JP2006004832A - Power supply circuit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a power supply circuit responding to downsizing, thinning and weight-saving by preparing a new back-up battery. <P>SOLUTION: Of the power supply circuit provided with a main power supply, an operating part equipped with a memory element, a main power supply monitoring part, and a back-up secondary battery, the back-up secondary battery is provided with a power generating part and a charging part, and the power generating part is provided with an acidic medium fitted with a first electrode and a basic medium fitted with a second electrode. The acidic medium and the basic medium set adjacent to each other, and at least either of them contains a reactive matter. The charging part is provided with a reactive matter regenerating means for regenerating the reactive matter from a power generating product produced by power generation at the power generating part. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a power supply circuit, and more particularly to a power supply circuit using a backup secondary battery using an acidic medium and a basic medium in contact with the acidic medium.

Conventionally, power supply circuits have been used in many electronic devices. This power supply circuit generally includes a main power source that supplies power to the entire operation unit, an operation unit composed of a memory element for a central processing unit (CPU), and a secondary for backup for the purpose of backing up the operation unit. When the supply of power from the main power supply is stopped, the storage of the memory element can be held by switching the power supply from the main power supply to the secondary battery for backup. Is.
In recent years, electronic devices have been remarkably reduced in size, thickness, and weight. In particular, in the field of OA devices, the size and weight have been reduced. Accordingly, there is a great demand for downsizing, thinning, and weight reduction of power supply circuits.

As a secondary battery for backup which is a component of the power supply circuit, a secondary battery such as a button type or a coin type is known. For example, in the case of a lithium ion secondary battery (see, for example, Patent Document 1), these secondary batteries are excellent in electric energy and can be reused by charging. Since it is a very unstable ignitable substance against oxygen and oxygen, there is a problem that sufficient safety measures must be taken for the packaging and use environment of the battery in order to avoid the danger. In addition, since such secondary batteries need to be strictly packaged to avoid dangers, structural restrictions are imposed on the shape and size of the battery, resulting in thinner and smaller size. It was not enough to meet the demands for reduction in weight and weight.
Furthermore, since such a secondary battery uses an external charging device when it is reused by charging, it takes time and labor to attach and detach the battery every time it is charged.
For this reason, there is a problem that the power circuit itself including the secondary battery is not sufficiently small, thin, and lightweight, and that it takes time to charge. Currently.
JP-A-4-237969

In view of the above, an object of the present invention is to solve the above conventional problems.
That is, the present invention provides a power supply circuit that can be reduced in size, reduced in thickness, and reduced in weight by providing a new secondary battery for backup, and that saves the trouble of charging the secondary battery for backup. The purpose is to do.

The above object is achieved by the present invention described below.
That is, the present invention is a power supply circuit including a main power supply, an operation unit including a memory element, a main power supply monitoring unit, and a backup secondary battery,
The backup secondary battery comprises a power generation unit and a charging unit,
The power generation unit includes at least an acidic medium in which a first electrode is disposed and a basic medium in which a second electrode is disposed, and the acidic medium and the basic medium are adjacent to or close to each other. A reactive substance is contained in at least one of the acidic medium and the basic medium,
The charging unit includes a reactant regeneration unit that regenerates the reactant from a power generation product generated by power generation in the power generation unit.

  Further, the main power supply monitoring unit in the power supply circuit of the present invention has a switching means that operates to supply the power of the backup secondary battery to the memory element when the power supplied from the main power supply falls below a predetermined value. It is characterized by having.

In the backup secondary battery used in the power supply circuit of the present invention, it is preferable that at least one of the following first to eighteenth aspects is applied.
(1) A 1st aspect is an aspect in which the said charging part is further equipped with the medium reproduction | regeneration means to reproduce | regenerate the said acidic medium and / or the said basic medium from the said electric power generation product.
(2) A 2nd aspect is an aspect from which the said acidic medium consists of acidic aqueous solution, and the said basic medium consists of basic aqueous solution.
(3) A third aspect is an aspect in which the reactant is contained in each of the acidic medium and the basic medium.
(4) In the fourth aspect, the first substance as the reactant contained in the acidic medium is the same substance as the second substance as the reactant contained in the basic medium. This is an embodiment.
(5) A fifth aspect is an aspect in which the reactant is hydrogen peroxide.

(6) In a sixth aspect, the reactant regeneration means includes an anode and a cathode, and supplies the oxygen and water as the power generation products to the cathode to regenerate the hydrogen peroxide. It is a certain aspect.
(7) In a seventh aspect, the medium regeneration means arranges a cation exchange membrane, a bipolar membrane, and an anion exchange membrane to form a salt chamber, an acid chamber, and a base chamber, and the power generation in the salt chamber A mode in which a cell of a three-chamber cell system is provided in which a neutralized salt aqueous solution as a product is supplied and electrodialysis is performed, and the acidic aqueous solution and the basic aqueous solution are discharged from each of the acid chamber and the base chamber. is there.
(8) The eighth aspect is an aspect in which the power generation unit is provided with a flow path structure in which the acidic aqueous solution and the basic aqueous solution form a laminar flow therein.

(9) In a ninth aspect, the acidic aqueous solution is sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, periodic acid, orthophosphoric acid, Polyphosphoric acid, nitric acid, tetrafluoroboric acid, hexafluorosilicic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexachloroplatinic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, maleic acid, malonic acid, phthalic acid , Fumaric acid, and picric acid.
(10) In a tenth aspect, the basic aqueous solution contains sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, water One or more bases selected from the group comprising tetraethylammonium oxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, or sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, boron It is an embodiment containing one or more alkali metal salts selected from the group comprising potassium silicate, sodium silicate, potassium silicate, sodium tripolyphosphate, potassium tripolyphosphate, sodium aluminate, and potassium aluminate.

(11) The eleventh aspect is an aspect in which the acidic medium is composed of an acidic ion conductive gel and the basic medium is composed of a basic ion conductive gel.
(12) A twelfth aspect is an aspect in which the acidic ion conductive gel is obtained by gelling an acidic aqueous solution with water glass, anhydrous silicon dioxide, crosslinked polyacrylic acid, or a salt thereof.
(13) A thirteenth aspect is an aspect in which the basic ion conductive gel is formed by gelling a basic aqueous solution with carboxymethylcellulose, crosslinked polyacrylic acid, agar, or a salt thereof.

(14) In a fourteenth aspect, the first electrode is platinum, platinum black, platinum oxide-coated platinum, silver, gold, titanium whose surface is passivated, stainless steel whose surface is passivated, and passivated surface. It is an embodiment composed of one or more materials selected from the group consisting of activated nickel, aluminum whose surface is passivated, carbon structure, amorphous carbon, and glassy carbon.
(15) In the fifteenth aspect, the second electrode is platinum, platinum black, platinum oxide-coated platinum, silver, gold, titanium whose surface is passivated, stainless steel whose surface is passivated, and passivated surface. It is an embodiment composed of one or more materials selected from the group consisting of activated nickel, aluminum whose surface is passivated, carbon structure, amorphous carbon, and glassy carbon.

(16) A sixteenth aspect is an aspect in which the first electrode and the second electrode have a plate shape, a thin film shape, a mesh shape, or a fiber shape.
(17) The seventeenth aspect is an aspect in which the first electrode and the second electrode are respectively disposed on the acidic medium and the basic medium by an electroless plating method, a vapor deposition method, or a sputtering method. (18) The eighteenth aspect is an aspect further comprising a direct current power source for applying a direct current to the anode and the cathode of the reactant regeneration means.

  According to the present invention, by providing a new backup secondary battery, it is possible to provide a power supply circuit that can be reduced in size, reduced in thickness, and reduced in weight, and that saves the trouble of charging the backup secondary battery. can do.

