JP4873880B2 - FUEL CELL, MANUFACTURING METHOD THEREOF, POWER SUPPLY AND ELECTRONIC DEVICE - Google Patents

Description

  The present invention relates to a fuel cell, a fuel cell manufacturing method, a power source, and an electronic device.

  From the viewpoint of environmental problems represented by greenhouse gases, fuel cells as clean energy sources are being developed at a rapid pace. In particular, solid oxide fuel cells are actively researched and developed because they operate at low temperatures and are small and have high power density. However, a cause of deterioration of the fuel cell is a decrease in power generation characteristics due to decomposition of the electrolyte. As one of the factors, deterioration of the electrolyte by hydrogen peroxide generated in the fuel cell is known. There are various types of fuel and oxidizer supplied to the fuel cell, but the piping and the mechanism are generally composed of inexpensive SUS. SUS is generally stable, but may release (dissolve) a small amount of metal ions in fuel or oxidant. At this time, the metal ions can be a factor causing deterioration of the electrolyte in the oxidation-reduction atmosphere of the fuel cell. In particular, iron ions are known to act as strong oxidants when confused with hydrogen peroxide, and when introduced into the fuel cell and reach the catalyst layer or electrolyte membrane, the durability of the fuel cell is reduced. .

  In order to prevent metals and impurities that are not originally required from being introduced into the fuel cell, it is common to provide a filter such as a chemical filter or a physical filter in the supply path of fuel, oxidant, or the like. However, there is a problem that the size and cost of the fuel cell increase.

  Therefore, Patent Document 1 discloses a highly durable solid polymer electrolyte membrane comprising a composition containing a polymer having a hydrocarbon portion and a phosphate group-containing polymer obtained by polymerizing a phosphate group-containing unsaturated monomer. Is disclosed.

  Patent Document 2 discloses a polymer solid electrolyte containing a phosphate group-containing polymer obtained by polymerizing a (meth) acrylic acid ester containing a phosphate group at a side chain end alone or with another vinyl monomer. ing.

  Patent Document 3 discloses a polymer blend proton conductor obtained by mixing a polymer having a proton acid group and a non-conductive polymer having film-forming properties.

  Patent Document 4 discloses a solid polymer ion conductor obtained by electric field orientation of a polymer having an ion dissociable group.

However, a fuel cell obtained using such a material has a problem of insufficient durability.
JP 2004-79252 A Japanese Patent Laid-Open No. 2001-114834 JP 2002-294087 A JP 2003-234015 A

  The present invention has been made in view of the above-described problems of the prior art, and provides a fuel cell having excellent durability, a method for manufacturing a fuel cell having excellent durability, a power source having the fuel cell, and an electronic device having the power source. And

Invention according to claim 1, in the fuel cell to have a laminated structure in which a catalyst layer and a diffusion layer are sequentially stacked on the electrolyte membrane, the electrolyte membrane, at least one of the catalyst layer and the diffusion layer, Containing a polymer having a phosphoric acid group and a nonionic copolymer , wherein the nonionic copolymer has the chemical formula
-CF ₂ CH ₂ -,
Structural unit, chemical formula
-CF ₂ CFCl-
Structural unit and general formula
_{-CH 2 CH (CH 2 OCOOR 5} ) -
Wherein R ₅ is a chemical formula
—CH ₂ CH ₂ —
Structural unit and / or chemical formula
—CF ₂ CH ₂ —
It is a side chain which has a structural unit shown by these. )
It is a graft copolymer which has a structural unit shown by these.

According to the invention described in claim 1, it is possible to provide a fuel cell having excellent durability. Moreover, association of the polymer having a phosphate group can be suppressed.

The invention according to claim 2 is the fuel cell according to claim 1, wherein the polymer having a phosphate group is represented by the general formula:

（式中、Ｒ _１ は、水素原子又はメチル基であり、Ｒ _２ は、水素原子、メチル基又はクロロメチル基であり、ｎは、１以上６以下である。）
で示される化合物由来の構成単位を有することを特徴とする。

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, a methyl group or a chloromethyl group, and n is 1 or more and 6 or less.)
It has the structural unit derived from the compound shown by characterized by the above-mentioned.

According to the invention described in claim 2, it is possible to improve the oxidation resistance.

The invention according to claim 3 is the fuel cell according to claim 2, wherein the polymer having a phosphate group is represented by the general formula:

（式中、Ｒ _３ は、水素原子又はメチル基である。）
で示される化合物由来の構成単位及び／又は一般式

(In the formula, R ₃ is a hydrogen atom or a methyl group.)
A structural unit and / or a general formula derived from the compound represented by

（式中、Ｒ _４ は、水素原子又はメチル基である。）
で示される化合物由来の構成単位を有することを特徴とする。

(In the formula, R ₄ is a hydrogen atom or a methyl group.)
It has the structural unit derived from the compound shown by characterized by the above-mentioned.

According to the invention described in claim 3, it is possible to improve the ion-conductivity.

According to a fourth aspect of the present invention, in the fuel cell according to any one of the first to third aspects, the power generation is performed using a fuel containing alcohol.

According to the invention described in claim 4, it is possible to obtain a fuel cell using a high energy density fuel.

The invention according to claim 5 is the fuel cell according to claim 4 , wherein the alcohol is ethanol.

According to the invention described in claim 5, it is possible to environmental integrity to obtain a fuel cell using a high fuel.

Invention according to claim 6, in the manufacturing method of the fuel cell, forming a diffusion layer by polymerizing a monomer having a phosphoric acid group in a liquid containing multi porous material and a non-ionic copolymer It is characterized by having.

According to the invention described in claim 6, it is possible to provide a manufacturing method of a fuel cell having excellent durability.

The invention of claim 7 is a method of manufacturing a fuel cell, by polymerizing a monomer having a phosphoric acid group in the liquid in which catalytic contains a catalyst carrier and a non-ionic copolymer being carried It has the process of forming a catalyst layer, It is characterized by the above-mentioned.

According to the invention described in claim 7, it is possible to provide a manufacturing method of a fuel cell having excellent durability.

According to an eighth aspect of the present invention, the power source includes the fuel cell according to any one of the first to fifth aspects.

