JP2004206990A - Aluminum battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum battery with improved discharge capacity with liquid leakage prevented, in the battery using aluminum for a negative electrode. <P>SOLUTION: The aluminum battery has a positive electrode, a negative electrode containing aluminum or an aluminum alloy, and electrolyte solution interposed between the positive electrode and the negative electrode, and above all, barium is added to the electrolyte solution or the like. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００７０】
【表２】

【００７１】
【表３】

【００７２】
【表４】

【００７３】
【表５】

【００７４】
この表１〜表５から明らかなように、本実施例は、高容量である非水電解質二次電池の負極活物質を提供することができ、さらに高容量な非水電解質二次電池を提供することができる。
【００７５】
【発明の効果】
本発明によれば、漏液を防ぎ放電容量を向上させたアルミニウム電池を提供することができる。
【図面の簡単な説明】
【図1】本発明の実施例１〜実施例７および比較例１、２に関わるアルミニウム電池の断面図。
【図２】本発明の実施例８〜実施例１４および比較例３、４に関わるアルミニウム電池の断面図。
【図３】本発明の実施例１５〜実施例２１および比較例５、６に関わるアルミニウム電池の断面図。
【符号の説明】
１・・・外装体、
２・・・つば紙、
４・・・正極、
５・・・セパレータ、
６・・・負極、
７・・・負極端子、
８・・・封口板、
９・・・正極集電体、
２１・・・正極集電体、
２２・・・負極つば紙、
２３・・・正極つば紙、
２４・・・正極、
２５・・・セパレータ、
２６・・・負極、
２７・・・負極端子、
２８・・・負極集電体、
２９・・・正極端子、
３１・・・封口体、
３３・・・絶縁体、
３４・・・正極、
３５・・・セパレータ、
３６・・・負極、
３７・・・負極集電体を兼ねる負極端子
３９・・・正極集電体を兼ねる正極端子[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aluminum battery including a negative electrode containing aluminum.
[0002]
[Prior art]
2. Description of the Related Art Currently, portable electronic devices are used very frequently. Batteries, which are essential power supplies for portable electronic devices, are also required to have higher capacities. A battery that uses aluminum for the negative electrode has not been put to practical use, despite having a higher capacity than the current mainstream battery using zinc for the negative electrode. Japanese Patent Application Laid-Open No. 2002-110183 describes an aluminum battery having aluminum on the negative electrode.
[0003]
However, a battery using this aluminum as the negative electrode has a high possibility of causing liquid leakage during discharge. As a cause, it is considered that the liquid leakage phenomenon is caused by a product generated by oxidation of aluminum. This is because the aluminum discharge product generated near the negative electrode is hardly diffused and becomes very high in concentration, and the electrolytic solution located elsewhere (for example, the electrolytic solution near the positive electrode and the separator disposed on the opposite side of the separator) It is considered that the electrolyte held by the separator moves to the vicinity of the negative electrode due to the osmotic pressure effect, and the one that exceeds the amount that can be held between the separator and the negative electrode is discharged outside the battery. Such a problem is remarkable during discharge, and liquid leakage frequently occurs, which is a problem for practical use.
[0004]
[Patent Document 1]
JP-A-2002-110183 (Claims)
[0005]
[Problems to be solved by the invention]
The conventional aluminum battery has a problem in that a product is formed by a chemical reaction between aluminum and an electrolytic solution, thereby causing a liquid leakage and a reduction in discharge capacity.
[0006]
The present invention has been made in view of the above problems, and it is an object of the present invention to provide an aluminum battery in which aluminum is used for a negative electrode, in which leakage is prevented and discharge capacity is improved.
[0007]
[Means for Solving the Problems]
In order to solve the above problem, an aluminum battery according to claim 1, wherein the aluminum battery has a positive electrode, a negative electrode containing aluminum or an aluminum alloy, and an electrolytic solution interposed between the positive electrode and the negative electrode. Alternatively, the negative electrode contains barium ions or barium. "Containing barium" means a state in which barium ions or barium exists as an ionizable state, for example, a barium compound or an alloy containing barium.
[0008]
An aluminum battery according to a second aspect is characterized in that, in the first aspect, the electrolytic solution contains water.
