JP6947832B2 - A method for producing a battery having an electrolytic solution containing alkaline mineral ionized water, an electrolyte active material, and an electrolytic solution for a battery. - Google Patents

Description

The present invention relates to a battery, and more particularly, to a battery using an alkaline aqueous solution containing a specific mineral ion as an electrolytic solution, an electrolyte active material, and a method for producing an alkaline electrolytic solution for a battery.

Galvanic cells have long been famous as primary batteries. Galvanic cells include voltaic batteries in which a zinc plate and a copper plate are used as electrodes and sulfuric acid is used as an electrolytic solution between them; a Daniell cell in which a zinc plate is immersed in a zinc sulfate aqueous solution and a copper plate is immersed in a copper sulfate aqueous solution; etc. be. Further, as the primary battery, a manganese dry battery, a vaporized graphite lithium battery, a manganese dioxide lithium battery, a thionyl lithium chloride battery, an iron disulfide lithium battery, an alkali manganese battery, an air zinc battery, a silver oxide battery and the like are known.

The invention according to Patent Document 1 is an invention of a battery structure for fishing such as floating, in which magnesium, aluminum, zinc or the like is used as a negative electrode, and silver chloride, lead chloride, copper chloride, etc. are used as a positive electrode. A battery in which copper iodide, potassium persulfate, etc. are used and a water-absorbent material is arranged between them is described.

In Patent Document 2, the negative electrode is zinc, nickel, chromium or aluminum, the positive electrode is gold, silver, copper or stainless steel, and the electrolyte is obtained by electrolyzing a liquid containing a sulfate ion substance eluted from tuff. A battery using the "sulfate ion-containing electrolytic solution" is described.

Patent Document 3 describes a hybrid battery in which "lead dioxide and lead" or "copper (alloy) and aluminum (alloy)" are used as a combination of metals constituting the electrode plate, and the positive electrode plate and the negative electrode plate are arranged facing each other. It is described, and sulfuric acid or the like is used as the electrolytic solution thereof.

However, there are nickel hydrogen batteries and alkaline manganese batteries as batteries using an alkaline aqueous solution as an electrolytic solution, and the electrolytic solution is strongly alkaline potassium hydroxide. Since potassium hydroxide oxidizes or dissolves metals and metal oxides that have a high ionization tendency, the life of the electrical material is shortened when these electrolytes are used.
Mineral ionized water for improving battery performance, specific electrolytes, or electrolyte active materials containing them have not been known.

Japanese Unexamined Patent Publication No. 2004-158209 Japanese Unexamined Patent Publication No. 2010-153206 Japanese Unexamined Patent Publication No. 2013-247101

The present invention has been made in view of the above background technology, and an object of the present invention is to provide a battery that stably supplies electric power for a long period of time, and a novel electrolyte or electrolyte for a battery used in the battery. It is to provide active materials.

As a result of diligent studies to solve the above problems, the present inventor uses a specific positive electrode and a negative electrode, and mineral ionized water containing a specific substance (ion, compound, etc.) as an electrolytic solution existing between them. , And preferably, "a high-temperature calcined carbon group formed by supporting and calcining mineral ion water and an incinerated mineral ion precursor" or a paste-like electrolyte active material containing the incinerated mineral ion precursor is used. As a result, the present invention has been completed by finding that a simple and low-cost battery can be produced by stably supplying electric power for a long period of time and using a general-purpose metal for the electrode, and particularly even if the positive electrode is a carbon plate or carbon fiber. rice field.

That is, in the present invention, a metal body having a higher ionization tendency than hydrogen is used as the negative electrode, a conductor is used as the positive electrode, and the pH containing alkaline earth metal ions is used as the electrolytic solution existing between the negative electrode and the positive electrode. Provided is a battery characterized by containing 12 or more and 14 or less of mineral ionized water.

Further, the present invention is an electrolyte active material for a battery, which is in the form of a paste containing the alkaline earth metal ion and the ashed mineral ion precursor. Is to provide.

Further, in the present invention, a metal body having a higher ionization tendency than hydrogen is used as the negative electrode, a conductor is used as the positive electrode, and mineral ion water having a pH of 12 or more and 14 or less is used as the electrolytic solution existing between the negative electrode and the positive electrode. This is the method for producing the electrolytic solution for batteries used.
At a minimum, oxides, hydroxides, carbonates or bicarbonates of magnesium or calcium are dissolved in water to contain alkaline earth metal ions, the pH is adjusted, and the water-soluble components of biological ash are dissolved. The present invention provides a method for producing an electrolytic solution for a battery, which is characterized by the fact that the electrolytic solution for a battery is produced.