According to the invention described in claim 8, it is possible to provide a power supply which is excellent in durability.

According to a ninth aspect of the present invention, an electronic apparatus includes the power source according to the eighth aspect.

According to invention of Claim 9 , the electronic device which has a power supply excellent in durability can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the fuel cell excellent in durability, the fuel cell excellent in durability, the power supply which has this fuel cell, and the electronic device which has this power supply can be provided.

  The fuel cell of the present invention has at least a laminated structure in which a catalyst layer and a diffusion layer are sequentially laminated on an electrolyte membrane, and at least one of the electrolyte membrane, the catalyst layer, and the diffusion layer contains a compound having a phosphate group. contains. Thereby, decomposition | disassembly of electrolyte can be suppressed and the lifetime of a fuel cell can be improved. At this time, an electrode can be formed by laminating the catalyst layer and the diffusion layer, and the catalyst layers of the anode and the cathode contain catalysts for the respective electrode reactions. Thus, an electrolyte membrane / electrode assembly in which the electrolyte membrane is sandwiched between the anode and the cathode can be formed.

It is considered that the compound having a phosphate group used in the present invention suppresses the decomposition of the electrolyte because the phosphate group has an effect of capturing impurity ions such as iron ions. In the compound having a phosphate group, at least one of the counter ions of the ion dissociation part (—O ⁻ ) of the phosphate group is preferably a proton. When both counter ions are not protons, the effect of capturing impurity ions is reduced. For this reason, it is more preferable that both counter ions are protons.

  The compound having a phosphoric acid group may be a stable compound that is difficult to decompose or dissolve under various operating conditions of the fuel cell such as temperature, humidity, fuel type, and fuel concentration. (Alkyl) methacrylate), poly (acid phosphooxy (alkyl) acrylate), poly (acid phosphooxy (oxyalkyl) methacrylate) and poly (acid phosphooxy (oxyalkyl) acrylate) and their derivatives can be used. Specifically, poly (acid phosphooxyethyl methacrylate), poly (acid phosphooxy (chloropropyl) methacrylate), poly (acid phosphooxypropyl methacrylate), poly (acid phosphooxyethyl acrylate), poly (acid phosphooxyethyl acrylate) Polyoxyethylene glycol) methacrylate), poly (acid phosphooxy (polyoxypropylene glycol) methacrylate) and the like.

  In the present invention, the compound having a phosphate group has the general formula

で示される化合物を重合することにより得られる重合体であることが好ましい。ここで、Ｒ_１は、水素原子又はメチル基であり、Ｒ_２は、水素原子、メチル基又はクロロメチル基であり、ｎは、１以上６以下である。

It is preferable that it is a polymer obtained by superposing | polymerizing the compound shown by these. Here, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, a methyl group or a chloromethyl group, and n is 1 or more and 6 or less.

  In addition, the compound having a phosphate group has a general formula

で示される化合物及び一般式

And a compound represented by the general formula

で示される化合物の少なくとも一方を重合することにより得られる重合体であることが好ましい。ここで、Ｒ_３及びＲ_４は、それぞれ独立に水素原子又はメチル基であり、Ｘは、水素、メチル基又はクロロメチル基であり、ｎは、１以上６以下である。

It is preferable that it is a polymer obtained by superposing | polymerizing at least one of the compounds shown by these. Here, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, X is hydrogen, a methyl group or a chloromethyl group, and n is 1 or more and 6 or less.

  In addition, the compound which has a phosphoric acid group may be a copolymer obtained by copolymerizing the above-mentioned compound and another monomer.

  The phosphate group is a functional group that easily associates, but the association occurs by hydrogen bonding. The associated phosphate group is not preferable because the effect of capturing impurity ions is reduced. Moreover, the ion conductivity of a phosphate group also falls by association. For this reason, by suppressing the association of phosphate groups, the ion conductivity is improved and the ability to capture impurity ions is improved.

  In the present invention, the compound having a phosphate group is preferably used by mixing with a nonionic copolymer. Thereby, association of phosphate groups can be suppressed.

  Nonionic copolymers include vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoro. Examples thereof include an ethylene copolymer, and it is preferable to use a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer.

  A nonionic copolymer is a copolymer obtained by copolymerizing two or more kinds of nonionic monomers, but a copolymer obtained by copolymerizing three or more kinds of nonionic monomers is used as a copolymer. It is preferable to use it. The structural units constituting the nonionic copolymer have different compatibility with the medium. For this reason, the more types of structural units constituting the nonionic copolymer, the more compatible the nonionic copolymer and the compound having a phosphate group, the phosphoric acid in the liquid containing the nonionic copolymer. The dispersion stability of the compound having a group can be improved.

  In the present invention, the nonionic copolymer is preferably a graft copolymer. Thereby, the dispersion stability of the compound which has a phosphoric acid group in the liquid containing a nonionic copolymer can further be improved.

  Examples of such a graft copolymer include a graft copolymer obtained by graft polymerization of monomers such as vinylidene fluoride, tetrafluoroethylene, chlorofluoroethylene, and hexafluoropropylene.

In the present invention, the graft copolymer has the chemical structural formula —CF ₂ CH ₂ —,
—CF ₂ CFCl— and —CH ₂ CH (CH ₂ OCOOR ₅ ) —
It is preferable that it has a structural unit shown by these. Here, R ₅ represents a chemical structural formula —CH ₂ CH ₂ — and —CF ₂ CH ₂ —.
It is a side chain which has at least one of the structural units shown by. At this time, the constitutional unit derived from vinylidene fluoride is preferably 50 to 95%, particularly preferably 90 to 95%. Moreover, it is preferable that the length of the main chain and the length of the side chain are approximately the same.

  Such a nonionic copolymer is formed from a liquid containing a nonionic copolymer and a compound having a phosphate group, since the compatibility or dispersibility with respect to the compound having a phosphate group is good. The resin material has a more uniform distribution of the nonionic copolymer and the compound having a phosphate group, and has a more uniform mechanical strength and ionic conductivity throughout the resin material. The effect of supplementing is uniform and large.

  In the present invention, when a nonionic copolymer and a compound having a phosphate group are mixed, the compound having a phosphate group is added in a state where the nonionic copolymer is dissolved or melted in a solvent. And stirring and mixing is preferable. Thereby, the liquid which has ion conductivity can be prepared.

