JP2005019351A - Dispersion liquid and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a low-cost and safe battery by using the dispersion liquid of calcium salt as an electrolyte for the battery. <P>SOLUTION: The dispersion liquid showing a pH of 9 or more containing fine particles of calcium salt such as calcium phosphate, obtained by electric conduction under the existence of mineral having preferably a hydroxyl group or crystal water and ceramics is used as an electrolyte solution. As an electrode, lead, lead-containing compound, lead alloy, Al, Zinc, iron, copper, mercury, gold, platinum, carbon, nickel, iridium, tungsten, titanium, stainless steel, cadmium, and their compounds, and alloys are used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is applied to a dispersion having an electromotive force, and the dispersion of the present invention is useful as an electrolyte for a battery.
[0002]
[Prior art]
Conventionally, many primary batteries and secondary batteries are known, but each has drawbacks in terms of use period, cost, safety and the like.
[0003]
[Problems to be solved by the present invention]
The present invention provides a completely new electromotive method that solves the conventional battery problems.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have found that a specific calcium salt dispersion has an electromotive force, and that a battery made using the dispersion has excellent performance, thereby completing the present invention.
That is, the present invention provides a dispersion liquid containing calcium salt fine particles and exhibiting a pH of 9 or more in the absence of a pH regulator.
In the present invention, the calcium salt refers to a salt of calcium and an inorganic acid or an organic acid, for example, calcium and sulfuric acid, sulfurous acid, sulfonic acid, silicic acid, nitric acid, acetic acid, citric acid, tartaric acid, lactic acid, butyric acid, oxalic acid, Salts with acids such as stearic acid, hydrochloric acid, phosphoric acid, phosphorous acid, phosphonic acid. In the present invention, since the calcium salt forms fine particles, the calcium salt used is preferably water-insoluble or hardly water-soluble. Therefore, for example, calcium hydroxide is not included. Preferably the calcium salt is calcium phosphate, calcium sulfate or calcium hydrochloride, most preferably the calcium salt is calcium phosphate. However, depending on the shape and structure of the compound used as the calcium source, such as a part of the water-insoluble calcium salt that is calcium acetate, water-soluble calcium salt can also exist as fine particles. In some cases, for example, a water-soluble calcium salt such as calcium acetate can be used. A plurality of salts can be used in combination.
[0005]
In the present invention, the calcium salt dispersion refers to a liquid in which water is the main dispersion medium and calcium salt particles are dispersed. The diameter of the calcium particles can range from 1 nm to several tens of microns, preferably from 1 nm to 10 microns, more preferably from 1 nm to 1000 nm, and most preferably from 1 nm to 5000 nm. Further, other water-miscible solvents such as alcohol and glycol can be added within a range not impairing the effects of the present invention.
The amount of calcium salt particles in the dispersion is not particularly limited, but is preferably 0.1% to 20% by weight, more preferably 0.3% to 10% by weight, and still more preferably 0.5% by weight. % To 2% by weight.
[0006]
The dispersion of the present invention is characterized in that it exhibits a pH of 9 or more in the absence of a pH regulator. The pH of the dispersion of the present invention is preferably 10 or more, and most preferably 11 or more.
As used herein, a pH regulator refers to any substance that can change the pH of an added system when added to an aqueous system, for example, water of alkali metals such as sodium and potassium. Examples thereof include inorganic bases such as oxides, organic bases such as amine and ammonia, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid.
The calcium salt fine particles used in the present invention are chemically neutral, water-insoluble or poorly water-soluble particles reacted at an equivalent amount, and the dispersion of such particles stabilizes a pH as high as 9 or more. In general, it is not possible to show this, and in this respect, the dispersion of the present invention has very unique characteristics.
However, when a higher pH or a lower pH is preferred, the pH adjuster can be added.
[0007]
The present invention further provides a method for producing the dispersion of the present invention.
That is, this invention provides the manufacturing method of the dispersion liquid of this invention including supplying with electricity to the dispersion liquid of the fine particle of a calcium salt. Preferably, the energization is performed in the presence of at least one substance selected from the group consisting of minerals and ceramics having a hydroxyl group or crystal water.
[0008]
The manufacturing method of a calcium salt is well-known, For example, desired calcium salt can be obtained by mixing calcium compounds, such as calcium hydroxide, calcium carbonate, and calcium oxide, and said acid.
