WO2006057387A1

WO2006057387A1 - Biocell

Info

Publication number: WO2006057387A1
Application number: PCT/JP2005/021801
Authority: WO
Inventors: Takeo Yamaguchi; Takanori Tamaki
Original assignee: The University Of Tokyo
Priority date: 2004-11-26
Filing date: 2005-11-28
Publication date: 2006-06-01
Also published as: JP5059413B2; JPWO2006057387A1

Abstract

A material participating in the donation and receiving of electrons; a biofuel cell making use of the material that exhibits an enhanced output power density; and a process for producing them. In particular, there is provided a material comprising an electron conductor of ≥ 0.5 m2/g external specific surface area being a specific surface area relating to pores of ≥ 7 nm, a redox polymer and a biocatalyst or analogue thereof, wherein the redox polymer has an oxidation-reduction moiety exhibiting oxidation-reduction behavior and exhibits an electron conductivity of ≥ 10-16 S/cm.

Description

Specification

Bio battery

Technical field

[0001] The present invention relates to a material involved in electron transfer. The present invention also relates to a bio battery using the material as an electrode, particularly a bio fuel cell, and a method for producing the same. Background art

In recent years, research and development of fuel cells have become particularly active. The fuel cell here uses hydrogen itself or methanol as a hydrogen source.

On the other hand, there is a biofuel cell that uses a biocatalyst as a catalyst. This biofuel cell is composed of a reduced coenzyme generated when a fuel is oxidized by a biocatalyst (for example, an enzyme and a biological substance containing the enzyme), and a mediator that easily performs an oxidation / reduction reaction. It is a device that converts chemical energy of fuel into electrical energy by extracting electrons to an external circuit. As described above, in the biofuel cell, since the catalyst is a biocatalyst (for example, an enzyme), various substrates can be used as fuel by selecting the biocatalyst. For this reason, biomass-derived materials, such as glucose or ethanol, which have not been fully studied in conventional fuel cells, are used as devices for extracting electrical energy, and are operated by glucose or lactic acid present in the living body. Development of a nano fuel cell as a power source for medical devices is expected.

Non-patent literature l: A. Heller, Phys. Chem. Chem. Phys., 6, 209 (2004).

Patent Document 1: US Pat. No. 6,531,239.

Disclosure of the invention

Problems to be solved by the invention

However, the maximum power density of the biofuel cell in Non-Patent Document 1 is 35

It stays at 0 WZcm ² . This is mainly due to the fact that the amount of immobilization of the biocatalyst that works effectively in the apparent area of the electrode, that is, the projected area, is small.

Accordingly, an object of the present invention is to provide a biofuel cell with improved power density, an electrode material used therefor, and a method for producing them. In addition, an object of the present invention is to provide a material involved in electron transfer, not limited to the above-described fuel cell material.

Means for solving the problem

[0005] The inventors have decided to increase the apparent area of the electrode by using an electron conductor having a large external specific surface area and forming a three-dimensional network structure with the electron conductor. In addition, the amount of the fixed catalyst was increased by fixing a biocatalyst or an analog thereof (hereinafter sometimes simply abbreviated as “biocatalyst, etc.”) in the three-dimensional network. Furthermore, it has been found that by including a redox polymer, the redox polymer can mediate exchange of electrons between a biocatalyst and the like with an electron conductor having a large specific surface area, particularly an external specific surface area.

[0006] Specifically, the present inventors have found that the above-described problems can be solved by the following invention.

<1> A material having an electron conductor, a redox polymer, and a biocatalyst or an analog thereof, for example, a biocatalyst having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area acting on pores of 7 nm or more. And

The redox polymer has a redox site exhibiting redox behavior, and io — ¹⁶ s

The above materials exhibiting electronic conductivity of Zcm or more.

[0007] <2> having an electron conductor, a redox polymer, and a biocatalyst or an analog thereof, for example, a biocatalyst having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area that works on pores of 7 nm or more Material,

The redox polymer has a redox sites displaying a redox behavior, and shows electron conductivity than 10_ ¹⁶ SZcm,

The material that transfers electrons generated when the first substance in contact with the material is oxidized by the biocatalyst or an analog thereof to the electron conductor via the redox polymer.

<3> An electron conductor, a redox polymer, and a biocatalyst or an analog thereof, for example, a material having a biocatalyst having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area that works on pores of 7 nm or more. And The redox polymer has a redox site exhibiting redox behavior, and ^io_lb

Shows electronic conductivity above SZcm,

The material as described above, wherein the second substance in contact with the material is reduced by the biocatalyst or an analog thereof and transmits electrons to the redox polymer via the electron conductor.

<4> In any one of the above items <1> to <3>, an electron conductor force carbon, a conductive polymer, and a group force including a metal force may be selected. In the case of a conductive polymer, the molecular weight is 50 to 100 million, preferably 1000 to 100,000.

<5> According to any one of the above items <1> to <4>, the shape of the electron conductor may be granular or rod-shaped. The particle diameter should be 10 μm or less, preferably 1 μm or less, and more preferably lOOnm or less in the case of a granular shape.

<6> In the above <4> or <5>, the carbon is selected from the group force consisting of carbon black, carbon nanotube, and carbon nanohorn.

<7> According to any of <1> to <6> above, the external specific surface area of the electron conductor is lm ² Zg or more, preferably 6 to 5000 m ² Zg, more preferably 10 to 800 m ² Zg. There should be.

<8> In any one of the above items <1> to <7>, the redox polymer may have a redox polymer having a phencene derivative (e.g., phenoxycene group, carboxyphenocene, dicarboxyphenocene, methylphenocene, dimethylphenol). And quinone compounds (eg, benzoquinone, hydroquinone, naphthoquinone, pyroquinoline quinone), osmubiviridine complexes ([Os (4,4, -dimethyl-2,2, -biviridine) CI ] ^{+ / 2 +} , [Os (4,4,-

2

Diamino-2,2, -biviridine) Cl] ^{+ / 2 +} , [Os (4,4, -dimethoxy-2,2, -biviridine) Cl] ^{+ / 2}

twenty two

+, [Os (terpyridine) (4,4, -Dimethylol-2,2, -biviridine) Cl] ^{2 + / 3 +} , [Os (4,4, -Dichloro

2

Mouth-2,2, -biviridine) C1] ^{+ / 2 +} ), osmium biimidazole complexes ([Os (4,4, -di

2

Alkylated-2,2, -biimidazole)] ^{2 + / 3 +} ), viologen, and 2,2-azobis (3

Three

-Ethylbenzothiazoline-6-sulfonate) The power of the group is also chosen.

<9> In any one of the above items 1> to <8>, one end of the redox polymer may be chemically bonded to the electron conductor. <10> In any one of the above items <1> to <9>, the biocatalyst is preferably oxidase or dehydrogenase. In particular, glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2- The group power of dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, lactate dehydrogenase, aldose dehydrogenase, oligosaccharide dehydrogenase, bilirubin oxidase, laccase, and cytochrome oxidase zecta should be chosen! / ,.

<11> According to any one of the above items <1> to <10>, the material may be used as a negative electrode for a battery or a positive electrode for a battery.

[0011] <12> a first electronic conductor, a first redox polymer, and a first biocatalyst having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area that works on pores of 7 nm or more Or a negative electrode having an analogue thereof;

A positive electrode with proton conductivity; and

An electrolyte sandwiched between the positive electrode and the negative electrode;

The battery, wherein the first redox polymer has a first redox site exhibiting redox behavior, and exhibits an electronic conductivity of 10 ^_16 SZcm or more.

<13> In the above item <12>, the negative electrode preferably has proton conductivity. In particular, it is preferable to have a material exhibiting proton conductivity, such as Nafion, a hydrocarbon-based proton conductive polymer.

<14> In the above 12> or 13>, the first biocatalyst is glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase. , Selected from the group consisting of formate dehydrogenase, lactate dehydrogenase, aldo-dehydrogenase, and oligosaccharide dehydrogenase.

<0013><15> In any one of the above items 12> to <14>, the first redox site force ferrocene derivative (hue mouth sen group, carboxy phe mouth cene, dicarboxy phe mouth cene, methyl phe Cene, dimethylphenol, buluene, etc.), quinone compounds (benzoquinone, hydroquinone, naphthoquinone, pyroquinoline quinone, etc.), sumi-bibipyridine complexes ( [Os (4,4, -Dimethinole-2,2, -biviridine) CI] ^{+ / 2 +} , [Os (4,4, -Diamino-2,2, -biviridine)

2

) Cl] ^{+ / 2 +} , [Os (4,4, -dimethoxy-2,2, -biviridine) Cl] ^{+ / 2 +,} etc.), osmium biimi

twenty two

Dazole complexes (such as [Os (4,4, -dialkyl 2-2,2, -biimidazole)] ^{2 + / 3 +} ), and

Three

A group power consisting of viologen should be selected.