According to the present invention, it is possible to solve the above problems and to provide a battery that continuously and stably supplies electric power (voltage and current) for a long period of time extremely easily and inexpensively.
The battery of the present invention can continuously supply electric power for 600 hours or more even in a general-purpose simple laminating process in which the electrolytic solution is easily vaporized. At this time, if the electric power drops for more than 600 hours, the electrolytic solution can be dropped to allow repeated use. For a further long-life design, if a highly airtight encapsulation treatment is performed, it is possible to generate electricity indefinitely as long as the electrolytic solution is not vaporized and the negative electrode, for example, the aluminum electrode is not oxidized.

Further, preferably, by stacking a large number of these single cells (batteries), it can be easily used as electric power for mobile devices, cars, aircraft, robots, home appliances and the like. Further, if power using power from the battery of the present invention is used instead of power for discharging carbon dioxide, environment-friendly carbon dioxide-free power can be obtained.

For example, the electrolytic solution of a voltaic battery is an acidic aqueous solution such as sulfuric acid or hydrochloric acid. It is also known that an aqueous solution of a salt such as a saline solution can be used. Potassium hydroxide aqueous solution is known as an aqueous solution using an alkaline aqueous solution, which rapidly erodes and dissolves a metal having a high ionization tendency.
Since the battery of the present invention uses a specific electrolytic solution, it is difficult to oxidize metal electrodes and metal oxides even when the pH is 12 or more and 14 or less, and it is extremely simple, but for a long period of time. Power can be supplied continuously and stably.

Further, by containing "living ash" such as wood ash in the electrolytic solution, the redox reaction of the trace ionized mineral component in the electrolytic solution works gently and effectively, and the battery life performance is improved. Can be done.

Conventionally, nickel oxyhydroxide, manganese dioxide, etc., which have been required, are not basically essential, and are "high-temperature calcination in which the above-mentioned mineral ion water and the above-mentioned ashed mineral ion precursor are supported and fired. By using the "carbon group", a higher performance battery can be obtained.
However, the inclusion of a conventional active material is not excluded from the present invention.
Battery performance can also be improved by dispersing an electrolyte active material such as graphite, graphene, nickel oxyhydroxide, manganese dioxide, and tin oxide in the electrolytic solution to form a paste.

It is the schematic sectional drawing which shows an example of the basic form of the battery of this invention. It is the schematic which shows an example of the form of the battery of this invention. (A) Plan view (b) Vertical sectional view

Hereinafter, the present invention will be described, but the present invention is not limited to the following specific forms, and can be arbitrarily modified within the scope of the technical idea.

In the present invention, a metal body having a higher ionization tendency than hydrogen is used as the negative electrode, a conductor is used as the positive electrode, and the pH of containing alkaline earth metal ions as the electrolytic solution existing between the negative electrode and the positive electrode is 12 or more. It is a battery characterized by containing 14 or less mineral ionized water.
Further, it is effective to contain "the high-temperature calcined carbon group carrying the above-mentioned mineral ion water and the above-mentioned incinerated mineral ion precursor" as the electrolyte active material. Here, the "supported high-temperature calcined carbon group" includes a high-temperature calcined carbon group that is supported and then calcined at a high temperature. The same applies hereinafter.

Further, a paste containing alkaline earth metal ions, a paste containing an incinerated mineral ion precursor, and an electrolyte active material complexed with a carbon group on which an electrolytic solution is supported and fired at a high temperature are contained in the electrolytic solution. Is extremely effective and suitable. The "paste containing an ashed mineral ion precursor" is preferably an ashed paste of a biological product.

<Battery form>
The form of the battery is not particularly limited as long as the electrolytic solution 4 is provided between the negative electrode 1 and the positive electrode 2, and like a general-purpose dry battery, there is an electrode in the center and other electrodes along the housing. The form may be flat or flat, but as shown in FIGS. 1 and 2, a form in which the electrodes are flat or vertical cells is particularly preferable.

A form in which the electrolytic solution 4 having the above-mentioned or later-described electrolyte active material is between the two electrodes is more preferable. That is, it is particularly preferable to further contain the specific paste described above or below, or "a high-temperature calcined carbon group formed by supporting and calcining the mineral ion water and the ashed mineral ion precursor".
Further, the electrolytic solution 4 may be used by impregnating the water-absorbent base material 3. In that case, the portion of the electrode sandwiching the "portion impregnated with the electrolytic solution" acts as a positive electrode and a negative electrode.

As shown in FIG. 1, a current is taken out from the negative electrode 1 and the positive electrode 2 through a conducting wire 5 electrically bonded thereto. There is no particular limitation on the joining of the conductors.

In the case of the form shown in FIGS. 2A and 2B, the size of the electrode plate is not particularly limited, but the length or width is preferably 10 mm or more and 100 mm or less, and 20 mm or more and 70 mm or less is particularly preferable. The thickness of the electrode plate is not particularly limited, but is particularly preferably 0.5 mm or more and 1 mm or less.
Further, in the case of the form shown in FIG. 2B, that is, the water-absorbent base material 3 exists between the electrodes, and the water-absorbent base material 3 is impregnated with the electrolytic solution 4, and the portion thereof is substantially. In the case of a battery, the size of one electrode (the circular portion in which the electrolytic solution is impregnated in FIG. 2) is narrower than that of the electrode, and the length, width or diameter is preferably 1 mm or more and 45 mm or less, preferably 5 mm. More than 40 mm is more preferable, 8 mm or more and 35 mm or less is particularly preferable, and when it is neither rectangular nor circular, the above value is converted on an area basis.