[0009]
In the present invention, the manufactured dispersion solution containing calcium salt can be energized as it is, but preferably the calcium salt is precipitated, washed and crushed as necessary, and then dispersed in water to obtain a dispersion. .
[0010]
When the produced dispersion containing a calcium salt is used as it is, it is preferable that the calcium compound and the acid are reacted in an equivalent amount. In the present invention, the equivalent equivalent means a range of 0.9 to 1.1 equivalents of acid per equivalent of calcium, preferably a range of 0.95 to 1.05 equivalents of acid to one equivalent of calcium, most preferably calcium. The range of 0.98-1.02 equivalents of acid to 1 equivalent.
[0011]
In order to obtain the dispersion of the present invention, the calcium salt dispersion is energized. The energization is performed until the pH of the dispersion is 9 or more, preferably 10 or more, and most preferably 11 or more. The energization time, voltage, and current are experimentally determined as appropriate to achieve this purpose. Typically, the energization is from 1 to 20 A at 5 to 100 V, preferably from 1 to 15 A at 10 to 50 V, most preferably from 3 to 15 A at 10 to 30 V. The energization time varies depending on the type of calcium salt to be treated, the amount of the dispersion, etc., but is typically 1 to 30 hours, more typically 1 to 20 hours, and most typically about 2 to 15 hours. is there. Energization can usually be performed at normal temperature and pressure.
[0012]
The energization is preferably performed in the presence of minerals and / or ceramics having hydroxyl groups or crystal water. Minerals and / or ceramics having any hydroxyl group or crystal water can be used.
In the present invention, the term “crystal water” is used to include any of coordination water, lattice water, and structural water.
[0013]
Examples of the mineral preferably used in the present invention include heteropyrite (Zn ₄ Si ₂ O ₇ (OH) ₂ .H ₂ O), goethite (FeOOH), and nickelite (Ni-containing silicate). Compound), bauxite (Al (OH) ₃ ), lanthanum (Cu ₃ (CO ₃ ) (OH) ₂ ), peacock (Cu ₂ (CO ₃ ) (OH) ₂ ), alumite (KAl ₃ (SO) ₄ ) ₂ (OH) ₆ ), apatite (Ca ₅ (PO ₄ ) ₃ (Fe, Cl, OH)), syenite (Al ₂ SiO ₅ ), granite (Al ₂ Si ₄ O ₁₀ (OH) ₂ ), Talc (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ), kaolinite (Al ₄ Si ₄ O ₁₀ (OH) ₈ ), mordenite ((Na ₂ Ca, K ₂ ) ₄ (Al ₈ Si ₁₀ ) O ₉₆ · _28H 2 O), turquoise ( _{uAl 6 (PO 4) 4 (} OH) 8 · 4H 2 O), Topaz _{(Al 2 SiO 4 (F,} OH) 2), lithia tourmaline _{(Na (Li, Al) 3} Al 6 (BO 3) Si 6 O ₁₈ (OH) ₄ ), opal, chlorite (Ca ₂ (Mg, Fe) ₅ Si ₈ O ₂₂ (OH) ₂ ), phlogopite (K (Mg, Fe) ₃ (AlSi ₃ O ₁₀ ) (OH, F) ₂ ), muscovite (KAl ₂ (AlSi ₃ O ₁₀ ) (OH, F)), biotite, talc (Mg ₂ (OH) ₂ SiO ₁₀ ), mica (KAl ₂ (SiAlO ₁₀ ) (OH) ₂ ) Etc.
Examples of the ceramic preferably used in the present invention include synthetic zeolite (Na ₂ Al ₂ SiO ₃ O ₁₀ · xH ₂ 0) and those containing hydroxides of various elements.
Lithia tourmaline, chlorite, and phlogopite are preferred.
The dispersion containing calcium salt fine particles used in the present invention has a pH of 9 or more, but minerals and / or ceramics having a hydroxyl group or crystal water generate OH ⁻ ions when energized, and increase the pH. It is thought to have.
[0014]
The amount of mineral and / or ceramic added to the dispersion during energization is not particularly limited, but is typically in the range of 10 kg to 50 kg per 100 liter of dispersion. Further, the shape and size of the mineral and / or ceramics can be freely selected, but are appropriately determined so as not to cause a problem in handling properties while increasing the contact area with water.