  When stirring and mixing, it can be refined and mixed using various stirring, dispersion, and mixing methods. As a mixing method, a homogenizer for refining and mixing solids with a rotating blade, a three-roll mill for refining and mixing particles with a gap of three rotating rolls, particles by mixing and stirring beads A dispersion method such as a sand mill for refining and mixing the particles and an ultrasonic dispersion method for refining and mixing the particles by ultrasonic vibration can be used.

  After adding a porous body that forms a diffusion layer or a catalyst carrier that forms a catalyst layer in a liquid having ion conductivity, a compound having a phosphate group is compounded by mixing, collecting, and drying. A diffusion layer or a catalyst layer can be obtained.

  Moreover, an electrolyte membrane can be formed by applying a liquid having ion conductivity.

  In the present invention, the liquid having ion conductivity is preferably prepared by the following method.

  First, at least a monomer containing a monomer having a phosphate group is added to a liquid (solution or melt) containing a nonionic copolymer, and the mixture is stirred and mixed. Next, external energy such as heat and light is applied while stirring the obtained mixture. In addition, you may add a polymerization initiator to the mixture of the liquid and monomer containing a nonionic copolymer. Next, the monomer is polymerized by a polymerization initiator or self-polymerization property to obtain a liquid having ion conductivity.

  In such a method for producing a liquid having ion conductivity, a monomer is added to a liquid containing a nonionic copolymer without directly mixing the nonionic copolymer and the compound having a phosphate group. Therefore, the nonionic copolymer and the monomer can be mixed in a shorter time. When directly mixing a nonionic copolymer and a compound having a phosphate group, the steric hindrance due to the molecular chains of both resins is large and the molecular chains are not easily entangled. The time will be longer. On the other hand, in the above method, since a monomer having a small steric hindrance due to the molecular chain is used, mixing with the nonionic copolymer can be achieved in a shorter time.

  In addition, since the monomer is polymerized in the vicinity of the nonionic copolymer, a liquid having ion conductivity in which the compound having a phosphate group and the nonionic copolymer have good compatibility or dispersibility can be obtained. .

  Furthermore, when the nonionic copolymer and the compound having a phosphoric acid group are directly mixed, the compatibility and dispersibility of the nonionic copolymer and the compound having a phosphoric acid group are ionic conductive liquids. The mechanical strength or ionic conductivity of the electrolyte membrane formed from a liquid having ionic conductivity is uneven throughout the electrolyte membrane or locally. May be. Specifically, in the region where the proportion of the compound having a phosphate group in the electrolyte membrane is relatively high, the ion conductivity and the ability to capture impurity ions are sufficient, but the mechanical strength tends to be insufficient. In the region where the proportion of the nonionic copolymer in the electrolyte membrane is relatively high, the mechanical strength is sufficient, but the ion conductivity and the ability to capture impurity ions tend to be insufficient. In such a case, destruction of a region having a relatively low mechanical strength in the electrolyte membrane proceeds, and the function may not be maintained. On the other hand, in the liquid having ion conductivity obtained by the above method, the compatibility or dispersibility of the nonionic copolymer and the compound having a phosphate group is good. For this reason, in the electrolyte membrane formed from the liquid having ion conductivity, the nonionic copolymer and the compound having a phosphate group have a more uniform distribution, and the electrolyte membrane is more uniform throughout the electrolyte membrane. It can have mechanical strength, ionic conductivity, and the ability to capture impurity ions.

  In the present invention, the catalyst layer and the diffusion layer are preferably formed as follows. To a solution or melt of a nonionic copolymer, a monomer containing a monomer having a phosphoric acid group and a catalyst carrier on which a catalyst is supported or a porous material forming a diffusion layer are added and stirred. To do. While stirring this mixture, external energy such as heat and light is applied to polymerize the monomer, whereby a catalyst layer or a diffusion layer in which a compound having a phosphate group is combined can be obtained.

  Since the monomer is polymerized in the vicinity of the catalyst carrier or the porous body and the nonionic copolymer, the catalyst layer or the diffusion layer in which the compound having a phosphate group is complexed can maintain a good dispersion state. . For this reason, in this way, various characteristics of the catalyst layer or the diffusion layer can be made more uniform and good.

  The catalyst carrier or porous body used in the present invention is preferably a material having electron conductivity. Specifically, natural graphite or graphite-based carbon can be used. Also, a conductive carbon body, pitch, synthetic polymer or natural polymer obtained by firing coal, pitch, synthetic polymer or natural polymer in a reducing atmosphere at 800 to 1300 ° C. is reduced to 2000 ° C. or higher. A synthetic carbon body such as a conductive carbon body obtained by firing under the above can also be used. Furthermore, you may use these individually or in mixture of 2 or more types. By compounding the catalyst with these catalyst carrier and porous body, a catalytic reaction can be performed, and electrons and ions generated by the catalytic reaction can be propagated.

  A conventionally known method can be used as the catalyst combining method. As will be described later, it is preferable to use a catalyst comprising platinum and ruthenium or iridium for the oxidation of methanol, and for the oxidation of ethanol, two or more metals selected from the group consisting of ruthenium, iridium, tungsten and tin and It is preferable to use a catalyst made of platinum. The reason why these catalysts are preferable is that these media contribute to the promotion of the progress of the complex reactant processes of methanol and ethanol.

  As an example of a device to which the fuel cell of the present invention can be applied, a fuel cell using a proton conducting solid polymer electrolyte will be taken as an example and the concept of power generation will be described. As shown in FIG. 1, as a basic component, an electrolyte membrane 11 (proton conductor in the figure) is present at the center, and an anode 12 and a cathode 13 are arranged on both sides thereof. When a proton-conducting electrolyte is used, fuel such as hydrogen or alcohol serving as a proton source is supplied to the anode 12 side, and protons are generated from the fuel by the catalytic action in the anode 12. At this time, the simultaneously generated electrons flow out to the external circuit. The generated protons propagate through the electrolyte membrane 11 and reach the cathode 13. At the cathode 13, an oxidant such as air or oxygen supplied to the cathode 13 reacts with protons and electrons generated at the anode 12 to generate water. The above is the concept of power generation, and the reaction formula when hydrogen is used as the fuel is as follows.

