CN100486020C - Fuel cell, electronic equipment, movable body, power generation system and thermoelectricity combination system - Google Patents
Fuel cell, electronic equipment, movable body, power generation system and thermoelectricity combination system Download PDFInfo
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- CN100486020C CN100486020C CNB2005800268264A CN200580026826A CN100486020C CN 100486020 C CN100486020 C CN 100486020C CN B2005800268264 A CNB2005800268264 A CN B2005800268264A CN 200580026826 A CN200580026826 A CN 200580026826A CN 100486020 C CN100486020 C CN 100486020C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
A fuel cell capable of directly abstracting electric power from polysaccharides, such as starch. Fuel electrode (1) is produced by fixing on electrode of carbon, etc. (11) by means of a fixative an enzyme participating in decomposition of polysaccharides to monosaccharides, an enzyme participating in decomposition of formed monosaccharides, a coenzyme (e.g., NAD<+>, NADP<+>, etc.) whose reduced form is produced in accordance with an oxidation reaction during the process of monosaccharide decomposition, a coenzyme oxidase (e.g., diaphorase) capable of oxidizing the reduced form of coenzyme (e.g., NADH, NADPH, etc.), and an electron mediator (e.g., ACNQ, vitamin K3, etc.) capable of receiving electrons generated by the coenzyme oxidation from the coenzyme oxidase and delivering the same to the electrode (11). The fuel electrode (1) is disposed opposite to air electrode (5) through electrolyte layer (3) to thereby construct a fuel cell.
Description
Technical field
The present invention relates to fuel cell, electronic device, mobile (movablebody), electricity generation system and the CHP system of using enzyme to make catalyst.
Background technology
Fuel cell comprises fuel electrode (negative pole), oxidant electrode or air electrode (positive pole) and electrolyte (proton conductor) basically, and has the operation principle according to the back reaction of brine electrolysis, makes hydrogen and oxygen reaction form water (H
2O) and produce.Particularly, be supplied to the fuel (hydrogen) of fuel electrode oxidized and be broken down into electronics and proton (H
+), and electronics forwards fuel electrode to, and proton H
+Move to oxidant electrode by electrolyte.At oxidant electrode, proton H
+With the oxygen of supplying from the external world with by the electron reaction generation H of external circuit from the fuel electrode supply
2O.
Fuel cell is a kind of high efficiency generator, and its chemical energy with fuel is converted into electric energy, and can high conversion efficiency extracts electric energy from the chemical energy such as the fossil energy of natural gas, oil or coal, and no matter where or when use fuel cell.Therefore, conventional, fuel cell is researched and developed widely in extensive power generation applications and other field.For example, fuel cell is installed on the space shuttle, and this has proved that fuel cell not only can provide electric energy also to can be all members water is provided, and fuel cell is the generator of cleaning.
In addition, in recent years, from room temperature to about 90
0The fuel cell of work such as solid polymer fuel cell obtain exploitation and have caused attention in the relative low temperature range of C.Therefore, attempting that fuel cell not only is applied to extensive generating and also be applied to small size of systems, for example driving the power supply and the portable power supplies that is used for PC or mobile device of automobile.
As mentioned above, fuel cell can be applicable to from the extensive wide scope of application of generating on a small scale of generating electricity, and has caused sizable attention as high efficiency generator.Yet, fuel cell has various problems: fuel cell uses by reformer usually and acts as a fuel from the hydrogen that natural gas, oil or coal transform, therefore and consumed Limited resources and needed heat, and fuel cell need comprise the catalyst such as the noble metal of the costliness of platinum (Pt).In addition, when hydrogen or methyl alcohol self directly are used as fuel, must careful processing.
In order to address these problems, have been proposed in and be applied in the biological metabolism that live body carries out in the fuel cell, described biological metabolism is a kind of high efficiency energy conversion process.Biological metabolism used herein is included in the respiration of carrying out in the microbial body cell, photosynthesis etc.The advantageous characteristic that biological metabolism has is that not only generating efficiency is very high, also is to be reflected under about room temperature and carries out under temperate condition.
For example, respiration is such process: microbe or cell absorb the nutrients such as carbohydrate, fat and protein, and are generating carbon dioxide (CO by glycolytic pathway and tricarboxylic acids (TCA) circulation with many enzyme reaction steps
2) process in, nicotinamide adenine dinucleotide (NAD
+) be reduced with formation nicotinamide adenine dinucleotide reduced (NADH), thereby the chemical energy in the nutrients is converted into redox energy, i.e. electric energy, and further, in electron transport system, the electric energy of NADH directly changes into the proton gradient electric energy, and oxygen is reduced to form water.The electric energy that produces forms ATP by atriphos (ATP) synthase from adenosine diphosphate (ADP) (ADP), and ATP is used for microbe or the required reaction of cells survival.These Conversion of energy are carried out in cytosol and mitochondria.
Photosynthesis is such process: passing through through electron transport system nicotinamide-adenine dinucleotide phosphate (NADP
+) be reduced into NADPH (NADPH) luminous energy that absorbs is converted in the process of electric energy, water is oxidized to form oxygen.The electric energy that produces is used for by absorbing CO
2Carbon fixation reaction and carbohydrate synthetic.
As the technology of in fuel cell, using biological metabolism above-mentioned, the electron transport that the electric energy that wherein produces in microbe takes out and produces from described microbe through electron mediator to electrode with the microorganism battery that obtains electric current be in the news (referring to, for example, do not examine Japanese Patent Application Publication specification No.2000-133297).
Yet microbe and cell also have a lot of functions except comprising from the expected response that chemical energy to electrical energy transforms.Therefore, in the method for mentioning in the above, undesirable reaction consumes electric energy makes to be difficult to realize gratifying energy conversion efficiency.
In order to address this problem, proposed wherein to use enzyme and electron mediator advance the only reaction of expectation fuel cell (referring to, for example, Japanese Patent Application Publication No.2003-282124 and 2004-71559).In this fuel cell, fuel is resolved into proton and electronics by enzyme, and has developed the fuel cell that uses alcohols such as methyl alcohol or ethanol or carbohydrate such as glucose to act as a fuel.
Yet the conventional fuel cell that use alcohol above-mentioned or glucose act as a fuel is unsatisfactory on generating efficiency, therefore is difficult to practical application.
Therefore, the task that the present invention will realize provides a kind of fuel cell, and its advantage not only is and can directly extracts electric energy to realize efficient power generation from polysaccharide, is that also it does not need limited fossil fuel and helps to realize resources circulation society.