Hereinafter, the power supply circuit of the present invention will be described in detail.
The power supply circuit of the present invention includes a main power supply, an operation unit including a memory element, a main power supply monitoring unit, and a backup secondary battery. Hereinafter, the configuration of the power supply circuit of the present invention will be described with reference to FIG. Here, FIG. 1 is a block diagram showing the configuration of the power supply circuit of the present invention.
As shown in FIG. 1, the power supply circuit according to the present invention includes a main power supply 91, an operation unit 92 including a central processing unit (CPU) 93 and its memory element 94, a main power supply monitoring unit 95, and a backup secondary. Battery 96.

The main power supply 91 indicates a general commercial power supply, a battery, or the like, and is not particularly limited as long as it supplies sufficient power to drive the operation unit 92 including the CPU 93 and the memory element 94. .
Usually, when the operation unit includes a central processing unit (CPU) and a RAM memory as its memory element, a voltage of 5 V and a current of about 5 mA may be supplied.

  The operation unit 92 of the present invention is not particularly limited as long as it includes a central processing unit (CPU) 93 and its memory element 94. The configuration of the operation unit 92 is a basic structure included in most electronic devices.

The main power supply monitoring unit 95 monitors the power supply state of the main power supply 91, and when the power supplied from the main power supply 91 falls below a predetermined value, the power of the backup secondary battery 96 is stored in the memory element 94. There is no particular limitation as long as it is provided with a switching circuit that operates so as to be supplied. Specifically, an IC chip provided with such a switching circuit is preferable.
Usually, when the operation of the CPU is stopped, the backup voltage and current supplied from the backup secondary battery to hold the memory of the RAM memory of the CPU are about 3 V and 10 μA.

The secondary battery for backup 96 is used for the purpose of retaining the memory of the memory element 94 of the CPU 93 when the supply of power from the main power supply 91 to the operation unit 92 becomes a predetermined value or less.
The backup secondary battery 96 is roughly divided into two parts: (1) a power generation unit and (2) a charging unit. Hereinafter, (1) the power generation unit and (2) the charging unit will be described.

(1) Power generation unit:
(1) The power generation unit includes an acidic medium in which the first electrode is disposed and a basic medium in which the second electrode is disposed. The acidic medium and the basic medium are adjacent to each other or close to each other, and the reactive substance is contained in at least one of the acidic medium and the basic medium.
The battery of the present invention is a bipolar battery having a configuration including the above-described members. And it becomes possible to set it as a secondary battery by combining with the reproduction | regeneration means of the charging part mentioned later. In the present invention, a bipolar battery has a structure in which an acidic medium and a basic medium are adjacent or close to each other, and a substance (reactive substance) for extracting electric energy and an electrode are included in these. It is what you have.

The reactant contained in the acidic medium or the basic medium causes an electrode reaction on the positive electrode side and / or the negative electrode side by the following actions, and enables efficient generation of electric energy. That is, when such a reactive substance does not exist in an acidic medium or a basic medium, a sufficient electromotive force as a battery cannot be obtained.
For example, when the reactive substance is contained in each of an acidic medium and a basic medium, the first substance that is the reactive substance in the acidic medium is first with hydrogen ions contained in the acidic medium. Reaction that takes electrons away from the electrodes. On the other hand, the second substance, which is a reactant in the basic medium, causes a reaction to donate electrons to the second electrode with hydroxide ions contained in the basic medium. By these reactions, an electromotive force as a battery is obtained.

  In particular, the secondary battery 96 for backup is first (1) the first substance and hydrogen ions coexist in the above acidic medium or in the vicinity of the electrode in contact with the acid medium, and both are electrons from the first electrode as a reaction system substance. Cause a reaction to oxidize (oxidize). (2) The second substance and hydroxide ions coexist in the basic medium or in the vicinity of the electrode in contact with the basic medium, and both cause an electron (reduction) reaction to the electrode as a reaction system substance. Such reactions (1) and (2) proceed simultaneously to generate electrical energy for holding the memory of the memory element 94.

  In the secondary secondary battery 96, in the bipolar reaction field, hydrogen ions in the acidic medium participate in the reaction of taking electrons from the first electrode by the first substance, and the increase in the concentration causes the reaction. It has the effect of promoting (shifting the chemical equilibrium in the direction of the production system). On the other hand, the hydroxide ions constituting the basic medium participate in the reaction of donating electrons to the second electrode by the second substance, and the increase in concentration has the effect of promoting the reaction. For this reason, it is possible to enhance the reaction by increasing the hydrogen ion concentration or hydroxide ion concentration, that is, lowering the pH in an acidic medium and increasing the pH in a basic medium, thereby increasing the output. It is also effective in that it has a configuration capable of.

Hereinafter, (1) each member which comprises a power generation part is demonstrated in detail.
(Acid medium and basic medium)
In the present invention, the acidic medium refers to a medium having a pH of less than 7 (preferably, a pH of 3 or less), and is preferably capable of forming an acidic reaction field where hydrogen ions are present. Further, the basic medium is a medium exceeding pH 7 (preferably having a pH of 11 or more), and it is preferable that a basic reaction field where hydroxide ions are present can be formed.
Each of these acidic medium and basic medium may be independently in any form of a liquid state, a gel state, and a solid state, but it is preferable that both the mediums have the same aspect. Moreover, as an acidic medium and a basic medium, it can use regardless of the kind of organic compound and an inorganic compound.

  A preferable combination of the acidic medium and the basic medium is, for example, a combination of an aqueous solution of an acidic aqueous solution such as sulfuric acid, hydrochloric acid, or phosphoric acid and a basic aqueous solution such as sodium hydroxide, potassium hydroxide, ammonia, or an ammonium compound; And combinations of ion conductive gels obtained by gelling these aqueous solutions with a gelling agent.

  More specifically, as the acidic aqueous solution, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, periodic acid, orthophosphoric acid, polyphosphoric acid, Nitric acid, tetrafluoroboric acid, hexafluorosilicic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexachloroplatinic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, maleic acid, malonic acid, phthalic acid, fumaric acid It is preferable to use an aqueous solution containing at least one acid selected from the group consisting of picric acid, and it is more preferable to contain sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, which are strong acids.

  Basic aqueous solutions include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrahydroxide hydroxide. One or more bases selected from the group comprising propylammonium and tetrabutylammonium hydroxide, or sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, potassium borate, sodium silicate, An aqueous solution containing one or more alkali metal salts selected from the group comprising potassium silicate, sodium tripolyphosphate, potassium tripolyphosphate, sodium aluminate, and potassium aluminate can be used. Beam, and more preferably contains potassium hydroxide.

Furthermore, an acidic ion conductive gel as an acidic medium is obtained by gelling an acidic aqueous solution as described above using a gelling agent such as water glass, anhydrous silicon dioxide, crosslinked polyacrylic acid, or a salt thereof. Is preferred.
On the other hand, a basic ion conductive gel as a basic medium is obtained by gelling a basic aqueous solution as described above using, for example, carboxymethylcellulose, crosslinked polyacrylic acid or a salt thereof as a gelling agent. Is preferred.
In addition, said acid and base may use only 1 type, and may mix and use 2 or more types. The method of using the gelling agent is also the same.

  (1) In the power generation unit, it is essential that the acidic medium and the basic medium be adjacent to each other or close to each other. This is because the counter anion generated by releasing hydrogen ions in the acidic medium and the base This is because it is possible to balance the charge by forming a salt with the counter cation generated by releasing hydroxide ions in the organic medium. Therefore, for example, as described above, in the case where both media are composed of an acidic aqueous solution and a basic aqueous solution, a membrane having a property capable of transmitting the generated cation and / or anion, or the generated cation If a salt bridge capable of moving ions and / or anions is used, the acidic medium and the basic medium may be separated from each other. Moreover, it is not necessary for each of them to be adjacent to each other.