Anode reaction; H ₂ → 2H ⁺ + 2e ⁻
Cathode reaction: 2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O
Total reaction; H ₂ + 1 / 2O ₂ → H ₂ O
In such a fuel cell, the laminated structure of the anode diffusion layer / anode catalyst layer / electrolyte membrane / cathode catalyst layer / cathode diffusion layer is the part that actually generates power.

  Fuel and an oxidant are supplied to the anode diffusion layer and the cathode diffusion layer, respectively. The diffusion layer combined with the compound having a phosphate group used in the present invention can be applied to this portion.

  The anode catalyst layer and the cathode catalyst layer are made of a material capable of both electron conduction and ion conduction and capable of catalytic reaction. The catalyst layer combined with the compound having a phosphate group used in the present invention can be applied to this portion.

The fuel cell of the present invention is more suitable depending on the type of catalyst, but the fuel is not particularly limited. However, since the fuel is usually stored in a finite space such as a container, it is preferable to use a fuel having an excellent volume energy density and weight energy density. In particular, it is preferable to use a fuel having an excellent volume energy density. Since gaseous fuel is inferior in volume energy density, it is not preferable, and it is preferable to use liquid fuel or solid fuel. This is because, for example, the number of electrons that can be extracted by the oxidation reaction of one molecule of hydrogen, methanol, and ethanol is 2, 6, and 12, respectively, and the amount of coulomb that can be extracted from 1 mol of each molecule is the theoretical value. 96500 × 2C, 96500 × 6C, and 96500 × 12C. Considering density and molecular weight of each, in terms of coulombs per each molecule 1 cm ^3, hydrogen, volumetric energy density of methanol and ethanol, respectively about 9C / cm ^3, from about 14400C / cm ³ and 15200C / cm ³ It becomes. Hydrogen as a normal pressure gas has a significantly low volumetric energy density. As shown in the following reaction formula, one molecule and three molecules of water are required for the oxidation reaction of one molecule of methanol and ethanol, respectively, but it is clear that liquid fuel is excellent even if this is added. .

CH ₃ OH + H ₂ O → 6H ⁺ + 6e ⁻ + CO ₂
C ₂ H ₅ OH + 3H ₂ O → 12H ⁺ + 12e ⁻ + 2CO ₂
Although hydrogen or liquid hydrogen in a high pressure state can be used, it is necessary to make the container robust, and in consideration of the energy density contained in the container, liquid or solid fuel is excellent at normal temperature and pressure. Specifically, hydrogen, gasoline, hydrocarbon, alcohol, or other solid fuel or liquid fuel stored in a hydrogen storage alloy can be used, but the main body fuel cell can be miniaturized, and the volume energy density is excellent. It is more preferable to use a fuel containing alcohol. By using a fuel containing alcohol, a small fuel cell with improved driving time can be formed. The alcohol is preferably an alcohol having 4 or less carbon atoms, and ethanol is particularly preferable from the viewpoint of high safety and biosynthesis (environmental aspect). Since the fuel cell of such a form is excellent in volume energy density and weight energy density, it is especially preferable when used for a relatively small electronic device.

  Further, the fuel cell of the present invention is a so-called reformed fuel type in which a liquid fuel such as liquefied natural gas (LNG) or methane gas or a liquid fuel such as methanol is reformed to obtain hydrogen to be used as fuel for the fuel cell. The present invention can also be applied to other fuel cells. In this case, there is a problem (catalyst poisoning) that impairs the function of the fuel cell due to carbon monoxide present in the hydrogen gas fuel obtained by reforming the raw fuel and other trace impurities. The problem of carbon monoxide poisoning of the catalyst has been studied conventionally, and there is a platinum-ruthenium alloy catalyst as a catalyst for reducing this problem.

  However, the inhibitory factor of the catalytic chemical reaction in the anodic oxidation of methanol and ethanol in a solution cannot often be explained by carbon monoxide poisoning. This is because methanol and ethanol are oxidized through a number of elementary reactions, unlike hydrogen and carbon monoxide. According to this embodiment, it is preferable to use a catalyst comprising platinum and ruthenium or iridium for the oxidation of methanol, and two or more selected from the group consisting of ruthenium, iridium, tungsten and tin for the oxidation of ethanol. It is preferable to use a catalyst comprising the above metals and platinum. The reason why these catalysts are suitable is that they contribute to the promotion of the progress of complex reactant processes of methanol and ethanol. Moreover, ethanol can be preferably used as a fuel capable of reducing the carbon dioxide gas load from the viewpoint that biosynthesis can be performed from a raw material of biological origin.

  Based on FIGS. 2-5, the embodiment of the electronic device of this invention and a power supply is described. An information processing apparatus such as a portable personal computer will be described as an example of the electronic apparatus of the present embodiment.

  FIG. 2 is a diagram schematically illustrating an example of a personal computer, FIG. 3 is a block diagram schematically illustrating an example of an information processing apparatus, and FIG. 4 is a diagram schematically illustrating an example of a power source. FIG. 5 is a block diagram thereof.

  As shown in FIG. 3, the information processing apparatus includes a CPU (Central Processing Unit) 31 that performs various operations and controls each unit intensively, a ROM (Read Only Memory) 32 that stores a BIOS (Bios), and the like. A RAM (Random Access Memory) 33 serving as a work area of the CPU 31 is connected by a bus 34. The bus 34 includes data from a hard disk drive (HDD) 35, a display device 36 such as an LCD (Liquid Crystal Display), an input device 37 such as a keyboard and a mouse, and a storage medium 38 such as a CD and a DVD. A data reading device 39 such as an optical disk device and a power supply 21 for supplying power are connected via various controllers (not shown).

  Various programs are stored in the storage medium 38. These programs are read by the data reading device 39 and installed in the HDD 35. As the storage medium 38, various types of media such as optical disks such as CD and DVD, magneto-optical disks, and flexible disks can be used. As the data reading device 39, an optical disk device, a magneto-optical disk device, an FDD, or the like is used according to the method of the storage medium 38. Various programs may be downloaded from a network (not shown) and installed in the HDD 35 instead of being read from the storage medium 38.

