JP3518461B2 - Power generation method and battery - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to polysaccharides, disaccharides,
The present invention relates to a power generation method and a battery using an electrochemical oxidation reaction of sugar such as monosaccharide.

[0002]

2. Description of the Related Art Sugar is an important energy source for animals as well as proteins and lipids. For example, a typical sugar,
When the glucose represented by the chemical formula C ₆ H ₁₂ O ₆ is completely oxidized, 24 electrons are released per glucose molecule to generate carbon dioxide and water. In the animal body, this 2
Four electrons are used as an energy source. According to thermodynamic calculation, 2872k per mole of glucose
It has an energy of 4.43Wh per 1g of J. This is an energy density of 3.8 Wh / g or more of the weight energy density of metallic lithium used for the negative electrode of a lithium battery known as a high energy density battery.

[0003]

However, the method of utilizing the chemical energy of sugar is to use ATP as heat energy by direct combustion in air or by the action of 12 or more kinds of oxidases in the animal body. At present, only the method of using it as chemical energy such as (Essential by Alberts et al.
Cell Biology (Garland Pub
lighting, Inc. ) (1997) p. 107). That is, there is no method for directly utilizing the chemical energy of sugar directly as electric energy.

The present invention solves such a problem and provides a power generation method and a battery which directly utilize the chemical energy of sugar as electric energy.

[0005]

The present invention relates to a method of generating electricity, which comprises a positive electrode and a negative electrode provided via an electrolyte as constituent elements, wherein at least one carbon-carbon present in a sugar molecule in the negative electrode. Bond (hereinafter referred to as C-C bond)
A method of generating electricity by generating an electromotive force between the positive electrode and the negative electrode by an oxidation reaction that electrochemically cleaves
The oxidation reaction forms a complex via the hydroxyl group of the sugar.
The process has a step of charging the sugar to the negative electrode through the complex.
Provided is a power generation method characterized in that a child moves .

[0006] It is preferable that the oxidization reaction of the sugar has a complex formation process via the hydroxyl group of the sugar.

Here, it is preferable to dispose a component forming a complex with the hydroxyl group of sugar in the negative electrode.

Further, it is preferable that the component forming a complex with the hydroxyl group of the sugar contains a metal element forming an amphoteric hydroxide.

The above metal elements are Mg, Ti, V,
It is preferably at least one metal element selected from the group consisting of Ni, Cu, Zn, Zr, Ag, In, Sn, Sb and Pb.

Further, the present invention is a battery comprising a positive electrode and a negative electrode provided via an electrolyte as constituent elements, wherein in the negative electrode, at least one C—C existing in a sugar molecule is present.
A battery that generates an electromotive force between the positive electrode and the negative electrode by an oxidation reaction that electrochemically cleaves a bond ,
The oxidation reaction forms a complex via the hydroxyl group of the sugar.
The process has a step of charging the sugar to the negative electrode through the complex.
Provided is a battery characterized in that a child moves .

In the above positive electrode, it is preferable that the reduction reaction occurs at a potential nobler than the oxidation reaction of the sugar in the negative electrode.

The positive electrode is preferably an oxygen electrode that reduces oxygen.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The power generation method according to the present invention comprises a positive electrode and a negative electrode provided via an electrolyte as constituent elements, and in the negative electrode,
An electromotive force is generated between the positive electrode and the negative electrode by an oxidation reaction that electrochemically cleaves at least one C—C bond existing in the sugar molecule. This makes it possible to directly use the chemical energy stored in the sugar molecule in the form of a C—C bond as electric energy. C-C that cleaves
The larger the number of bonds, the larger the number of electrons involved in the oxidation reaction and the more energy that can be used, which is preferable.

The sugar used here is not particularly limited, but simple substances such as glucose, mannose, galactose, fructose, glyceraldehyde, dihydroxyacetone, erythrose, ribulose, xylulose, cedoheptulose, ribose, deoxyribose, sorbose, glucosamine and galactosamine. Examples thereof include sugars, disaccharides such as isomaltose, maltose, cellobiose, lactose, raffinose and sucrose, oligosaccharides, and polysaccharides such as starch, glycogen, cellulose, glycoproteins, glycosaminoglycans and glycolipids. Among these, glucose, mannose, galactose, and fructose are preferable because the current efficiency of the electrochemical oxidation reaction in the negative electrode is high. Further, glucose, mannose and galactose are preferable in terms of current efficiency.

The above-mentioned oxidization reaction of sugar preferably has a complex formation process via the hydroxyl group of sugar. By this process, a primary chemical bond is generated between the sugar hydroxyl group-forming component and the sugar hydroxyl group, and an electron is transferred from the sugar to the complex-forming component through the chemical bond. In concert with this, the bond between the C and C bonds weakens, and the bond is finally cleaved. In this way, the CC bond can be effectively weakened by going through the process of forming a complex through the hydroxyl group bonded to the carbon atom forming the C-C bond of the sugar, so that the activation energy is lower. It becomes possible to electrochemically oxidatively cleave the C—C bond of sugar. Therefore, since the oxidation potential of sugar in the negative electrode shifts to the base, the obtained electromotive force increases.