<16> In any one of the above items <12> to <15>, the positive electrode preferably has the second electronic conductor.

<17> In any one of the above items 12> to <16>, the positive electrode has a second redox polymer, the redox polymer has a second redox site exhibiting redox behavior, and 10 ^{It should} show electronic conductivity of ^_16 S / cm or more.

[0014] <18> In any one of the above 12> to <17>, the second redox polymer strength Sumiumbipyridine complex ([Os (terpyridine) (4,4'-dimethinole-2,2 ' -Bipyridine) C1

2

] ₂ + / 3 +, [os (4,4, -dichloro-2,2, -biviridine) Cl] ^{+ / 2 +} ), and 2,2-azobis (3-

2

Ethyl benzothiazoline-6-sulfonate) The power of the group is also chosen! /.

<19> In any one of the above items 12> to <18>, the positive electrode may have a proton conductive polymer.

<20> In any one of the above items 12> to <19>, the positive electrode preferably has a catalyst.

<21> In the above item 20>, the catalyst may be the second biocatalyst or an analogue thereof.

<22> In the above 21>, the second biocatalyst should also be selected as a group force that also has pyrilbinoxidase, laccase, and cytochrome oxidase power! /.

[0015] <23> According to any one of the above items <12> to <22>, the first, seventh, or second electronic conductor is selected from a group force consisting of carbon, a conductive polymer, and a metal force. It is good. In the case of a conductive polymer, the molecular weight is 50 to: L00000, preferably 1,000 to 100,000.

<24> According to any one of the above items <12> to <23>, the first and / or second electronic conductors may independently have a granular shape or a rod shape. In the case of granules, the particle diameter is 10 / zm or less, preferably 1 m or less, more preferably lOOnm or less.

<25> In the above 23> or 24>, it is preferable that carbon is selected as a group force consisting of carbon black, carbon nanotube, and carbon nanohorn force.

<26> According to any of <12> to <25> above, the external specific surface area of the first and / or second electronic conductor is lm ² Zg or more, preferably 6 to 5000 m ² Zg. It is preferably 10 to 800 m ² Zg.

<27> In any one of the above items 12> to <26>, the battery may be a fuel cell.

<28> Manufacture of a material having an electron conductor, a redox polymer, and a biocatalyst or an analog thereof having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area that is effective for pores of 7 nm or more A method as described above, wherein the following a) to c) are carried out in random order and either Z or a) to c) two or three at the same time:

a) A step of mixing and Z or bonding an electron conductor and a redox polymer or redox polymer precursor (however, when a redox polymer precursor having no redox site is used, the acid-reduction site is redoxed). Steps a) to c) that are introduced into a polymer precursor to form a redox polymer.

B) forming the electron conductor precursor into a three-dimensional electron conductor;

c) A step of introducing a biocatalyst or an analog thereof.

[0017] <29> In the above item 28>, it is preferable that an electron conductor force carbon, a conductive polymer, and a group force composed of a metal be selected. In the case of a conductive polymer, the molecular weight is 50 to: LOO 10,000, preferably 1,000 to 100,000.

<30> In any one of the above items <28> or <29>, the electron conductor precursor may have a granular shape or a rod shape. In the case of a granular shape, the particle diameter thereof, and in the case of a rod shape, the diameter of the cross section thereof is 10 μm or less, preferably 1 μm or less, more preferably 1 OOnm or less! /.

<31> In the above item 29> or item 30>, carbon is preferably selected from a group force consisting of carbon black, carbon nanotube, and carbon nanohorn force.

<32> Outside <28> to <31> above, the external specific surface of the electron conductor The product should be lm ² / g or more, preferably 6 to 5000 m ² Zg, more preferably 10 to 800 m ² / g.

<33> In any one of the above 28> to <32>, the oxidation reduction site of the redox polymer may be a phenoxycene derivative (for example, phenoxycene group, carboxyphenoxycene, dicarboxyphenoxycene, methylphenoxycene). , Dimethylphenol, buluene, etc.), quinone compounds (eg, benzoquinone, hydroquinone, naphthoquinone, pyroquinolinequinone), osmium biviridine complexes ([Os (4,4, -dimethyl-2,2,- Biviridine) CI] ^{+ / 2 +} , [Os (4,

2

4, -Diamino-2,2, -biviridine) Cl] + Z ²⁺ , [Os (4,4, -dimethoxy-2,2, -biviridine) C1]

twenty two

^{+ / 2 +} , [Os (terpyridine) (4,4, -dimethyl-2,2, -biviridine) Cl] ^{2 + / 3 +} , [Os (4,4, -di

2

Black mouth-2,2, -biviridine) C1] ^{+ / 2 +} ), osmium biimidazole complexes ([Os (4,4,-

2

Dialkylated-2,2, -biimidazole)] ^{2 + / 3 +} ), viologen, and 2,2-azobis (

Three

3-Ethylbenzothiazoline-6-sulfonate) Power is a group power.

[0019] <34> In steps a) of the above <28> to <33>, the electron conductor and the redox polymer or the redox polymer precursor are: an end of the redox polymer or its precursor is an electron conductor or an electron It may be chemically bonded to the conductor precursor.

<35> In any one of the above 28> to <34>, the biocatalyst is glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase. A group force consisting of formate dehydrogenase, lactate dehydrogenase, aldose dehydrogenase, oligosaccharide dehydrogenase, pyrilbinoxidase, laccase, and cytochrome oxidase may also be selected.

<36> In any one of the above items 28> to <35>, the material may be used as a negative electrode for a battery or a positive electrode for a battery.

[0020] <37> A battery having l to n battery regions, in which fuel is decomposed in n stages (n is an integer of 2 or more) by n or more biocatalytic reactions or biocatalytic similar reactions,

1 ~! Battery areas are the 1st to nth battery areas, and the 1st to nth battery areas are wired in series and Z or in parallel,

The first battery region includes a first negative electrode, a first positive electrode, and the first positive electrode and the first negative electrode A first electrolyte sandwiched between and

The first negative electrode has a specific surface area that acts on pores of 7 nm or more, and the external specific surface area is 0.5 m ² / g or more, preferably 6 to 5000 m ² Zg, more preferably 10 to 800 m ² / g. A first redox polymer, and a first biocatalyst or an analog thereof, wherein the first redox polymer has a first redox site exhibiting redox behavior, And exhibits electronic conductivity of 10 ^_16 S / cm or more,

The first positive electrode has electronic conductivity;

The m-th battery region (m is an integer from 2 to n) is the m-th negative electrode, the m-th positive electrode, and the m-th positive electrode and the m-th negative electrode. m electrolyte,

Anode electron conductor of the m is external specific surface area 0. 5 m ² Zg least a force mowing specific surface area than the pores 7 nm (electron conductor of the m of the m-th, first to (m — The same as or different from the electron conductor of 1), m-th redox polymer (the m-th redox polymer may be the same as the first to (m-1) redox polymers) And the m-th biocatalyst or its analog (the m-th biocatalyst or its analog is different from the first to (m-1) biocatalyst or its analog, respectively). The m-th redox polymer has an m-th redox site exhibiting redox behavior (the m-th redox site is the same as the 1st to (m-1) acid-oxidized sites. I also different from each other! /,) have, and shows an electron conductivity of more than 10_ ¹⁶ SZcm,

The mth positive electrode has electronic conductivity;

In the first negative electrode, the fuel is decomposed into the first decomposition product by the first biocatalyst or an analog thereof and generates one or more electrons,

In each of the m-th negative electrodes, the (m-1) decomposition product is decomposed into the m-th decomposition product by the m-th biocatalyst or an analog thereof and generates one or more electrons.

<38> In the above 37>, the first to n-th electrolytes are formed on a substantially flat surface, the first to n-th negative electrodes are on one surface of the substantially flat surface, and the first to n-th positive electrodes are substantially the same. The first to nth fuels are formed on the other surface of one plane and the first to nth decomposed products are in contact with each other on the substantially one plane on which the first to nth negative electrodes are formed. An nth negative electrode is preferably formed.

In <39> above 37> or 38>, the (m−l) positive electrode and the mth negative electrode are The first to nth battery regions are preferably connected in series by being energized.