  As shown in FIG. 5, the power source is provided between the fuel cell 41, the liquid fuel cartridge 42 containing the liquid fuel, the mixer 43 connected to the liquid fuel cartridge 42, and between the liquid fuel cartridge 42 and the mixer 43. A valve 44, a liquid fuel pump 45 for supplying fuel to the fuel cell 41, a concentration sensor 46 for detecting fuel concentration, a gas-liquid separator 47 for separating the liquid fuel after power generation into gas and liquid, and a temperature sensor 48. And a heat exchanger 50 having a cooling element 49, an air pump 51 for supplying air to the fuel cell 41, a moisture condenser 54 having a temperature sensor 52 and a cooling element 53, and water containing moisture from the moisture condenser 54 A tank 55, a valve 56 provided between the water tank 55 and the mixer 43, a control circuit 57 for controlling these parts, and a positive and negative electrode of the fuel cell are connected. And it is configured from the DCDC converter 58, and the like. In addition, each part through which liquid fuel etc. pass is connected by flow paths, such as a tube.

  In such a power source, the liquid fuel that has passed through the mixer 43 is guided to the concentration sensor 46 via the liquid fuel pump 45. When the concentration of the liquid fuel detected by the concentration sensor 46 is lower than a predetermined concentration, the control circuit 57 opens the valve 44 of the liquid fuel cartridge 42. The liquid fuel is guided to the fuel cell 41. The liquid fuel after power generation is divided into a gas component (carbon dioxide gas) and a liquid component by the gas-liquid separator 47, and the liquid component is guided to the heat exchanger 50. When the temperature of the liquid component detected by the temperature sensor 48 is lower than the predetermined temperature, the control circuit 57 does not cool the liquid component by the cooling element 49, and when the temperature of the liquid component is higher than the predetermined temperature. The control circuit 57 cools the liquid component by the cooling element 49. The liquid component that has passed through the heat exchanger 50 is returned to the mixer 43 again. Such a flow functions as a fuel line.

Air from the air pump 51 is guided to the fuel cell 41. The gas-liquid mixed gas that has passed through the fuel cell 41 is guided to the moisture condenser 54. When the temperature of the gas-liquid mixed gas detected by the temperature sensor 52 is lower than the predetermined temperature, the control circuit 57 does not cool the gas-liquid mixed gas by the cooling element 53 and the temperature of the gas-liquid mixed gas is the predetermined temperature. When the temperature is higher than the temperature, the control circuit 57 cools the gas-liquid mixed gas by the cooling element 53. The exhaust gas is discharged outside the power source. Here, an exhaust port (not shown) for exhausting the exhaust gas is preferably provided at a position facing the outside of the information processing apparatus, although it varies depending on the position of the power supply in the information processing apparatus. The water condensed by the water condenser 54 is returned to the mixer 43 via the water tank 55. Such a flow functions as an oxidant line (air line). In this way, fuel (including air) is supplied to the fuel cell 41, so that the fuel cell 41 generates power and generates predetermined power (startup). Power) is applied to the DCDC converter 58. In the present embodiment, the power storage element is not used, but the present invention is not limited to this. For example, the power storage element may be provided inside or outside the power supply.

  In FIG. 5, the arrows indicate the flow of fuel and the like.

  As a nonionic copolymer, fluororesin 1, fluororesin 2 and fluororesin 3 were prepared.

  The fluororesin 1 is a graft copolymer having 93 to 95% of structural units derived from vinylidene fluoride, about 3 to 4% of structural units derived from chlorofluoroethylene, and about 2 to 3% of structural units derived from alkylpropylene carbonate. And the side chain is composed of a structural unit derived from vinylidene fluoride. The composition of the fluororesin 1 was calculated from the abundance ratio of each element obtained by XPS. XPS was measured using AXIS ULTRA (manufactured by Shimadzu Corporation), and the abundance ratios of F, O, C and Cl were 47.08, 1.71, 50.49 and 0.72, respectively. .

The fluororesin 2 is a linear copolymer having 40% structural units derived from vinylidene fluoride, 11% structural units derived from hexafluoropropylene, and 49% structural units derived from tetrafluoroethylene. The composition of the fluororesin 2 was determined by measuring ¹ HNMR and ¹⁹ FNMR using a Bruker DRX-500. As an internal standard substance, fluororesin 2 was mixed with 8.045% by weight of 1,1,2,2-tetrabromoethane, and ¹ HNMR was measured. From the integrated intensity ratio of the peak, the H content was It was found to be 28% by weight. Furthermore, when the integrated intensity ratio of CF ₃ and CF ₂ was determined using ¹⁹ FNMR, it was CF ₃ : CF ₂ = 3.858: 34.234.

The fluororesin 3 is polyvinylidene fluoride.
(Production Example 1 of Resin Material)
3.75 g of fluororesin 1 and 3.75 g of acid phosphooxyethyl methacrylate were added to dimethylformamide to obtain a uniform solution, and then azobisisobutyronitrile was added in an amount of 2% by weight with respect to acid phosphooxyethyl methacrylate. %added. While stirring the solution, it was kept at 75 ° C. for 24 hours and 85 ° C. for 1 hour, and then slowly cooled to obtain a liquid containing the resin material 1. The obtained liquid was milky white and uniform. The liquid containing the resin material 1 was applied onto a releasable plastic, and the solvent was removed by heating under vacuum. The obtained resin material 1 was thoroughly washed in heated methanol, then heated in boiling water, and stored in ion-exchanged water. The obtained resin material 1 was homogeneous.