The term "complex" as used herein means a complex formed between the reactants in the path from the reaction system of the chemical reaction to the production system. In this complex, in addition to the active complex located at a high energy level in a normal chemical reaction, one or more kinds of ligands are coordinate-bonded to one or more kinds of central ions. The mononuclear complex or the multinuclear complex to be formed is included.

Here, the place where the above-mentioned complex formation occurs is
It may be at the negative electrode / electrolyte interface or in the electrolyte. When complex formation occurs in the electrolyte, an electron can be extracted from the complex through the current collecting material by providing the current collecting material in contact with the complex in the electrolyte.

Here, it is preferable that the component forming a complex with the hydroxyl group of the sugar is arranged in the negative electrode. This allows
As shown in FIG. 1, at the negative electrode 11 / electrolyte interface, a complex 13 of a component arranged in the negative electrode 11 and the sugar 12 is formed at high density in a state where the hydroxyl group of the sugar 12 faces the negative electrode 11 side. Electrons transfer from 12 to the negative electrode 11 through the complex 13 to the external circuit, the C—C bond of the sugar 12 is cleaved, and the sugar 12 is oxidized to oxalic acid, formic acid, CO ₂ or the like having a small number of carbon atoms. . Therefore, the concentration of the sugar 12 involved in the reaction is increased at the negative electrode 11 / electrolyte interface, and the electron transfer from the sugar 12 to the negative electrode 11 via the complex 13 is facilitated, so that a large oxidation current density can be obtained. .

The above-mentioned component is a component containing a cationic site, which is a cation of a metal forming an amphoteric hydroxide, or a simple metal containing a metal element forming an amphoteric hydroxide,
Alloys, oxides, hydroxides, basic carbonates, sulfates, nitrates, sulfides, fluorides, chlorides and iodides, iron-
Examples include porphyrins such as porphyrin and zinc-porphyrin. Among these, a cation of a metal forming an amphoteric hydroxide, a metal simple substance containing a metal element forming an amphoteric hydroxide, an alloy, an oxide, a hydroxide, a basic carbonate,
Sulfates, nitrates, sulfides, fluorides, chlorides and iodides are preferred. Since the metal element forming the amphoteric hydroxide has a high affinity with the hydroxyl group, the activation energy of the oxidative reaction of the sugar is lowered and the oxidative potential of the sugar can be shifted to a more base because of this. In addition, higher electromotive force can be obtained. Further, it is preferable that the above component is a simple metal, alloy, oxide, hydroxide or basic carbonate containing a metal element forming an amphoteric hydroxide.

Here, the above metal elements are Mg, Ti, V, Ni, Cu, Zn and Z in terms of the ability to form an amphoteric hydroxide.
It is preferably at least one metal element selected from the group consisting of r, Ag, In, Sn, Sb and Pb. Of these, Pb is more preferable.

The above components may be used alone or in combination of two or more. In addition, amino acids such as glycine and alanine, alkylammoniums such as tetramethylammonium and tetrabutylammonium, 4-ethylpyridinium, and 2-butylpyridinium having a functional group that forms a hydrogen bond through a hydrogen atom of a hydroxyl group. Such as alkylpyridiniums, alcohols such as amyl alcohol and glycerin, thiols such as dithiobisalkylamine, thiocyanuric acid and bismuthiol, at least primary amino group, secondary amino group, 3
A compound having a primary amino group, a quaternary amino group, an ammonium group, a pyridinium group, an alcohol group or a thiol group may be used in combination with the above components.

As the component containing Pb, specifically, metallic lead, Pb-Sn, Pb-In, Pb-Mg,
Pb-Ag, Pb-Sb, or lead alloys such as Pb-Sb-Sn, PbO, PbO 2, Pb 3 O 4, PbCO 3, Pb
(OH) ₂ , (PbCO ₃ ) ₂ · Pb (OH) ₂ , PbSO
₄ , PbS, PbF ₂ , PbCl ₂ , PbI ₂ , Pb (NO
₃ ) ₂ , PbTiO ₃ , PbZrO ₃ , Pb (Ti, Zr)
Examples include compounds such as O ₃ .

Of these compounds, PbO and Pb
O _2, Pb ₃ O ₄ lead oxide such as, Pb (OH) ₂ hydroxide and the like lead, the use of _{(PbCO 3) 2 · Pb (} OH) , such as _dibasic lead carbonate, or a mixture thereof, sugars Since the oxidation reaction can be performed at a potential in the negative region of −0.6 V or less with respect to the Hg / HgO standard electrode, a battery with high electromotive force can be obtained, which is particularly preferable.