40> A battery having l to n battery regions, in which fuel is decomposed in n stages (n is an integer of 2 or more) by n or more biocatalytic reactions or biocatalytic similar reactions,

The first battery region has a first negative electrode, a first positive electrode and a first electrolyte sandwiched between the first positive electrode and the first negative electrode;

The first negative electrode has a first electronic conductor, a first redox polymer, and a first biocatalyst or an analog thereof, and the first redox polymer exhibits a redox behavior. has a site, and shows the 10 ^{_ 16} SZcm more electron conductivity,

The first positive electrode has electronic conductivity;

The mth negative electrode is the mth electronic conductor (the mth electronic conductor may be the same as or different from the first to (m-1) th electronic conductors), the mth redox polymer ( The m-th redox polymer may be the same as or different from the first to (m-1) redox polymers), and the m-th biocatalyst or an analog thereof (the m-th biocatalyst or the like). Each body has a first to (m-1) biocatalyst or an analogue thereof, and the m-th redox polymer has an acid-reduction behavior. (The m-th acid-reduction site may be the same as or different from the 1st to (m-1) -th acid reduction sites! /), And 10 ^{_ 16} S Zcm Showing the above electronic conductivity,

The mth positive electrode has electronic conductivity;

The first to nth electrolytes are formed on substantially one plane, the first to nth negative electrodes are formed on one surface of the substantially one plane, and the first to nth positive electrodes are formed on the other surface of the substantially one plane. And the first to nth negative electrodes are The battery, wherein the first to nth negative electrodes are formed so that the fuel and the first to nth decomposition products are in contact with each other on a substantially flat surface formed.

<41> In the above item 40, it is preferable that the first to n-th cell region forces be arranged along the fuel flow direction.

<42> In the above 40> or 41>, it is preferable that the (m−l) positive electrode and the m-th negative electrode are energized and the first to n-th battery regions are wired in series.

<43> In any one of the above items <40> to <42>, the first to n-th electron conductors of the first to n-th negative electrodes have an external specific surface area that is a specific surface area acting on pores of 7 nm or more. Is 0.5m ² Zg or more.

<44> In any one of the above items 37> to <43>, the fuel is methanol, n force S3, the first biocatalyst is alcohol dehydrogenase, and the first decomposition product is hole. Is a aldehyde, the second biocatalyst is an aldehyde dehydrogenase, the second degradation product is formic acid, the third biocatalyst is formate dehydrogenase, and the third degradation product is diacid-carbon. It is good.

<45> Above 37> to <43>! In any case, the fuel is ethanol, n is 2, the first biocatalyst is alcohol dehydrogenase, and the first degradation product is It is acetoaldehyde, the second biocatalyst is aldehyde dehydrogenase, and the second degradation product is acetic acid.

[0025] <46> In any one of the above items 37> to <43>, the fuel is glucose, n force S3 or more, the first biocatalyst is glucose oxidase, and the first degradation product is Gluconorataton, the second biocatalyst is dalconate 2-dehydrogenase, the second degradation product is 2-ketogluconic acid, the third biocatalyst is ketogluconate dehydrogenase, and the third degradation product Should be 2,5-diketogluconic acid.

<47> In any one of the above items 37> to <46>, the first to nth negative electrodes preferably have proton conductivity. In particular, it is preferable to have a material exhibiting proton conductivity, such as Nafion or a hydrocarbon-based proton conductive polymer.

<48> In any one of the above items <37> to <47>, the first to nth electron conductors may be selected from a group force composed of carbon, a conductive polymer, and a metal. Conductive In the case of a conductive polymer, the molecular weight is 50 to: LOO million, preferably 1,000 to 100,000.

<49> In any one of the above items <37> to <48>, the first to nth electron conductors may have a granular shape or a rod shape. In the case of a granular shape, the particle diameter thereof, and in the case of a rod shape, the diameter of the cross section thereof is 10 m or less, preferably 1 μm or less, more preferably 1 OOnm or less.

<50> In the above item 48> or 49>, it is preferable that carbon is selected as a group force consisting of carbon black, carbon nanotube, and carbon nanohorn force.

<51> In any of the above <37> to <50>, the first to nth electron conductors each have an external specific surface area of lm ² / g or more, preferably 6 to 5000 m ^2. / g, more preferably 10 to 800 m ² Zg.

<52> According to any of <37> to <51> above, each of the 1S to nth acid reduction sites of each of the 1st to 11th redox polymers 1S Mouthcene derivatives (for example, pheophene group, carboxy phen cene, dicarboxy phen cene, methyl phen cene, dimethyl phen cene, bul ue cene sen), quinone compounds (eg benzoquinone, hydroquinone, naphthoquinone, pyroquinoline) quinones, etc.), old Sumi © beam bipyridine complexes ([Os (4,4 '- dimethylol Le - ^2, ^2, - ^{Bibirijin) Cl] + / 2 +,} [Os (4, 4, - Jiamino - ^2, ² , -Biviridine) Cl] ^{+ / 2 +} , [Os

twenty two

(4,4, -dimethoxy-2,2, -biviridine) Cl] ^{+ / 2 +} , [Os (terpyridine) (4,4, -dimethyl-2,2

2

, -Biviridine) Cl] ^{2 + / 3 +} , [Os (4,4, -dichloro-2,2, -biviridine) Cl] ^{+ / 2 +,} etc.), male

2 2 Mumbiimidazole complexes ([Os (4,4, -dialkylated-2,2, -biimidazole)] ^{2 + / 3 +}

3), viologen, and 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate).

<53> In any one of the above items 37> to <52>, one end of each of the first to n-th redox polymers is chemically bonded to each of the first to n-th electronic conductors. It is good.

<54> In any one of the above 37> to <53>, the first to n-th positive electrodes each have the first to p-th electron conductors (p is an integer of 2 to n). No ...!

<55> In the above item 54, the first to p-th electron conductors may be selected from carbon, a conductive polymer, and a group force including a metal force. In the case of conductive polymers, Has a molecular weight of 50 to 100 million, preferably 1,000 to 100,000.

<56> In the above item 54> or 55>, the first to p-th electron conductors may have a granular shape or a rod shape. In the case of a granular shape, the particle diameter thereof, and in the case of a rod shape, the diameter of the cross section thereof is 10 μm or less, preferably 1 μm or less, more preferably ΙΟΟηm or less.

<57> In the above 55> or 56>, it is preferable that carbon is selected as a group force consisting of carbon black, carbon nanotube, and carbon nanohorn force.

<58> From the above <54> to <57>, the first to pth electron conductors are

The external specific surface area of each is lm ² / g or more, preferably 6 to 5000 m ² / g, more preferably 10 to 800 m ² Zg.

[0030] <59> In any one of the above items 37> to <58>, each of the first to nth positive electrodes is

It is preferable to have proton conductivity.

<60> In any of the above 37> to <59>, each of the first to n-th positive electrodes has a first to ρ-th redox polymer (p is an integer from 2 to n). The first to ρ redox polymers preferably have first to p-th redox sites exhibiting strong redox behavior, and exhibit an electronic conductivity of 10 ^_16 S / cm or more.

[0031] <61> In the above item <60>, each force of the first to p-th acid-reduction sites of each of the first to p-th redox polymers is osmium biviridine complex ([Os (terpyridine) (4 , 4, -Dimethyl-2,2, -biviridine) Cl] ^{2 + / 3 +} , [Os (4,4, -Dichloro-2,2, -biviridine) Cl] ^{+ / 2 +}

2 2) and 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate).

<62> In any one of the above items 37> to <61>, each of the first to n-th positive electrodes preferably has a proton-conductive polymer.

<63> In any one of the above items 37> to <62>, each of the first to nth positive electrodes preferably has a catalyst.

<64> In the above item 63, the catalyst may be a biocatalyst for a positive electrode or an analogue thereof.

<65> In the above item 64>, the biocatalyst for the positive electrode is pyrilvinoxydase, Choose a group power that also has laccase and cytochrome oxidase power! /.

<66> In any one of the above items <37> to <65>, the first to nth positive electrodes may be an oxidizing gas or an oxidizing liquid (e.g., oxygen gas, oxygen-dissolved liquid, oxygen carrier-containing liquid (with oxygen carrier and Is a generic term for compounds with oxygen carrying function, such as hemoglobin and hemoglobin mimics !, u))).

The invention's effect

[0033] According to the present invention, it is possible to provide a biofuel cell with improved power density, an electrode material used therefor, and a production method thereof.

Further, according to the present invention, not only the material for the fuel cell described above but also a material involved in electron transfer can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0034] Hereinafter, the present invention will be described in detail.

The present invention provides materials, particularly materials involved in electron transfer. The material of the present invention provides, for example, a battery material, for example, a biofuel cell material. The materials of the present invention also provide materials that are counter-reactive with fuel cells, i.e., provide hydraulic hydrogen and Z or oxygen. Furthermore, the present invention provides a material that is not limited to the above-described action but can participate in electron transfer.

[0035] The material of the present invention includes an electron conductor, a redox polymer, and a biocatalyst or an analog thereof.

(Hereinafter, sometimes simply abbreviated as “biocatalyst” or “biocatalyst”). The material of the present invention operates as follows. That is, electrons generated when the first substance in contact with the material of the present invention is oxidized by a biocatalyst or the like are transferred to the electron conductor via the redox polymer, or contacted with the material of the present invention. The electrons when the second substance is reduced by a biocatalyst or the like are transferred to the redox polymer via the electron conductor.