A sufficient current value can be obtained even if the size of the electrode plate and the electrolytic solution portion is small, and the life is extended as long as the water can be replenished even if the amount of the electrolytic solution 4 is small. This effect is a special effect as mineral ionized water, which is extremely mild even at a pH of 12 to 14 and does not damage the electrodes for a long period of time.
On the other hand, if the electrode plate or the electrolyte portion is too large, it may be difficult to maintain a uniform distance between the electrodes due to the structure, and it is sufficient to connect them in series and stack them in a cell, so that the electrode area becomes wide and the current strays. In addition, problems such as increased cost and heavy weight may occur.

The distance between the electrodes is not particularly limited as long as power can be supplied satisfactorily, but is preferably 0.03 mm or more and 8 mm or less, more preferably 0.05 mm or more and 3 mm or less, and particularly preferably 0.1 mm or more and 2 mm or less. If the distance between the electrodes is too small, a short circuit may occur.
It is preferable to install an insulator around the gap contact interface between the two electrodes.

<Negative electrode>
In the battery of the present invention, in the negative electrode 1, metal cations are emitted into the electrolytic solution 4 from the metal body constituting the negative electrode 1, and electrons are left behind in the negative electrode 1, so that voltage and current are generated. Therefore, the metal used as the negative electrode 1 is not particularly limited as long as it is a "metal having a higher ionization tendency than hydrogen", but specifically, aluminum, zinc, magnesium, lithium, iron, nickel, tin, lead and the like are used. Can be mentioned.
Of these, aluminum or zinc is particularly preferable from the viewpoint of electromotive force, stability, price and the like. Although the alloy is not excluded, it is preferable that it is a simple substance metal because it does not change the composition of the electrolytic solution 4. Further, it is preferable to use a metal wire such as an aluminum wire or a zinc wire (particularly preferably an aluminum wire) for the negative electrode because the size can be reduced (to a very small cell).

<Positive electrode>
The positive electrode 2 of the battery of the present invention is not particularly limited as long as it is a conductor, but the conductive substance forming the conductor is preferably copper, silver, palladium, gold or platinum, or an alloy thereof. Further, it may be a carbonaceous material such as graphite (graphite), high-temperature calcined carbon, or carbon fiber. Further, it may be a conductive structure in which fine particles of these conductive substances are dispersed or press-compressed, or a structure having a thin oxide film on the surface.
The metal is more preferably copper or silver or an alloy thereof from the viewpoint of electromotive force, stability, price (cost) and the like, and particularly preferably copper from the viewpoint of cost. The carbon material is more preferably a carbon fiber in terms of light weight, stability over time, price (cost), and the like. It is preferable to use carbon fiber for the positive electrode because it can be miniaturized (in a very small cell).

<Composition and physical characteristics of electrolyte>
<< pH of electrolyte >>
The electrolytic solution 4 of the battery of the present invention is characterized by containing mineral ion water having a pH of 12 or more and 14 or less, which contains alkaline earth metal ions. The pH is particularly preferably 13 or more and 14 or less.
When such an electrolytic solution 4 is used, unlike a potassium hydroxide solution that dissolves a metal, a battery having a long life can be produced with stable electric power. Although the principle of action is not limited, it is considered that the electrode (surface) is stabilized by changing the electrolytic solution 4 to alkaline "mineral ionized water" and further adjusting the pH to a specific range. In particular, it is considered that the chemical reaction due to the redox reaction of the negative electrode 1 is suppressed by mineral ions and the redox is oxidized and reduced very gradually, but the positive electrode 2 (surface) is not oxidized.

The pH can be adjusted by using a "compound that dissolves in water to give alkaline earth metal ions", which will be described later, or can be adjusted by adding a "compound that exhibits alkalinity in water". Is. It is preferable to adjust the pH with "a compound that dissolves in water to give alkaline earth metal ions" or "an ashed mineral ion precursor composed of biological ash", which will be described later.

The pH (range) refers to the pH of the initial electrolytic solution 4 at the time of battery supply, etc., but the electrolytic solution such that the pH at the time of use (from the start of use to the end of use) is always within the above range. 4 is desirable.

<< Alkaline earth metal ions in electrolyte >>
As the alkaline earth metal ion (ion of Group 2 element), magnesium ion, calcium ion, strontium ion, barium ion and the like are preferable.
More preferably, a long-life battery can be produced with stable power, the compound containing the ion is inexpensive, the compound containing the ion can be easily obtained from a substance, limestone; organisms such as coral stone, egg shell or shell. ^{Magnesium ion (Mg 2+} ) or calcium ion (Ca ²⁺ ), particularly preferably calcium ion (Ca ²⁺ ), from the viewpoint of being easily obtained from the derived product. These ions may be contained alone or in combination of two or more.