Lead oxides such as PbO, PbO ₂ and Pb ₃ O ₄ , lead hydroxides such as Pb (OH) ₂ and (PbCO ₃ ) ₂
An electrode in which a basic lead carbonate such as Pb (OH) ₂ or a mixture thereof is arranged on a conductive substrate can be easily manufactured by electrolyzing lead or a lead alloy in an alkaline electrolyte. Lead or lead alloy as the working electrode,
With platinum or the like as the counter electrode, set the potential of the working electrode to Hg / HgO.
-1.2V to + 0.8V against standard electrode
Electrolysis is carried out at an appropriate potential region between. The potential is plus 0.
When electrolyzing in the positive region near 8 V, PbO ₂ , Pb ₃ O ₄
Rich lead compounds can be placed. When electrolysis is performed in the presence of carbon dioxide in the minus range of minus 1.2 V to zero volt, a lead compound rich in basic carbonate can be arranged. Further, by coexisting iodide, fluoride, chloride and sulfate ions in the electrolytic solution, PbF ₂ , PbCl ₂ , PbI ₂ and PbI ₂
A lead compound including bSO ₄ can be placed.

The method of arranging the lead compound is not limited to the electrolysis method in the alkaline electrolyte described above, and the conductive substrate is immersed in a solution in which the lead compound is dissolved, and then the conductive substrate containing the solution is placed. It can be prepared by drying and dissipating the solvent. Further, the electrode thus prepared may be fired in an oxidizing atmosphere. Furthermore, a lead compound is chemically vapor-deposited (C
It may be arranged on the conductive substrate by VD), physical vapor deposition (PVD), sputtering, ion plating or the like.

As the above-mentioned conductive substrate, gold, platinum,
Tin, copper, silver, lead, iron, their alloys, metallic materials such as stainless steel, conductive polymers such as polyaniline, polythiophene and polyacetylene, conductive metal oxides such as ITO (indium-tin oxide), man-made Carbon materials such as graphite and natural graphite can be used. Among them, lead and lead alloys are preferable because the lead compound can be easily arranged by electrolysis. Since the lead compound is arranged by changing a part of the substrate to a lead compound by electrolysis, the lead compound can be firmly arranged on the substrate by a chemical bond.
Further, there is an advantage that the composition of the lead compound to be arranged can be freely changed depending on the electrolytic potential and the composition of the electrolytic solution.

Further, the battery according to the present invention is a battery having a positive electrode and a negative electrode, which are provided via an electrolyte, as constituent elements, and in the negative electrode, at least 1 existing in the sugar molecule is present.
An electromotive force is generated between the positive electrode and the negative electrode by an oxidation reaction that electrochemically cleaves one CC bond.

Here, the reaction of the positive electrode is a reduction reaction that occurs at a nobler potential than the oxidation reaction of the sugar in the negative electrode, and the electrons extracted from the sugar molecule are electrochemically applied to the positive electrode through an external load. Any reduction reaction is acceptable.

As the reaction of the positive electrode, reduction reaction of water or oxygen, NiOOH, MnOOH, Pb (OH)
₂ , PbO, MnO ₂ , Ag ₂ O, LiCoO ₂ , LiMn
₂ O ₄ , LiNiO ₂ and other hydroxides or oxide reduction reactions, TiS ₂ , MoS ₂ , FeS, Ag ₂ S and other sulfide reduction reactions, AgI, PbI ₂ , CuCl ₂ and other metal halides A reduction reaction, a reduction reaction of organic sulfur compounds such as quinones and organic disulfide compounds, and a reduction reaction of conductive polymers such as polyaniline and polythiophene can be used.

Of these, the positive electrode is preferably an oxygen electrode that reduces oxygen. In this case, since a gas containing oxygen can be used as the positive electrode active material, it becomes unnecessary to hold the positive electrode active material in the battery, so that a battery having a high energy density can be configured.

As the oxygen electrode, any substance having an oxygen reducing ability can be used. Examples of such substances include activated carbon, manganese lower oxides such as Mn ₂ O ₃ , platinum, palladium, iridium oxide, platinum ammine complex,
Examples thereof include a cobalt phenylenediamine complex, a metal porphyrin (metal: cobalt, manganese, zinc, magnesium, etc.), and a perovskite oxide such as La (Ca) CoO ₃ or La (Sr) MnO ₃ .

Any electrolyte can be used as long as it can move anions or / and cations from the positive electrode to the negative electrode or / and from the negative electrode to the positive electrode so that the oxidation / reduction reaction in the positive electrode and the negative electrode can proceed continuously. Any organic substance, inorganic substance, liquid or solid can be used. These electrolytes include water containing ZnCl ₂ , NH ₄ C
Metal salts such as l, alkalis such as KOH and NaOH, H ₃ P
L dissolved in an acid such as O ₄ or H ₂ SO ₄ or a mixed organic solvent of propylene carbonate and ethylene carbonate
An ion exchange membrane made of a polymer material such as a solution of a metal salt such as iBF ₄ or LiPF ₆ , a fluororesin having a sulfonic acid group, an amide group, an ammonium group, a pyridinium group or the like, LiBF ₄ , LiCl ₄ , A polymer electrolyte such as polypropylene oxide or polyethylene oxide in which (C ₄ H ₉ ) ₄ NBF ₄ or the like is dissolved can be used.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples.