[0036] <Electronic conductor>

Electron conductor used with the present invention, an external specific surface area of 0. 5 m ² Zg or more, preferably 1 m ² Zg more, preferably 6~5000m ² Zg, more preferably good is 10~800m ² Zg .

Here, the external specific surface area means a specific surface area applied to pores of 7 nm or more. Main departure In the description, “external specific surface area” has the above meaning unless otherwise specified.

[0037] The external specific surface area can be estimated as follows. That is, as will be described later, the electron conductor can be formed by three-dimensionally accumulating particulate materials or rod-like materials having electron conductivity. The specific surface area of one particle or rod-like substance of these granular substances or rod-like substances can be estimated as the “external specific surface area” as it is.

For example, when the electron conductor is derived from a particulate material, the “external specific surface area” is estimated as follows. That is, if the particle radius r [m] and the particle density: d [gZm ³ ], the external specific surface

P

The product S [m ² Zg] is expressed as

[0038] S = (surface area of one particle) Z {(volume of one particle) X (density)}

8 = 4 π τ ² / (4/3 π Γ ³ X d) = 3 / (r X d).

P P P

In short, when the electron conductor is derived from a granular material, the radius r and the particle of the granular material

P

From the density d of the child, the external specific surface area can be estimated. The radius r of the granular material is

P

Thus, the diameter force of the granular material in the electron microscopic image of the obtained electron conductor can be obtained. The density of the particles can be determined from the mass and the particle size distribution.

[0040] When the electron conductor is derived from a rod-like substance, the "external specific surface area" can be estimated in the same manner as described above. That is, the radius r [m] of the cross-section of the rod-shaped material, the length L [m] of the rod-shaped material, rod

Density of rod-shaped substance: If d [gZm ³ ], the external specific surface area S [m ² Zg] is expressed as follows.

[0041] S = (surface area of one rod-like substance) Z {(volume of one rod-like substance) X (density)}

S = (27u r ² + 2 π r XL) / (π τ X then X d)

rod rod rod

Here, "2 π Γ ² " is almost negligible, so S can be estimated as follows.

rod

S = 2 / (r X d).

rod

In short, when the electron conductor is derived from a rod-shaped material, the external specific surface area can be estimated from the radius r rod of the cross-section of the rod-shaped material and the density d of the rod-shaped material.

[0043] The electron conductor may be formed by three-dimensionally collecting particulate materials or rod-like materials having electron conductivity, or may have the above external specific surface area from the beginning. . When particles are three-dimensionally accumulated, the particles have a particle size of 10 m or less, preferably 1 μm or less, more preferably lOOnm or less. In addition, when the rod-shaped material is formed by integrating three-dimensionally, the cross-sectional diameter is preferably 10 m or less. 1 μm or less, more preferably lOOnm or less. Further, in this case, the external specific surface area of the granular material or the rod-shaped substance itself may have the above-mentioned numerical value, or the whole aggregate such as the granular material or the rod-shaped substance may have the above-mentioned numerical value.

[0044] Examples of the electronic conductor include, but are not limited to, carbon, a conductive polymer, and a metal. For example, the electronic conductor may include two or more types of materials. In the case of a conductive polymer, the molecular weight is 50 to: LOO 10,000, preferably 1,000 to 100,000.

In addition, when carbon is used as the electron conductor, the force that can include carbon black, carbon nanotube, carbon nanohorn, and the like is not limited to these.

[0045] <Redox polymer>

The redox polymer used in the present invention preferably has a redox site exhibiting redox behavior. The redox polymer may have electronic conductivity. The electronic conductivity of the redox polymer depends on the polymer chain length, but it should be 10 ^_16 SZcm or more. That is, when the chain length of the redox polymer is long, it may have higher electron conductivity, but when the chain length is short, it may have low electron conductivity (however, ^10_16 SZcm or more).

Redox polymers have redox sites. The redox polymer having the site may be a block copolymer of a monomer having the site and another monomer, or may be prepared by a reaction that gives a redox site to a homopolymer or a copolymer! /. In the case of a copolymer, it may have a monomer power of 2 or 3 or more.

[0046] The oxidation-reduction site of the redox polymer is not particularly limited as long as it exhibits redox behavior as described above. For example, phenecene derivatives (eg, phenecene group, carboxyphenecene, dicarboxyphenecene, methylpheocene, dimethylphenolate, bulueguchicene), quinone compounds (benzoquinone) , Hydroquinone, naphthoquinone, pyroquinoline quinone, etc.), sumumbipyridine complexes ([Os (4,4, -Dimethinole-2,2, bibilidine) Cl] ^{+ / 2 +} , [Os (4,4 , -Diamino-2,2, -biviridine) Cl] ^{+ / 2 +} , [Os (4,4,-

2 2 Dimethoxy-2,2, -bipyridine) Cl] ^{+ / 2 +} , [Os (terpyridine) (4,4, -dimethyl-2,2, -bipi Lysine) Cl] ^{2 + / 3 +} , [Os (4,4, -dichloro-2,2, -biviridine) Cl] ^{+ / 2 +} ), osmium bi

twenty two

Imidazole complexes (such as [Os (4,4, -dialkylated-2,2, -biimidazole)] ^{2 + / 3 +} ),

Three

Examples include, but are not limited to, viologen and 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate). In addition, as the acid reduction site, two or more kinds of the above may be included.

[0047] One end of the redox polymer may be chemically bonded to the electron conductor, or to a granular material or rod-shaped material that can form the electron conductor.

[0048] <Biocatalyst or analog thereof>

The material of the present invention has a biocatalyst or an analog thereof. An analog is a natural or artificial substance having a function similar to that of a biocatalyst. Examples of the analog include a modified natural biocatalyst or an artificial substance imitating a natural biocatalyst. In this specification, the biocatalytic reaction refers to a reaction caused by the action of the biocatalyst, and the biocatalyst-like reaction is a reaction caused by an action similar to that of the biocatalyst by an analog of the biocatalyst. Say.

[0049] The biocatalyst used in the present invention is preferably oxidase or dehydrogenase, but is not limited thereto.

For example, as a biocatalyst, glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, lactate dehydrogenase, aldos dehydrogenase, oligosaccharide Examples include, but are not limited to, dehydrogenase, pyrilbinoxidase, laccase, and cytochrome oxidase. The redox sites may include more than one of the above types! ,.

[0050] Further, depending on the biocatalyst used, in the case of a first substance that contacts the material of the present invention, for example, a biofuel cell, a fuel is selected. In other words, the biocatalyst used for the material of the present invention is selected depending on the fuel used. For example, when glucose oxidase or glucose dehydrogenase is used as a biocatalyst, glucose is used as a fuel. In addition, when (keto) dalconate 2-dehydrogenase is used as a biocatalyst, Keto) darconic acid is used. Similarly, alcohol is used as a fuel when alcoholoxidase or alcohol dehydrogenase is used as a biocatalyst. Hereinafter, a biocatalyst / fuel pair is referred to as (biocatalyst, fuel). (Aldehyde dehydrogenase, aldehyde), (formate dehydrogenase, formate), (lactate dehydrogenase, lactic acid), (aldose dehydrogenase, aldose), (oligosaccharide dehydrogenase, oligosaccharide), (pyrurubin oxidase, oxygen), ( Laccase, oxygen) and (cytochrome oxidase, oxygen).

[0051] The material of the present invention is composed of the above-described elements and has the following actions. Figure 1 is used to explain this effect. FIG. 1 is a diagram in which a material 1 of the present invention as an anode is attached on a polymer electrolyte as an electrolyte, and an enlarged conceptual diagram of the material 1. The material 1 of the present invention has an electron conductor 4 composed of a three-dimensional network of a plurality of carbon black particles 3, a redox polymer 6 having an acid reduction site 5, and a biocatalyst 7 (eg, glucose oxidase). Glucose force When contacted with the anode, in particular glucose oxidase, which is the biocatalyst 7, it is oxidized to darconoraton. Electron e− generated in the biocatalyst is transferred to the electron conductor 4, that is, the carbon black particle 3 through the redox polymer 6 having the redox site 5. By this electron transfer, the material of the present invention can act as a negative electrode.

On the other hand, when acting as a positive electrode (cathod), it is as follows. In other words, the positive electrode is not shown, but has substantially the same configuration as the negative electrode shown in FIG. That is, the positive electrode has a conductor having electron conductivity and proton conductivity, a redox polymer, and a catalyst (including a biocatalyst) (for example, cytochrome oxidase). Oxygen comes into contact with the positive electrode, in particular with cytochrome oxidase, which is a catalyst, and reacts with protons moving from the polymer electrolyte force and electrons transferred from the outside to produce water. Therefore, the material of the present invention can also act as a positive electrode.

Further, when configured in combination with the above-described negative electrode, it can function as a fuel cell.