(Reactive substance)
When the reactive substance is contained in an acidic medium, any substance may be used as long as it is a substance (oxidant) that generates an oxidation reaction that takes away electrons from the first electrode with hydrogen ions in the acidic medium. Can be used. On the other hand, when contained in a basic medium, if it is a substance (reducing agent) that generates a reduction reaction that donates electrons to the second electrode with hydroxide ions in the basic medium, Any thing can be used.
Here, as a preferred embodiment, the first substance as the reactive substance contained in the acidic medium and the second substance as the reactive substance contained in the basic medium will be described in detail below.

  The first substance is preferably a substance that promotes the reaction when the hydrogen ion concentration is high. Specifically, in addition to hydrogen peroxide and oxygen, hypohalous acid such as hypochlorous acid, hypobromous acid, and hypoiodous acid can be used. Alternatively, the first substance may be supplied in the state of a liquid containing these substances or a liquid that releases these substances by a chemical change.

  Further, the second substance is preferably a substance that promotes the reaction when the hydroxide ion concentration is high. Specifically, hydrogen peroxide, hydrogen, hydrazine, or the like can be used. Alternatively, the second substance may be supplied in the state of a liquid containing these substances or a liquid that releases these substances by chemical change.

  As the first substance or the second substance, metal ions such as iron, manganese, chromium, and vanadium that can change their valence by an oxidation / reduction reaction, or a metal complex thereof can be used, and a liquid containing these also. Etc. can be used to supply these substances.

  Among the above, it is preferable that the first substance and the second substance are composed of the same component. Such a substance generates an oxidation reaction that takes electrons from the first electrode with hydrogen ions in an acidic medium, and in a basic medium, electrons move to the second electrode with hydroxide ions. It has the property of causing a reduction reaction to donate. In this case, the configuration of the battery becomes easy, the degree of freedom in selecting the separation membrane for the chemical substances on the positive electrode side and the negative electrode side, which has been a big problem with the conventional battery, is expanded, and the acidic medium and the basic medium are mixed. A separation membrane is not necessarily required when the state can be kept.

As a substance that can be used as both an oxidizing agent and a reducing agent, hydrogen peroxide is particularly preferable. The reason for this will be described later in detail. Note that it is preferable to supply hydrogen peroxide using a liquid containing hydrogen peroxide or a liquid that releases hydrogen peroxide by a chemical change in terms of easier handling. The “liquid” that is a means for supplying hydrogen peroxide may be in the form of a solution (including water, organic solvent, etc. as a solvent), a dispersion, or a gel. Moreover, it is desirable that these usage forms are selected by a preferable combination with the above-described acidic medium and basic medium forms.
Further, as will be apparent from the reaction formula as will be described later, the hydrogen peroxide concentration is not excessive or insufficient, so that the hydrogen ion concentration in the acidic medium and the hydroxide ion concentration in the basic medium are 1 (excessive). Hydrogen oxide): 2 (hydrogen ion, hydroxide ion) is preferable, and the hydrogen ion concentration in the acidic medium and the hydroxide ion concentration in the basic medium are more preferably the same.
In addition, hydrogen peroxide is mixed or dispersed in the medium before the start of the reaction, through a flow path installed in the vicinity of the electrode, by using a capillary, or directly into the medium. It is good also as a system added.

According to such a configuration, when the hydrogen ion H ⁺ and the hydroxide ion OH ⁻ are involved in the reaction at the electrode, the first substance is accompanied by the hydrogen ion H ⁺ from the first electrode in the acidic medium. An oxidation reaction that takes away electrons occurs, and a second substance in the basic medium causes a reduction reaction that donates electrons to the electrode with hydroxide ions OH ⁻ . At this time, the electromotive force due to the oxidation reaction in the acidic medium is larger in principle than the oxidation reaction in the basic medium. This is because the hydrogen ion H ⁺ is a substance in the reaction system, so that in an acidic medium having a high hydrogen ion concentration, the chemical equilibrium is inclined to the production system, and as a result, the oxidation potential is increased. Further, the electromotive force due to the reduction reaction in the basic medium becomes larger in principle than the reduction reaction in the acidic medium. This is because the hydroxide ion OH ⁻ is a substance in the reaction system, so that in a basic medium having a high hydroxide ion concentration, the chemical equilibrium is inclined to the production system, and as a result, the oxidation potential is lowered.
For this reason, in the configuration of the bipolar battery of the present invention, the electromotive force generated by the oxidation / reduction reaction at the electrode is the main source of voltage obtained from the battery, and the location of the neutralization reaction inside the battery fluctuates. Compared with a bipolar battery in which an electromotive force is mainly used in a region having such a property, electric power can be stably generated.

(First electrode and second electrode)
In the present invention, the first electrode functions as a positive electrode, and the second electrode functions as a negative electrode. As materials for the first electrode and the second electrode, the same materials as those in the conventional battery can be used. More specifically, examples of the first electrode (positive electrode) include platinum, platinum black, platinum oxide-coated platinum, silver, and gold. Moreover, titanium, stainless steel, nickel, aluminum, etc. whose surface has been passivated can be mentioned. Furthermore, carbon structures such as graphite and carbon nanotubes, amorphous carbon, glassy carbon and the like can be mentioned. However, platinum, platinum black, and platinum oxide-coated platinum are more preferable from the viewpoint of durability.

  Examples of the second electrode (negative electrode) include platinum, platinum black, platinum oxide-coated platinum, silver, and gold. Moreover, titanium, stainless steel, nickel, aluminum, etc. whose surface has been passivated can be mentioned. Furthermore, carbon structures such as graphite and carbon nanotubes, amorphous carbon, glassy carbon and the like can be mentioned. However, platinum, platinum black, and platinum oxide-coated platinum are more preferable from the viewpoint of durability.

  In the present invention, it is preferable that both the first electrode and the second electrode have a plate shape, a thin film shape, a mesh shape, or a fiber shape. In particular, in the case of the embodiment of the present invention, it is preferable to have a mesh shape so as to be a discharge passage for the gas generated in the battery. Here, “mesh-like” indicates at least a porous state in which a through passage through which a gas to be discharged passes is present.

Specifically, as the mesh electrode, the above electrode material may be attached to a metal mesh, a punching metal plate, or a foamed metal sheet by an electroless plating method, a vapor deposition method, or a sputtering method. In addition, the above electrode material may be attached to cellulose or synthetic polymer paper using the same method or a combination thereof.
Further, when the first electrode and the second electrode are arranged in both media having high shape retention such as an ion exchange resin and an ion conductive gel, on the surface of the ion exchange resin and the ion conductive gel, It is also a preferred embodiment that a desired electrode material is disposed by using an electroless plating method, a vapor deposition method, or a sputtering method.

(Power generation mechanism)
(1) The power generation mechanism in the power generation unit includes an acidic medium and a basic medium in a state where the acidic medium in which the first electrode is disposed and the basic medium in which the second electrode is disposed are adjacent to each other. This is a power generation method for generating power by causing an oxidation reaction in an acidic medium and / or a reduction reaction in a basic medium by a reactant contained in at least one of the media. Then, the reactant is regenerated from the power generation product generated by power generation and supplied to at least one of the acidic medium and the basic medium.