In addition, minerals and / or ceramics are arranged so that an electric current flows in water around the minerals and / or ceramics when energized. For example, it is preferable to place minerals and / or ceramics on the bottom of the tank and arrange the electrodes in the vicinity of the surface, and to fill the mesh-like container with minerals and / or ceramics and arrange the electrodes at both ends thereof.
[0015]
The present invention further provides a battery using the dispersion of the present invention.
The battery according to the present invention uses the dispersion of the present invention as an electrolyte.
As the electrode, any substance that can be used as an electrode can be used. For example, lead, lead-containing compounds, lead alloys, Al, zinc, iron, copper, mercury, silver, gold, platinum, carbon, nickel, Iridium, tungsten, titanium, stainless steel, cadmium, and their appropriate compounds and alloys can be used.
The shape of the electrode can be any shape, and for example, a plate shape, a rod shape, a net shape, a spherical shape, a foil shape, or the like can be used.
Further, as used in known batteries, a separator can be used as necessary to avoid a short circuit between the positive electrode and the negative electrode. The material and shape of the separator can be appropriately determined by those skilled in the art based on known techniques.
Moreover, in a known battery, a battery having excellent characteristics can be obtained by replacing a part of the electrolyte with the electrolyte of the present invention. For example, in a storage battery for automobiles, if a part of the dilute sulfuric acid in the electrolyte is replaced with the dispersion of the present invention, a storage battery that can be used for a long time can be obtained, and also in a battery composed of other electrolytes and electrodes It is the same.
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this Example is shown for description of this invention, and does not restrict | limit the scope of the present invention at all. Further, modifications and substitutions apparent to those skilled in the art are included in the scope of the present invention.
[0016]
Example 1 Preparation of Dispersion 1100 g of calcium hydroxide was dissolved in 10 liters of water, and 2500 g of phosphoric acid was added thereto. The reaction was carried out at room temperature for 0.5 hours with stirring.
The product calcium phosphate was obtained as a precipitate. The precipitate was filtered and washed with water to obtain clean calcium phosphate.
1 kg of the obtained calcium phosphate was dispersed in 100 liters of water in a water tank to obtain a dispersion. The pH of this dispersion was about 7. 10 kg of a mixture of equal amounts of Lithia tourmaline, chlorite, and phlogopite was spread on the bottom of the aquarium. In the vicinity of the surface, a positive electrode and a negative electrode were disposed at intervals of 4 cm, and electrodes were disposed on both sides thereof. When energized at 24 V and 10 A for about 4 hours, the pH increased to about 11.
[0017]
Example 2
The dispersion obtained in Example 1 was put in a container, an aluminum plate was used as the negative electrode, a copper plate was used as the positive electrode, and the change in electromotive force when the distance between the electrodes was changed was examined.
The results were as follows.
4cm 1.354V
3cm 1.358V
2cm 1.356V
1cm 1.359V
When the dispersion liquid of the present invention is used as an electrolyte, no change is seen in the electromotive force even when the distance between the electrodes is changed.
[0018]
Example 3
Carbon was dispersed in the dispersion liquid of Example 1, and a non-woven fabric impregnated with this was used as a positive electrode, and a copper mesh was brought into contact with it as a lead. An aluminum mesh was used as the negative electrode. Nonwoven paper was used as a separator and inserted between the positive electrode and the negative electrode. The size of the positive electrode and the negative electrode was 10 cm × 10 cm.
A current of 0.7 V and 100 mA was measured between the two electrodes.
[0019]
By using the dispersion of the present invention as a battery electrolyte, an inexpensive and safe battery can be obtained.
In particular, a battery that can use aluminum as an electrode has not been known. In this respect, the present invention provides a battery having a very wide range of applications.

Claims (7)

A dispersion containing fine particles of calcium salt and exhibiting a pH of 9 or more in the absence of a pH regulator. The dispersion according to claim 1, wherein the calcium salt is calcium phosphate. The method for producing a dispersion according to claim 1, comprising energizing a dispersion of fine particles of calcium salt. The method for producing a dispersion according to claim 1, wherein energization is performed in the presence of at least one substance selected from the group consisting of minerals and ceramics having a hydroxyl group or crystal water. The method for producing a dispersion according to claim 3, wherein the calcium salt is calcium phosphate. A battery using an electrode other than lead, a lead compound and a lead alloy as an electrode and using the dispersion according to claim 1 as an electrolyte. The battery according to claim 6, wherein the negative electrode is Al and the positive electrode is carbon.