Therefore, the material of the present invention can be used as a battery material, particularly a battery negative electrode or a battery positive electrode. In particular, it is preferably used as a negative electrode for a battery. [0053] The material of the present invention is not limited to the above-described battery material, in particular, a fuel cell material, but acts as a material involved in various electron exchanges. For example, it acts as a reverse reaction with fuel cells, ie, a material that brings hydrogen and Z or oxygen from water. For example, in the case of bringing hydrogen from water, the substance that comes into contact with the material is water. By using a biocatalyst or an analog thereof as porphyrin, it is possible to provide a material that brings about hydrogen.

[0054] The present invention further provides a fuel cell, particularly a biofuel cell.

The fuel cell of the present invention, particularly the biofuel cell, has a negative electrode; a positive electrode; and an electrolyte sandwiched between the positive electrode and the negative electrode, and the negative electrode and Z or the positive electrode are configured by using the above-described materials.

[0055] <Negative electrode>

As described above, the above materials can be used for the negative electrode. Hereinafter, the case where the material of the present invention is used as a negative electrode will be described.

The negative electrode may have proton conductivity. In particular, the negative electrode may have a material exhibiting proton conductivity, such as Nafion, a hydrocarbon-based proton conductive polymer.

As a negative electrode biocatalyst (first biocatalyst), glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, lactate dehydrogenase, aldo Examples thereof include, but are not limited to, monodehydrogenase and oligosaccharide dehydrogenase.

[0056] In addition, as the acid-reduction site (first acid-reduction site) of the redox polymer of the negative electrode, a phencene derivative (a phenoxycene group, a carboxyphenocene, a dicarboxyphenocene, a methicene) Ruferocene, dimethylphenol, buluene, etc.), quinone compounds (benzoquinone, hydroquinone, naphthoquinone, pyroquinoline quinone, etc.), osmium bibilidine complexes ([Os (4,4, -Dimethylolene-2,2, bibilidine) CI] ^{+ /}

2 ²⁺ , [Os (4,4, -Damino-2,2, -biviridine)

Cl] ^{+ / 2 +} , [Os (4,4, -dimethoxy-2,2, -biviridine) Cl] ^{+ / 2 +} , etc.), osmium biimi

twenty two

Three

The power that can include viologen etc.

[0057] <Positive electrode> The positive electrode has proton conductivity. The positive electrode may have a material exhibiting proton conductivity, such as Naf ion, a hydrocarbon proton conductive polymer.

The positive electrode has a second electronic conductor which may be the same as or different from the negative electron conductor (first electronic conductor).

In addition, the positive electrode may have a second redox polymer that may be the same as or different from the redox polymer (first redox polymer) of the negative electrode. The redox polymer preferably has a second acid-reduction site exhibiting acid-acid reduction behavior and exhibits an electron conductivity of 10 ^-16 SZcm or more.

Furthermore, the positive electrode has a catalyst including a biocatalyst.

[0058] The catalyst of the positive electrode may be a metal (for example, Pt) and a biocatalyst or an analog thereof (second biocatalyst or an analog thereof).

The second biocatalyst can include, but is not limited to, pyrilvinoxidase, laccase, and cytochrome oxidase.

[0059] As the second acid-reduction site of the positive electrode, osmium bibilidine complexes ([Os (terpyridine)

(4,4, -Dimethylol-2,2, -biviridine) Cl] ^{2 + / 3 +} , [Os (4,4, -Dichloro-2,2, -biviridine)

twenty two

C1] ^{+ / 2+} ), and 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate), and the like, but are not limited thereto.

[0060] <Electrolyte>

As the electrolyte, a conventionally known electrolyte, particularly an electrolyte having proton conductivity can be used. The electrolyte is disposed between the positive electrode and the negative electrode.

As described above, the battery can be configured to operate as follows. That is, when the negative electrode has, for example, glucose oxidase as the first biocatalyst, glucose is used as a fuel in contact with the negative electrode. In the negative electrode, glucose is converted to dalconoratone by darcosoxidase, while electrons are transferred to the first electronic conductor through the first biocatalytic force first redox polymer. Electrons are transmitted from the negative electrode of the battery to the outside.

[0062] On the other hand, when, for example, cytochrome oxidase is used as the second biocatalyst in the positive electrode, oxygen is used as a medium in contact with the positive electrode. (Move from negative electrode to electrolyte In addition, water is generated by the reaction of protons, oxygen, and electrolytes, which also transfer electrolyte forces, in the positive electrode, particularly the second biocatalyst of the positive electrode.

In the above example, glucose is used as the negative electrode fuel, dalcosoxidase is used as the first negative electrode biocatalyst, oxygen is used as the positive electrode fuel (medium), and cytochrome oxidase is used as the second positive electrode biocatalyst. However, the above-described biocatalyst for negative electrode and fuel for negative electrode can be used. Also, other combinations can be used for the positive electrode.

Thus, the present invention can provide a biofuel cell. When configured as a biofuel cell, it is preferable to have a fuel supply container (for each of the negative electrode and the positive electrode).

<Multi-stage reaction type battery>

The present invention also provides the following multi-stage reaction type battery.

That is, according to the present invention, fuel is decomposed in n stages (n is an integer of 2 or more) by n or more biocatalytic reactions or biocatalytic reactions 1 to! A battery having a number of battery areas,

The first battery region has a first negative electrode, a first positive electrode, and a first electrolyte sandwiched between the first positive electrode and the first negative electrode,

The first negative electrode has a specific surface area that acts on pores of 7 nm or more, and the external specific surface area is 0.5 m ² / g or more, preferably 6 to 5000 m ² Zg, more preferably 10 to 800 m ² / g. A first redox polymer, a first biocatalyst, and the like. The first redox polymer has a first redox site exhibiting redox behavior, and 10 ^_16 S show electron conductivity of / cm or more,

The first positive electrode has electronic conductivity;

Anode electron conductor of the m is external specific surface area 0. 5 m ² Zg least a force mowing specific surface area than the pores 7 nm (electron conductor of the m of the m-th, first to (m — 1) electron The m-th redox polymer (the m-th redox polymer may be the same as or different from the first to (m-1) redox polymers) , And the m-th biocatalyst (the m-th biocatalyst is different from the first to (m-1) biocatalysts, etc.), and the m-th redox polymer is a redox polymer It has a m-th acid-reduction site that exhibits behavior (the m-th acid-reduction site may be the same as or different from the first to (m-1) redox sites). And an electronic conductivity of 10 ^_16 SZcm or more, and the mth positive electrode has electronic conductivity,

In the first negative electrode, the fuel is decomposed into the first decomposition product by the first biocatalyst and the like, and one or more electrons are generated,

In each of the m-th negative electrodes, the battery in which the (m-1) decomposition product is decomposed into the m-th decomposition product by the m-th biocatalyst and generates one or more electrons. The first to n-th negative electrodes and the first to n-th positive electrodes used in the first to n-th battery regions can also be made of the same material as the above-described battery.

[0064] Further, in the battery described above, the first to nth electrolytes are formed on a substantially flat surface, the first to nth negative electrodes are on one surface of the substantially flat surface, and the first to nth positive electrodes are The first to nth fuels and the first to nth decomposition products are in contact with each other on one surface of the substantially one plane on which the first to nth negative electrodes are formed. An nth negative electrode is preferably formed.

Further, in the above battery, it is preferable that the (m−1) positive electrode and the mth negative electrode are energized, and the first to nth battery regions are wired in series. U ヽ is preferred because it can provide batteries with high electromotive force by arranging in series.

[0065] The present invention also provides an embodiment of the configuration of the multistage reaction battery shown below.

The first negative electrode is the first electronic conductor, the first redox polymer, and the first biocatalyst Has a like, said first redox polymer has a first redox sites displaying a redox behavior, and shows the 10 ^{_ 16} SZcm more electron conductivity,

The first positive electrode has electronic conductivity;

The mth negative electrode is the mth electronic conductor (the mth electronic conductor may be the same as or different from the first to (m-1) th electronic conductors), the mth redox polymer ( The m-th redox polymer may be the same as or different from the first to (m-1) redox polymers), the m-th biocatalyst, etc. To the (m-1) biocatalyst), and the m-th redox polymer has an m-th acid-reduction site that exhibits redox behavior (the m-th acid-reduction site is The first to (m-1) acid-reduction sites may be the same or different, and exhibit an electronic conductivity of 10 ^_16 SZcm or more,

The mth positive electrode has electronic conductivity;

In each of the mth negative electrodes, the (m-1) decomposition product is decomposed into the mth decomposition product by the mth biocatalyst and the like, and one or more electrons are generated,

The first to nth electrolytes are formed on substantially one plane, the first to nth negative electrodes are formed on one surface of the substantially one plane, and the first to nth positive electrodes are formed on the other surface of the substantially one plane. In addition, the first to nth negative electrodes are formed so that the fuel and the first to nth decomposition products are in contact with each other on a substantially flat surface on which the first to nth negative electrodes are formed. The battery is provided. The first to n-th negative electrodes and the first to n-th positive electrodes used in the first to n-th battery regions are not limited to the same materials as the above-mentioned batteries, but The same material as that of the battery can also be used. In the battery described above, the first to nth battery regions are arranged along the direction of fuel flow, the first battery, the second battery, the third battery region, · · · · · · It should be arranged in the order of. By arranging in this way, the biocatalytic reaction or biocatalyst-like reaction is performed along the flow direction such that the fuel is the first decomposition product, the first decomposition product is the second decomposition product, and so on. Because is done The above arrangement is preferable.