When magnesium ion (Mg ²⁺ ) and calcium ion (Ca ²⁺ ) are contained, a Ca ²⁺ rich molar ratio is preferable in terms of cost performance, and Ca ²⁺ / Mg ²⁺ = 15/15 to 19 1/1 (molar ratio) is particularly preferable.

The above-mentioned "compound that dissolves in water and gives alkaline earth metal ions" (hereinafter, the parentheses are abbreviated as "alkaline earth metal ion supply compound") includes oxides and hydroxides of the alkaline earth metals. Examples include compounds, carbonates, hydrogen carbonates, and the like. More preferably, it is an oxide, hydroxide, carbonate, hydrogen carbonate or the like of magnesium or calcium, and more preferably, it is an oxide, hydroxide, carbonate, hydrogen carbonate or the like of calcium. Particularly preferred is calcium hydroxide (slaked lime). Moreover, what is so-called "calcareous" including the above is also preferable.

The amount of the alkaline earth metal ion in the electrolytic solution 4 and the alkaline earth metal ion supply compound used for preparing the electrolytic solution is in the range of the amount so that the finally obtained electrolytic solution 4 is in the pH range. Is preferable.
The alkaline earth metal ion supply compound can be put into water (preferably dissolved and aged in a state where air is blocked), and if necessary, filtered after aging to obtain a desired electrolytic solution 4. These compounds may be used alone or in combination of two or more.
At this time, it is preferable to use the "partially dissolved alkaline earth metal ion paste" as an electrolyte active material, which will be described later, or as a raw material for the electrolyte active material.
It is preferable to adjust the pH with only the "compound that dissolves in water and gives alkaline earth metal ions" and keep it within the above range, but if appropriate, add another "ionic compound that exhibits alkalinity in water" to adjust the pH. It can also be adjusted.

It is preferable to use a biological product as the alkaline earth metal ion supply compound from the viewpoints of cost advantage, human body and nature friendliness, and the like.
As the biological product, coral stones; egg shells; shells such as oyster shells; and the like are also preferable because they can be obtained at low cost and as waste.

<< Biological ashes in electrolyte >>
The electrolytic solution in the present invention preferably further contains "an ashed mineral ion precursor composed of a biological ash" in addition to the above-mentioned one. When these are contained, oxidation is suppressed, the electrode (surface) and the active material of the electric material become stable, and a long-life battery can be obtained with a constant and stable power supply.
Although the principle of action is not limited, it is considered that the inclusion of this stabilizes the electrode (surface) by a compound or ion containing a trace element in an organism. In particular, it was considered that the excessive oxidation of the negative electrode 1 was suppressed and the negative electrode 1 was gradually oxidized but not dissolved, and the chemical reaction of the positive electrode 2 (surface) was suppressed. Examples of trace elements in living organisms include sodium, potassium, magnesium, calcium, phosphorus, zinc, manganese, selenium, iron and the like. Of these, metal ions other than the metal ions already contained in the "mineral ion water" are considered to further improve the battery performance.

In particular, it is more preferable that the organism is a protist or a plant containing a large amount of mineral components. Examples of the protist include algae, protozoa and the like, and examples of the plant include seed plants and the like.
Seaweeds and the like are preferable as the algae, and among them, green algae; brown algae such as mozuku, kombui, wakame seaweed, sargassum, and hijiki; red algae; diatomaceae and the like are more preferable.
As the seed plant, tea plant and the like are preferable, and among them, their leaves, stems, roots and the like are more preferable.
The electrolytic solution in the present invention preferably contains an ashed mineral ion precursor composed of an ashed product of an organism, and the organism is particularly preferably a plant or seaweed.

It is also preferable to obtain the above-mentioned "organism" (including processed biological products and biological products) from the above-mentioned organism or waste containing a part of the above-mentioned organism.
Examples of such wastes include tea husks, root vegetable processing residues, seed plant-derived products such as weeds; seaweeds such as brown algae (preferably desalted); sargassum and the like. Moreover, as the waste, the fungus bed residue and the like can also be mentioned.

Since the above-mentioned "organism" or a part of the above-mentioned "organism" and the above-mentioned "waste containing (a part of) the organism" are calcined to become carbon, in the present invention, these are referred to as "carbon precursor". It may be referred to as "biological carbon precursor" or the like.

The "ashed organism" is an ashes of the above-mentioned organism, and those available as wood ash can also be preferably used.
The electrolytic solution in the present invention preferably contains "water-soluble mineral component of biological ash", but the water-soluble component is separately separated from the ash and contained in the electrolytic solution 4. However, it may be added to the water constituting the electrolytic solution 4 and filtered after aging so that only the water-soluble ionic component is contained in the electrolytic solution 4.