[0009]
An aluminum battery according to a third aspect is characterized in that, in the first aspect, the electrolytic solution contains one or a plurality of types of ions selected from chloride ions, sulfate ions, and nitrate ions.
[0010]
An aluminum battery according to a fourth aspect is characterized in that, in the first aspect, the barium ion concentration is in the range of 0.0001 mol / l (liter) to 5 mol / l (liter).
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
(A) Positive electrode
The positive electrode includes a positive electrode mixture in which a binder is added to a positive electrode active material, a conductive agent, and the like as necessary, and a current collector that forms the positive electrode mixture on the surface.
[0012]
Examples of the positive electrode active material include metal oxides, metal sulfides, and conductive polymers. As the metal oxide, in addition to manganese dioxide (MnO2), lead dioxide (PbO2), nickel oxyhydroxide, nickel hydroxide {NiOOH or Ni (OH) 2}, silver oxide (Ag2O), for example, FeO, Fe2O3 , FeOX (where x is x> 1.5), and iron oxides such as MXFeO4 (where M is at least one selected from Li, K, Sr and Ba, and x is x ≧ 1). . Examples of the conductive polymer include polyaniline and polypyrrol, such as disulfide compounds and organic sulfur compounds such as sulfur. Among them, manganese dioxide is preferred in view of the balance between cost and performance.
[0013]
The positive electrode mixture desirably contains a conductive agent in addition to the positive electrode active material. Examples of the conductive agent include graphite, acetylene black, graphite, and carbon black. In particular, acetylene black and graphite are preferable because they are stable with respect to the electrolytic solution.
[0014]
By including a conductive agent in the positive electrode mixture, the electronic conductivity between the positive electrode mixture and the current collector can be improved. The content of the conductive agent in the positive electrode mixture is preferably in the range of 1 to 20% by weight. That is, if the amount is less than 1% by weight, the electron conductivity in the positive electrode mixture cannot be sufficiently increased, and if the amount exceeds 20% by weight, the content of the positive electrode active material decreases, and the positive electrode reaction becomes sufficient. May not be possible.
[0015]
The positive electrode mixture can also be prepared by, for example, mixing a powdery positive electrode active material and a conductive agent, and then pressing and molding the mixture into pellets. Further, a positive electrode active material may be fixed on the surface of the current collector by mixing a binder in the positive electrode mixture as needed.
[0016]
Examples of the binder contained in the positive electrode mixture include polytetrafluoroethylene.
[0017]
The positive electrode current collector supporting the positive electrode mixture is for improving electron conductivity between the positive electrode mixture and the positive electrode terminal.
[0018]
As the material used for the positive electrode current collector, for example, one or more selected from tungsten (W), molybdenum (Mo), lead (Pb), and titanium nitride (TiN), or a conductive material such as a carbonaceous material is contained. Preferably, one is used.
[0019]
The positive electrode current collector can be porous or non-porous. In the positive electrode current collector, tungsten (W), molybdenum (Mo), and lead (Pb) may exist in a single state, but are included as an alloy of two or more selected from tungsten, molybdenum, and lead. May be. Examples of the positive electrode current collector containing titanium nitride (TiN) include a positive electrode current collector made of titanium nitride and a metal plate such as a nickel plate whose surface is coated (plated) with titanium nitride. . In particular, at least one metal selected from the group consisting of tungsten (W) and molybdenum (Mo) or a carbonaceous material is preferable.
[0020]
The content of the conductive material composed of at least one selected from tungsten (W), molybdenum (Mo), lead (Pb) and titanium nitride (TiN) as the positive electrode current collector is preferably 99% by weight or more. A more preferred range is 99.9% by weight or more.
[0021]
A positive electrode current collector using a carbonaceous material as a conductive agent is produced, for example, by mixing a carbonaceous material powder and a binder and then press-molding.
[0022]
Examples of the carbonaceous material powder include graphite powder and carbon fiber.
[0023]
The carbonaceous material content in the positive electrode current collector is preferably set to 80% by weight or more. More preferably, it is 90% by weight or more.
[0024]
This positive electrode may be used by mixing it with an electrolytic solution described later in advance. The positive electrode current collector may be a porous body or a non-porous body, and may be appropriately selected as needed.