  According to such a power generation mechanism, the electromotive force generated by the oxidation / reduction reaction at the electrode becomes the main source of the voltage obtained from the battery, and as a result, the power can be stably generated. Further, by using the charging unit (2) as will be described later, it is possible to charge and discharge while reusing the electrolyte components (reactive substances, acidic medium and basic medium) with a simple configuration.

(1) It is considered that the power generation mechanism in the power generation unit is as described below.
That is, the first substance contained in the acidic medium causes a reaction to take electrons from the first electrode with hydrogen ions, and the second substance contained in the basic medium converts the hydroxide ions. Along with this, it is considered that power generation occurs by causing a reaction of donating electrons to the second electrode.
By this reaction, the first substance and the second substance are chemically changed into a plurality of substances having low internal energy, so that the corresponding energy can be released to the outside as electric energy to obtain electric power.

  In particular, when the acidic medium is an acidic aqueous solution, the basic medium is a basic aqueous solution, and the first substance and the second substance are both hydrogen peroxide, the hydrogen peroxide is separated from water and oxygen by a decomposition reaction. Generate. When this chemical reaction is performed separately in an oxidation reaction and a reduction reaction with separate electrodes as in the battery of the present invention, an electromotive force is generated. That is, since hydrogen peroxide has an oxidizing action in an acidic reaction field, and has a reducing action in a basic reaction field, an electromotive force is generated. Such power generation is realized by utilizing such an acid-base bipolar reaction field.

  The power generation mechanism in the power generation unit having such a configuration will be specifically described with reference to FIG. As shown in FIG. 2, in an acidic reaction field (acidic medium) in which a positive electrode (first electrode) is arranged, hydrogen peroxide acts as an oxidant, and as shown in (Equation 1) below, Hydrogen oxide oxygen atoms receive electrons from the electrode and produce water. In the basic reaction field (basic medium) in which the negative electrode (second electrode) is arranged, hydrogen peroxide acts as a reducing agent, and as shown in the following (Formula 2), oxygen of hydrogen peroxide Atoms donate electrons to the electrode to produce oxygen and water. By these reactions, an electromotive force is generated and power generation is performed.

H ₂ O ₂ (aq) + 2H ⁺ + 2e ⁻ → 2H ₂ O (Formula 1)
H ₂ O ₂ (aq) + 2OH ⁻ → O ₂ + 2H ₂ O + 2e ⁻ (Formula 2)
In the above formula, “(aq)” indicates a hydrated state (the same applies to the following (formula 3)).

In the reaction field, a counter anion of hydrogen ions present in an acidic medium (corresponding to sulfate ion SO ₄ ^2- in FIG. 2) and a counter cation of hydroxide ions present in a basic medium. (Corresponding to sodium ion Na ⁺ in FIG. 2) forms a salt at the interface between the two media, so that the charge can be balanced. At this time, since the salt formed is more stable when ionized in an aqueous solution, the effect of the salt formation on the electromotive force is much smaller than the electromotive force in the oxidation or reduction reaction at the electrode. As a result, the bipolar battery according to the present invention, in which the electrode reaction is dominant, has the property of generating stable power compared to the bipolar battery mainly based on the neutralization reaction at the acidic / basic medium interface. It will be.

  The ionic reaction formula (when the charge balance is taken by ionic decomposition of water at the acidic / basic medium interface) that summarizes the half-reaction formulas of (Formula 1) and (Formula 2) is shown below (Formula 3) Show.

H ₂ O ₂ (aq) → H ₂ O + 1 / 2O ₂ (Formula 3)

  According to thermodynamic calculation, the enthalpy change (ΔH), entropy change (ΔS), Gibbs free energy change (ΔG, temperature T: unit is Kelvin (K)) of this reaction is ΔH = −94.7 kJ / mol, ΔS = 28 J / Kmol, and ΔG = ΔH−TΔS = −103.1 kJ / mol.

  The theoretical electromotive force (n is the number of electrons involved in the reaction, F is the Faraday constant) and the theoretical maximum efficiency (η) are E = −ΔG / nF = 1.07 V, η = ΔG / ΔH × 100 = Calculated as 109%. The theoretical feature of this reaction is that the entropy is increased by the hydrogen peroxide decomposition reaction and the sign of ΔS becomes positive. Therefore, the absolute value of ΔG becomes larger than ΔH, and the theoretical maximum efficiency exceeds 100%. In contrast, in other fuel cell reactions such as a hydrogen-oxygen system and a direct methanol system, the sign of ΔS is negative.

From these, in the power generation mechanism of the present invention, the theoretical characteristics when hydrogen peroxide is used for the first substance and the second substance are listed below.
In other conventionally known fuel cells, in principle, the entropy change amount TΔS cannot be used for power generation and is released as heat. On the other hand, in this mechanism, the increase in entropy obtained by absorbing heat from the outside world can be used for power generation. When the reaction temperature T is high, the absolute value of ΔG increases and the electromotive force increases.

  In a practical battery, the output voltage is not determined only by the theoretical electromotive force of the ion reaction type, but the voltage is lowered due to an overvoltage or the like, and heat is simultaneously generated. For example, this heat becomes a big problem when unit batteries are stacked and integrated, or when batteries are incorporated into products. However, as described above, according to this mechanism, theoretically, the heat can be reused for power generation, and the overall heat generation may be reduced. In addition, ΔG corresponding to the total amount of energy that can be used for power generation is about half that of a hydrogen / oxygen fuel cell, but n = 1 (n = 2 in the case of a hydrogen-oxygen fuel cell). The theoretical electromotive force is about the same.

  The system for regenerating the reactant from the power generation product and supplying it to at least one of the acidic medium and the basic medium is the same as that of the above-described backup secondary battery.

  From the above, (1) in the power generation unit, when hydrogen peroxide is used for the first substance and the second substance, in addition to the effects described above, the following effects can be obtained. can get.

(A) Hydrogen peroxide does not release carbon dioxide with the reaction of converting chemical energy into electrical energy, but instead releases oxygen. In addition, since no ignitables, combustibles, harmful heavy metals, or the like are used as structural elements in the battery, the power generation unit can be configured with an easy exterior. Therefore, it has excellent environmental safety over the entire manufacturing, use, and disposal product cycle.
(B) Since hydrogen peroxide is a liquid at normal temperature and pressure, it does not require heavy metal cylinders for storage, and can be freely mixed with water, making it easy to gel, storability and portability Is excellent.
(C) Since it is not necessary to use oxygen as an oxidant, there is no problem in its use even in a closed environment where the amount of air is limited, or even in a harsh environment where the air contains a lot of dust or dirt.
(D) Hydrogen peroxide is an organic method as an industrial production method (method of synthesizing anthraquinone as an intermediate (not consumed because it is reused many times), catalytic catalytic hydrogen reduction and air oxidation), etc. Has already been established, and even now, it is stably and inexpensively supplied. In addition, since the power generation unit can be configured with a simple structure with few peripheral components, the weight and volume of the backup secondary battery 96 can be reduced, and cost reduction and high durability can be achieved.

(2) Charging part:
(2) The charging unit includes a reactant regeneration unit that regenerates the reactant from the power generation product generated by the power generation in the power generation unit described above. That is, when hydrogen peroxide is used as the reactant, the power generation product contains oxygen and water, and the hydrogen peroxide is regenerated from the power generation product by the reactant regeneration means.

  A known technique (for example, Journal of Applied Electrochemistry Vol. 25 613- (1995)) can be used to regenerate reactants such as hydrogen peroxide. For example, when the reactant is hydrogen peroxide, a means such as an electrolysis cell that has an anode and a cathode, supplies oxygen and water as power generation products to the cathode, and regenerates hydrogen peroxide is applied. It is preferable. By synthesizing (regenerating) hydrogen peroxide from water and oxygen generated by the power generation reaction in this way, it is not necessary to replenish substances from the outside.