(Example 1) In Example 1, a test electrode was prepared in which a component containing Pb as a component forming a complex with a hydroxyl group of sugar was arranged, and the electrolytic oxidation characteristic of sugar was evaluated, and the test electrode was used. A battery was constructed as a negative electrode and electricity was generated.

(Preparation of Test Electrode) As a conductive substrate, tin containing 61.9 weight percent (wt%), thickness 50 μm
The Pb-Sn alloy foil of was cut into a size of 1 x 0.5 cm to bond the nickel lead wire, and then the joint part and the nickel lead were coated with an epoxy resin. The obtained test piece was placed in a cell shown in FIG. 2 in a 3.1% KOH aqueous solution with respect to the Hg / HgO standard electrode 25 minus 1.
A test electrode A was prepared by electrolyzing while changing the potential at a potential sweep rate of 20 mV / sec in the range of 2V to 0V. The electric potential increases from minus 1.2V to 0V and becomes 0V
5 cycles of electrolysis were performed, with the change decreasing toward −1.2 V as one cycle. A test electrode A having a white deposit on the surface was obtained from the test piece having a metallic luster. It was confirmed by X-ray photoelectron spectroscopy (hereinafter abbreviated as XPS) that this white deposit was a lead compound containing basic lead carbonate and stannate.

The cell shown in FIG. 2 has a glass container 21, a rubber stopper 22, a working electrode (negative electrode) 23 composed of a test electrode or a test piece, a platinum counter electrode 24, a Hg / HgO standard electrode 25,
It is composed of an electrolytic solution 26 and a positive electrode 27.

Next, a test electrode B was prepared in the same manner as the test electrode A except that the potential sweep range of the test piece was changed from minus 1.2V to plus 0.8V. A test electrode B having a dark brown deposit on the surface was obtained from the test piece having a metallic luster. This deposit is PbO by XPS.
And a lead compound containing stannate.

Next, a test electrode C was prepared in the same manner as the test electrode A except that a Pb--Sb alloy foil containing 13 wt% of antimony and having a thickness of 100 μm was used. A test electrode C having a white deposit on the surface was obtained from the test piece having a metallic luster. It was confirmed by XPS that this white deposit was a lead compound containing basic lead carbonate and antimony oxide.

Next, a test electrode D was prepared in the same manner as the test electrode B except that a Pb--Sb alloy foil containing 13 wt% of antimony and having a thickness of 100 μm was used. A test electrode D having a dark brown deposit on the surface was obtained from the test piece having a metallic luster. This white deposit is
It was confirmed to be a lead compound containing PbO and antimony oxide.

Next, a test electrode E was prepared in the same manner as the test electrode A except that a lead foil having a purity of 99.9% and a thickness of 500 μm and a 6.2% KOH alkaline aqueous solution were used as the electrolytic solution.
A test electrode E having a white deposit on the surface was obtained from the test piece having a metallic luster. This white deposit is XP
By S, it was confirmed to be a lead compound containing basic lead carbonate.

Next, a test electrode F was prepared in the same manner as the test electrode B except that a lead foil having a purity of 99.9% and a thickness of 500 μm and a 6.2% KOH alkaline aqueous solution were used as the electrolytic solution. A test electrode F having a dark brown deposit on the surface was obtained from the test piece having a metallic luster. It was confirmed by XPS that this white deposit was a lead compound containing PbO.

Next, using a chemical vapor deposition apparatus, di as evaporation sources in one molybdenum boat - iso - propoxy lead (Pb (O-i-C 3 H 7) 2), another in another molybdenum boat one of the evaporation source as tetraethoxy tin _{((Sn (OC 2 H 5} ) 4), was further placed tetraethoxy titanium _{(Ti (OC 2 H 5)} 4) as yet another evaporation source to another molybdenum boat. In a reactor on the downstream side of these evaporation sources, an electrically conductive substrate having Ni lead wire bonded to a size of 1 × 0.5 cm and graphite fibers having a thickness of 0.5 mm was placed, and the temperature was raised to 400 ° C. The evaporation source was heated while flowing argon gas from the upstream side to the downstream side of the evaporation source, and the thermally decomposed products of lead alkoxide, tin alkoxide, and titanium alkoxide were deposited on the surface of the conductive substrate for 5 minutes. After the depositing. Evaporation source cooled,
By flowing an argon gas containing 1 vol% of oxygen for 60 minutes, a test electrode G having a lead compound containing lead oxide, tin oxide and titanium oxide arranged on the surface of the conductive substrate was prepared.

Next, the size of the Ni lead wire bonded 1 ×
The Ni foil having a thickness of 0.5 cm and a thickness of 100 μm was placed in a reactor substituted with argon gas, and then heated to 600 ° C. with an infrared lamp. Di-iso-propoxy lead 0.05 mol / l,
An ethanol solution in which 0.05 mol / l of tetraethoxy titanium was dissolved was sprayed on the heated Ni foil for 10 minutes, and then argon gas containing 1 vol% of oxygen was supplied to the reactor. Ni in argon gas containing 1 vol% oxygen gas
By leaving the foil for 60 minutes, a test electrode H having a lead compound containing lead oxide and titanium oxide arranged on the surface of the Ni foil was obtained.

