Proton conductor film, manufacturing method therefor, fuel cell provided with proton conductor film and manufacturing method therefor

Abstract

A proton conductor and film thereof, electrochemical device, such as a fuel cell, employing same and methods of manufacturing same are provided. The proton conductor material film includes a proton conductor and polyvinyl alcohol as a binder for the proton conductor. The proton conductor film develops a high output by an electrode reaction and has superior hydrogen gas intercepting performance.

1 : A proton conductor film for a fuel cell comprising: 
 a proton conductor and polyvinyl alcohol as a binder for the proton conductor; wherein    the proton conductor film is heated at a temperature ranging from about 150° C. to about 43° C.    
     
     
         2 : The proton conductor film according to  claim 1  wherein the proton conductor film has a thickness ranging from about 0.1 μm to about 20 μm.  
     
     
         3 : The proton conductor film according to  claim 1  wherein a layer of a proton conductor not containing polyvinyl alcohol is provided on each surface of the proton conductor film.  
     
     
         4 : The proton conductor film according to  claim 3  wherein the layer of the proton conductor not containing polyvinyl alcohol has a thickness of about 5 μm to about 20 μm.  
     
     
         5 : The proton conductor film according to  claim 1  wherein the proton conductor is formed by a fullerene derivative composed of proton dissociative groups introduced to the carbon atoms of fullerene molecules.  
     
     
         6 : The proton conductor film according to  claim 5  further comprising: 
 a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         7 : The proton conductor film according to  claim 6  wherein the hydrogen gas intercepting layer is formed on at least one surface of the proton conductor film.  
     
     
         8 : The proton conductor film according to  claim 7  wherein the hydrogen gas intercepting layer is formed on a surface towards an oxygen electrode of the proton conductor film.  
     
     
         9 : The proton conductor film according to  claim 7  wherein the hydrogen gas intercepting layer is formed on a surface towards a hydrogen electrode of the proton conductor film.  
     
     
         10 : The proton conductor film according to  claim 6  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         11 : The proton conductor film according to  claim 5  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         12 : The proton conductor film according to  claim 11  wherein the proton dissociative groups are selected from the group consisting of —OH, —YOH, and combinations thereof where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         13 : The proton conductor film according to  claim 12  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         14 : The proton conductor film according to  claim 5  wherein one or more electrophilic groups are introduced, along with the proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         15 : The proton conductor film according to  claim 14  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combination thereof.  
     
     
         16 : The proton conductor film according to  claim 5  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling at least one 36, 60, 70, 76, 78, 80, 82 and 84 in number.  
     
     
         17 : A proton conductor film for a fuel cell comprising: 
 a proton conductor and polyvinyl alcohol as a binder for the proton conductor; wherein    the proton conductor film is heated at a temperature ranging from about 3° C. to about 43° C.    
     
     
         18 : The proton conductor film according to  claim 17  wherein the proton conductor film has a thickness ranging from about 0.1 μm to about 20 μm.  
     
     
         19 : The proton conductor film according to  claim 17  wherein a layer of a proton conductor not containing polyvinyl alcohol is provided on each surface of the proton conductor film.  
     
     
         20 : The proton conductor film according to  claim 19  wherein the layer of the proton conductor not containing polyvinyl alcohol has a thickness of about 5 μm to about 20 μm.  
     
     
         21 : The proton conductor film according to claims  17  wherein the proton conductor is formed by a fullerene derivative composed of proton dissociative groups introduced to the carbon atoms of fullerene molecules.  
     
     
         22 : The proton conductor film according to  claim 21  further comprising: 
 a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         23 : The proton conductor film according to  claim 22  wherein the hydrogen gas intercepting layer is formed on at least one surface of the proton conductor film.  
     
     
         24 : The proton conductor film according to  claim 23  wherein the hydrogen gas intercepting layer is formed on a surface towards an oxygen electrode of the proton conductor film.  
     
     
         25 : The proton conductor film according to  claim 23  wherein the hydrogen gas intercepting layer is formed a surface towards a hydrogen electrode of the proton conductor film.  
     