Another task that the present invention will realize provides electronic device, mobile, electricity generation system and the CHP system of using above-mentioned outstanding fuel cell.
Summary of the invention
The inventor has carried out extensive research in order to solve the problem of following in the above-mentioned prior art.Hereinafter sketch this research.
The glucose that is used as fuel in above-mentioned conventional fuel cell decomposes multiple polysaccharide by industry and produces.On the other hand, at occurring in nature, do not exist with the material of the monose form that comprises glucose, and many materials exist with the polysaccharide form.Usually, organism does not obtain energy from glucose, and in fact obtains energy by absorbing polysaccharide and decomposing polysaccharide by enzyme.Thisly extract energy realization biomass (biomass) system of using rubbish for example to act as a fuel etc. from polysaccharide.This system is by the chemical substance of biomass generation such as hydrogen or methyl alcohol, and the many chemical substances that produced provide heat energy by burning.Further, the heat that produces by biological agent is in order to obtain heat energy.Use turbine etc. changes into kinetic energy with heat energy, and further changes into electric energy by generator.In each stage of Conversion of energy, energy loss takes place, and the energy of fuel is wasted significantly.
Therefore, when the polysaccharide that uses nature to exist acts as a fuel the fuel cell that produces electric energy can realize the time, electric energy not only can be directly from rubbish, extract can also be directly from the chemical substance of nature generation (for example, starch and cellulose) extract, thus make it possible to not use limited fossil fuel to obtain electric energy.Further, rubbish or waste paper can effectively utilize, and therefore reduce the amount of refuse, and this helps realizing resources circulation society.In addition, plant is by photosynthesis CO in the fixed air in polysaccharide is synthetic
2, this has and helps reduce airborne CO
2, airborne CO
2It is a current problem.
The inventor has carried out extensive research.As a result, find in fuel cell, to use act as a fuel all problems above solving of polysaccharide such as starch, and the present invention finishes.
Specifically, in order to solve top problem,
First invention relates to by using the enzyme decomposition fuel to produce the fuel cell of electric energy, it is characterized in that fuel comprises polysaccharide.
Second invention relates to the electronic device that uses fuel cell, it is characterized in that this fuel cell produces electric energy by using the enzyme decomposition fuel, and wherein this fuel comprises polysaccharide.
The 3rd invention relates to the mobile that uses fuel cell, it is characterized in that this fuel cell produces electric energy by using the enzyme decomposition fuel, and wherein this fuel comprises polysaccharide.
The 4th invention relates to the electricity generation system of using fuel cell, it is characterized in that this fuel cell produces electric energy by using the enzyme decomposition fuel, and wherein this fuel comprises polysaccharide.
The 5th invention relates to the CHP system of using fuel cell, it is characterized in that this fuel cell produces electric energy by using the enzyme decomposition fuel, and wherein this fuel comprises polysaccharide.
Fuel cell in each invention of first to the 5th has the structure that comprises anodal and negative pole usually, and this positive pole and negative pole are clipped in the middle proton conductor.
In fuel cell, decompose polysaccharide by using enzyme, electric energy can directly extract from polysaccharide.
Can be used as the example (polysaccharide of broad sense of the polysaccharide of the fuel in the fuel cell, be meant the carbohydrate that can form two molecules or polymolecular monose by hydrolysis, and comprise oligosaccharides, for example disaccharides, trisaccharide and tetrose) comprise starch, amylose, amylopectin, glycogen, cellulose, maltose, sucrose and lactose.These polysaccharide comprise the two or more polysaccharide that combine, and each polysaccharide comprises glucose as monose (it is combining unit).Amylose and amylopectin are the compositions of starch, and starch is the mixture of amylose and amylopectin.Act as a fuel, can use any fuel, as long as fuel contains decomposable polysaccharide, and fuel can contain the glucose as the polysaccharide catabolite.Therefore, rubbish etc. can be used as fuel.
In fuel cell, as enzyme, be used to promote the catabolic enzyme that decomposes at least and the monose oxidation that is used to promote form to decompose the oxidizing ferment of monose, for example decompose Polysaccharides to form monose such as glucose.Further, also be used for the coenzyme by the oxidizing ferment reduction is transformed into the coenzyme oxidizing ferment of oxide.
When the coenzyme of reduction becomes oxide owing to the oxidasic effect of coenzyme, produce electronics, and electronics is transferred to electrode (negative pole) from the coenzyme oxidizing ferment by electron mediator.As coenzyme, for example use NAD
+, and, for example, use diaphorase as the coenzyme oxidizing ferment.
Using glucoamylase to decompose the catabolic enzyme of polysaccharide and use glucose dehydrogenase as the oxidasic fuel cell that is used to decompose monose as being used for, can be decomposed into the polysaccharide of glucose by glucoamylase, for example, comprising material any in starch, amylose, amylopectin, glycogen and the maltose can be used as fuel and produces electric energy.Glucoamylase is to make as the alpha-glucans hydrolysis of starch forming the catabolic enzyme of glucose, and glucose dehydrogenase is to be the oxidizing ferment of D-glucopyrone with β-D-glucose oxidase.
Use cellulase as catabolic enzyme and use glucose dehydrogenase as oxidasic fuel cell in, the cellulose that can resolve into glucose by cellulase can be used as fuel.More particularly, cellulase is for being selected from least a in cellulase (EC 3.2.1.4), circumscribed cellobiose hydrase (EC 3.2.1.91) and the β-Pu Tangganmei (EC 3.2.1.21).As catabolic enzyme, can use the mixture of glucoamylase and cellulase, and in this case, catabolic enzyme can decompose nearly all polysaccharide that exists naturally, and therefore use contain a large amount of polysaccharide material for example the electricity generation system that acts as a fuel of rubbish can realize.
Use alpha-Glucosidase as catabolic enzyme and use glucose dehydrogenase as oxidasic fuel cell in, the maltose that can resolve into glucose by alpha-Glucosidase can be used as fuel.
Use invertase as catabolic enzyme and use glucose dehydrogenase as oxidasic fuel cell in, the sucrose that can resolve into glucose and fructose by invertase can be used as fuel.More clearly, invertase is for being selected from least a in alpha-Glucosidase (EC 3.2.1.20), sucrose-alpha-Glucosidase (EC 3.2.1.48) and the saccharase (EC 3.2.1.26).
Use beta galactosidase as catabolic enzyme and use glucose dehydrogenase as oxidasic fuel cell in, the lactose that can resolve into glucose and galactolipin by beta galactosidase can be used as fuel.