(Evaluation of Sugar Oxidation Property of Test Electrode) Using the cell shown in FIG. 2, as the electrolytic solution 26, 0.62% KOH was used.
Alkaline solution or glucose 0.02 mol /
1 dissolved 0.62% KOH alkaline aqueous solution, the test electrode B as the working electrode 23, platinum counter electrode 24, Hg / H
Electrolysis was performed using the gO standard electrode 25. The potential of the working electrode 23 increases from minus 1.2V to plus 0.8V in a state where the electrolytic solution 26 is allowed to stand at room temperature, and decreases toward minus 1.2V when it reaches plus 0.8V. The electrolysis was performed for 20 cycles, with the change being 1 cycle. The current-potential characteristic at the 20th cycle is shown in FIG.

In the electrolytic solution containing glucose, the oxidation current around −0.4V accompanying the dissolution of the lead alloy was smaller than that in the electrolytic solution containing no glucose, and the dissolution of the lead alloy was suppressed. In addition, the oxidation current peaks due to the oxidation of glucose are −1.0V, −0.8V,
Appeared around minus 0.6V. After electrolysis, the electrolytic solution containing glucose was analyzed by liquid chromatography, and the oxidation product of glucose, gluconic acid,
Oxalic acid and formic acid were detected. When the same characteristic evaluation was performed on the test electrode A and the test electrodes C to H, the same results as in the case of the test electrode B showing the oxidation of sugar were obtained. Further, instead of glucose, galactose which is a monosaccharide,
Mannose, sorbose, fructose, disaccharides maltose, sucrose, lactose, raffinose,
When the test electrodes A to H were characterized using starch, which is a polysaccharide, the results showing the oxidation of sugar were obtained as in the case of glucose. Therefore, it was possible to confirm the electrochemical oxidation of sugar using the test electrode of this example.

FIG. 4 shows that glucose is 0.02 mol / l.
FIG. 3 shows a redox current-potential response of the test electrode B of this example and a redox current-potential response of an oxygen electrode composed of activated carbon and manganese lower oxide in a dissolved 0.62% KOH aqueous solution. The oxygen electrode gave a reduction current due to the reduction of oxygen in the potential region in the minus direction from around + 0.1V. The test electrode B of this example provided an oxidation current due to the oxidation of glucose in the vicinity of -1 V to -0.4 V. Therefore, it was found that a battery having an electromotive force of 1 V to 0.4 V can be constructed by combining the above oxygen electrode as a positive electrode and the test electrode of this example as a negative electrode.

Next, using the cell shown in FIG. 2, 0.31% KOH alkaline aqueous solution or 0.31% KO in which 0.5 mol / l of glucose was dissolved as the electrolytic solution 26.
Electrolysis was performed using an aqueous solution of H alkali and using the test electrode A as the working electrode 23 and the platinum counter electrode 24 and the Hg / HgO standard electrode 25. While stirring the electrolytic solution 26 at room temperature, a constant current of 2 mA is applied to the working electrode 23 in the oxidizing direction at 120
It was passed for 0 seconds, and the time-potential characteristics at that time were evaluated. The obtained time-potential characteristics are shown in FIG.

In the electrolytic solution containing glucose, electrolysis 12
The potential of the working electrode 23 is minus 58 even after 00 seconds.
Giving a constant value of 0 mV, it was found that glucose was continuously oxidized. On the other hand, in an electrolyte solution containing no glucose, the potential of the working electrode 23 is around −610 mV which indicates the oxidative dissolution of the lead alloy, and the potential of the higher order oxide of the lead alloy is 400 m near 300 seconds after electrolysis.
It moved to the vicinity of V.

When the same characteristic evaluation was performed on the test electrodes B to H, the result showing the continuous oxidation of sugar was obtained in the electrolytic solution containing glucose as in the case of the test electrode A. The electric potential of the test electrode in each electrolytic solution after 1200 seconds of electrolysis is shown in (Table 1).

[0051]

[Table 1]

The test electrodes A to H were characterized by using galactose, mannose, sorbose, fructose, which are monosaccharides, maltose, sucrose, lactose, raffinose, which is a disaccharide, and starch, which is a polysaccharide. As with glucose, results were obtained showing continuous oxidation of sugars. Pb-Sn on the conductive substrate,
Test electrodes A to D in which a lead alloy such as Pb-Sb is used and alloy components are mixed in a component containing Pb, and test electrodes in which tin oxide and titanium oxide are mixed in a component containing Pb G and H are test electrodes E using lead for the conductive substrate.
Electrolysis in an electrolytic solution containing glucose compared to F and 1
Since the potential after 200 seconds showed a more negative oxidation potential, it is understood that the oxidation of sugar was promoted by the alloy component and the added metal element.

As alloy components and additive metal elements having such an effect of promoting electrolytic oxidation of sugar, indium (In) is used in addition to tin (Sn), antimony (Sb) and titanium (Ti) used in the examples. And magnesium (Mg) is effective.