Similarly to the battery described above, it is preferable that the (m−l) positive electrode and the mth negative electrode are energized, and the first to nth battery regions are wired in series.

Further, as in the case of the battery described above, the first to n-th electron conductors of the first to n-th negative electrodes have an external specific surface area of 0.5 m ² Zg, which is a specific surface area acting on pores of 7 nm or more. That's it.

[0067] The above-described multistage reaction type battery will be described with reference to the drawings. FIG. 2 is a schematic cross-sectional view showing one embodiment of the above-described multi-stage reaction type battery 20. The substantially flat part in FIG. 2 shows the negative electrode part, the positive electrode part, the electrolyte part sandwiched between the negative electrode part and the positive electrode part, the upper part of FIG. 2 is the negative electrode side, and the lower part is the positive electrode side. Hereinafter, a more detailed description will be given with respect to FIG.

The substantially flat plate portion includes a first battery region 22, a second battery region 23, a third battery region 24, and a fourth battery region 25. The first to fourth battery regions respectively have first to fourth negative electrodes 22a to 25a, first to fourth electrolytes 22b to 25b, and first to fourth positive electrodes 22c to 25c.

The first positive electrode 22c and the second negative electrode 23a are energized by the wiring 30. Similarly, the second positive electrode 23c and the third negative electrode 24a are energized by the wiring 31, and the third positive electrode 24c and the fourth negative electrode 25a are energized by the wiring 32. The insulator 33 is provided with a hole (not shown) through which the wiring 30 passes while insulating the first and second battery regions. The insulators 34 and 35 are also provided in the same manner as the insulator 33. The wiring 37 and the wiring 38 act as a negative electrode and a positive electrode as a battery, respectively.

[0068] On the negative electrode side in the upper part of FIG. 2, the fuel contacts the first to fourth regions, particularly the first to fourth negative electrodes, in the direction from right to left (in the direction of arrow A). In addition, the fuel is introduced. On the other hand, on the positive electrode side at the bottom of FIG. 2, the right force is also applied to the first to fourth regions, particularly the first to fourth positive electrodes in the direction to the left (in the direction of arrow B). An acidic gas or an acidic liquid is configured to flow in such a way that the acidic liquid contacts.

Here, the first to fourth electrolytes have proton conductivity. In general, the first to n-th electrolytes can be electrolytes having various properties depending on the fuel used and the acidic gas or the acidic liquid. For example, solid electrolyte membranes, more specifically, commonly used solid electrolyte membranes such as Nafion, in the pores of porous membranes Proton conductive materials such as electrolyte membranes filled with proton conductive liquids (for example, proton conductive polymers, proton conductive buffers, etc.) can be used.

The first to fourth positive electrodes have proton conductivity and electron conductivity.

[0069] As described above, each of the first to fourth negative electrodes has different first to fourth biocatalysts. The first biocatalyst or the like causes the fuel to be decomposed into the first decomposed material in the first negative electrode, and one electron or more and one or more protons are generated due to the biocatalytic reaction or the biocatalyst-like reaction. Generated. The first decomposition product is flowed along with the fuel in the vicinity of the second negative electrode along the flow direction, and is decomposed into the second decomposition product by the second biocatalyst or the like at the second negative electrode. In addition, with this biocatalytic reaction or biocatalyst-like reaction, more than: L electrons are generated. The second decomposed product is flown along with the fuel and the first decomposed product in the vicinity of the third negative electrode along the flow direction, and the third decomposed product is generated in the third negative electrode by the third biocatalyst or the like. Is broken down into In addition, one or more electrons and one or more protons are generated along with this biocatalytic reaction or biocatalyst-like reaction. Furthermore, the third decomposition product is caused to flow in the vicinity of the fourth negative electrode along the flow direction together with the fuel and the first and second decomposition products, and in the fourth negative electrode, the fourth biocatalyst, etc. Decomposed into a fourth degradation product. In addition, one or more electrons and one or more protons are generated with this biocatalytic reaction or biocatalyst-like reaction.

[0070] Since the first to fourth electrolytes have proton conductivity, the protons generated in the first to fourth negative electrodes can be moved to the first to fourth positive electrodes, respectively.

In the first to fourth positive electrodes, an acidic gas such as oxygen reacts with the moving protons and electrons to generate water. In general, the positive electrode preferably has a catalyst in a reaction for generating water from oxygen, protons, and electrons contained in an oxidizing gas or an oxidizing liquid. Although the positive electrode catalyst depends on the oxidizing gas or oxidizing liquid used, the above-described biocatalyst for the positive electrode can be used.

As described above, the battery shown in FIG. 2 is a battery in which the first to fourth batteries are arranged in series. By using the fuel to be used, the first to fourth biocatalysts to be used, etc., a battery that provides a higher voltage (electromotive force) than the voltage (electromotive force) obtained in a single battery region is obtained. it can.

[0072] Here, the fuel to be used and the first to nth biocatalysts used for the negative electrode will be described with examples. An example using methanol as the fuel is shown below.

[0073] [Chemical 1]

[0074] When methanol is used as a fuel, a battery having the first to third battery regions can be obtained, and alcohol dehydrogenase can be used as the first biocatalyst of the first battery region. Also, aldehyde dehydrogenase can be used as the second biocatalyst, and formate dehydrogenase can be used as the third biocatalyst. As a result, in the first negative electrode, two electrons are generated along with the biocatalytic reaction from methanol to formaldehyde. In the second negative electrode, two electrons are generated along with the biocatalytic reaction from formaldehyde to formic acid. Furthermore, in the third negative electrode, two electrons are generated along with the biocatalytic reaction from formic acid to carbon dioxide. Therefore, a battery that uses methanol as a fuel and has the first to third battery area power is a battery that generates six electrons as a whole, and can provide a high voltage (electromotive force) based on the six-electron reaction. it can.

[0075] Further, an example in which ethanol is used as a fuel is shown below. [0076] [Chemical 2]

ethanol

Alcohol

dehydrogenase

acetaldehyde

Aldehyde

dehydrogenase

acetic acid

k

[0077] When ethanol is used as a fuel, the details are as shown in the above formula. A total of 4 electrons are generated by a two-stage reaction from ethanol to acetic acid. Thus, the battery using ethanol as a fuel and having the first and second battery area power is a battery that generates four electrons as a whole, and provides a high voltage (electromotive force) based on the four-electron reaction. Can do. Furthermore, an example using glucose as a fuel is shown below.

[0078] [Chemical 3]

ffi HH ffi O

〇 ^K 〇〇

O "*" ¹

Hl lH HH The above example is an example when glucose is used as a fuel. Here, Glucosca is also a three-step biocatalytic reaction scheme to 2,5-diketo-D-dalconic acid, which shows a total of 6 electrons generating a biocatalytic reaction scheme. 5-Diketo -D-Dalcon The acid can be further decomposed by a biocatalytic reaction, for example, to carbon dioxide. In this case, ie in the case of a biocatalytic reaction scheme from glucose to carbon dioxide

A total of 24 electrons can be generated. Therefore, when glucose is used as a fuel, a fuel that provides a high electromotive force based on the 24-electron reaction can be provided.

[0080] <Production method of material>

The material of the present invention can be prepared by the following production method.

That is, it can be prepared by simultaneously carrying out any two or three of the following a) to c) in any order and Z or a) to c).

a) A step of mixing and Z or bonding an electron conductor and a redox polymer or redox polymer precursor (however, when a redox polymer precursor having no redox site is used, the acid-reduction site is redoxed). Introduced into polymer precursor to form redox polymer

c) A step of introducing a biocatalyst or an analog thereof.

Here, the terms “electron conductor”, “redox polymer”, “biocatalyst or analog thereof”, and “acid-reducing site” have the same definition as the material.

[0081] For example, I. a) step → b) step → c) step; v. A) step → c) step → b) step; III. B) step → a) step → c) step; IV. B ) Step → c) Step → a) Step; V. c) Step → a) Step → b) Step; VI. C) Step → b) Step → a) Step;

Also, two or more processes can be performed at the same time, such as a) process and b) process, and then c) process.

Further, in the step a), when a redox polymer precursor having no oxidation reduction site is used instead of the redox polymer having an acid reduction site, the step of introducing the oxidation reduction site into the precursor is performed. It can also be carried out before, after or simultaneously with the above steps a) to c).