The resin material 1 was punched with a metal mold having a diameter of 3 mm, and the impedance of the resin material 1 was measured using an impedance analyzer. The measured values of the real part and the imaginary part of the impedance were subjected to Cole-Cole plot, and the intersection of the extrapolation of the straight line from the low frequency part to the high frequency part and the real number axis was taken as the resistance value. The ionic conductivity was 1.0 × 10 ⁻² S / cm.
(Production Example 2 of Resin Material)
Resin material 2 was produced in the same manner as in Resin Material Production Example 1 except that the addition amounts of fluororesin 1 and acid phosphooxyethyl methacrylate were 4.73 g and 2.78 g, respectively. The liquid containing the resin material 2 was milky white and uniform. Moreover, the obtained resin material 2 was also homogeneous and the ionic conductivity was 2.9 * 10 < ^-3 > S / cm.
(Production Example 3 of Resin Material)
Resin material 3 was produced in the same manner as in Resin Material Production Example 1 except that the addition amounts of fluororesin 1 and acid phosphooxyethyl methacrylate were set to 5.63 g and 1.88 g, respectively. The liquid containing the resin material 3 was milky white and uniform. Moreover, the obtained resin material 3 was also homogeneous and the ionic conductivity was 2.1 * 10 < ^-3 > S / cm.
(Production Example 4 of Resin Material)
Resin material 4 was produced in the same manner as in Resin material production example 1 except that the addition amounts of fluororesin 1 and acid phosphooxyethyl methacrylate were 6.45 g and 1.05 g, respectively. The liquid containing the resin material 4 was milky white and uniform. Moreover, the obtained resin material 4 was also homogeneous and the ionic conductivity was 6.2 * 10 < ^-4 > S / cm.
(Production Example 5 of Resin Material)
Resin material 5 was produced in the same manner as in Production Example 1 for resin materials, except that the addition amounts of fluororesin 1 and acid phosphooxyethyl methacrylate were 1.83 g and 5.63 g, respectively. The liquid containing the resin material 5 was milky white and uniform. Moreover, the obtained resin material 5 showed a swell of about 1 mm in diameter on a part of the surface. The ionic conductivity was 5.8 × 10 ⁻² S / cm.
(Production Example 6 of Resin Material)
To dimethylformamide, 5.62 g of fluororesin 1 was added and dissolved. 1.88 g of poly (acid phosphooxyethyl methacrylate) was added to this solution, and primary dispersion was performed at 10,000 rpm using a rotary blade type homogenizer. Next, the liquid containing the resin material 6 became uniform by performing the treatment five times using a three-roll mill. The liquid containing the obtained resin material 6 was apply | coated on the moldable plastic, and the solvent was removed by heating under vacuum. The obtained resin material 6 was heated in boiling water and stored in ion-exchanged water. In addition, the obtained resin material 6 was homogeneous. As described above, the ionic conductivity was evaluated and found to be 1.5 × 10 ⁻³ S / cm.
(Comparative production example 1 of resin material)
2.78 g of acid phosphooxyethyl methacrylate was added to dimethylformamide to obtain a uniform solution, and then 2% by weight of azobisisobutyronitrile was added to the acid phosphooxyethyl methacrylate. Gelation occurred when the solution was heated to 75 ° C. with stirring. From the comparison with the result of the resin material production example 2, it can be seen that the fluororesin 1 has an effect of suppressing association.
(Comparative production example 2 of resin material)
To dimethylformamide, 4.73 g of fluororesin 3 and 2.78 g of acid phosphooxyethyl methacrylate were added to obtain a uniform solution, and then azobisisobutyronitrile was added at 2% by weight with respect to acid phosphooxyethyl methacrylate. added. While stirring the solution, it was kept at 75 ° C. for 24 hours and 85 ° C. for 1 hour, and then slowly cooled to obtain a liquid containing a resin material. Since the resin material was deposited, it was not uniform. From the comparison with the result of the resin material production example 2, it can be seen that the fluororesin 1 has an effect of improving the dispersion stability.
(Comparative Production Example 3 of Resin Material)
A poly (acid phosphooxyethyl methacrylate) powder was pressed at 200 kg / cm ² to form a disk having a diameter of about 10 mm. When this was added to ion-exchanged water, the disk swelled and collapsed. This shows that the fluororesin 1 has an effect of improving moldability.
(Production Example 7 of Resin Material)
Instead of acid phosphooxyethyl methacrylate, the chemical structural formula CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _n PO (OH) ₂
Resin material 7 was produced in the same manner as in Resin Material Production Example 2 except that the monomer represented by (n = 4 to 5) was used. The obtained resin material 7 was homogeneous, but the ionic conductivity was 1.7 × 10 ⁻³ S / cm.
(Production Example 8 of Resin Material)
Resin material 8 was produced in the same manner as in Resin Material Production Example 1 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The liquid containing the resin material 8 was light milky white and uniform. Moreover, the obtained resin material 8 was also homogeneous and the ionic conductivity was 8.2 * 10 < ^-3 > S / cm.
(Production Example 9 of Resin Material)
Resin material 9 was produced in the same manner as in Resin Material Production Example 2 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The liquid containing the resin material 9 was light milky white and uniform. Moreover, the obtained resin material 9 was also homogeneous and the ionic conductivity was 3.4 * 10 < ^-3 > S / cm.
(Production Example 10 of Resin Material)
Resin material 10 was produced in the same manner as in Resin Material Production Example 3 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The liquid containing the resin material 10 was light milky white and uniform. Moreover, the obtained resin material 10 was also homogeneous and the ionic conductivity was 2.3 * 10 < ^-3 > S / cm.
(Production Example 11 of Resin Material)
Resin material 11 was produced in the same manner as in Resin Material Production Example 4 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The liquid containing the resin material 11 was light milky white and uniform. Moreover, the obtained resin material 11 was also homogeneous and the ionic conductivity was 5.4 * 10 < ^-4 > S / cm.
(Production Example 12 of Resin Material)
Resin material 12 was produced in the same manner as in Resin Material Production Example 5 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The liquid containing the resin material 12 was milky white and uniform. In addition, the obtained resin material 12 showed a swell of about 1 mm in diameter on a part of the surface. The ionic conductivity was 1.6 × 10 ⁻² S / cm.
(Production Example 13 of Resin Material)
Resin material 13 was produced in the same manner as in Resin Material Production Example 6 except that acid phosphooxychloropropyl methacrylate was used instead of acid phosphooxyethyl methacrylate. The obtained resin material 13 was homogeneous. The ionic conductivity was 1.5 × 10 ⁻³ S / cm.
(Comparative Production Example 4 of Resin Material)
A poly (acid phosphooxychloropropyl methacrylate) powder was pressed at 300 kg / cm ² to form a disk having a diameter of about 10 mm. When this was added to ion-exchanged water, the disk swelled and collapsed. This shows that the fluororesin 1 has an effect of improving moldability.
(Production Example 14 of Resin Material)
Resin material 14 was produced in the same manner as in Resin Material Production Example 8 except that fluororesin 2 was used instead of fluororesin 1 and methyl ethyl ketone was used instead of dimethylformamide. The liquid containing the resin material 14 was milky white and uniform. The ionic conductivity was 0.011 S / cm.
Example 1
Using a doctor blade, the liquid containing the resin material 1 was applied to a releasable plastic sheet, dried, and then washed with methanol to obtain an electrolyte membrane (8 cm × 8 cm) having a thickness of about 180 μm.