In order effectively to catch near occur in the negative pole enzyme reaction phenomenon, preferably coenzyme oxidizing ferment, coenzyme and electron mediator are immobilized on the negative pole with fixing agent as the signal of telecommunication.Preferably oxidizing ferment also is immobilized on the negative pole.Further, the catabolic enzyme that is used to decompose polysaccharide can be immobilized in negative pole, and finally the polysaccharide as fuel also can be immobilized on the negative pole.
In the fuel cell that uses starch to act as a fuel, can use gelatinization solid fuel by starch gelatinization is obtained.In this case, can use wherein with gelatinized starch with have enzyme and the negative pole of other the materials method that contact of immobilization on it, perhaps use wherein gelatinized starch is immobilized in method on the negative pole with enzyme and other materials.When using kind electrode, to compare with the concentration that the starch that uses the solution form reaches, it is very high that the starch concentration on the negative terminal surface keeps.Therefore, faster by the decomposition reaction of enzyme, thereby and improve and export, and further solid fuel is than the easier processing of solution fuel, and can simplify fuel feed system, and in addition, fuel cell can move up and down, thereby and is very beneficial for being used on the mobile device.
Any device that the fuel cell of first invention can be used for needing electric energy and have virtually any size, and can be used for, for example, electronic device, mobile, power device, building machinery, lathe, electricity generation system and CHP system, and output, size or the form of the application of fuel cell decision fuel cell or the type of fuel.
The electronic device of second invention can be any electronic device basically, and comprise pocket electronic device and fixed electronic device, and, can mention cellular phone, moving device, robot, PC, game machine, be installed in device, household electrical appliance and industrial products on the automobile as object lesson.
The mobile of the 3rd invention can be any mobile basically, and its object lesson comprises automobile, sulky vehicle, aircraft, rocket and spaceship.
The electricity generation system of the 4th invention can be any electricity generation system basically, and can be extensive or on a small scale, and acts as a fuel and can use polysaccharide, comprise the rubbish of polysaccharide etc.
The CHP system of the 5th invention can be any CHP system basically, and can be extensive or on a small scale, and acts as a fuel and can use polysaccharide, comprise the rubbish of polysaccharide etc.
In the present invention with said structure, the glycocalix enzyme that contains in the fuel resolves into monose, and can effectively extract electric energy by oxydasis monose the time.
In the present invention, enzyme is as catalyst, and the material that contains polysaccharide produces the fuel cell of electric energy as fuel thereby can obtain to use polysaccharide to act as a fuel with high efficiency.Fuel cell makes it possible to directly directly extract electric energy from the rubbish that for example contains a large amount of polysaccharide, therefore make and can effectively utilize rubbish.Further, fuel cell does not need limited fossil fuel, and helps to realize resources circulation society.In addition, the polysaccharide of safety can be used as fuel when edible, therefore can obtain to be advantageously used for the fuel cell of mobile product.In addition, for example, when using gelatinized starch to act as a fuel, the easier processing of described fuel ratio solution fuel, and can simplify fuel feed system, therefore obtain to be advantageously used for the fuel cell of mobile product.Use this outstanding fuel cell can realize high-performance electronic device, mobile, electricity generation system or CHP system.
Description of drawings
[Fig. 1] Fig. 1 is the schematic diagram that shows according to the fuel cell configurations of one embodiment of the present invention.
[Fig. 2] Fig. 2 is the schematic diagram that glucose is resolved into starch and cellulose by enzyme in explanation.
[Fig. 3] Fig. 3 is the schematic diagram according to the fuel cell configurations of one embodiment of the present invention that show to use amylan.
[Fig. 4] Fig. 4 be show in the fuel cell of one embodiment of the present invention at the figure that distributes perpendicular to the concentration of glucose on the direction on fuel electrode surface.
[Fig. 5] Fig. 5 is the sketch of the fuel element that uses in the fuel cell that shows according to one embodiment of the present invention.
[Fig. 6] Fig. 6 is the sketch that is used to illustrate to according to the fuel cell fuel supplying method of one embodiment of the present invention.
[Fig. 7] Fig. 7 is the sketch that is used to illustrate to according to the fuel cell fuel supplying method of one embodiment of the present invention.
[Fig. 8] Fig. 8 is the sketch that is used to illustrate to according to an example of the fuel cell fuel supplying method of one embodiment of the present invention.
[Fig. 9] Fig. 9 is the sketch that is used to illustrate to according to another example of the fuel cell fuel supplying method of one embodiment of the present invention.
[Figure 10] Figure 10 is the figure that shows the CV measurement result in the embodiment of the invention 1.
[Figure 11] Figure 11 is presented in the electrochemical measurement of the embodiment of the invention 1 and 2, when work electrode is 0V with respect to the constant voltage of reference electrode, and the time dependent figure of current density.
[Figure 12] Figure 12 is the figure that shows the CV measurement result in the embodiment of the invention 3.
[Figure 13] Figure 13 is the sketch of the fuel cell that is used to estimate in the embodiment of the invention 4.
[Figure 14] Figure 14 is the figure that is presented at the I-E characteristic measurement result of the fuel cell that is used to estimate in the embodiment of the invention 4.
Embodiment
Hereinafter, an embodiment of the invention will be described with reference to the drawings.
Fig. 1 roughly shows the fuel cell of one embodiment of the present invention.As shown in Figure 1, fuel cell comprises fuel electrode (negative pole) 1, and its use enzyme decomposes the polysaccharide of the supply that acts as a fuel with electron gain and generation proton (H
+); Dielectric substrate 3, it is proton conducting only; And air electrode (positive pole) 5, it separates from fuel electrode 1 by dielectric substrate 3, and will form water through the proton of dielectric substrate 3 transmission, electronics and the airborne oxygen of supplying with through external circuit from fuel electrode 1 from fuel electrode 1.
The polysaccharide that can be used as fuel comprises two or more monose that combine.The example of polysaccharide comprises the disaccharides such as maltose, sucrose and lactose, comprise amylose with linear molecule and starch with amylopectin of branched chain molecule, macromolecule glycogen with branched chain molecule of similar amylopectin, has the cellulose of linear molecule and as the carbohydrate of product in the middle of it.
As the enzyme of being responsible for decomposing polysaccharide, use can be by the catabolic enzyme of cut-out glycosidic bonds such as hydrolysis.When polysaccharide was starch, the example of catabolic enzyme comprised hydrolase, for example glucoamylase (EC 3.2.1.3), AMS (EC 3.2.1.1) and beta amylase (EC 3.2.1.2).In these enzymes, glucoamylase (GAL) starch-splitting is a glucose.EC represents enzyme number.
