption removing device 140c and the adsorption removing device 140b. When a large amount of water vapor is contained in the cathode off gas, the water vapor is absorbed and circulated by the absorbent together with the fuel. However, when water is used as the absorbent, the off gas discharged from the absorption removing device 140c has some degree. Of water vapor is contained. This water vapor may cause condensation or solidification (freezing) due to a decrease in the outside air temperature, causing problems such as blockage, corrosion, destruction, and corrosion of peripheral equipment. Can be prevented. As the dehydrating device, a water vapor aggregating device, a container filled with a desiccant, or the like can be used.

5). Relationship between water permeability and fuel permeability and battery output (reference example)
As described above, in the present invention, since the anion exchange type electrolyte membrane 111 having water permeability is used as the electrolyte membrane in the MEA of the solid polymer electrolyte fuel cell 110, high battery output can be obtained. Can do. This is also supported by the results of the following experiment (reference example) conducted by the present inventors.

Reference example:
After impregnating the polyethylene porous membrane with a p-chloromethylstyrene-based polymerization curable composition, this is polymerized and cured, and then treated with trimethylamine to introduce an anion exchange group (quaternary ammonium base), and Two anion exchange-type solid polymer electrolyte membranes were produced by converting counter ions into hydroxide ions. At this time, the amount of divinylbenzene used as a cross-linking agent was changed, and the water permeability (water permeability) ) Was controlled. The water permeability and fuel permeability of the two obtained solid polymer electrolyte membranes (hereinafter referred to as membrane A and membrane B, respectively) were measured.

Next, for each of membrane A and membrane B, a mixture of an anion exchange resin tetrahydrofuran solution (resin concentration 5 wt%) in which counter ions are converted to hydroxide ions and a Ni catalyst is applied onto carbon paper. Thus, a gas diffusion electrode was prepared, and the gas diffusion electrode was hot-pressed on both surfaces of each of the membrane A and the membrane B to obtain an electrolyte membrane-electrode assembly. This is incorporated into the fuel cell having the structure shown in FIG. 1, the temperature of the fuel cell is set to 50 ° C., and a 10% by mass aqueous methanol solution (KOH concentration: 5% by mass) containing KOH is added to the fuel electrode side. Atmospheric pressure of oxygen was 200 ml · min. ^A power generation test was performed by supplying the voltage at ⁻¹ , and the terminal voltage of the cell at a current density of 0.05 A · cm ⁻² was measured.

The water permeability is measured by sandwiching the membrane A or membrane B between fuel cells (electrolyte membrane area 5 cm ² ) installed in a constant temperature bath at 25 ° C., and supplying water in one space with a supply pump for liquid chromatography And argon gas was supplied to the space on the opposite side of the membrane at 300 ml · min. ^-1 and the argon gas that has passed through the fuel cell is collected in a gas collection container, and the water concentration in the argon gas is measured by gas chromatography, so that water per unit time and unit membrane area is measured. The amount of permeation was determined. The fuel permeability was determined in the same manner except that a 30% by mass aqueous methanol solution was used instead of water in the above measurement.

The water permeability, fuel permeability, and cell terminal voltage for membrane A and membrane B were as follows.
[Membrane A]
Water permeability: 2020 g · m ⁻² · hr ⁻¹
Fuel permeability: 710 g · m ⁻² · hr ⁻¹
Voltage: 0.60 (V)
[Membrane B]
Water permeability: 850 g · m ⁻² · hr ⁻¹
Fuel permeability: 130 g · m ^-2 · hr ^-1
Voltage: 0.25 (V).

  The present invention has been described above with reference to the drawings. However, the present invention is not limited to the embodiments shown in these drawings, and can be implemented in various modes without departing from the spirit of the present invention.