[0082] In the step a), "bonding" is preferably performed as follows. That is, it is preferable to introduce a polymerization initiating group into the electron conductor and bond the polymerization initiating group to the redox polymer or a precursor thereof. The following is an example of a process for introducing a carbon black hair group (polymerization initiating group) when carbon black is used as the electron conductor. As shown in the simplified chemical reaction equation below, an azo group was introduced into carbon black. This involves first introducing an isocyanate (one NCO) group by reacting a diisocyanate with a phenolic OH group or COOH group on carbon black. Thereafter, this isocyanate (—NCO) group is reacted with an azo compound having a carboxyl group at both ends, thereby introducing an azo (one N = N—) group into carbon black.

[0083] [Chemical 4]

[0084] During the step b), the electron conductor precursor is preferably granular or rod-shaped. In the case of a granular shape, the particle diameter thereof, and in the case of a rod shape, the diameter of the cross section thereof should be 10 m or less, preferably 1 μm or less, more preferably lOOnm or less. Examples of electron conductor precursors include, but are not limited to, carbon, conductive polymers, and metals. These precursors are constructed three-dimensionally to form a three-dimensional network. An electronic conductor having an external specific surface area of 0.5 m ² Zg or more, preferably lm ² / g or more, preferably 6 to 5000 m ² Zg, more preferably 10 to 800 m ² / g by forming a three-dimensional network Form.

[0085] A method for forming an electron conductor having a three-dimensional network using carbon black having a particle size of 30 nm as an electron conductor precursor will be specifically described. Carbon ink is prepared by mixing carbon black and a binder (eg, PTFE suspension). This carbon ink is applied to the coated surface by screen printing, dried, and hot-pressed at an appropriate temperature and pressure, whereby an electronic conductor having carbon black and having a three-dimensional network can be formed.

[0086] "Introduction of a biocatalyst or an analog thereof" in the step c) may be conducted by simply mixing into a material (for example, mixing into an electronic conductor or mixing into a redox polymer). Chemically bonded to the redox polymer even if introduced to bind chemically to the body Please guide him to do it.

“Introduction of a biocatalyst or an analog thereof” may be simply introduced by mixing into a material, for example, by using a cross-linking reaction between biocatalysts or a cross-linking reaction between biocatalyst, ushi serum albumin and dartaldehyde. Introduce it to be fixed to the material.

[0087] When the biocatalyst or an analog thereof is deactivated, the deactivated biocatalyst or the like can be removed, and then the active biocatalyst or the like can be recombined. For example, when the initial biocatalyst or the like is chemically bonded or physically bonded to the redox polymer, desorption / rebonding is performed by the weak bond, which is inconsequential to normal battery operation. As a result, the deactivated biocatalyst and the like can be removed, and the active biocatalyst and the like can be recombined. As this technique, for example, there is a technique in which a functional group having a charge is introduced into a redox polymer and a biocatalyst or the like is immobilized by electrostatic interaction. Examples of the electrostatic interaction include control of the pH of the liquid in which the material of the present invention is immersed. More specifically, when the battery is operated, a liquid adjusted to a pH at which the charged functional group on the redox polymer and the charge of the biocatalyst are reversed is used, so that the electrostatic charge is generated between the functional group and the biocatalyst. By adsorption, a biocatalyst or the like can be fixed. On the other hand, the biocatalyst and the like can be desorbed by flowing a liquid whose pH is adjusted so that the charged functional group on the redox polymer is equal to the charge of the biocatalyst (that is, a desorbing liquid). If the redox polymer is bonded to the electron conductor, the redox polymer may leak into the liquid even if the biocatalyst etc. is desorbed by the pH change of the liquid. It is preferable because it is not.

[0088] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

Example 1

[0089] <Preparation of azo group (polymerization initiating group) -introduced carbon black>

Ketjen black (specific surface area: about 800 m ² Zg; external specific surface area: about 200 m ² Zg; particle size: 30 nm) was used as carbon black (hereinafter simply abbreviated as “CB”).

CB2.5 (5 g), dehydrated dimethyl sulfoxide (hereinafter simply abbreviated as “DMSO”) (65 ml), a monopicoline (1 ml), and 2,4-diisocyanate tolylene (1 ml) at 60 ° C under nitrogen atmosphere for 4 hours By reacting for a while, an isocyanate (one NCO) group was introduced into CB.

After cooling the reaction solution to room temperature, add 4,4, -azobis (4-cyananovaleric acid) 2. Og in DMSO (8m 1) to the reaction solution and react at room temperature for 8 hours under nitrogen atmosphere. An azo (one N = N—) group was introduced into CB. After the reaction, the reaction solution was removed by filtration and stirred in a methanol solution for 10 minutes to remove unreacted substances. Then, it filtered under reduced pressure and wash | cleaned several times with methanol. Unless otherwise specified, reagents were used without purification.

[0090] <Graft polymerization of redox polymer>

Graft polymerization of acrylamide (hereinafter simply abbreviated as “AAm”) and bull ferrocene (hereinafter simply abbreviated as “VFc”) was performed on the CB-introduced CB. Add azo group to CBO. 3 g, [AAm] = l. 41 molZL, [VFc] = 0.4 ml of dioxane solution of 42 molZL was degassed and purged with nitrogen, then reacted at 70 ° C for 24 hours. It was. In order to remove the non-grafting polymer and unreacted substances, ultrasonic cleaning was performed in a methanol solution for 10 minutes, and then Soxhlet extraction was performed using water as a solvent for 24 hours.

[0091] <Preparation of carbon 3D electrode (screen printing)>

The carbon ink obtained by grafting the redox polymer obtained above and untreated CB and the PTFE suspension as a binder is applied to the carbon paper by screen printing, dried, and 130 ° Hot pressing was performed at C and 0.25 MPa, and a redox polymer graft-polymerized CB force prepared carbon 3D electrode Ered-1 and untreated CB force prepared carbon 3D electrode E-2 were obtained.

[0092] <Introduction of biocatalyst>

The three-dimensional electrode Ered-1 obtained above was impregnated with 0.1 M phosphate buffer (PBS) containing 30 mgZml glucose oxidase (hereinafter simply abbreviated as “GOx”) for 10 minutes. Washed with 1M PBS for 30 seconds. Subsequently, 0.1 M PBS containing 20 mg Zml ushi serum albumin (BSA) was impregnated for 10 minutes, and washed with 0.1 M PBS for 30 seconds. Then, the biocatalyst was introduced into the 3D electrode by impregnating in 0.1M PBS containing 2% glutaraldehyde (GA) for 10 minutes and washing with 0.1M PBS for 1 minute. Got.

[0093] <Electrochemical measurement> Electrochemical measurements were performed on the electrodes Ered-1, E-2, and Eredlen obtained above. Specifically, a gold wire was fixed to each electrode with a carbon paste to form a working electrode, and electrochemical measurements were performed. A silver / salt / silver silver electrode in saturated KC1 was used as the reference electrode, and a platinum black electrode was used as the counter electrode. Measurements were performed in 0.1 M PBS with 0.1 M glucose and pH 7.0. Before the measurement, the measurement solution was N-published for 30 minutes to remove dissolved oxygen.

2

The results of electrochemical measurements are shown in Figs.

[0094] Figure 3 shows the results of electrochemical measurements of electrodes Ered-1 and E-2 (cyclic voltamgram

(CV)). In Fig. 3, the solid line shows the result for electrode Ered-1, and the dotted line shows the result for electrode E-2. From FIG. 3, the electrode Ered-1 showed oxidation and reduction peaks in the vicinity of 0.3V. From this, the graft polymerization of redox polymer onto carbon black was confirmed. Figure 4 shows the CV results for the electrode Ered-len. In FIG. 4, the solid line shows the result with a solution containing 0.1 M dalcose, and the dotted line shows the result with a solution not containing glucose. The electrode Ered-len gave a sigmoid response in which the oxidation peak current increased in the glucose solution and almost no reduction peak was observed. On the other hand, no sigmoid response was observed for the electrode E-len in the solution containing no glucose (the dotted line in Fig. 4). This is thought to be due to the reduction of the acid-redox polymer by the reduced coenzyme generated when the biocatalyst in the electrode oxidizes glucose, and it was fixed in the carbon three-dimensional electrode. Biocatalysts have been shown to exchange electrons with redox polymers. Brief Description of Drawings

FIG. 1 is a diagram in which a material 1 of the present invention as a negative electrode (anode) is deposited on a polymer electrolyte and an enlarged conceptual diagram of the material 1.

FIG. 2 is a schematic cross-sectional view showing one embodiment of a multistage reaction type battery 20.

FIG. 3 shows the results of electrochemical measurements (cyclic voltamgram (CV)) of electrodes Ered-1 and E-2.

[Figure 4] Electrode Ered-len CV results are shown.