Other polysaccharide can be decomposed by the catabolic enzyme for example.
＜glycogen 〉
Glucoamylase (EC 3.2.1.3)
AMS (EC 3.2.1.1)
＜dextrin 〉
Glucoamylase (EC 3.2.1.3)
＜cellulose 〉
Cellulase (EC 3.2.1.4)
Circumscribed cellobiose hydrase (EC 3.2.1.91)
β-Pu Tangganmei (EC 3.2.1.21)
Here, can be collectively referred to as " cellulase " by cellulolytic enzyme.As the example of cellulase, can mention top three types enzyme, cellulose can be decomposed into glucose in the presence of described three kinds of enzymes at least a being selected from.
＜maltose 〉
Alpha-Glucosidase (EC 3.2.1.20)
This enzyme also is called maltose, but it acts on sucrose.Maltose also can be decomposed by glucoamylase.
＜sucrose 〉
Alpha-Glucosidase (EC 3.2.1.20)
Sucrose-alpha-Glucosidase (EC 3.2.1.48)
Saccharase (EC 3.2.1.26)
Here, enzyme that can sucrose hydrolysis is referred to as " invertase ".As the example of invertase, can mention top three types enzyme.Be selected from the presence of described three kinds of enzymes at least a and can forming glucose from sucrose.
＜lactose 〉
Beta galactosidase (EC 3.2.1.23)
＜1, the 3-beta glucan 〉
In the glucan-1,3-β-D-glucosidase (EC 3.2.1.39)
＜α, α-trehalose 〉
α, α-trehalase (EC 3.2.1.28)
α, α-trehalose phosphorylase (EC 2.4.1.64)
＜stachyose 〉
Alpha-galactosidase (EC 3.2.1.22)
Alpha-Glucosidase (EC 3.2.1.20)
＜glucoside 〉
β-Pu Tangganmei (EC 3.2.1.21)
Fig. 2 has showed the example that starch and cellulose is resolved into glucose by enzyme.
The enzyme of being responsible for decomposition monose comprises oxidizing ferment, and it participates in the redox reaction in decomposable process.When polysaccharide was starch, glycogen, cellulose or maltose, the monose that forms by polysaccharide hydrolysis was glucose; When proper polysaccharide was sucrose or lactose, glucose constituted half of the monose that forms.As the example of the enzyme of being responsible for decomposition glucose, can mention glucose dehydrogenase (GDH).Use the oxidable β of this oxidizing ferment-D-glucose to be the D-glucopyrone.
In addition, the D-glucopyrone of gained is can be decomposed into 2-ketone-6-phosphoric acid-D-gluconate in the presence of gluconokinase and the phosphogluconate dehydrogenase (PhGDH) at two kinds of enzymes.Specifically, the D-glucopyrone is hydrolyzed into the D-gluconate, and is adenosine diphosphate (ADP) (ADP) and phosphoric acid by hydrolysis atriphos (ATP) in the presence of gluconokinase, and the D-gluconate is by phosphorylation, thus formation 6-phosphoric acid-D-gluconate.Because the effect of oxidizing ferment PhGDH, the 6-phosphoric acid-D-gluconate of gained is oxidized to 2-ketone-6-phosphoric acid-D-gluconate.
Decomposable process except top utilizes glycometabolism, and glucose can be decomposed into CO
2The breakdown of glucose and the pyruvic acid that utilize glycometabolic decomposable process generally to be divided into by glycolytic pathway form the circulation with TCA, and these are known reaction systems.
Oxidation reaction in the monose decomposable process is accompanied by the reduction reaction of coenzyme.Almost the enzyme that always depends on use is determined coenzyme, and when enzyme is GDH, NAD
+As coenzyme.Specifically, make β-when the D-glucose oxidase becomes the D-glucopyrone, NAD as GDH
+Be reduced into NADH to produce H
+
The NADH of gained is oxidized to NAD immediately in the presence of diaphorase (DI)
+To form two electronics and two proton H
+In other words, in the oxidation reaction of phase I, per molecule glucose forms two electronics and two proton H
+In the oxidation reaction of second stage, form four electronics and four proton H altogether
+
The electronics that generates in said process is transferred to electrode 11 through electron mediator from diaphorase, proton H
+Be transferred to air electrode 5 through dielectric substrate 3.
The electron mediator transmission electronic is to electrode, and fuel cell voltage depends on the redox potential of electron mediator.In other words, in order to obtain higher voltage, preferably be chosen in fuel electrode 1 side and have the more electron mediator of negative potential, but must consider that the affinity reaction of electron mediator and enzyme, the electron exchange speed that is used for electrode 11, electron mediator are to the structural stability of inhibition factor (for example light or oxygen) etc.From this viewpoint, as the electron mediator that is used for fuel electrode 1, for example, ACNQ or prokeyvit are preferred.Perhaps, has for example compound of benzoquinones skeleton, the metal complex of Os, Ru, Fe or Co, violegen compound such as benzyl violegen, compound with niacinamide structure has the compound of riboflavin structure, or the compound with nucleosides-phosphoric acid structure can be used as electron mediator.
In order to realize effective and stable electrode reaction, preferred enzyme, coenzyme and electron mediator use the buffer solution such as TRIS buffer or phosphate buffer to maintain under the best pH of enzyme, and for example pH about 7.In addition, too big or too little ionic strength (I.S.) has adverse influence to enzymatic activity, and from realizing the viewpoint of outstanding electrochemical response, ionic strength is preferably desired value, and for example about 0.3.Separately the enzyme that uses has best pH and best ion intensity, so pH and ionic strength are not limited to top numerical value.
Enzyme, coenzyme and electron mediator can the solution form in buffer solution use, but, preferably use fixing agent that coenzyme oxidizing ferment and electron mediator are immobilized on the electrode 11 at least in order to catch near electrode, take place enzyme reaction phenomenon effectively as the signal of telecommunication.When the enzyme that is used for decomposition fuel and coenzyme further were immobilized on the electrode 11, the enzyme reaction system in fuel electrode 1 can be stablized.As fixing agent, for example, glutaraldehyde (GA) and poly-L-Lysine (PLL) use capable of being combined.They also can use separately, and perhaps other polymer also can use.Comprise the fixing agent of glutaraldehyde and poly-L-Lysine combination by use, the enzyme immobilization ability of component can make full use of separately, makes described fixing agent demonstrate whole outstanding enzyme immobilization ability.In this case, glutaraldehyde changes according to the substrate of enzyme that will be immobilized and enzyme the best proportion of poly-L-Lysine, but usually, this ratio can be arbitrarily.Particularly, glutaraldehyde water solution (0.125%) is 1:1,1:2 or 2:1 with the ratio of the poly-L-Lysine aqueous solution (1%).