Moreover, it is preferable that a charging part is further provided with the medium reproduction | regeneration means to reproduce | regenerate an acidic medium and / or a basic medium from an electric power generation product.
For regeneration of an acidic medium / basic medium, a known technique for electrically synthesizing an acid / base (for example, JP-A-7-178319) can be used. For example, when a sulfuric acid aqueous solution is used for the acidic medium and a sodium hydroxide aqueous solution is used for the basic medium, a three-chamber cell using a cation exchange membrane, a bipolar membrane, and an anion exchange membrane from the aqueous sodium sulfate solution produced after the reaction. A sulfuric acid aqueous solution and a sodium hydroxide aqueous solution may be synthesized by electrodialysis using a (salt chamber, acid chamber and base chamber) type cell.
In this way, by regenerating the reactant, acidic medium and basic medium in the charging section, the electromotive force is easy to recover even after reuse (re-discharge) after charging, and the reaction field is always fresh. Can provide. Such an effect is exhibited because the backup secondary battery 96 (especially when hydrogen peroxide is used as a reactant) has a simple structure as compared with the lithium secondary battery. Therefore, the backup secondary battery of the present invention does not cause a drop in electromotive force even when it is repeatedly used as compared with various secondary batteries.

  Further, in the case of using a gel-like medium as an acidic medium and a basic medium, these regeneration methods are such that the neutralized salt aqueous solution generated by the reaction is discharged from the gel, and a new acidic aqueous solution and basic aqueous solution are put into the gel. You just have to supply it. What is necessary is just to reproduce | regenerate the acidic aqueous solution and basic aqueous solution which are newly supplied to a gel from the neutralized salt aqueous solution discharged | emitted in that case by said means.

  Hereinafter, although preferable embodiment of the secondary battery 96 for backups is described with reference to drawings, this invention is not limited to these forms. For convenience of explanation, the secondary battery of the present invention will be described using an example in which hydrogen peroxide is used as a reactant.

The backup secondary battery shown in FIG. 3 includes two parts, that is, a power generation unit 100 and a charging unit 200, and in addition, a charging power source 300 for charging is provided.
The charging unit 200 includes a reactant regeneration unit 210 for regenerating hydrogen peroxide and a medium regeneration unit 220 for regenerating an acidic medium and / or a basic medium.

As described above, the power generation unit 100 has an acid-base bipolar reaction field using a liquid such as a sulfuric acid aqueous solution as an acidic medium and a liquid such as a sodium hydroxide aqueous solution as a basic medium. As will be described later, oxygen, water, and sodium sulfate are generated as power generation products from hydrogen peroxide, aqueous sulfuric acid solution, and sodium hydroxide as power generation occurs. When the electromotive force decreases as the power generation products increase, the charging unit 200 performs charging.
In charging, first, oxygen and water are supplied to the reactant regeneration means 210, regenerated into hydrogen peroxide using the charging power source 300, and again into the acidic medium and / or basic medium of the power generation unit. Supply. On the other hand, sodium sulfate, which is a neutralized salt, is supplied to the medium regeneration means, regenerated into sulfuric acid and sodium hydroxide using the charging power source 300, and these are again supplied into the acidic medium and the basic medium, respectively. In this way, power generation and charging of the secondary battery of the present invention are performed.

A specific configuration of the power generation unit 100 will be described with reference to FIG.
FIG. 4A is a schematic top perspective view of the power generation unit. As shown here, in the power generation section, the capillary channel 1 (depth 50 μm, width 1000 μm) is interposed between the slide glass 11 and the cover glass 10 via a spacer (member 12 in FIG. 4B). Is formed. The capillary channel 1 has an inlet 2 and an inlet 3 for supplying a liquid acidic medium and a liquid basic medium, and an outlet 4 and an outlet 5 for discharging. For example, when the acidic aqueous solution a flows from the inlet 2 and the basic aqueous solution b flows from the inlet 3 to the capillary channel 1, if the viscosity and flow rate of both liquids are appropriate, at the confluence portion of the capillary channel 1 A laminar flow (Reynolds flow) is formed.

This laminar flow will be described with reference to FIG. FIG. 4B is a cross-sectional view seen from the flow direction of both media when the power generation section of FIG. 4A is cut along AA ′. As shown in this figure, the acidic aqueous solution a and the basic aqueous solution b form a laminar flow a and a laminar flow b, respectively, even at the confluence portion of the capillary channel 1, and cross each other even though they are in contact with each other. Without flowing through the capillary channel 1. And while forming the laminar flow a and the laminar flow b, it passes through a confluence | merging part and isolate | separates again in a branch part, the acidic aqueous solution a is discharged | emitted from the exit 4, and the basic aqueous solution b is discharged | emitted from the exit 5, respectively. And recovered.
Two electrodes 6 and 8 are provided at the bottom of the merged portion of the capillary channel 1 forming such a laminar flow, and power is taken out through the connection terminals 7 and 9 to the outside. Can do.

  Thus, in order to form a laminar flow and form a state in which two liquids are in contact with each other but do not mix, it can be realized by applying the characteristics of the viscous fluid in the capillary channel. This is a phenomenon (Reynolds flow phenomenon) that occurs when the constant Reynolds number (Re) is less than about 2000 depending on the viscosity and flow velocity of the liquid and the flow channel shape (tube diameter or flow channel width and depth). is there. When this phenomenon is used, the two liquids having an appropriate viscosity and moving speed in the capillary tube become laminar and are imparted with characteristics that are very difficult to mix. Therefore, when an electrode is placed in each laminar flow with the first substance and the second substance coexisting in both laminar flows, the oxidation reaction in the acidic medium and the reduction in the basic medium A reaction occurs, an electromotive force is developed, and a battery is obtained.

  When this power generation unit is a single unit cell, an increase in current amount and voltage can be achieved by arranging a plurality of unit cells in parallel or in series. The structure of such a capillary channel is such as ultrasonic grinding or semiconductor photolithography for substrates (chips) such as glass, quartz, silicon, polymer film, plastic resin, ceramic, graphite, metal, etc. It can be easily manufactured by applying existing processing techniques such as sandblasting, injection molding, and silicon resin molding. Therefore, it is possible to construct a power generation unit having desired performance (current and voltage) by integrating unit cells and stacking a plurality of chips.

Here, in general, since almost no current is required for storage (memory backup) of the memory element of the CPU, in order to use the unit cell composed of the power generation unit as a backup secondary battery, The required voltage is divided by the electromotive force of the open voltage of the unit cell, and the number rounded up to the nearest decimal point may be connected in series.
At this time, the inlet 2 and the inlet 3 for supplying the liquid acidic medium and the liquid basic medium of all the unit cells and the outlet 4 and the outlet 5 for discharging are connected in series of the unit cells. Regardless of the parallel connection, it is preferable to join each in parallel to stabilize the output.

On the other hand, the reactant regeneration means 210 in the charging unit 200 is an electrolytic cell that has, for example, an anode and a cathode, and supplies oxygen and water generated by a power generation reaction to the cathode to produce hydrogen peroxide. .
Further, the medium regeneration means 220 is formed by, for example, arranging a plurality of cation exchange membranes, bipolar membranes, and anion exchange membranes in order to form a salt chamber, an acid chamber, and a base chamber, and generating a salt chamber by a power generation reaction. In addition, an aqueous solution of neutralized salt (sodium sulfate aqueous solution) is supplied to perform electrodialysis, and an acidic aqueous solution and a basic aqueous solution are discharged from the acid chamber and the basic chamber.
(2) The power source used for the charging unit is not particularly limited as long as it is a DC power source capable of applying a DC current to the anode and the cathode. A secondary battery is configured by combining the power generation unit and the charging unit.