<< Electrolyte active material in electrolyte >>
The electrolytic solution contains the mineral ionized water and further contains an electrolyte active material, and the electrolyte active material is obtained by firing a "biological carbon precursor" carrying the electrolytic solution. Is preferable.
The electrolytic solution further comprises, as an electrolyte active material (preferably in a "biologically-derived carbon precursor"), "high-temperature calcined carbon obtained by supporting and calcining the mineral ion water and the incinerated mineral ion precursor". It is preferable to contain "group".
The high-temperature calcined carbon group is particularly preferably one in which a "biological carbon precursor" (carrying the above-mentioned electrolytic solution or the like) is calcined by high-temperature plasma by microwave excitation.
Here, the above-mentioned one is mentioned as the "supporting electrolytic solution", and the electrolytic solution actually used for the battery is exactly the same as the electrolytic solution actually used for the battery by containing the "high temperature calcined carbon group obtained by firing". It does not have to be an electrolytic solution having the composition of.
The electrolyte active material is more preferably a high-temperature calcined carbon group formed by high-temperature calcining in a state where mineral ionized water is supported on a "biologically-derived carbon precursor". It is particularly preferable that it is a high-temperature calcined carbon group exhibiting strong alkalinity. Here, since the "biologically-derived carbon precursor" includes organisms such as tea and seaweed, these organisms become carbon (carbonized) during high-temperature firing, and are referred to as "high-temperature calcined carbon group". The form is included. The above "organism" can also be read as "waste".

The electrolytic solution 4 in the present invention is, in addition to the usual "mineral ionized water containing alkaline earth metal ions and having a pH of 12 or more and 14 or less", as a new electrolyte active material, "alkaline soil containing the above-mentioned mineral ionized water". "Metallic ion paste", "" paste containing ashed mineral ion precursor ", preferably" ashed paste of biological product ", particularly preferably" vegetation ash paste "", "the above-mentioned electrolyte solution" It is extremely preferable to contain "a carbon group that is supported and fired at a high temperature". The high-temperature calcined carbon group is preferably carbonized by high-temperature calcining in a state where the above-mentioned electrolytic solution or mineral ionized water is supported on the "biologically-derived carbon precursor".

It is also preferable to contain it in an electrolytic solution such as graphite or graphene, which is a conventional active material, and it is also preferable to contain an electrolyte active material such as nickel oxyhydroxide or manganese dioxide, although it is not essential.
It is particularly preferable that the electrolytic solution further contains graphene in which graphite is delaminated with the mineral ionized water.

Graphite refers to a laminated structure of graphene. "Graphite" also includes those that are in the form of powder by stacking several layers.
The shape of the electrolyte active material such as graphite, graphene, nickel oxyhydroxide, and manganese dioxide in the electrolytic solution 4 is preferably powdery.
When these electrolyte active materials are contained, there are effects such as improving the conductivity of the electrolytic solution 4, stabilizing the electrodes, extending the battery life, and stabilizing the voltage and current values for a long period of time.

The electrolyte active material may not be contained, but when it is contained, it is preferably 30% by mass or more and 70% by mass or less, more preferably 60% by mass or more and 80% by mass or less, based on the entire electrolytic solution. It is particularly preferably 85% by mass or more and 90% by mass or less.

The electrolyte active material is preferably used by kneading the powder with the above-mentioned mineral ion water electrolytic solution and containing it in the electrolytic solution 4, applying it to an electrode, or performing screen printing.

<< Thickeners in electrolytes and other substances >>
It is also preferable to add a thickener to the electrolytic solution of the present invention to thicken it. The thickener is not particularly limited, but a naturally derived product is preferable, and a natural polysaccharide such as fucoidan or xanthan gum, which is heat-extracted with an electrolytic solution and concentratedly precipitated as a low molecular weight polymer, is particularly preferable.
Existing carboxymethyl cellulose (CMC) and the like may cause conduction inhibition.
Further, the electrolytic solution of the present invention may contain "other substances" other than the above substances as long as the battery performance is not deteriorated.

<Water-absorbent base material>
As shown in the schematic cross-sectional view of FIG. 2B, the battery of the present invention may be impregnated with the water-absorbent base material 3 and sandwiched between the negative electrode 1 and the positive electrode 2.
Examples of the water-absorbent base material 3 include cotton, non-woven fabric, felt, woven fabric, paper, and through-cell cells.
The size of the water-absorbent base material 3 is preferably within the range of the sizes of the electrode plates and electrodes described above, and the thickness of the water-absorbent base material 3 is within the range of the distance between the electrodes described above. Is preferable. Further, it is preferable that the electrode is sandwiched between the two electrodes.

<Battery electrolyte>
The present invention is also an electrolytic solution for a battery having the above-mentioned composition, which is used for the above-mentioned battery. The electrolytic solution for a battery of the present invention is suitable for the above-mentioned battery of the present invention.