Fig. 1 has showed an example, and wherein polysaccharide is a starch; The enzyme that responsible decomposition polysaccharide is a monose is glucoamylase (GAL), and it is decomposed into glucose with starch; The enzyme of being responsible for the formed monose of decomposition (β-D-glucose) is glucose dehydrogenase (GDH); The coenzyme that forms reduzate owing to the oxidation reaction in the monose decomposable process is NAD
+The coenzyme oxidizing ferment that is used for oxidation NADH (it is the reduzate of coenzyme) is diaphorase (DI); Are ACNQ with being used for receiving the electronics that produces owing to the oxidation coenzyme and transmission electronic from the coenzyme oxidizing ferment to the electron mediator of electrode 11.
On air electrode 5, from the proton H of dielectric substrate 3
+With from the electronics of fuel electrode 1 in the presence of catalyst the oxygen in the reducing atmosphere to form water.
In having the fuel cell of said structure, when the polysaccharide such as starch supplied to fuel electrode 1, the glycocalix enzyme hydrolysis became the monose such as glucose, and further the involved oxidasic catabolic enzyme of monose decomposes.In fuel electrode 1 one sides, oxidizing ferment participates in the monose decomposable process to produce electronics and proton H
+, make it possible between fuel electrode 1 and air electrode 5, produce electric current.
In fuel cell, the type of decomposable polysaccharide depends on the type that keeps or be immobilized in the catabolic enzyme on the fuel electrode 1.When the mixture that contains multiple polysaccharide acts as a fuel, be used for decomposing the enzyme maintenance of each polysaccharide respectively or being immobilized in fuel electrode 1, thereby improve fuel efficiency.In addition, rubbish etc. can be used as fuel and produce electric energy, make effectively to utilize rubbish etc.
In addition, top fuel battery energy uses the polysaccharide with high-energy-density to be fuel, safety when it is edible, and further can at room temperature work, therefore be advantageously used in mobile product.For the energy density that when using polysaccharide to act as a fuel, obtains, with the rice that boils is example, the energy of the starch that the rice (being equivalent to a rice bowl and about 160kca1) that boils at about 100g contains is equivalent to the energy of 64 AA type alkaline dry batteries (the about 3wh of each battery), and it is the high-energy-density that is equal to or greater than from the energy density of glucose solution acquisition.The polysaccharide that acts as a fuel can aqueous solution form use, but, can use wherein polysaccharide as amylan gelatinization and the method that contacts with fuel electrode 1, perhaps use the method that wherein polysaccharide is arranged in the fuel electrode 1, thereby solidification fuel can be used for fuel cell, and this is further favourable for mobile product.The problem that glucose has is: compare with methyl alcohol or ethanol, the glucose with little diffusion coefficient is disadvantageous for the fuel molecule diffusion controlled reaction that carries out when glucose is used as fuel with the solution form.Yet, when using wherein when starch gelatinization and the method that contact with fuel electrode 1 or use wherein be arranged in starch method in the fuel electrode 1, starch concentration on fuel electrode 1 surface or in fuel electrode 1, it is very high to be that concentration of glucose can keep, make the output that obtains when using starch compare, can improve output with the solution form.In addition, than the easier processing of liquid fuel, and can simplify fuel feed system such as the solidification fuel of amylan, therefore when fuel cell was used for mobile product, it was very effective.Fig. 3 has showed an example, and the amylan 6 that wherein acts as a fuel is immobilized on the fuel electrode 1.
The concentration of glucose that obtains during with the glucose that uses as monose is compared, and when as the starch of polysaccharide during as fuel, the concentration of glucose on fuel electrode 1 surface or in fuel electrode 1 can keep very high.Specifically, for example, the amylose that contains in the starch comprises hundreds of to several thousand glucose molecules that combine, and when a part amylose of the molecule that acts as a fuel by diffusion arrived fuel electrode 1 surface, glucose transport was that the hundreds of of the speed that realizes when acting as a fuel with glucose arrives several thousand times to the speed on fuel electrode 1 surface.That is, using starch to act as a fuel makes it possible to higher speed glucose transport be arrived fuel electrode 1 surface.
Fig. 4 A has shown in the solution that contains starch and glucoamylase (GAL) to use to have the enzyme-immobilized electrode that is immobilized in ACNQ on the electrode 11 and glucose dehydrogenase (GDH) by fixing agent and carry out CA and measure (under constant voltage in the electric current measurement over time, wherein the state of stable current flows is a diffusion-state of a control), and the state of gratifying long-time passage (diffusion-state of a control).Similarly, Fig. 4 B has shown that using identical enzyme-immobilized electrode to carry out CA in glucose solution measures, and gratifying state (diffusion control state) of having passed for a long time.Enzyme reaction in enzyme-immobilized electrode is quick satisfactorily, that is, the glucose that arrives electrode surface by diffusion can very rapidly decompose with to the electrode transmission electronic.Under the situation of Fig. 4 B, on electrode surface, balance each other by the glucose consumption of enzyme-immobilized electrode and from supplying with by the glucose of diffusion, thereby demonstrate constant concentration of glucose gradient away from the glucose solution of enzyme-immobilized electrode.Described concentration of glucose gradient decision electric current, the concentration of glucose gradient is big more, and electric current is big more.That is to say that electric current can improve by improving concentration of glucose.On the other hand, under the situation of Fig. 4 A,, do not have glucose to exist in solution, but contain starch and glucoamylase in the solution, thereby the glucoamylase hydrolyzed starch is a glucose measuring at first.In this case, on electrode surface, glucose consumption by enzyme-immobilized electrode and the glucose that in the solution that contains starch and glucoamylase, forms by diffusion supply and owing to be present in the supply of the glucose that the glucoamylase on the electrode surface forms and balance each other, determined electric current.What obtain when using glucose solution compares (comparing with extreme glucose saturated solution), has improved the concentration of glucose on the electrode surface at the glucose that forms on the electrode surface.When glucoamylase and starch further are immobilized on the enzyme-immobilized electrode, when just using structure shown in Figure 3, top effect can further be improved.
Then, the method that supplies fuel to fuel cell is described.Here, put down in writing the situation of starch as fuel.