(B) negative electrode
When a current collector is used, a negative electrode active material is applied to the surface to form a negative electrode. The negative electrode active material contains aluminum. For example, 99.9% aluminum or 97.5% aluminum-2.5% zinc alloy can be used. The form may be any of powdery, granular, bobbin, and bottomed hollow hollow structures. In the case of powder, a conductive agent or a gel electrolyte may be included. This negative electrode active material is applied to a current collector.
[0025]
In addition, aluminum or an aluminum alloy can be directly used for the negative electrode.
[0026]
When aluminum is used as the negative electrode, it is preferable to use aluminum having a purity of 99.5 wt% or more, that is, aluminum having an impurity of 0.5 wt% or less. If the impurities are contained in an amount exceeding 0.5 wt%, they are likely to be corroded by the electrolytic solution, which may cause severe self-discharge or gas generation. A more preferred range of the purity is 99.9 wt% or more.
[0027]
Specific examples of the negative electrode active material or the aluminum alloy used for the negative electrode include, for example, an alloy composed of Al and at least one metal selected from Mn, Cr, Sn, Ca, Mg, Pb, Si, In, and Zn. be able to. Especially, it is desirable to use an alloy containing Mg and Cr in Al. Examples of the aluminum alloy include 94.5 wt% Al-2 wt% Mg-3.5 wt% Cr, 95% Al-5 wt% Mg, 99.5% Al-0.3 wt% Mn-0.2 wt% Zn, and the like. be able to.
[0028]
This negative electrode may be used by being mixed in advance with an electrolytic solution described later. In addition, on the surface of the negative electrode, an organic acid, a salt of an organic acid, an anhydride of an organic acid, an ester of an organic acid, an ion of an organic acid, and a derivative thereof, COOH), a sulfonic acid group (SO3H), a hydroxyl group (OH), a nitro group (NO2), and a compound or polymer compound containing at least one functional group selected from the group of derivatives thereof.
[0029]
Further, the substance composed of the additive present on the aluminum or aluminum alloy surface will be described in the section of (d-2) additive below.
[0030]
When barium is added to the negative electrode active material, a method of using barium as an alloy in the negative electrode, a method of including barium in an oxide film on the surface of the negative electrode active material, and the like can be considered.
[0031]
The amount of alloying barium is preferably in the range of 10 ppm to 50% by weight. If the amount is less than 10 ppm, the effect is less likely to appear, and if it exceeds 50% by weight, the discharge capacity may be reduced. Particularly preferably, it is in the range of 0.1% to 5%.
When barium is contained in the oxide film, the amount thereof is desirably in the range of 1 ppm to 80% by weight based on the weight of the oxide film. If it is less than 1 ppm, the effect is less likely to appear, and if it exceeds 50% by weight, self-discharge may be promoted. Particularly preferably, it is in the range of 0.1% to 50%.
(C) Separator
The separator hinders the transfer of electrons between the positive electrode and the negative electrode, and is made of an insulating material. However, a porous body is usually used because the electrolyte must be held in the separator and the electrolyte ionized in the electrolyte needs to be movable.
[0032]
Some separators are suitable depending on the electrolyte. However, it is possible to use a separator made of cellulose, such as a nonwoven fabric of polyolefin, through which ions can pass.
[0033]
Examples of the material used for the separator include kraft paper, synthetic fiber sheet, natural fiber sheet, nonwoven fabric, glass fiber sheet, and polyolefin porous membrane.
[0034]
Instead of the separator, a substance having ionic conductivity such as a solid electrolyte or a gel electrolyte and having almost no electronic conductivity can be used.
[0035]
The thickness of the separator is preferably in the range of 10 to 200 μm. If the thickness is less than 10 μm, a short circuit may occur between the positive electrode and the negative electrode. If the thickness is more than 1000 μm, the moving distance of the ionized electrolyte increases, and the ion conduction efficiency decreases.
[0036]
Note that a separator is not necessarily required as long as the battery is arranged so that the positive electrode and the negative electrode are not in contact with each other and can hold an electrolytic solution between the positive electrode and the negative electrode.
[0037]
Alternatively, a thickener may be added to the electrolytic solution and subjected to a gelling treatment, so as to be used as a so-called solid electrolyte. In that case, the thickener phase functions as a separator, and the electrolyte solution phase is held in the thickener phase.