(Evaluation of Battery Characteristics) Using the cell shown in FIG. 2, as an electrolytic solution 26, a 0.62% KOH alkaline aqueous solution or 0.5 mol / l of glucose dissolved at a concentration of 0.
Using 62% KOH alkaline aqueous solution, the test electrode A was used as the negative electrode 23, and the oxygen electrode with a diameter of 3 cm composed of activated carbon and manganese lower oxide was used as the positive electrode 27 to form a battery cell.
The battery characteristics were evaluated.

While stirring the electrolytic solution 26 at room temperature, the battery cell was discharged at a constant current of 0.2 to 50 mA for 20 seconds,
The current-voltage characteristics obtained at that time are shown in FIG.

Regarding the test electrodes A to H, at room temperature,
Stirring the electrolytic solution 26 at a constant current of 1 mA for 1 hour,
The voltages when the battery cells are discharged are summarized in (Table 2).

[0057]

[Table 2]

As is clear from the current-voltage characteristics of FIG. 6 and the results of the continuous discharge test shown in (Table 2), the oxidation reaction of sugar was utilized by the battery having the test electrode of this example as the negative electrode. Was able to extract electrical energy.

Further, instead of glucose, the monosaccharides galactose, mannose, sorbose, fructose, the disaccharides maltose, sucrose, lactose, raffinose, and the polysaccharide starch were used to characterize the test electrodes A to H. As a result, it was confirmed that the battery operated as in the case of glucose.

(Example 2) In Example 2, a component containing Ag or Cu was used as a component forming a complex with a hydroxyl group of sugar, and a test electrode in which these components were arranged was prepared to evaluate the electrolytic oxidation characteristics of sugar. Along with the evaluation, batteries having these test electrodes as negative electrodes were constructed and electricity was generated.

(Preparation of Test Electrode) A silver foil (Ag) having a purity of 99.9% and a thickness of 50 μm was cut into a size of 1 × 0.5 cm, and nickel lead wires were joined together. Coated with epoxy resin. The test piece obtained was treated in the same manner as in Example 1 in the cell shown in FIG.
Electrolysis was performed in the potential range of −1.2 V to +0.8 V with respect to the Hg / HgO standard electrode 25 to obtain a test electrode I.

Next, using a 100 μm thick Ag—Cu alloy foil containing 75 wt% of silver and 25 wt% of copper, the test electrode I was used.
A test electrode J was obtained in the same manner as in.

Next, 55 wt% silver and 4 magnesium
Using a 5 wt% Ag-Mg alloy foil with a thickness of 100 μm,
A test electrode K was obtained in the same manner as the test electrode I.

Next, using a copper foil (Cu) having a purity of 99.9% and a thickness of 30 μm, the test electrode L was prepared in the same manner as the test electrode I.
Got

Next, 65 wt% of copper and 35 wt% of zinc
A test electrode M was obtained in the same manner as the test electrode I using a Cu—Zn alloy foil having a thickness of 100 μm.

Finally, 80 wt% copper and 20 nickel
A test electrode N was obtained in the same manner as the test electrode I using a wt% Cu-Ni alloy foil having a thickness of 100 μm.

(Evaluation of Sugar Oxidation Property of Test Electrode) Using the cell shown in FIG. 2, 0.62% KOH was used as the electrolytic solution 26.
0.2 mol / alkaline solution or fructose
1 dissolved in 0.62% KOH alkaline aqueous solution, the test electrodes I to N as working electrodes 23, platinum counter electrode 24,
Electrolysis was performed using the Hg / HgO standard electrode 25. While stirring the electrolytic solution 26 at room temperature, a constant current of 2 mA was passed through the working electrode 23 in the oxidizing direction for 1200 seconds, and the time-potential characteristics at that time were evaluated. The electric potential of the test electrode in each electrolytic solution after 1200 seconds of electrolysis is shown in (Table 3).

[0068]

[Table 3]

In the electrolytic solution containing fructose, electrolysis 1
Even after 200 seconds, the potential of the working electrode 23 is minus 3
A value of 80 mV to −250 mV is given, and it can be seen that fructose is continuously oxidized. On the other hand, in the electrolytic solution containing no fructose, when the test electrodes I to K containing silver or a silver alloy were used, a constant potential around plus 400 mV indicating the oxidation of silver was exhibited. When the test electrodes L to N containing copper or copper alloy were used, 120 after electrolysis
In the vicinity of the second, the potential of the working electrode 23 shifts from around −400 mV, which indicates oxidation dissolution of copper, to around −700 mV, which indicates oxygen generation due to electrolysis of water.

Further, instead of fructose, glucose, galactose, mannose, sorbose, which are monosaccharides, maltose, sucrose, lactose, raffinose, which are disaccharides, and starch, which is a polysaccharide, were used to characterize test electrodes I-N. As a result, the results showing continuous oxidation of sugar were obtained. Therefore, it was possible to confirm the continuous oxidation of sugar using the test electrode of this example.