Fig. 5 A has shown a not card type fuel element 32 of usefulness, and it is filled with the fuel 31 that comprises starch solution (amylose, amylopectin), amylan etc.Fuel 31 can contain glucose, NADH etc., and in this case, compares with the electric current that uses fuel 31 acquisitions that only contain starch, and the electric current when starting working is big.Fig. 5 B has shown the fuel element that has used 32 that has used all fuel 31.In Fig. 5 A and 5B, Reference numeral 33a, 33b represent the fuel pusher.Reference numeral 33c represents to be used to push away the spring of fuel, has the two ends that are fixed on fuel pusher 33a and the 33b.Fuel pusher 33a is fixed on the fuel element 32, and spring 33c makes fuel pusher 33b pushing fuel 31.
Fig. 6 has shown that fuel element 32 has wherein used the fuel cell of all fuel 31.Fuel element 32 is included in the fuel box 34.Fuel box 34 has element inlet 34a and element outlet 34b, and fuel element 32 inserts in the fuel box by element inlet 34a, and shifts out container by element outlet 34b.Fuel cell has following structure: the air electrode 5 that configuration is made of the enzyme immobilization carbon electrode that has at immobilized enzyme on the porous carbon and as embodiment 1 by having by the fixing agent fuel electrode 1 that the enzyme immobilization carbon electrode of immobilized enzyme and electron mediator constitutes on porous carbon, make they pass through as proton conductor spacer 35 (being equivalent to dielectric substrate 3) toward each other.In Fig. 6, as the example of external circuit load, bulb 36 is connected to air electrode 5 and fuel electrode 1.Fuel element 32 has used all fuel 31, so electric light big gun 36 does not work.Fuel element 32 is bigger than the size of air electrode 5 or fuel electrode 1 usually.
Followingly will change the not fuel element 32 of usefulness into the fuel element of crossing 32.As shown in Figure 7, open element import 34a, the fuel element 32 of usefulness is not inserted the fuel element 32 of fuel boxs 34 to promote use, allow it export 34b and leave container by element.When with the time point of the fuel element of crossing 32 when element outlet 34b shifts out fully, the fuel element 32 of usefulness is not arranged on preposition.This state as shown in Figure 8.As shown in Figure 8, when the fuel element 32 of usefulness is not arranged on described position, between fuel element 32 and fuel electrode 1, be formed for the feeding-passage of fuel 31, make fuel 31 be supplied to fuel electrode 1 by feeding-passage.This can realize in electromechanical system easily.In this case, in fuel element 32, fuel pusher 33b promotes fuel 31, so fuel 31 can be supplied to fuel electrode 1 inside, and fuel electrode 31 constitutes by having by fixing agent enzyme immobilization carbon electrode of immobilized enzyme and electron mediator on porous carbon.When for example having full-bodied liquid as fuel 31, this is effective.When fuel 31 can only arrive fuel electrode 1 inside by diffusion, fuel pusher 33a, 33b and spring 33c can omit, and still, when using fuel pusher 33a, 33b and spring 33c, fuel 31 can more guarantee to supply to fuel electrode 1 inside.Therefore, fuel 31 supplies to fuel electrode 5 to begin generating, so bulb 36 is luminous.
Preferably, the CO that produces during generating
2Or H
2The two is stored in O or they in the free space of the fuel element 32 that stays after all fuel 31 uses up.Particularly, CO
2Or H
2O can discharge from fuel cell, but considers from the environment viewpoint, more specifically, considers from the viewpoint that prevents global warming, from fuel cell exhaust CO
2Not preferred, and in addition, from fuel cell exhaust H
2O also has problems: when the cellular phone that fuel cell for example is installed was placed in pocket or the handbag, the water that pocket or handbag can be discharged was got wet, therefore preferably stored CO in fuel element 32
2Or H
2O or they the two.CO
2Or H
2O can be stored in the free space that the fuel element 32 that stays after all fuel 31 uses up stays effectively.
Amylase can be put in the part of the fuel element 32 that contains fuel 31.In this case, the concentration of glucose that supplies to fuel electrode 1 surface improves, and therefore makes it possible to obtain big electric current and big initial current.
For the processing of starch, the starch in unhulled rice or the potato mainly contains β-starch crystallite and constitutes, and amylase do not show activity substantially, and still, after the starch heating, β-starch becomes the alphalise starch of gelatinization, and it is active to make amylase show.Therefore, preferably alphalise starch being acted as a fuel 31 supplies to fuel electrode 1, but alphalise starch becomes β-starch after (wearing out) through after a while.
Can use moisture considerably less or do not have the fuel 31 of moisture substantially.Starch can be cured by compression.Glucose also can adopt this method to solidify, but its formability is poor.In solidification fuel 31, molecule unlikely spreads, so solidification fuel can not use according to original state.In this case, when fuel 31 and fuel electrode 1 contact with each other, can be from fuel element 32 outsides or internal feed water (wherein starch solids material and water are separated from each other), make fuel cell begin generating.As water, use the water that on air electrode 5, forms based on the principle that is similar to the direct methanol fuel cell (DMFC) of using 100% methanol fuel.This is fuel electrode 1 and air electrode 5 common systems that form water in principle wherein.Reaction in this individual system is represented with following formula:
C
6H
12O
6+6O
2→6CO
2+6H
2O AG°＝-4,928kJ/mol
Below, the method for the fuel cell fueling that the primary cell of abandoning after the picture usefulness is used as dry cell is described.
In this case, do not need to shift out and insert the mechanism of fuel element 32 from fuel cell.As shown in Figure 9, fuel element 32 becomes one with fuel electrode 1 in advance.In this case, similar from fuel element 32 to the method and the above-described method of fuel electrode 1 fueling 31.
Hereinafter, will the present invention be described with reference to the following examples.
＜embodiment 1 〉
At vitreous carbon (GC) electrode (BAS, dropwise apply 3 μ l diaphorase (DI) (UNITIKA LTD. on the φ=3.0mm), from bacillus stearothermophilus) PBS (83 μ M), the PBS of 6 μ l glucose dehydrogenase (GDH) (TOYOBO LTD.) (60 μ M), 3 μ l glucoamylase (GAL) (Oriental Yeast Co., Ltd.) PBS (1.4mM), the aqueous solution (1%) of 3 μ l poly-L-Lysines (PLL), the PBS (0.4M) of 2 μ l NADH, the aqueous solution (0.125%) of the ethanolic solution of 2 μ lACNQ (28mM) and 3 μ l glutaraldehydes (GA), and with them mixing and at room temperature air drying mutually, with the distilled water washing, prepare GAL/GDH/NADH/DI/ACNQ immobilized electrode (see figure 1) then.