  For example, in the above (1) power generation unit, when an aqueous sulfuric acid solution is used as the acidic medium and an aqueous sodium hydroxide solution is used as the basic medium, oxygen gas and aqueous sodium sulfate solution are generated by the power generation reaction. (2) In the charging part, an operation of regenerating hydrogen peroxide, sulfuric acid aqueous solution, and sodium hydroxide aqueous solution as reactants from these products is performed.

(2) A specific configuration of the charging unit will be described with reference to FIGS.
FIG. 5 is an explanatory diagram schematically showing the overall configuration of the charging unit. First, an aqueous sodium sulfate solution is supplied to the electrodialysis tank 20. The electrodialysis tank 20 has a structure composed of a desalting chamber 22 and a concentrating chamber 24 by alternately combining a cation exchange membrane and an anion exchange membrane in some cases. And an anode and a cathode are arrange | positioned at the both ends, a direct current is applied, and dialysis operation is performed. As a result, water desalinated from the desalting chamber 22 and concentrated sodium sulfate aqueous solution are generated from the concentration chamber 24. The desalinated water is appropriately supplied to the cathode chamber 34 and the anode chamber 32 of the reactant regeneration means 30, and the salt chamber 42, the acid chamber 44, and the base chamber 46 of the medium regeneration means 40. The concentrated sodium sulfate aqueous solution is supplied to the salt chamber 42 of the medium regeneration means 40.

As shown in FIG. 6, the reactant regeneration means (represented by reference numeral 30 in FIG. 5) used for the regeneration of hydrogen peroxide is divided into the anode chamber 32 having the anode 32a and the cathode chamber 34 having the cathode 34a separated by a diaphragm 36. The obtained electrolytic cell structure is taken. Water supplied from the desalting chamber 22 is supplied to the anode chamber 32 and the cathode chamber 34, oxygen generated by power generation is supplied to the cathode chamber 34, and a direct current voltage is applied between the anode and the cathode, thereby allowing excess water at the cathode. Hydrogen oxide is generated and the aqueous hydrogen peroxide solution is regenerated. The hydrogen peroxide solution generated in the cathode chamber 34 is supplied to the power generation unit. On the other hand, the liquid in the anode chamber 32 (water that did not contribute to the reaction) is again circulated and supplied to the reactant regeneration means 30, and oxygen generated in the anode chamber 32 is also circulated and supplied to the cathode chamber 34 again. It can also be used.
It should be noted that there is no problem in the regeneration of the aqueous hydrogen peroxide solution even if the above-mentioned salted water is used.

  As shown in FIG. 7, the medium regeneration means (reference numeral 40 in FIG. 5) used for regeneration of the acidic medium and the basic medium is an electrodialysis tank, and includes a cation exchange membrane 47, an anion exchange membrane 48, and By alternately combining the bipolar membranes 49, the salt chamber 42, the acid chamber 44, and the base chamber 46 are formed. The aqueous sodium sulfate solution supplied from the concentration chamber 24 is supplied to the salt chamber 42 in the medium regeneration means 40 that is an electrodialysis tank using a bipolar membrane. A direct current is applied to the anode and the cathode arranged at the end, and electrodialysis with water decomposition is performed. As a result, sulfuric acid is regenerated in the acid chamber 44 from hydrogen ions generated by the water splitting phenomenon in the bipolar membrane 49 and sulfate ions permeated from the salt chamber 42, and in the base chamber 46 in the bipolar membrane 49. Sodium hydroxide is regenerated from hydroxide ions generated by the water splitting phenomenon and sodium ions permeated from the salt chamber 42. A part of the water discharged from the desalting chamber 22 is supplied to the acid chamber 44 and the base chamber 46 to adjust the concentration of the acid / base and supply it to the power generation unit. The liquid supplied to the salt chamber 42 is desalinated and supplied again to the medium regeneration means 40.

By providing the charging part (2) as described above, it is possible to charge and discharge while reusing the electrolyte constituent components (reactive substances, acidic medium, and basic medium) with a simple configuration.
In addition, what is necessary is just to provide a reactive material reproduction | regeneration means for each, when using 2 types of reactive materials.

The power generation unit and the charging unit described above are connected by a microtube via a micropump, and consumption and regeneration of the reactant and / or medium (acidic medium and basic medium) are repeated. Such a mass transfer route will be specifically described with reference to FIG. In addition, FIG. 8 is explanatory drawing which shows an example of a substance movement path | route. Here, a case where the reactant is an aqueous hydrogen peroxide solution, the acidic medium is an aqueous sulfuric acid solution, and the basic medium is an aqueous sodium sulfate solution will be described.
First, when hydrogen peroxide and sulfuric acid aqueous solution are supplied from the inlet 2 of the power generation unit and hydrogen peroxide and sodium hydroxide are supplied from the inlet 3, power generation occurs and electric energy is obtained. Oxygen, water, and sodium sulfate that are generated along with this are recovered from the outlet 5, and water and sodium sulfate are recovered from the outlet 4. At this time, a gas separation unit 7 a for separating only oxygen gas from the liquid discharged from the outlet 5 is provided, and the oxygen gas separated and recovered here is supplied to the reactant regeneration means 30. Further, the water recovered from the outlet 4 and the outlet 5 and sodium sulfate are combined and supplied to the electrodialysis tank 20, where the desalinated water is concentrated to the medium regeneration means 40 and the reactant regeneration means 30. The aqueous sodium sulfate solution is supplied to the medium regeneration means 40. Here, it is desirable to provide storage chambers 5a and 5b for temporarily storing each recovered component before regeneration as necessary, and micro pumps 6a and 6b for circulating the liquid.

The gas separation part 7a described above may have a simple structure for separating oxygen bubbles and liquid. For example, a part of the flow path is thickened to create a part where bubbles are accumulated, and a certain amount of bubble mass is formed. By the way, it may be something that blows bubbles in another path.
As the micropumps 6a and 6b, piezoelectric diaphragm type pumps are known as small and thin, and are preferable in this case because of low power consumption.
Subsequently, the aqueous hydrogen peroxide solution regenerated by the reactant regeneration means 30 in the charging section is divided into two directions, and the sulfuric acid aqueous solution regenerated in the acid chamber 44 of the medium regeneration means 40 and the base chamber 46, respectively. Mix in aqueous sodium hydroxide. At this time, means such as a micro valve for adjusting the flow rate so that the concentration ratio of hydrogen peroxide to sulfuric acid is 1: 1 and the concentration ratio of hydrogen peroxide to sodium hydroxide is 1: 2. In this way, an aqueous solution of hydrogen peroxide and sulfuric acid is again supplied to the inlet 2 of the power generation unit, and an aqueous solution of hydrogen peroxide and sodium hydroxide is supplied to the inlet 3 again. Also here, it is desirable to provide storage chambers 5c, 5d and 5e for temporarily storing the regenerated components as necessary, and further micro pumps 6c, 6d and 6e for circulating the liquid.
Here, in the power supply circuit of the present invention, the power generation unit responsible for the memory backup of the power supply circuit is mounted on the circuit board together with the main power supply, the operation unit, and the main power supply monitoring unit, and the charging unit is various other than the circuit board. It is preferable to install in a space corresponding to the electronic device.