     
         26 : The proton conductor film according to  claim 22  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         27 : The proton conductor film according to  claim 21  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         28 : The proton conductor film according to  claim 27  wherein the proton dissociative groups are selected from the group consisting of —OH, —YOH, and combinations thereof where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         29 : The proton conductor film according to  claim 28  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         30 : The proton conductor film according to  claim 21  wherein the electrophilic groups are introduced, along with the proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         31 : The proton conductor film according to  claim 30  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combination thereof.  
     
     
         32 : The proton conductor film according to  claim 21  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling at least one 36, 60, 70, 76, 78, 80, 82 and 84 in number.  
     
     
         33 : A method for producing a proton conductor film comprising: 
 heating a proton conductor film at a temperature of about 150° C. to about 43° C., wherein the proton conductor film is composed of a proton conductor admixed with polyvinyl alcohol that is formed into a film.    
     
     
         34 : The method according to  claim 33  wherein the temperature ranges from about 3° C. to about 43° C.  
     
     
         35 : The method according to  claim 33  wherein the proton conductor film is formed to a thickness of about 0.1 μm to about 20 μm.  
     
     
         36 : The method according to  claim 33  wherein a layer of a proton conductor not containing polyvinyl alcohol is provided on each surface of the proton conductor film.  
     
     
         37 : The method according to  claim 36  wherein the layer of the proton conductor not containing polyvinyl alcohol has a thickness of about 5 μm to about 20 μm.  
     
     
         38 : The method according to  claim 33  wherein the proton conductor is formed by a fullerene derivative composed of proton dissociative groups introduced to the carbon atoms of fullerene molecules.  
     
     
         39 : The method according to  claim 38  further comprising: 
 a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         40 : The method according to  claim 39  wherein the hydrogen gas intercepting layer is formed on at least one surface of the proton conductor film.  
     
     
         41 : The method according to  claim 40  wherein the hydrogen gas intercepting layer is formed on a surface facing an oxygen electrode of the proton conductor film.  
     
     
         42 : The method according to  claim 40  wherein the hydrogen gas intercepting layer is formed on a surface towards a hydrogen electrode of the proton conductor film.  
     
     
         43 : The method according to  claim 39  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         44 : The method according to  claim 38  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         45 : The method according to  claim 44  wherein the proton dissociative groups are at least one of —OH, —YOH, where Y is any optional bivalent atom or atom group and wherein H is a hydrogen atom.  
     
     
         46 : The method according to  claim 45  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         47 : The method according to  claim 39  wherein one or more electrophilic groups are introduced, along with the proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         48 : The method according to  claim 47  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combinations thereof.  
     
     
         49 : The method according to  claim 39  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling in number at least one of 36, 60, 70, 76, 78, 80, 82 and 84.  
     
     
         50 : A fuel cell comprising: 
 a hydrogen electrode, an oxygen electrode, and a proton conductor and polyvinyl alcohol acting as a binder for the proton conductor that is sandwiched between the hydrogen electrode and the oxygen electrode wherein    the proton conductor including a proton conductor film that is heated at a temperature ranging from about 150° C. to about 43° C.    
     
     
         51 : The fuel cell according to  claim 50  wherein the proton conductor film is heated at a temperature varying from about 3° C. to about 43° C.  
     
     
         52 : The fuel cell according to  claim 50  wherein the proton conductor film has a thickness of about 0.1 μm to about 20 μm.  
     
     
         53 : The fuel cell according to  claim 50  wherein a layer of a proton conductor not containing polyvinyl alcohol is provided on each surface of the proton conductor film.  
     
     
         54 : The fuel cell according to  claim 53  wherein the layer of the proton conductor not containing polyvinyl alcohol has a thickness of about 5 μm to about 20 μm.  
     
     
         55 : The fuel cell according to claims  50  wherein the proton conductor is formed by a fullerene derivative composed of proton dissociative groups introduced to the carbon atoms of fullerene molecules.  
     
     
         56 : The fuel cell according to  claim 55  further comprising: 
 a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         57 : The fuel cell according to  claim 56  wherein the hydrogen gas intercepting layer is formed on at least one surface of the proton conductor film.  
     
     
         58 : The fuel cell according to  claim 57  wherein the hydrogen gas intercepting layer is formed on a surface towards an oxygen electrode of the proton conductor film.  
     
     
         59 : The fuel cell according to  claim 57  wherein the hydrogen gas intercepting layer is formed on a surface towards a hydrogen electrode of the proton conductor film.  
     