Zhi Bei immobilized electrode is as work electrode like this, the Ag/AgCl electrode is as reference electrode, the Pt electrode is as pole plate, and the electrolytic cell of being made by polytetrafluoroethylene of volume 1ml is as reactive tank, and 1ml contains the 0.1M PBS of water soluble starch concentration of concentration 1%, and (pH 7; I.S.=0.3) as reaction solution, and with Ar gas they are carried out deoxygenation, under room temperature (25 ℃), carry out electrochemical measurement then.
＜embodiment 2 〉
Carry out electrochemical measurement in mode substantially the same manner as Example 1, except on the GAL/GDH/NADH/DI/ACNQ immobilized electrode that is coated in embodiment 1 preparation by the 5mg material that obtains in the starch phosphate salt buffer solution gelatinization that makes 50% under 70 ℃ and reaction solution become the 0.1M PBS of 1ml (pH 7; I.S.=0.3) in addition.
＜comparative example 1 〉
Carry out electrochemical measurement in mode substantially the same manner as Example 1, except in the step of immobilized electrode of preparation embodiment 1, omitting glucoamylase (GAL), thereby beyond the preparation GDH/NADH/DI/ACNQ immobilized electrode.
For embodiment 1, be that the voltage scanning method (CV) of 20mV/ second is carried out voltage scanning according to sweep speed.CV measures the results are shown in Figure 10 (solid line among the figure).In Figure 10, as a reference, not amyloid 0.1M PBS as the CV measurement result under the situation of reaction solution shown in dotted line b and containing starch concentration be 0.1% 0.1M PBS as the CV measurement result under the situation of reaction solution shown in chain-dotted line c.In use contains measurement under the situation that starch concentration is 0.5% solution, obtain and the essentially identical result of solid line a.
As can be seen from Figure 10, when containing starch in the reaction solution, observe oxidation current, the starch that this meaning is immobilized in the film on the electrode is decomposed into glucose by GAL, and glucose decomposed by GDH, and reaction carries out successively, makes electrode receive electronics.
[table 1]
| Stabling current (μ A/cm 2 @0V vs Ag|AgCl) | |
| |
58 |
| |
395 |
| Comparative example 1 | 2 |
As can be seen from Table 1, exist therein among the embodiment 1 and 2 as the glucoamylase of diastatic enzyme, use starch to act as a fuel and to produce electric current.Especially, starch gelatinization and being immobilized among the lip-deep embodiment 2 of electrode therein can obtain the big electric current of electric current that obtains than embodiment 1, and the starch of solution form contacts with electrode in embodiment 1.Its reason is the starch concentration on the electrode surface as mentioned above, and promptly concentration of glucose can keep very high, makes it possible to promote the decomposition reaction of fuel.
Glucose has such problem: the glucose with little diffusion coefficient of comparing with methyl alcohol or ethanol is disadvantageous for may carry out diffusion controlled reaction when glucose is used as fuel with the solution form, but it is evident that from top result, can be by using starch to act as a fuel or the starch of immobilization gelatinization on electrode surface solves this problem.In addition, use the feasible processing easily of the solid fuel fuel of gelatinization, and can simplify fuel feed system, so the gained fuel cell is very useful as being installed in such as the fuel cell on the mobile device of cellular phone.
＜embodiment 3 〉
Immobilization amylan 6 thereon acts as a fuel and glucoamylase (GAL) is the fuel electrode 1 of glucose as starch-splitting for having, with identical condition that embodiment 1 uses under carry out CV and measure.(curve a) to the results are shown in Figure 12.In Figure 12, as a reference, shown that also wherein glucose solution is as the CV measurement result (curve b) under the situation of fuel.As can be seen from Figure 12, (concentration of glucose: the maximum current that obtains during 200mM) as fuel is compared, and when amylan 6 is used as fuel, can obtain sizable electric current with glucose solution.As mentioned above, this result shows very high concentration of glucose on electrode 1 surface.In addition, the reason that electric current increases along with effluxion is starch little by little by glucoamylase (GAL) hydrolysis, so the concentration of glucose on the electrode surface increases along with effluxion.Curve b has the shape of having only diffusion controlled reaction just to have.
＜embodiment 4 〉
Fuel cell shown in installation diagram 13A and the 13B and estimating.Shown in Figure 13 A and 13B, fuel cell has following structure: configuration is by having at 0.25cm
2The air electrode 5 that the enzyme immobilization carbon electrode of immobilized enzyme constitutes on the carbon ribbon and as embodiment 1 by having by fixing agent at 0.25cm
2The fuel electrode 1 of the enzyme immobilization carbon electrode of immobilized enzyme and electron mediator on the carbon ribbon makes them pass through as the spacer 35 of proton conductor toward each other.In this case, spacer 35 is by the predetermined film with proton conduction character, and for example glassine paper constitutes.Ti collector body 41,42 be separately positioned on air electrode 5 times and fuel electrode 1 on, promote collected current thus.Reference numeral 43,44 expression clamping plate.Clamping plate 43,44 usefulness screws 45 interfix, and it is all to clip air electrode 5, fuel electrode 1, spacer 35 and Ti collector body 41,42 between them.The ring-shaped depression part 43a that is used for drawing air forms in a side (outside) of clamping plate 43, and a plurality of hole 43b forms on the bottom of sunk part 43a, makes them penetrate clamping plate 43 to opposite side.Hole 43b is as the air feed passage to air electrode 5.On the other hand, the ring-shaped depression part 44a that is used for injecting fuel forms in a side (outside) of clamping plate 44, and a plurality of hole 44b forms on the bottom of sunk part 44a, makes them penetrate clamping plate 44 to opposite side.Hole 44b is as the fuel feed channel to fuel electrode 1.Sept 46 is arranged on the periphery of clamping plate 44 opposite sides, makes to have predetermined space between the clamping plate of fixing with screw 45 43,44.
Shown in Figure 13 B, load 47 is connected with Ti collector body 41,42, starch/cushioning liquid act as a fuel inject clamping plate 44 sunk part 44a to generate electricity.Working temperature is 25 ℃.Figure 14 has shown the I-E characteristic of this fuel cell.The about 0.86V of open circuit voltage.In Figure 14, curve a represents current density, and curve b represents power density.As shown in figure 14, the most about 1mA/cm of current density
2, the most about 0.4mW/cm of power density
2, this represents that these two values all are high.
Above, describe an embodiment of the invention and several embodiment in detail, but the present invention is not limited in top execution mode or embodiment, and can changes or revise based on technical conceive of the present invention.