The power generation unit and the charging unit of the backup secondary battery 96 have been described above, but these configurations are not limited to the configurations described above.
For example, in the power supply circuit of the present invention, the power generation unit having the above configuration and a conventional power generation unit using hydrogen fuel or methanol fuel can be combined and used as a combined power generation unit.
(1) The power generation unit of the backup secondary battery 96 in the present invention is a power generation unit itself by combining the first and second electrodes, the acidic medium and the basic medium, and the reactants, which are constituent members. The shape and size of the secondary battery 96 can be arbitrarily set, and stable power can be supplied by the above-described power generation mechanism. Weight reduction can be achieved. In particular, since the power generation unit can be configured without using harmful substances, the exterior can be simplified, and further reduction in size, thickness, and weight can be achieved.
Further, since the backup secondary battery 96 includes both (1) a power generation unit and (2) a charging unit, charging and discharging can be repeated in the backup secondary battery 96. With this configuration, there is no need to attach or detach the power generation unit each time the power generation unit is charged, and thus there is an advantage that there is no need for charging.

  The effects of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Example 1]
About the backup secondary battery provided with the electric power generation part shown in FIG. 4 and the charging part shown in FIGS. 5-7, the electric power generation experiment was performed on the following conditions, the electric current-voltage characteristic was calculated | required, and the battery was evaluated.
The details of the power generation unit and the charging unit are as follows.

(Power generation part)
First, sulfuric acid (special grade 96%, Kanto Chemical Co., Inc.) and distilled water are mixed with a commercially available 3% by mass hydrogen peroxide aqueous solution (Japanese Pharmacopoeia Oxol, Kenei Pharmaceutical Co., Ltd.) and sample solution A (peroxidation). Hydrogen (9.1 mmol / l, sulfuric acid 0.1 N (0.05 mol / l)) was prepared.
Further, sodium hydroxide (special grade 97%, Kanto Chemical Co., Inc.) and distilled water were mixed with the same hydrogen peroxide aqueous solution as sample liquid A, and sample liquid B (hydrogen peroxide 9.1 mmol / l, sodium hydroxide 0 .1N (0.05 mol / l)) was prepared.

  Then, the sample liquid A was injected from the inlet 2 shown in FIG. 4 and the sample liquid B was injected from the inlet 3 by an external pump. The flow rates of the sample liquids A and B were both 24 μl / sec (Reynolds number Re: about 670) at the center of the flow path, and the experimental temperature was room temperature (about 20 ° C.).

Gas generation was not observed on the surface of the first electrode (platinum thin film, area: 0.026 cm ² ) 8 on the bottom surface of the flow channel in contact with the sample liquid A, whereas on the bottom surface of the flow path in contact with the sample liquid B Oxygen gas generation was observed on the surface of the second electrode (platinum thin film, area: 0.026 cm ² ) 6. This is because the first electrode 8 functions as a positive electrode by generating water by the reaction of (Formula 1) described above, and the second electrode 6 is oxygenated by the reaction of (Formula 2) described above. This is because water is generated and functions as a negative electrode.
As described above, a power generation unit as a unit cell in the present invention was produced.

FIG. 9 shows the current-voltage characteristics of the power generation unit as the obtained unit cell. In the case of this example, an open circuit voltage of 650 mV and a maximum output of 160 μW / cm ² (electromotive voltage: 230 mV, current of 0.7 mA / cm ² ) were obtained.
As shown in FIG. 10, five power generation units as unit cells were connected in series to produce a power generation unit for a backup secondary battery.
That is, the connection electrode 7 of this unit cell 400 and the connection electrode 9 of another unit cell 410 were connected, and the connection electrode 7 of another unit cell 410 and the connection electrode 9 of another unit cell 420 were connected. By repeating in this manner, five unit cells were connected in series. In addition, the inlet 2, the inlet 3, the outlet 4, and the outlet 5 of each unit power generation unit are connected in parallel. The open voltage of the five series cells was 3.2 V, and almost no deterioration in the performance of each unit power generation unit due to the series connection of unit cells was observed.

As shown in FIG. 1, the power generation unit of the obtained backup secondary battery was mounted on a substrate together with a CPU 93, a RAM memory 94 as a memory element, and a main power supply monitoring unit 95 to produce a power supply circuit. The main power supply monitoring unit 95 is an IC for monitoring the voltage of the main power supply 91 for driving. The main power supply voltage is detected, and the voltage is not more than a predetermined value (4 V in this embodiment). An IC provided with a switching circuit that operates to supply the voltage of the backup secondary battery 96 to the RAM memory 94 when the voltage drops to the value shown in FIG.
Note that a voltage of 5 V was supplied from the main power supply 91 for the CPU operation, and the CPU operating current was about 5 mA.
Next, the voltage supplied from the backup secondary battery 96 to the RAM memory 94 when the power supply from the main power supply 91 was stopped was 3.2V. It was also confirmed that the memory was saved when power was again supplied from the main power supply 91 to the operating unit 92.

(Charging part)
The charging unit is provided in a space other than the substrate on which the power generation unit, the CPU 93, the RAM memory 94, and the main power supply monitoring unit 95 are mounted, and the charging unit is connected to the inlet 2 of the power generation unit as in the mass transfer path shown in FIG. The supply of each component to the inlet 3, the recovery of each component from the outlet 4 and outlet 5 of the power generation unit to the charging unit, and the movement of each substance in the charging unit are performed by connecting a microtube having an inner diameter of 150 μm. It was. And after performing the backup using the said secondary battery 96 for backups 500 times, it charged as shown to FIGS. 5-7 (however, it was set as the structure except the electrodialysis tank 20). That is, as shown in FIG. 11, first, the sodium sulfate aqueous solution generated after power generation in the power generation section was supplied to the salt chamber 42 of the three-chamber bipolar membrane electrodialysis tank (medium regeneration means 40). While the water generated after power generation is continuously supplied to the acid chamber 44 and the base chamber 46, the DC voltage between the anode and the cathode {the charging power source is a constant voltage constant current DC stabilized power source driven by a commercial power source (100V) (PMC-35-0.5A, manufactured by Kikusui Electronics Co., Ltd.) was used (the same applies to the reactant recycling means 30)} and 4V was applied. As a result, it was confirmed that a certain concentration of sulfuric acid and sodium hydroxide were continuously regenerated from each of the acid chamber 44 and the base chamber 46.

In addition, the anode chamber 32 and the cathode are applied to a hydrogen peroxide cell (produced by Permerec Electrode Co., Ltd., 1.25 dm ² diaphragm type) as a reactant regeneration means 30 while applying a DC voltage (5 V) between the anode 32a and the cathode 34a. When the sodium sulfate aqueous solution generated after power generation was adjusted to 0.02 mol / l and supplied at a rate of 5 ml / min in each of the chambers 34, the cathode chamber 34 was opened to the atmosphere and oxygen generated after power generation was simultaneously supplied. It was confirmed that a 1 mol / l aqueous hydrogen peroxide solution could be regenerated continuously.

  When power generation was performed using hydrogen peroxide, sulfuric acid, and sodium hydroxide regenerated in the charging section as reactants, acidic medium, and basic medium, respectively, the same characteristics as the first power generation were obtained.

[Comparative Example 1]
A power generation unit as a unit cell was produced in the same manner as in Example 1 except that hydrogen peroxide was not included in the sample solution. This power generation unit was evaluated in the same manner as in Example 1. The sulfuric acid and sodium hydroxide concentrations of the sample liquids A and B injected from the inlet 2 and the inlet 3 of the power generation unit were both 0.1 N. The flow rate and the experimental temperature are the same as in Example 1.
The current-voltage characteristics are shown in FIG. In Comparative Example 1, the open circuit power (200 mV) due to the liquid voltage was measured, but no significant current was obtained.
Further, as shown in FIG. 10, five power generation units were connected in series to produce a secondary battery for backup, and a power supply circuit was produced in the same manner as in Example 1, but the power generation unit had sufficient power. Thus, it was confirmed that the battery did not function as a backup secondary battery 96.