     
         60 : The fuel cell according to any one of claims  56  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         61 : The fuel cell according to  claim 55  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         62 : The fuel cell according to  claim 61  wherein the proton dissociative groups are at least one of —OH, and —YOH, where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         63 : The fuel cell according to  claim 62  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         64 : The fuel cell according to  claim 55  wherein one or more electrophilic groups are introduced, along with proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         65 : The fuel cell according to  claim 64  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combinations thereof.  
     
     
         66 : The fuel cell according to  claim 55  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling in number at least one of 36, 60, 70, 76, 78, 80, 82 and 84.  
     
     
         67 : A method for producing a fuel cell comprising applying a proton conductor film between a hydrogen electrode and an oxygen electrode, the proton conductor film containing a proton conductor and polyvinyl alcohol as a binder for the proton conductor, wherein 
 the proton conductor film is heated at a temperature of about 150° C. to about 43° C.    
     
     
         68 : The method according to  claim 67  wherein the proton conductor film is heated at a temperature of about 3° C. to about 43° C.  
     
     
         69 : The method according to  claim 67  wherein the proton conductor film is formed to a thickness of about 0.1 μm to about 20 μm.  
     
     
         70 : The method according to  claim 67  wherein the proton conductor film is formed on at least one of the hydrogen electrode and the oxygen electrode and heated.  
     
     
         71 : The method according to  claim 67  wherein the proton conductor film is heated prior to forming the proton conductor film on at least one of the hydrogen electrode and the oxygen electrode.  
     
     
         72 : The method according to  claim 67  wherein a layer of a proton conductor not containing polyvinyl alcohol is formed on at least one of the hydrogen electrode and the oxygen electrode and wherein the proton conductor film is then formed on the layer of the proton conductor not containing polyvinyl alcohol and subsequently heated.  
     
     
         73 : The method according to  claim 67  wherein a layer of a proton conductor not containing polyvinyl alcohol is formed on one of the hydrogen electrode and the oxygen electrode, the proton conductor film is then formed on the layer of the proton conductor not containing polyvinyl alcohol, a layer of a proton conductor not containing polyvinyl alcohol is formed on the surface of the proton conductor film, and wherein the other of the hydrogen electrode and the oxygen electrode is tightly contacted on the layer of the proton conductor, not containing the polyvinyl alcohol, formed on the surface of the proton conductor film, and is subsequently heated.  
     
     
         74 : The method according to  claim 72  wherein the layer of the proton conductor not containing polyvinyl alcohol is formed to a thickness of about 5 μm to about 20 μm.  
     
     
         75 : The method according to claims  67  wherein the proton conductor is formed by a fullerene derivative composed of proton dissociative groups introduced into carbon atoms of fullerene molecules.  
     
     
         76 : The method according to  claim 75  wherein a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol is formed between the hydrogen electrode and the oxygen electrode.  
     
     
         77 : The method according to  claim 76  wherein the hydrogen gas intercepting layer is formed on at least one surface of the proton conductor film.  
     
     
         78 : The method according to  claim 77  wherein the hydrogen gas intercepting layer is formed on a surface towards the oxygen electrode of the proton conductor film.  
     
     
         79 : The method according to  claim 77  wherein the hydrogen gas intercepting layer is formed on a surface towards the hydrogen electrode of the proton conductor film.  
     
     
         80 : The method according to  claim 76  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         81 : The method according to  claim 75  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         82 : The method according to  claim 81  wherein the proton dissociative groups are at least one of —OH and —YOH, where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         83 : The method according to  claim 82  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         84 : The method according to  claim 75  wherein one or more electrophilic groups are introduced, along with proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         85 : The method according to  claim 84  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combinations thereof.  
     
     
         86 : The method according to  claim 75  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling in number at least one of 36, 60, 70, 76, 78, 80, 82 and 84.  
     
     
         87 : A proton conductor film for a fuel cell comprising: 
 a layer of a proton conductor containing a fullerene derivative; and    a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         88 : The proton conductor film according to  claim 87  wherein the hydrogen gas intercepting layer is formed on at least one surface of the layer of the proton conductor containing the fullerene derivative.  
     