For example, numerical value, structure, structure, shape and the material of mentioning among execution mode and the embodiment only is example in the above, and if necessary, also can use and top different numerical value, structure, structure, shape or material.
Specifically, for example, the shape of fuel cell or fuel element 32 can be different with the shape that top execution mode or embodiment mention.
Claims (19)
1, a kind of by using the enzyme decomposition fuel to produce the fuel cell of electric energy, it is characterized in that:
Described fuel comprises polysaccharide,
Described enzyme comprises and is used to promote described polysaccharide to decompose with the catabolic enzyme that forms monose and is used to promote formed monose oxidation so that the oxidizing ferment of its decomposition,
Described enzyme comprises the coenzyme oxidizing ferment, and its coenzyme that is used for reducing owing to the monose oxidation becomes oxide and by electron mediator electronics supplied with negative pole.
2, fuel cell as claimed in claim 1 is characterized in that: described fuel comprises and is selected from least a of starch, amylose, amylopectin, glycogen, cellulose, maltose, sucrose and lactose.
3, fuel cell as claimed in claim 1 is characterized in that: described fuel is gelatinized starch.
4, fuel cell as claimed in claim 1 is characterized in that: the oxide of described coenzyme is NAD
+, and described coenzyme oxidizing ferment is a diaphorase.
5, fuel cell as claimed in claim 1 is characterized in that: described fuel comprises and is selected from least a of starch, amylose, amylopectin, glycogen and maltose, and described enzyme comprises glucoamylase and glucose dehydrogenase.
6, fuel cell as claimed in claim 1 is characterized in that: described fuel package fibre-bearing element, and described enzyme comprises cellulase and glucose dehydrogenase.
7, fuel cell as claimed in claim 1 is characterized in that: described fuel comprises maltose, and described enzyme comprises alpha-Glucosidase and glucose dehydrogenase.
8, fuel cell as claimed in claim 1 is characterized in that: described fuel comprises sucrose, and described enzyme comprises invertase and glucose dehydrogenase.
9, fuel cell as claimed in claim 1 is characterized in that: described fuel comprises lactose, and described enzyme comprises beta galactosidase and glucose dehydrogenase.
10, fuel cell as claimed in claim 1 is characterized in that: described coenzyme oxidizing ferment, described coenzyme and described electron mediator are immobilized on the negative pole.
11, fuel cell as claimed in claim 10 is characterized in that: described oxidizing ferment is immobilized on the described negative pole.
12, fuel cell as claimed in claim 10 is characterized in that: described oxidizing ferment and described catabolic enzyme are immobilized on the described negative pole.
13, fuel cell as claimed in claim 12 is characterized in that: described polysaccharide is immobilized on the described negative pole.
14, fuel cell as claimed in claim 13 is characterized in that: described polysaccharide is a gelatinized starch.
15, fuel cell as claimed in claim 10 is characterized in that: the fixing agent that comprises glutaraldehyde and poly-L-Lysine is used in described immobilization.
16, a kind of electronic device that uses fuel cell, it is characterized in that: described fuel cell produces electric energy by using the enzyme decomposition fuel, wherein said fuel comprises polysaccharide, described enzyme comprises and is used to promote that described polysaccharide decomposes the catabolic enzyme with formation monose, with be used to promote formed monose oxidation so that the oxidizing ferment of its decomposition, described enzyme comprises the coenzyme oxidizing ferment, and its coenzyme that is used for reducing owing to the monose oxidation becomes oxide and by electron mediator electronics supplied with negative pole.
17, a kind of mobile that uses fuel cell, it is characterized in that: described fuel cell produces electric energy by using the enzyme decomposition fuel, wherein said fuel comprises polysaccharide, described enzyme comprises and is used to promote that described polysaccharide decomposes the catabolic enzyme with formation monose, with be used to promote formed monose oxidation so that the oxidizing ferment of its decomposition, described enzyme comprises the coenzyme oxidizing ferment, and its coenzyme that is used for reducing owing to the monose oxidation becomes oxide and by electron mediator electronics supplied with negative pole.
18, a kind of electricity generation system of using fuel cell, it is characterized in that: described fuel cell produces electric energy by using the enzyme decomposition fuel, wherein said fuel comprises polysaccharide, described enzyme comprises and is used to promote that described polysaccharide decomposes the catabolic enzyme with formation monose, with be used to promote formed monose oxidation so that the oxidizing ferment of its decomposition, described enzyme comprises the coenzyme oxidizing ferment, and its coenzyme that is used for reducing owing to the monose oxidation becomes oxide and by electron mediator electronics supplied with negative pole.
19, a kind of CHP system of using fuel cell, it is characterized in that: described fuel cell produces electric energy by using the enzyme decomposition fuel, wherein said fuel comprises polysaccharide, described enzyme comprises and is used to promote that described polysaccharide decomposes the catabolic enzyme with formation monose, with be used to promote formed monose oxidation so that the oxidizing ferment of its decomposition, described enzyme comprises the coenzyme oxidizing ferment, and its coenzyme that is used for reducing owing to the monose oxidation becomes oxide and by electron mediator electronics supplied with negative pole.
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| CN106450399A (en) * | 2016-11-11 | 2017-02-22 | 青岛大学 | High-performance starch/oxygen fuel cell based on microbial surface co-display sequential enzyme |
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| JP4931784B2 (en) * | 2007-12-07 | 2012-05-16 | ソニー株式会社 | NOVEL ELECTRODE, ENZYME SENSOR OR FUEL CELL USING THE ELECTRODE, ELECTRIC DEVICE USING THE ENZYME SENSOR OR FUEL CELL, AND POLYOL DECOMPOSITION METHOD |
| BRPI0912418A2 (en) * | 2008-05-15 | 2019-09-24 | Sony Corp | fuel cell, method for manufacturing a fuel cell, electronic apparatus, enzyme immobilization electrode, biosensor, bioreactor, energy conversion element, and apparatus that uses enzymatic reaction. |
| JP5899885B2 (en) * | 2011-01-31 | 2016-04-06 | ソニー株式会社 | Fuel cell, fuel cell production method, electronic device, nicotinamide adenine dinucleotide-immobilized electrode, nicotinamide adenine dinucleotide-immobilized carrier, enzyme reaction utilization apparatus, protein-immobilized electrode, and protein-immobilized carrier |
| JP5904491B2 (en) * | 2012-03-22 | 2016-04-13 | ユニ・チャーム株式会社 | Biofuel cell |
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