(Evaluation of Battery Characteristics) Using the cell shown in FIG. 2, a 3.1% KOH alkaline aqueous solution or a 3.1% KOH alkaline aqueous solution in which fructose was dissolved at 0.5 mol / l was used as the electrolytic solution 26. , Test electrodes I-N
Was used as the negative electrode 23, and the same oxygen electrode as in Example 1 was used as the positive electrode 27 to form a battery cell, and the battery characteristics were evaluated.

At room temperature, stirring the electrolytic solution 26 at 1 mA.
(Table 4) shows the voltages when the battery cells are discharged at a constant current for 1 hour.

[0073]

[Table 4]

As is clear from the results of the continuous discharge test shown in (Table 4), the battery of this example was able to extract electric energy by utilizing the oxidation reaction of sugar.

Further, instead of fructose, glucose, galactose, mannose, sorbose, which are monosaccharides, maltose, sucrose, lactose, raffinose, which are disaccharides, and starch, which is a polysaccharide, were used to characterize test electrodes I to N. As a result, it was possible to confirm that it could operate as a battery as in the case of fructose.

(Example 3) In Example 3, a component containing Pb, Ag or Cu was used as a component forming a complex with the hydroxyl group of sugar, and a hydrogen bond was formed with these components via the hydrogen atom of the hydroxyl group. Thiocyanuric acid (s-triazine-2,4, which is an organic sulfur compound having a functional group
6-trithiol) (hereinafter referred to as TCA) or 2,2′-dithiobisethanamine (hereinafter referred to as CYST) was combined to prepare a test electrode to evaluate the electrolytic oxidation characteristics of sugar and A battery having a test electrode as a negative electrode was configured to generate electricity.

(Preparation of test electrode) TCA was set to 0.05 mo.
1 / l dissolved ethanol solution (A), CYST.
An ethanol solution (B) dissolved in 01 mol / l was prepared. Each of the test electrode A of Example 1 and the test electrode J and test electrode N of Example 2 was dipped in the solution (A) or the solution (B) and then air-dried to obtain TCA molecules or CYS on the surface.
A test electrode O, a test electrode P, a test electrode Q, a test electrode R, a test electrode S, and a test electrode T modified with T molecules were prepared.

(Evaluation of Sugar Oxidation Property of Test Electrode) 0.31% KOH was used as the electrolytic solution 26 using the cell shown in FIG.
0.5 mol / l of alkaline aqueous solution or glucose
Using a dissolved 0.31% KOH alkaline aqueous solution, the test electrodes O to T were used as the working electrode 23, and the platinum counter electrode 24 and Hg were used.
Electrolysis was performed using the / HgO standard electrode 25. At room temperature,
While stirring the electrolytic solution 26, a constant current of 2 mA was passed through the working electrode 23 in the oxidizing direction for 1200 seconds, and the time-potential characteristics at that time were evaluated. The electric potential of the test electrode in each electrolytic solution after 1200 seconds of electrolysis is shown in (Table 5).

[0079]

[Table 5]

In the electrolytic solution containing glucose, electrolysis 12
Even after 00 seconds, the potential of the working electrode 23 is −62.
It was found that glucose was continuously oxidized by giving a value of 0 mV to −380 mV. On the other hand, in a glucose-free electrolytic solution, when the test electrode O or the test electrode P containing a lead alloy is used, the potential of the working electrode 23 in the vicinity of 600 seconds after electrolysis causes the formation of higher order lead oxides. It moved to around +400 mV. When the test electrode Q or the test electrode R containing a silver alloy was used, a constant potential around plus 300 mV, which indicates oxidation of silver, was exhibited. With the test electrode S or the test electrode T containing the copper alloy, 580 after electrolysis
In the vicinity of the second, the potential of the working electrode 23 shifted from around −400 mV, which indicates oxidation dissolution of copper, to around −650 to 700 mV, which indicates oxygen generation due to electrolysis of water.

The test electrodes O to T were characterized by using galactose, mannose, sorbose, fructose which is a monosaccharide, maltose, sucrose, lactose, raffinose which is a disaccharide, and starch which is a polysaccharide, instead of glucose. However, the results showing continuous oxidation of sugars were obtained. Therefore, it was possible to confirm the continuous oxidation of sugar using the test electrode of this example.

(Evaluation of Battery Characteristics) Using the cell shown in FIG. 2, a 3.1% KOH alkaline aqueous solution or a 3.1% KOH alkaline aqueous solution in which fructose was dissolved at 0.5 mol / l was used as the electrolytic solution 26. , Test electrodes OT
Was used as the negative electrode 23, and the same oxygen electrode as in Example 1 was used as the positive electrode 27 to form a battery cell, and the battery characteristics were evaluated.

At room temperature, stirring the electrolytic solution 26 at 1 mA.
The voltages when the battery cells are discharged at a constant current for 1 hour are summarized in (Table 6).

[0084]

[Table 6]

As is clear from the results of the continuous discharge test shown in (Table 6), the battery of this example was able to extract electric energy by utilizing the oxidation reaction of sugar.