After adding 1 g of carbon carrying 50% by weight of platinum catalyst and 7.4 g of 5% by weight Nafion ™ liquid to 10 g of distilled water, dispersion treatment was performed to obtain a cathode catalyst layer coating solution. The cathode catalyst layer coating solution was spray-coated on one surface of the electrolyte membrane so that the amount of platinum applied was 1 mg / cm ² . The application area was 5 cm × 5 cm.

After adding 1 g of carbon carrying 40% by weight of platinum-ruthenium catalyst (element ratio 1: 1) and 7.4 g of 5% by weight Nafion ™ liquid to 10 g of distilled water, dispersion treatment was performed, and the anode catalyst layer A coating solution was obtained. The anode catalyst layer coating solution was spray coated on the surface of the electrolyte membrane opposite to the surface coated with the platinum catalyst so that the coating amount of platinum was 1 mg / cm ² . The application area was 5 cm × 5 cm.

  The obtained electrolyte membrane was heat-treated at 110 ° C., and then a fuel cell shown in FIG. 6 was produced. The electrolyte membrane 61 is sandwiched between the anode catalyst layer 62 and the cathode catalyst layer 63. Further, the fuel cell includes a diffusion layer 64 (thickness 200 μm, 53 mm × 53 mm) made of carbon paper, a liquid fuel supply unit 65 and an oxidant supply unit 66 (thickness 10 mm, 80 mm × 80 mm) made of resin-impregnated high-density artificial graphite. , Flow path shape: serpentine, flow path outer dimension 50 mm × 50 mm), current collector plate 67 plated with gold on copper, insulating plate 68 (thickness 500 μm, 80 mm × 80 mm), end plate 69 (SUS304, thickness 12 mm, 120 mm × 120 mm) and a Teflon (registered trademark) sealing member 70 (thickness 200 μm, outer dimensions 80 mm × 80 mm, inner diameter 54 mm × 54 mm).

  In addition, the end plate 69 was fixed at three places (12 places in total) with respect to one side using the bolt 71 and the support rod 72. The liquid fuel supply port 73, the liquid fuel discharge port 74, the oxidant supply port 75, and the oxidant discharge port 76 are provided on the side surface of the end plate 69. The insulating plate 68, the liquid fuel supply unit 65, and the oxidant supply unit 66 are provided with holes for guiding the liquid fuel and the oxidant, and an O-ring (not shown) is provided on the surface of the current collector plate 67. Prevented leakage.

When the flow rate of a 1 wt% methanol aqueous solution (liquid fuel) was 3 ml / min and the flow rate of air (oxidant) was 50 ml / min and supplied to the fuel cell, the open circuit voltage was 0.59 V.
(Example 2)
A fuel cell was produced in the same manner as in Example 1 except that the resin material 8 was used instead of the resin material 1.

When the flow rate of a 1 wt% aqueous methanol solution was 3 ml / min and the air flow rate was 50 ml / min and the fuel cell was supplied, the open circuit voltage was 0.6V.
( Reference Example 3)
Using a doctor blade, the liquid containing the resin material 14 was applied to a releasable plastic sheet, dried, and then washed with methanol to obtain an electrolyte membrane having a thickness of about 250 μm (8 cm × 8 cm).

  A fuel cell was produced in the same manner as in Example 1 except that the obtained electrolyte membrane was used.

When the flow rate of a 1 wt% aqueous methanol solution was 3 ml / min and the air flow rate was 50 ml / min and the fuel cell was supplied, the open circuit voltage was 0.61V.
Example 4
Using a doctor blade, the liquid containing the resin material 1 was applied to a releasable plastic sheet, dried, and then washed with methanol to obtain an electrolyte membrane having a thickness of about 250 μm (8 cm × 8 cm).

  To 10 g of dimethylformamide, 2.7 g of a liquid containing 1 g of carbon carrying 50% by weight of a platinum catalyst and a liquid containing resin material 1 diluted 3.6 times with dimethylformamide was added and dispersed to obtain a cathode catalyst. A layer coating solution was obtained.

  2.7 g of a liquid containing 1 g of carbon carrying 40% by weight of platinum-ruthenium catalyst (element ratio 1: 1) and a liquid containing resin material 1 diluted to 1.6 times with dimethylformamide is added to 10 g of dimethylformamide. Then, dispersion treatment was performed to obtain an anode catalyst layer coating solution.

  Carbon paper (thickness 200 μm, 53 mm × 53 mm) was immersed in a liquid obtained by diluting and dispersing the liquid containing the resin material 1 with dimethylformamide 3.6 times, and vacuum degassing was performed. Next, the carbon paper was taken out, washed, and dried to obtain a diffusion layer.

  A fuel cell was produced in the same manner as in Example 1 except that the obtained electrolyte membrane, cathode catalyst layer coating solution, anode catalyst layer coating solution and diffusion layer were used.

When the flow rate of the 1% by weight methanol aqueous solution was 3 ml / min and the air flow rate was 50 ml / min and the fuel cell was supplied, the open circuit voltage was 0.63V.
(Example 5)
Using a doctor blade, the liquid containing the resin material 1 was applied to a releasable plastic sheet, dried, and then washed with methanol to obtain an electrolyte membrane having a thickness of about 250 μm (8 cm × 8 cm).

  1.5 g of fluororesin 1 was added to 10.5 g of dimethylformamide and dissolved. To this was added 1.5 g of acid phosphooxyethyl methacrylate to obtain a uniform solution, and then azobisisobutyronitrile was added. Further, 2.2 g of carbon carrying 50% by weight of a platinum catalyst was added and mixed. The mixture was kept at 75 ° C. for 24 hours and 85 ° C. for 1 hour with stirring, and then slowly cooled to obtain a cathode catalyst layer coating solution.