  As described above, in the power generation unit of the backup secondary battery in Example 1, it was found that good voltage and current were obtained and electric energy could be supplied as shown in FIG. In addition, it was confirmed that the power supply circuit including the backup secondary battery having the power generation unit and the charging unit can hold the memory of the RAM memory 94 which is a memory element and is practical. In addition, it was confirmed that charging and discharging are possible while reusing the electrolyte constituent components with a simple configuration.

It is a block diagram which shows the structure of the power supply circuit of this invention. It is a figure which shows the electric power generation mechanism in this invention. It is explanatory drawing which shows the structure of the secondary battery for backups of this invention. (A) is a schematic top perspective view of one embodiment of the power generation unit in the battery of the present invention, and (b) is a diagram of both media when the power generation unit shown in (a) is cut along AA ′. It is sectional drawing seen from the direction of the flow. It is explanatory drawing which showed the whole structure of the charging part roughly. It is explanatory drawing which showed schematically the structure of the reactive material reproduction | regeneration means. It is explanatory drawing which showed schematically the structure of the medium reproduction | regeneration means. It is explanatory drawing which shows an example of a mass transfer path | route. It is a figure which shows the current-voltage characteristic in an Example and a comparative example. It is a schematic diagram which shows the example of a connection of the unit cell in an Example and a comparative example. It is explanatory drawing which shows the mass transfer path | route in an Example and a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Capillary flow path 2, 3 ... Inlet 4, 5 ... Outlet 6 ... Electrode (2nd electrode)
7: Connection terminal 8: Electrode (first electrode)
DESCRIPTION OF SYMBOLS 9 ... Connection terminal 10 ... Cover glass 11 ... Slide glass 12 ... Spacer a ... Acidic aqueous solution b ... Basic aqueous solution 20 ... Electrodialysis tank 22 ... Desalination chamber 24 ... Concentration chamber 30 ... Reactive substance regeneration means 32 ... Anode chamber 32a ... Anode 34 ... Cathode chamber 34a ... Cathode 36 ... Separator 40 ... Medium regeneration means 42- ··· Salt chamber 44 ··· Acid chamber 46 ··· Base chamber 47 · · · Anion exchange membrane 48 · · · Cation exchange membrane 49 · · · Bipolar membrane 47 · · · Anion exchange membrane 48 Cation exchange membrane 49: Bipolar membranes 5a, 5b, 5c, 5d, 5e ... Storage chambers 6a, 6b, 6c, 6d, 6e ... Micro pump 7a ... Gas separator 91 ...・ Main power source 92... Operation unit 93... CPU
94 ... Memory element 95 ... Main power supply monitoring unit 96 ... Backup battery 100 ... Power generation unit 200 ... Charging unit 300 ... Charging power source 210 ... Reactant regeneration means 220- ..Media reproduction means 400 ... first unit power generation unit 410 ... second unit power generation unit 420 ... third unit power generation unit

Claims (20)

A power supply circuit including a main power supply, an operation unit including a memory element, a main power supply monitoring unit, and a backup secondary battery,
The backup secondary battery comprises a power generation unit and a charging unit,
The power generation unit includes at least an acidic medium in which a first electrode is disposed and a basic medium in which a second electrode is disposed, and the acidic medium and the basic medium are adjacent to or close to each other. A reactive substance is contained in at least one of the acidic medium and the basic medium,
The power supply circuit according to claim 1, wherein the charging unit includes a reactant regeneration unit that regenerates the reactant from a power generation product generated by power generation in the power generation unit.   The main power supply monitoring unit includes switching means that operates to supply the power of the backup secondary battery to the memory element when the power supplied from the main power supply drops below a predetermined value. The power supply circuit according to claim 1.   The power supply circuit according to claim 1, wherein the charging unit further includes medium regeneration means for regenerating the acidic medium and / or the basic medium from the power generation product.   The power supply circuit according to claim 1, wherein the acidic medium is made of an acidic aqueous solution, and the basic medium is made of a basic aqueous solution.   The power supply circuit according to claim 1, wherein the reactant is contained in each of the acidic medium and the basic medium.   The first substance as the reactant contained in the acidic medium and the second substance as the reactant contained in the basic medium are the same substance. 5. The power supply circuit according to 5.   The power supply circuit according to claim 1, wherein the reactant is hydrogen peroxide.   8. The reactant regenerating means has an anode and a cathode, and supplies the oxygen and water as the power generation products to the cathode to regenerate the hydrogen peroxide. The power supply circuit described in 1.   The medium regeneration means arranges a cation exchange membrane, a bipolar membrane and an anion exchange membrane to form a salt chamber, an acid chamber and a base chamber, and a neutralized salt aqueous solution which is the power generation product in the salt chamber. 5. The cell according to claim 4, further comprising a three-chamber cell type cell that supplies and electrodialyzes and discharges the acidic aqueous solution and the basic aqueous solution from each of the acid chamber and the base chamber. Power supply circuit.   5. The power supply circuit according to claim 4, wherein the power generation unit is provided with a flow path structure in which the acidic aqueous solution and the basic aqueous solution form a laminar flow therein.   The acidic aqueous solution is sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, periodic acid, orthophosphoric acid, polyphosphoric acid, nitric acid, tetrafluoroboric acid , Hexafluorosilicic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexachloroplatinic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, maleic acid, malonic acid, phthalic acid, fumaric acid, and picric acid The power supply circuit according to claim 4, comprising at least one acid selected from the group.   The basic aqueous solution is sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide. And one or more bases selected from the group comprising tetrabutylammonium hydroxide, or sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, potassium borate, sodium silicate, potassium silicate, 5. The power supply circuit according to claim 4, comprising at least one alkali metal salt selected from the group comprising sodium tripolyphosphate, potassium tripolyphosphate, sodium aluminate, and potassium aluminate.   The power supply circuit according to claim 1, wherein the acidic medium is composed of an acidic ion conductive gel, and the basic medium is composed of a basic ion conductive gel.   14. The power supply circuit according to claim 13, wherein the acidic ion conductive gel is obtained by gelling an acidic aqueous solution with water glass, anhydrous silicon dioxide, crosslinked polyacrylic acid, agar, or a salt thereof.   14. The power supply circuit according to claim 13, wherein the basic ion conductive gel is obtained by gelling a basic aqueous solution with carboxymethyl cellulose, crosslinked polyacrylic acid, or a salt thereof.   The first electrode is platinum, platinum black, platinum oxide coated platinum, silver, gold, surface passivated titanium, surface passivated stainless steel, surface passivated nickel, surface passivated 2. The power supply circuit according to claim 1, wherein the power supply circuit is made of one or more materials selected from the group consisting of aluminum, carbon structure, amorphous carbon, and glassy carbon.   The second electrode is platinum, platinum black, platinum oxide coated platinum, silver, gold, titanium with passivated surface, stainless with passivated surface, nickel with passivated surface, passivated surface 2. The power supply circuit according to claim 1, wherein the power supply circuit is made of one or more materials selected from the group consisting of aluminum, carbon structure, amorphous carbon, and glassy carbon.   The power supply circuit according to claim 1, wherein the first electrode and the second electrode have a plate shape, a thin film shape, a mesh shape, or a fiber shape.   The said 1st electrode and the said 2nd electrode are respectively arrange | positioned by the electroless-plating method, a vapor deposition method, or the sputtering method of the said acidic medium and the said basic medium respectively. Power supply circuit.   9. The power supply circuit according to claim 8, further comprising a direct current power source for applying a direct current to the anode and the cathode of the reactant regenerating means.

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