<Manufacturing method of electrolyte for batteries>
The present invention is also the above-mentioned manufacturing method of the above-mentioned battery. That is, a metal body having a higher ionization tendency than hydrogen is used as the negative electrode 1, a conductor is used as the positive electrode 2, and alkaline water having a pH of 12 or more and 14 or less is used as the electrolytic solution 4 existing between the negative electrode 1 and the positive electrode 2. The method for producing an electrolytic solution for a battery used, which comprises dissolving at least an oxide, hydroxide, carbonate or bicarbonate of magnesium or calcium in water to contain alkaline earth metal ions, and adjusting the pH. It is also a method for producing an electrolytic solution for a battery, which is characterized by adjusting and dissolving a water-soluble component of a biological ash.
Although not limited, it is preferable that the dissolution is performed in a state where the air is shut off.

The preferred range of the production method is as described above. To adjust the pH, water is added to the "alkaline earth metal ion supply compound", and the mixture is preferably aged (standing) for 12 hours or more in a state where the air is blocked, and then "alkaline earth metal ion" is adjusted. Part or all of the "supply compound" is dissolved as mineral ions (alkaline earth metal ions), and when the pH is within the desired range, the pH adjustment is completed (the pH is adjusted accordingly). Can be regarded as).
It is preferable to produce an electrolytic solution for a battery by filtering in the middle and / at the end.

<Battery manufacturing method>
Although not limited, it is preferable that the water-absorbent base material 3 is sandwiched between the electrodes, the electrolytic solution 4 is impregnated therein, and the electrolytic solution 4 is sealed by a laminating treatment so as not to vaporize the water content. In cold climate specifications, it is more preferable to have a heat insulating structure after encapsulating the laminate.
If the electrolytic solution 4 is reinjected, the power generation function can be repeated.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

Example 1
Slaked lime (calcium hydroxide) is added to demineralized water so that the pH of the solution is 13.5 or more and 14.0 or less, and after aging for 12 hours or more with the air shut off, it is filtered to consist of mineral ion water. An electrolyte was obtained.

A battery having the form shown in FIG. 2 was produced. An aluminum plate (20 mm × 20 mm × thickness 0.3 mm) is used as the negative electrode 1, a copper plate (25 mm × 20 mm × thickness 0.3 mm) is used as the positive electrode 2, and cotton felt (thickness 0.3 mm) is used between the electrodes. ) Was sandwiched. That is, the distance between the electrodes was set to 0.3 mm. In addition, as an electrode, a battery of about 0.03 mm of aluminum foil and copper foil was also manufactured.
The cotton felt was impregnated with the electrolytic solution to prepare a battery as shown in FIG.

When the voltage between the aluminum plate of the negative electrode 1 and the copper plate of the positive electrode 2 was measured, the current value of 0.605V was 0.35 mA. That is, it was confirmed that only mineral ionized water could generate electricity.
At this time, the electrode size was slightly 15 mm × 20 mm for the aluminum electrode and 15 mm × 17 mm for the copper electrode, and the size of the cotton felt was extremely small at 12 mm × 15 mm.

Even if it was left without laminating, it continued to be energized with the voltage and current values as it was for about 98 hours, but after that, when the electrolyzed water vaporized due to the released state, the voltage and current values gradually decreased. rice field.
However, when the electrolytic solution was slightly dropped in the gap portion, the voltage / current value immediately returned to the original state.

Example 2
In Example 1, instead of slaked lime (calcium hydroxide) alone, a mixture of slaked lime (calcium hydroxide) and magnesium oxide (Ca ²⁺ / Mg ²⁺ = 20 / 0.3 (molar ratio)) is further replaced with pH. Mineral ionized water was prepared in the same manner as in Example 1 except that the value was set to 14, and a battery was prepared in the same manner.

The voltage between the aluminum plate of the negative electrode 1 and the copper plate of the positive electrode 2 was measured and found to be 0.803V. The current value improved to 0.8 mA.
As a result, energization was continued as it was for about 108 hours under the same conditions as described above.

Example 3
In Example 1, instead of slaked lime (calcium hydroxide) alone, the ratio of slaked lime (calcium hydroxide) and quicklime (calcium oxide) was set to "10/1 (molar ratio of calcium ions)" and the pH was set to 14. Except for the above, a battery was produced in the same manner as in Example 1.

When the voltage between the electrodes was measured, the voltage was 0.85 V and the current value was 0.89 mA.
Since quicklime also contains iron ions as impurities, it is considered that the voltage and current values have improved accordingly.
As a result, under the same conditions as described above, energization was continued for about 98 hours as it was, but the temperature was high and the electrolytic solution vaporized early in that environment. When the encapsulation process was changed to a completely highly airtight encapsulation process, continuous electric power was obtained at the above voltage and current for the same time as in Example 1.