  1.5 g of fluororesin 1 was added to 10.5 g of dimethylformamide and dissolved. To this was added 1.5 g of acid phosphooxyethyl methacrylate to obtain a uniform solution, and then azobisisobutyronitrile was added. Further, 2.2 g of carbon carrying 40% by weight of a platinum-ruthenium catalyst (element ratio 1: 1) was added and mixed. While stirring, the mixture was held at 75 ° C. for 24 hours and 85 ° C. for 1 hour, and then slowly cooled to obtain an anode catalyst layer coating solution.

  7.5 g of fluororesin 1 was added to 280 g of dimethylformamide and dissolved. To this was added 7.5 g of acid phosphooxyethyl methacrylate to obtain a uniform solution, and then azobisisobutyronitrile was added. Furthermore, carbon paper (thickness 200 μm, 53 mm × 53 mm) was immersed and vacuum deaeration was performed. While stirring, the mixture was held at 75 ° C. for 24 hours and 85 ° C. for 1 hour, and then gradually cooled. Next, the carbon paper was taken out, washed, and dried to obtain a diffusion layer.

  A fuel cell was produced in the same manner as in Example 1 except that the obtained electrolyte membrane, cathode catalyst layer coating solution, anode catalyst layer coating solution and diffusion layer were used.

When the flow rate of a 1% by weight methanol aqueous solution was 3 ml / min and the air flow rate was 50 ml / min and the fuel cell was supplied, the open circuit voltage was 0.65V.
(Example 6)
When the fuel cell of Example 1 was supplied to the fuel cell at a flow rate of 50 ml / min with excessively humid hydrogen and at a flow rate of 100 ml / min with excessively humidified oxygen, the open circuit voltage was 0.72V. When left open for 170 hours, the open circuit voltage was 0.69V.
(Example 7)
When the fuel cell of Example 5 was supplied to the fuel cell at a flow rate of 50 ml / min of overhumid hydrogen and at a flow rate of 100 ml / min of overhumid oxygen, the open circuit voltage was 0.74V. When left in an open circuit for 170 hours, the open circuit voltage was 0.74V.
(Oxidation resistance of resin material)
The resin material 1 was immersed in 3 wt% hydrogen peroxide containing 1 ppm of ferric sulfate and heated. When the weight was measured after 2 hours, it was 82% of the weight before immersion.

  The resin material 4 was immersed in 3 wt% hydrogen peroxide containing 1 ppm of ferric sulfate and heated. When the weight was measured after 2 hours, it was 64% of the weight before immersion.

It is a figure which shows the electric power generation concept of a fuel cell. It is a figure which shows an example of a personal computer schematically. It is a block diagram which shows an example of information processing apparatus roughly. It is a figure which shows an example of a power supply schematically. It is a block diagram which shows an example of a power supply schematically. It is a figure which shows the fuel cell of an Example.

Explanation of symbols

11 Electrolyte membrane 12 Anode 13 Cathode 14 Separator 21 Power supply 31 CPU
32 ROM
33 RAM
34 bus 35 HDD
36 Display Device 37 Input Device 38 Recording Medium 39 Data Reading Device 41 Fuel Cell 42 Liquid Fuel Cartridge 43 Mixer 44, 56 Valve 45 Liquid Fuel Pump 46 Concentration Sensor 47 Gas-Liquid Separator 48, 52 Temperature Sensor 49, 53 Cooling Element 50 Heat exchanger 51 Air pump 54 Water condenser 55 Water tank 57 Control circuit 58 DCDC converter 59 Terminal 61 Electrolyte membrane 62 Anode catalyst layer 63 Cathode catalyst layer 64 Diffusion layer 65 Liquid fuel supply unit 66 Oxidant supply unit 67 Current collector plate 68 Insulating plate 69 End plate 70 Seal member 71 Bolt 72 Support rod 73 Liquid fuel supply port 74 Liquid fuel discharge port 75 Oxidant supply port 76 Oxidant discharge port

Claims (9)

In the fuel cell to have a laminated structure in which a catalyst layer and a diffusion layer are sequentially stacked on the electrolyte membrane,
Wherein at least one of the electrolyte membrane, the catalyst layer and the diffusion layer contains a polymer having a phosphoric acid group and a non-ionic copolymer,
The nonionic copolymer has the chemical formula
-CF ₂ CH ₂ -,
Structural unit, chemical formula
-CF ₂ CFCl-
Structural unit and general formula
_{-CH 2 CH (CH 2 OCOOR 5} ) -
Wherein R ₅ is a chemical formula
—CH ₂ CH ₂ —
Structural unit and / or chemical formula
—CF ₂ CH ₂ —
It is a side chain which has a structural unit shown by these. )
A fuel cell comprising a graft copolymer having a structural unit represented by The polymer having a phosphate group has a general formula

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, a methyl group or a chloromethyl group, and n is 1 or more and 6 or less.)
The fuel cell according to claim 1, comprising a structural unit derived from a compound represented by the formula: The polymer having a phosphate group has a general formula

(In the formula, R ₃ is a hydrogen atom or a methyl group.)
A structural unit and / or a general formula derived from the compound represented by

(In the formula, R ₄ is a hydrogen atom or a methyl group.)
The fuel cell according to claim 2, comprising a structural unit derived from a compound represented by the formula: The fuel cell according to any one of claims 1 to 3 , wherein power is generated using a fuel containing alcohol. The fuel cell according to claim 4 , wherein the alcohol is ethanol. Method for manufacturing a fuel cell characterized by comprising the step of forming a diffusion layer by polymerizing a monomer having a phosphoric acid group in a liquid containing multi porous material and a non-ionic copolymer. Catalysts of the fuel cell characterized by comprising the step of forming a catalyst layer by polymerizing a monomer having a phosphoric acid group in a liquid containing the catalyst carrier and a non-ionic copolymer being carried Production method. A power supply comprising the fuel cell according to any one of claims 1 to 5 . An electronic apparatus comprising the power supply according to claim 8 .

Images