Claims

The scope of the claims

[1] A material having an electronic conductor, a redox polymer, and a biocatalyst or an analog thereof having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area acting on pores of 7 nm or more,

The above materials exhibiting electronic conductivity of Zcm or more.

[2] A material having an electron conductor, a redox polymer, and a biocatalyst or an analog thereof having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area acting on pores of 7 nm or more,

[3] A material having an electron conductor, a redox polymer, and a biocatalyst or an analog thereof having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area that is effective for pores of 7 nm or more,

The redox polymer has a redox sites displaying a redox behavior, and 10_ ¹⁶

Shows electronic conductivity above SZcm,

[4] The material according to any one of claims 1 to 3, wherein the electronic conductor is selected from a group force consisting of carbon, a conductive polymer, and a metal force.

5. The material according to claim 4, wherein the carbon is selected from the group force of carbon black, carbon nanotube, and carbon nanohorn.

6. The material according to any one of claims 1 to 5, wherein the external specific surface area of the electron conductor is lm ² Zg or more, preferably 6 to 5000 m ² Zg.

[7] Acid-reduction site strength of the redox polymer: Phenocene derivatives, quinone compounds, 7. The method according to claim 1, selected from the group consisting of sumumbipyridine complexes, osmium biimidazole complexes, viologen, and 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate). Material.

8. The material according to any one of claims 1 to 7, wherein one end of the redox polymer is chemically bonded to the electron conductor.

[9] The biocatalyst is glucose oxidase, glucose dehydrogenase, darconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, lactate dehydrogenase, aldo-is dehydrogenase, oligosaccharide. The material according to any one of claims 1 to 8, which is selected from the group consisting of dehydrogenase, pyrurubinoxidase, laccase, and cytochrome oxidase.

10. The material according to any one of claims 1 to 9, wherein the material is used as a negative electrode for a battery or a positive electrode for a battery.

[11] A method for producing a material having an electronic conductor, a redox polymer, and a biocatalyst or an analog thereof, wherein the external specific surface area, which is a specific surface area acting on pores of 7 nm or more, is 0.5 m ² Zg or more. The above method wherein the following a) to c) are carried out in random order and Z or any two or three of a) to c) are simultaneously performed:

B) a step of forming particles that are electron conductor precursors into a three-dimensional electron conductor; c) introduction of a biocatalyst or an analog thereof. Process.

[12] The first specific electron conductor, the first redox polymer, and the first biocatalyst or the like having an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area acting on pores of 7 nm or more A negative electrode having:

A positive electrode having electronic and proton conductivity; and

An electrolyte sandwiched between the positive electrode and the negative electrode; The battery, wherein the first redox polymer has a first redox site exhibiting redox behavior, and exhibits an electronic conductivity of 10 ^_16 S / cm or more.

13. The battery according to claim 12, wherein the negative electrode has proton conductivity.

[14] The first biocatalyst is glucose oxidase, glucose dehydrogenase, gluconate 2-dehydrogenase, ketogluconate 2-dehydrogenase, alcohol oxidase, alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, lactate dehydrogenase, 14. The battery according to claim 12 or 13, wherein a group power comprising aldos dehydrogenase and oligosaccharide dehydrogenase is also selected.

[15] The structure according to any one of claims 12 to 14, wherein the first redox site is selected from the group consisting of pheucose derivatives, quinone compounds, osmium bibilidine complexes, osmium biimidazole complexes, and viologen force. Power Battery according to item 1.

16. The battery according to any one of claims 12 to 15, wherein the positive electrode has a second electronic conductor.

[17] The positive electrode has a second redox polymer, the redox polymer has a second redox site exhibiting redox behavior, and exhibits an electronic conductivity of 10 ^_16 SZcm or more. The battery according to any one of ˜16.

[18] The second redox polymer force is selected from the group consisting of an osmium biviridine complex and a 2,2-azobis (3-ethylbenzothiazoline-6-sulfonate) force. The battery according to item.

[19] The battery according to any one of claims 12 to 18, wherein the positive electrode has a proton conductive polymer.

[20] The battery according to any one of claims 12 to 19, wherein the positive electrode has a catalyst.

21. The battery according to claim 20, wherein the catalyst is a second biocatalyst or an analog thereof.

22. The battery according to claim 21, wherein the second biocatalyst is selected from the group force consisting of pyrilvinoxydase, laccase, and cytochrome oxidase power.

[23] A battery having l to n battery regions, in which fuel is decomposed in n stages (n is an integer of 2 or more) by n or more biocatalytic reactions or biocatalytic analog reactions,

1 ~! ! Battery areas are the 1st to nth battery areas, and the 1st to nth battery areas are directly Wired in rows and Z or in parallel,

The first electronic conductor, the first redox polymer, and the first biocatalyst or the first specific negative electrode surface area of which the first negative electrode is a specific surface area that is effective for pores of 7 nm or more is 0.5 m ² Zg or more It has its analogues, wherein the first redox polymer has a first redox sites displaying a redox behavior, and shows the 10 ^{_ 16} SZcm more electron conductivity,

The first positive electrode has electronic conductivity;

The mth positive electrode has electronic conductivity;

[24] The 1st to nth electrolytes are formed on a substantially flat surface, the 1st to nth negative electrodes are on one surface of the substantially flat surface, and the 1st to nth positive electrodes are surfaces on the substantially flat surface. The first to n-th negative electrodes are formed so that the fuel and the first to n-th decomposed products are in contact with each other on a substantially flat surface on which the first to n-th negative electrodes are formed. 24. A battery according to claim 23 formed.

25. The battery according to claim 23 or 24, wherein the (m-1) positive electrode and the mth negative electrode are energized, and the first to nth battery regions are wired in series.

[26] A battery having l to n battery regions, in which fuel is decomposed in n stages (n is an integer of 2 or more) by n or more biocatalytic reactions or biocatalyst-like reactions,

The first negative electrode has a first electronic conductor, a first redox polymer, and a first biocatalyst or an analog thereof, and the first redox polymer exhibits a redox behavior. And has an electronic conductivity of 10 ^_16 SZcm or more,

The first positive electrode has electronic conductivity;

The mth negative electrode is the mth electronic conductor (the mth electronic conductor may be the same as or different from the first to (m-1) th electronic conductors), the mth redox polymer ( The m-th redox polymer may be the same as or different from the first to (m-1) redox polymers), and the m-th biocatalyst or an analog thereof (the m-th biocatalyst or the like). Each body has a first to (m-1) biocatalyst or an analogue thereof, and the m-th redox polymer has an acid-reduction behavior. (The m-th acid-reduction site may be the same as or different from the first to (m-1) acid-reduction sites! /), And 10 ^_16 S Zcm or more The electronic conductivity of

The mth positive electrode has electronic conductivity;

The first to nth electrolytes are formed on a substantially flat surface, and the first to nth negative electrodes are formed on a substantially flat surface. On the surface, the first to nth positive electrodes are formed on the other surface of the substantially one plane, and the fuel and the first to nth electrodes are disposed on one surface of the approximately one plane on which the first to nth negative electrodes are formed. The battery, wherein the first to n-th negative electrodes are formed so that the decomposition product of n comes into contact therewith.

27. The battery according to claim 26, wherein the first to nth battery regions are arranged along a fuel flow direction.

[28] The battery according to claim 26 or 27, wherein the (m-1) positive electrode and the mth negative electrode are energized, and the first to nth battery regions are wired in series.

[29] The first to n-th electron conductors of the first to n-th negative electrodes have an external specific surface area of 0.5 m ² Zg or more, which is a specific surface area acting on pores of 7 nm or more. A battery according to ~ 28.

[30] The fuel ethanol, n is 3, the first biocatalyst is alcohol dehydrogenase, the first decomposition product is formaldehyde, and the second biocatalyst is aldehyde dehydrogenase. The battery according to any one of claims 23 to 29, wherein the second decomposition product is formic acid, the third biocatalyst is formate dehydrogenase, and the third decomposition product is diacid-carbon. .

[31] The fuel is ethanol, the n is 2, the first biocatalyst is alcohol dehydrogenase, the first decomposition product is acetoaldehyde, and the second biocatalyst is aldehyde. 30. The battery according to claim 23, wherein the battery is dehydrogenase and the second degradation product is acetic acid.

[32] The fuel is glucose, the n is 3 or more, the first biocatalyst is dalcosoxidase, the first degradation product is darconoraton, and the second biocatalyst is dalconic acid. A 2-dehydrogenase, the second degradation product is 2-ketogluconic acid, the third biocatalyst is ketogluconate dehydrogenase, and the third degradation product is 2,5-dikegluconic acid. 29. The battery according to 1 above.

[33] The battery according to any one of claims 23 to 32, wherein the first to n-th negative electrodes have proton conductivity.

[34] The first and m-th redox sites may each be selected from the group forces consisting of pheucose derivatives, quinone compounds, osmium biviridine complexes, osmium biimidazole complexes, and pyrogens. The battery according to any one of 23 to 33.