Example 4
To the "electrolyte solution consisting of mineral ionized water" prepared in Example 1, wood ash (ashed from tea leaves or ashed from Sargassum) is further added as "biological ash", and after aging for 12 hours, the mixture is filtered. The insoluble material was filtered off. As a result, "a plurality of ionic components such as water-soluble sodium, potassium, calcium, phosphorus, zinc, manganese, selenium, iron, etc. of biological ashes" are dissolved in the electrolytic solution, and the pH is adjusted to 12.5. It was used as an electrolytic solution. That is, the electrolytic solution contained "an ashed mineral ion precursor composed of biological ash".

When the voltage between the electrodes was measured, both the ashes of tea leaves and the ashes of Sargassum had a voltage of 1.2 V and a current value of 0.92 mA.
As a result, under the same conditions as described above, energization was continued for 113 hours as it was.

Example 5
To the "electrolyte solution consisting of mineral ionized water" prepared in Example 1, wood ash (ashed tea leaves) was added as "animal ash", and a small amount of slaked lime (calcium hydroxide) was used at pH. The pH was adjusted to 12.0, and an electrolytic solution was prepared. That is, the electrolytic solution contained "an ashed mineral ion precursor composed of biological ash". The electrolytic solution mainly ^{contained calcium ion (Ca 2+} ), magnesium ion (Mg ²⁺ ), and other potassium ion (K ⁺ ).

When the voltage between the electrodes was measured, the voltage was 0.56 V and the current value was 1.13 mA.
As a result, under the same conditions as described above, energization was continued as it was for 122 hours.

Example 6
An electrolytic solution was prepared by adding 2 parts by mass of a high-temperature calcined carbon group to 98 parts by mass of the electrolytic solution prepared in Example 1. The pH was 14.

The high-temperature calcined carbon group was obtained, for example, as follows, but is not specifically limited thereto.
That is, the sencha husks (corresponding to "biological carbon precursor") are put into a dry state, and the dry mass of 1 kg is contained in the electrolytic solution (containing mineral ionized water) prepared in each of Examples 1 to 5. ) Was sufficiently moistened, left for 2 hours, dried again, and placed in a heat-resistant container.
On the other hand, 10 g of "a dried product obtained by impregnating a paper material with an electrolytic solution and drying it" was partially carbonized by a gas fire.
Then, the "partially carbonized paper" and the "tea husk which is the carbon precursor" were lightly mixed together and irradiated with microwaves. First, high-temperature thermal plasma was generated from the carbonized part, and the heat conduction at about 1000 ° C. gradually emitted smoke while carbonizing the tea leaves and burned them. As the smoke subsided, the tea leaves themselves became hot and red hot. When the red-hot state passed for about 2 minutes, a high-temperature calcined carbon group, which is an amorphous carbon, was obtained. When the heat cooled, it was refined in a mortar to obtain an electrolyte active material consisting of high-temperature calcined carbon groups. Five kinds of electrolyte active materials were obtained corresponding to sufficient moistening with the electrolytic solution prepared in each of Examples 1 to 5.

When the voltage between the electrodes was measured, it was 1.29V in each case. The current value was 3.1 mA in each case.
As a result, under the same conditions as described above, energization was continued as it was for about 115 hours.

Example 7
An electrolytic solution was prepared by adding 3 parts by mass of "high-temperature calcined carbon group used in Example 6" to 97 parts by mass of the electrolytic solution prepared in Example 1. The pH was 14.

The voltage between the electrodes was measured and found to be 1.83V. The current value was 5.1 mA.
As a result, the power was continued to be energized as it was for about 108 hours under the same conditions as described above.

Example 8
95 parts by mass of the electrolytic solution prepared in Example 1 was sufficiently moistened with the electrolytic solution prepared in Example 4 (containing mineral ion water) used in Example 6, dried, and then carbonized to obtain a high temperature. An electrolytic solution was prepared by adding 5 parts by mass of "electrolyte active material composed of calcined carbon".

When the voltage between the electrodes was measured, the initial voltage was 3.6V, the stable voltage was 1.287V, and the current value was 8.05mA.
As a result, under the same conditions as in Example 1, energization was continued as it was for 111 hours.

Example 9
In Example 8, except that "an electrolyte active material obtained by using the electrolytic solution of Example 5 used in Example 6 instead of the electrolytic solution of Example 4 used in Example 6" was used. A battery was prepared in the same manner as in Example 8 and evaluated in the same manner. The pH was 14.

When the voltage and current values between the electrodes were measured, it was 1.13V and 11.07mA.
As a result, under the same conditions as in Example 1, energization was continued for 118 hours as it was.

Example 10
Add an appropriate amount of 53.3 parts by mass of wood ash and 24.4 parts by mass of slaked lime, 22.3 parts by mass of the same "high temperature calcined carbon group" as in Example 6, and mineral ion water of Example 1 and stir and mix. The kneaded electrolyte was prepared.