Further, instead of fructose, monosaccharides glucose, galactose, mannose, sorbose, disaccharides maltose, sucrose, lactose, raffinose, and polysaccharides starch were used to characterize test electrodes O to T. As a result, it was possible to confirm that it could operate as a battery as in the case of fructose.

(Embodiment 4) Using the cell shown in FIG.
Instead of the oxygen electrode, a manganese dioxide positive electrode (MnO ₂ ) used in a manganese dry battery, a nickel positive electrode (NiOOH) used in a nickel hydrogen storage battery, a lead positive electrode (PbO ₂ ) used in a lead storage battery, or Cobalt acid positive electrode (LiCoO 2) used in lithium ion batteries
₂ ) as the positive electrode 27, the test electrode A of Example 1
A battery having G or H as the negative electrode 23 was constructed. The electrolytic solution contains 0.1 mol / l of mannose (monosaccharide), raffinose (disaccharide), or starch (polysaccharide), a ZnCl ₂ aqueous solution, a KOH aqueous solution, an H ₂ SO ₄ aqueous solution, or PC-EC-Gly. -Using LiPF ₆
The battery characteristics were evaluated.

(Table 7), (Table 8), (Table 9), 1 mA
The battery voltage when the battery was discharged at a constant current for 1 hour is shown together. The ZnCl ₂ aqueous solution used here is an aqueous solution containing 30% by weight of ZnCl ₂ and a saturated concentration of ZnO, and
In aqueous H aqueous solution containing KOH 6.2 wt%, H ₂ S
The O ₄ aqueous solution is an aqueous solution containing 18% by weight of H ₂ SO ₄ , PC
-EC-Gly-LiPF ₆ was added to a mixed solvent containing propylene carbonate (PC), ethylene carbonate (EC), and glycerin (Gly) in a volume ratio of 1: 1: 0.5 to obtain L.
This is a solution of iPF ₆ dissolved in 1.2 mol / l.

[0089]

[Table 7]

[0090]

[Table 8]

[0091]

[Table 9]

As is clear from (Table 7) to (Table 9),
With the battery of the present invention, electric energy could be extracted by utilizing the oxidation reaction of sugar.

[0093]

INDUSTRIAL APPLICABILITY The present invention provides a power generation method and a battery using an oxidation reaction that electrochemically cleaves at least one C—C bond existing in a sugar molecule. According to the present invention, the chemical energy of sugar can be effectively utilized directly as electric energy.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an electrochemical oxidation process of sugar according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view of a cell used for production of a test electrode, evaluation of sugar oxidation characteristics, and evaluation of battery characteristics in one example of the present invention.

FIG. 3 is a current-potential characteristic diagram of a test electrode in one example of the present invention.

FIG. 4 is a redox current-potential characteristic diagram of a test electrode and an oxygen electrode in the same example.

FIG. 5 is a time-potential characteristic diagram of the test electrode in the example.

FIG. 6 is a current-voltage characteristic diagram of the battery in the example.

[Explanation of symbols]

11 Negative electrode 12 sugar 13 Complex 21 glass container 22 Rubber stopper 23 Working electrode (negative electrode) 24 Platinum counter electrode 25 Hg / HgO standard electrode 26 Electrolyte 27 Positive electrode

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) H01M 6/00-6/22 H01M 8/00-8/24 H01M 12/00-14/00

Claims (7)

(57) [Claims] 1. A power generation method using a positive electrode and a negative electrode provided via an electrolyte, wherein an oxidation reaction of electrochemically cleaving at least one carbon-carbon bond present in a sugar molecule in the negative electrode. by performing, a power generation method comprising the step of generating an electromotive force between the positive electrode and the negative electrode, the oxidation reaction, to form a complex through the hydroxyl groups of the sugar
From the sugar to the negative electrode through the complex.
A power generation method characterized in that electrons move . 2. The power generation method according to claim 1, wherein a component forming a complex with a hydroxyl group of sugar is arranged in the negative electrode. 3. The power generation method according to claim 2, wherein the component forming a complex with the hydroxyl group of the sugar is a metal element capable of forming an amphoteric hydroxide. 4. The metal element is Mg, Ti, V, N
The power generation method according to claim 3, wherein the power generation method is at least one selected from the group consisting of i, Cu, Zn, Zr, Ag, In, Sn, Sb, and Pb. 5. A battery comprising a positive electrode, a negative electrode, an electrolyte interposed between the positive electrode and the negative electrode, and sugar supplied to the negative electrode, wherein at least one of the sugar molecules present in the sugar molecule is present in the negative electrode. carbon - by the oxidation reaction electrochemically cleaved carbon bonds, wherein a battery for generating an electromotive force between the positive electrode and the negative electrode, the oxidation reaction, to form a complex through the hydroxyl groups of the sugar
From the sugar to the negative electrode through the complex.
A battery characterized by the movement of electrons . 6. The battery according to claim 5, wherein the reduction reaction occurs in the positive electrode at a potential nobler than the oxidation reaction of the sugar in the negative electrode. 7. The battery according to claim 6, wherein the positive electrode is an oxygen electrode that reduces oxygen.