This figure is a conceptual diagram showing the basic structure of a polymer electrolyte fuel cell. This figure is a block diagram of a typical solid polymer electrolyte fuel cell power generation system of the present invention. This figure is a block diagram of a typical solid polymer electrolyte fuel cell power generation system of the present invention including a concentration adjusting mechanism. FIG. 1 is a block diagram of a typical solid polymer electrolyte fuel cell power generation system of the present invention including a fuel reformer. This figure is a block diagram of a typical solid polymer electrolyte fuel cell power generation system of the present invention using a fuel absorption and removal device as a cathode offgas device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Battery partition wall 2; Fuel gas flow hole 3; Oxidant gas flow hole 4; Fuel chamber side gas diffusion electrode 5; Oxidant chamber side gas diffusion electrode 6; Solid polymer electrolyte (anion exchange membrane)
7; fuel chamber 8; oxidant chamber 100; solid polymer electrolyte fuel cell power generation system 111 of the present invention; anion exchange electrolyte membrane 112; anode 113; cathode 114; electrolyte membrane-electrode assembly 120; 121; fuel tank 122; fuel supply line (piping)
123; Fuel transfer mechanism 123a; Fuel transfer amount adjustment means 124; Concentration adjustment mechanism 125a; Raw fuel tank 125b; Pipe 125c for transferring raw fuel from the raw fuel tank to the fuel tank; Transfer mechanism 125d; Raw fuel transfer amount adjustment Means 126a; Water tank 126b; Pipe 126c for transferring water from the water tank to the fuel tank; Transfer mechanism 126d; Water transfer amount adjusting means 127a; Burner 127b; Evaporating part 127c; Reforming part 127d; Anode off gas (or liquid) discharge line 130; oxidant gas supply device 131; oxidant gas supply source 132; oxidant gas supply line (pipe)
133; Oxidant gas transfer mechanism 133a; Flow rate regulator 134; Cathode offgas discharge line 140; Cathode offgas treatment device 140a; Fuel decomposition and removal device 140b; Fuel adsorption and removal device 140c; Fuel absorption and removal device 150;

Claims (7)

An electrolyte membrane-electrode assembly comprising an anode bonded to one surface of an anion exchange type electrolyte membrane that allows fuel and water to permeate, and a cathode bonded to the other surface, supplying fuel to the anode, and oxidizing agent A solid polymer electrolyte fuel cell that generates electricity by supplying gas and water to the cathode, a fuel supply device for supplying fuel to the anode, and an oxidant for supplying oxidant gas to the cathode A solid polymer electrolyte fuel cell power generation system comprising a gas supply device, wherein water can be supplied from at least one selected from the fuel supply device and the oxidant gas supply device, from a cathode of the fuel cell And a cathode offgas treatment device for removing the fuel from the cathode offgas containing the fuel discharged and mixed through the electrolyte membrane. Solid polymer electrolyte fuel cell power generation system according to. The solid polymer electrolyte fuel cell power generation system according to claim 1, wherein a water-soluble fuel is used as the fuel. 3. The solid polymer electrolyte fuel according to claim 1, wherein the cathode offgas treatment device is at least one selected from the group consisting of a fuel decomposition and removal device, a fuel adsorption and removal device, and a fuel absorption and removal device. Battery power generation system. The solid polymer electrolyte fuel cell power generation system according to claim 1 or 2, wherein the fuel separated from the cathode offgas in the cathode offgas treatment apparatus is reused. The fuel device supplies water-soluble fuel and water, and the cathode offgas treatment device is a fuel absorption and removal device using water as an absorbent, and the water absorbed in the cathode offgas treatment device 5. The solid polymer electrolyte fuel cell power generation system according to claim 4, wherein the fuel separated from the cathode off gas by being supplied to the molecular electrolyte fuel cell is reused. 6. 6. The solid polymer electrolyte fuel cell power generation system according to claim 1, wherein the anode and the cathode in the solid polymer electrolyte fuel cell both contain a transition metal catalyst. 7. The solid polymer according to claim 6, wherein the catalyst contained in the anode is active with respect to the fuel, and the activity of the catalyst contained in the cathode with respect to the fuel is lower than the activity of the catalyst contained in the anode with respect to the fuel. Electrolytic fuel cell power generation system.

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