On the other hand, one copper plate and one aluminum plate having a length of 30 mm, a width of 35 mm, and a thickness of 0.3 mm were prepared.
The electrolyte 4 is applied onto the copper plate so that the average diameter is 18 mm and the coating thickness is 1.2 mm (distance between electrodes 1.2 mm), and a thin cotton felt is placed on the copper plate, and electrolysis is performed in the center thereof. The liquid was dropped, an aluminum plate was placed on the aluminum plate, and the electrolyte and cotton felt were sandwiched between them, and the space between the two electrodes was fixed with masking tape.

When the voltage between the electrodes was measured, the voltage was 3.58 V and the current value was 24.74 mA.
As a result, the power was continued to be energized as it was for about 88 hours under the same conditions as described above.

<Result>
All the batteries of the examples were able to supply electric power stably. The electrolytic solutions of Examples 1 to 8 were not paste-like but low-viscosity liquids, but the electrolytic solutions of Examples 9 and 10 were paste-like.

The electrolytic solution consisting only of mineral ionized water containing no wood ash (animal ash) obtained high voltage and high current due to its high pH, but did not invade the electrodes.
The electrolytic solution containing vegetation ash (biological ash) also contains an "electrolyte active substance in which mineral ion water and vegetation ash (biological ash) (ashed mineral ion precursor) are combined". In addition, if the pH of the "electrolyte solution in which these electrolytes and the high-temperature calcined carbon group are combined" is 12 or more and 14 or less (even if the pH is around 14), a high voltage and a high current value can be obtained. It did not attack the electrodes.
The electrolytic solution containing vegetation ash (biological ash) was extremely mild even at around pH 12, and vegetation ash (biological ash) also functioned as an inhibitor that did not excessively oxidize and dissolve the electrodes.
By effectively varying these basic functions, the required battery performance can be ensured.

Furthermore, the life of the electrolytic solution can be further extended by the encapsulation laminating treatment in which the water content of the electrolytic solution is not vaporized. In addition, even if the electrolyte was dried over time, the power generation function could be repeated immediately by re-injecting mineral ion water.

The battery using the specific electrolytic solution 4 of the present invention is simple, has a long life, and is inexpensive, and is therefore widely used in the field of manufacturing or using the battery.

1 Negative electrode 2 Positive electrode 3 Water-absorbent base material 4 Electrolyte 5 Conductor

Claims (12)

A metal body having a higher ionization tendency than hydrogen is used as the negative electrode, a conductor is used as the positive electrode, and an alkaline earth metal ion-containing mineral having a pH of 12 or more and 14 or less is used as the electrolytic solution existing between the negative electrode and the positive electrode. A battery characterized by containing ionized water. The battery according to claim 1, wherein the alkaline earth metal ion contained in the electrolytic solution is magnesium ion or calcium ion. The battery according to claim 1 or 2, wherein the electrolytic solution further contains an ashed mineral ion precursor composed of an ashed product of an organism. The battery according to claim 3, wherein the organism is a plant or seaweed. The electrolytic solution contains the mineral ionized water and further contains an electrolyte active material, and the electrolyte active material is formed by firing a "biological carbon precursor" carrying the electrolytic solution. The battery according to any one of claims 1 to 4. A claim that the electrolytic solution further contains, as an electrolyte active material, "a high-temperature calcined carbon group formed by supporting and calcining the mineral ion water and the incinerated mineral ion precursor on a carbon precursor derived from a living body". The battery according to item 3 or claim 4. The high temperature firing carbon group, battery according to the "biobased carbon precursor" in der Ru請Motomeko 6 that high temperature plasma sintering with microwave excitation. The battery according to any one of claims 1 to 7, wherein the electrolytic solution further contains graphene obtained by delaminating graphite with the mineral ionized water. The electrolyte active material for a battery according to any one of claims 3 to 8, which is a paste containing the alkaline earth metal ion and the ashed mineral ion precursor. An electrolyte active material characterized by being present. A battery electrolyte solution using a metal body having a higher ionization tendency than hydrogen as the negative electrode, a conductor as the positive electrode, and mineral ion water having a pH of 12 or more and 14 or less as the electrolytic solution existing between the negative electrode and the positive electrode. It is a manufacturing method of
At a minimum, oxides, hydroxides, carbonates or bicarbonates of magnesium or calcium are dissolved in water to contain alkaline earth metal ions, the pH is adjusted, and the water-soluble components of biological ash are dissolved. A method for producing an electrolytic solution for a battery, which is characterized by allowing the mixture to be used. The method for producing an electrolytic solution for a battery according to claim 10, wherein a biological product is used as the above-mentioned "oxide, hydroxide, carbonate or hydrogen carbonate of magnesium or calcium". The method for producing an electrolytic solution for a battery according to claim 11, wherein the biological product is a coral stone, an egg shell, or a shell.

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