     
         89 : The proton conductor film according to  claim 88  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         90 : The proton conductor film according to  claim 88  wherein the hydrogen gas intercepting layer is formed on a surface towards the oxygen electrode of the layer of the proton conductor containing the fullerene derivative.  
     
     
         91 : The proton conductor film according to  claim 88  wherein the hydrogen gas intercepting layer is formed on a surface towards the hydrogen electrode of the layer of the proton conductor containing the fullerene derivative.  
     
     
         92 : The proton conductor film according to  claim 87  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         93 : The proton conductor film according to  claim 87  wherein the fullerene derivative is composed of carbon atoms of fullerene molecules and proton dissociative groups introduced into the carbon atoms.  
     
     
         94 : The proton conductor film according to  claim 93  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         95 : The proton conductor film according to  claim 94  wherein the proton dissociative groups are at least one of —OH and —YOH, where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         96 : The proton conductor film according to  claim 95  wherein the proton dissociative groups are selected from the group consisting of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         97 : The proton conductor film according to  claim 93  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having a plurality of carbon atoms equaling a number of at least one of 36, 60, 70, 76, 78, 80, 82 and 84.  
     
     
         98 : The proton conductor film according to  claim 87  wherein one or more electrophilic groups are introduced, along with proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         99 : The proton conductor film according to  claim 98  wherein the fullerene molecules are selected from the group consisting of spheroidal carbon cluster molecules having plurality of carbon atoms equaling in number at least one of 36, 60, 70, 76, 78, 80, 82 and 84.  
     
     
         100 : The proton conductor film according to  claim 98  wherein the electrophilic groups include one or more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combinations thereof.  
     
     
         101 : A fuel cell comprising: 
 a hydrogen electrode;    an oxygen electrode;    a proton conductor film between the hydrogen electrode and the oxygen electrode layer; and    the proton conductor film including a proton conductor layer containing a fullerene derivative and a hydrogen gas intercepting layer composed of a fullerene derivative admixed with polyvinyl alcohol.    
     
     
         102 : The fuel cell according to  claim 101  wherein the hydrogen gas intercepting layer is formed on at least one surface of the layer of the proton conductor containing the fullerene derivative.  
     
     
         103 : The fuel cell according to  claim 102  wherein the hydrogen gas intercepting layer is formed on at least the surface towards the oxygen electrode of the layer of the proton conductor containing the fullerene derivative.  
     
     
         104 : The fuel cell according to  claim 102  wherein the hydrogen gas intercepting layer is formed on at least the surface towards the hydrogen electrode of the layer of the proton conductor containing the fullerene derivative.  
     
     
         105 : The fuel cell according to  claim 101  wherein the hydrogen gas intercepting layer has a thickness of about 0.1 μm to about 10 μm.  
     
     
         106 : The fuel cell according to  claim 101  wherein the fullerene derivative is composed of proton dissociative groups introduced into carbon atoms of fullerene molecules.  
     
     
         107 : The fuel cell according to  claim 106  wherein the proton dissociative groups are —XH, where X is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         108 : The fuel cell according to  claim 107  wherein the proton dissociative groups are at least one of —OH and —YOH, where Y is a bivalent atom or atom group thereof and wherein H is a hydrogen atom.  
     
     
         109 : The fuel cell according to  claim 108  wherein the proton dissociative groups are selected from the group consists of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO(OH) 2  and combinations thereof.  
     
     
         110 : The fuel cell according to  claim 106  wherein the fullerene molecules include spheroidal carbon cluster molecules having carbon atoms selected from the group consisting of 36, 60, 70, 76, 78, 80, 82, 84 and combinations thereof.  
     
     
         111 : The fuel cell according to  claim 101  wherein one or more electrophilic groups are introduced, along with proton dissociative groups, into carbon atoms of fullerene molecules of the fullerene derivative.  
     
     
         112 : The fuel cell according to  claim 111  wherein the electrophilic groups include one more of functional groups and atoms selected from the group consisting of a nitro group, a carbonyl group, a carboxylic group, a nitrile group, a halogenated alkyl group, fluorine, a halogen atom and combinations thereof.  
     
     
         113 : The fuel cell according to  claim 111  wherein the fullerene molecules include spheroidal carbon cluster molecules having carbon atoms selected from the group consisting of 36, 60, 70, 76, 78, 80, 82, 84 and combinations thereof.