(D) Electrolyte
The electrolyte used in the present invention contains an electrolyte, a solvent for dissolving the electrolyte, and an additive for suppressing a corrosion reaction between the electrolyte and the negative electrode. Water can be used as a solvent for the electrolytic solution. As a solvent other than water, an organic solvent such as γ-butyrolactone or acetonitrile can be used alone or by mixing a plurality of these organic solvents with water. Further, a separator impregnated with these electrolytic solutions may be used.
[0038]
When barium ions are contained in the electrolytic solution, during the discharge reaction, barium ions participate in the reaction between the above-mentioned solvent such as water and aluminum, and a composite oxide or hydroxide of aluminum and barium, for example, barium aluminum oxide And aluminum barium oxide hydrate, aluminum barium hydroxide, aluminum barium hydroxide hydrate, and the like. These compounds have a higher solubility and are more easily diffused than aluminum oxides and aluminum hydroxides usually generated during a discharge reaction in a conventional aluminum battery in which barium ions are not present, so that leakage is suppressed. It is desirable that the barium ion concentration in the electrolyte is in the range of 0.0001 mol / l to 5 mol / l. If the amount is less than 0.0001 mol / l, the effect may be difficult to be obtained. If the amount is more than 5 mol / l, dissolution of other electrolytes may be hindered. Particularly preferably, it is in the range of 0.01 mol / l to 2 mol / l.
(D-1) Electrolyte
As the electrolyte, one that supplies at least one ion selected from the group consisting of sulfate ions (SO42-) and nitrate ions (NO3-) dissolved in a solvent is used.
[0039]
As described above, it is possible to increase the output of a battery obtained by supplying highly reactive ions such as sulfate ions (SO42−) or nitrate ions (NO3−) into the electrolytic solution.
[0040]
Examples of the electrolyte include aluminum chloride, potassium chloride, lithium chloride, manganese chloride, sulfuric acid, manganese sulfate, aluminum sulfate, potassium sulfate, lithium sulfate, nitric acid, potassium nitrate, aluminum nitrate, and lithium nitrate. The concentration of the electrolyte is desirably 0.001 mol or more. If the amount is less than 0.001 mol / l, the function as an electrolyte may not be obtained well.
[0041]
An inhibitor for suppressing self-discharge may be added to the electrolytic solution.
[0042]
As the electrolyte for providing sulfate ions, for example, sulfuric acid, aluminum sulfate, sodium sulfate, ammonium sulfate, lithium sulfate and the like are particularly desirable.
[0043]
Particularly preferred are those that provide nitrate ions, such as nitric acid, aluminum nitrate, sodium nitrate, ammonium nitrate, and lithium nitrate.
[0044]
The amount of the electrolyte in the electrolytic solution is preferably such that the concentration of nitrate ions or sulfate ions is in the range of 0.2 to 16 M / L. This is due to the following reasons. When the concentration of the nitrate ion or the sulfate ion is less than 0.2 M / L, the ionic conductivity is small, and the formation of a film on the surface of the negative electrode by an additive described below becomes insufficient, and the corrosion reaction of the negative electrode is sufficiently performed. There is a possibility that it cannot be suppressed. On the other hand, when the concentration of nitrate ions or sulfate ions exceeds 16 M / L, the film growth on the negative electrode surface becomes remarkable, the interface resistance of the negative electrode increases, and a high voltage may not be obtained. A more preferred range is from 0.5 to 10 M / L.
(D-2) Additive
The additive comprises at least one selected from the group consisting of organic acids and their salts, esters, anhydrides, and ions.
[0045]
It is considered that this additive is present on the surface of a negative electrode made of aluminum or an aluminum alloy or the like due to a functional group of the additive, and suppresses a corrosion reaction between an electrolyte such as H2SO4 and a negative electrode such as aluminum. Some of these are adsorbed on the negative electrode. In addition, some of them adhere to form a film. In some cases, a specific layer is formed. Some exist near the negative electrode. It demonstrates its performance in each state.
[0046]
When the corrosion reaction represented by the formula (3) is shown for sulfuric acid and aluminum, the reactions represented by the following formulas (4) and (5) occur.
[0047]
That is, the coating of the additive component present on the negative electrode surface has a low electron conductivity, so that electrons are not quickly exchanged between sulfuric acid and aluminum, and as a result, the corrosion reaction of the negative electrode is suppressed. I think that the.
[0048]
As the additive contained in the electrolyte, specifically, at least one kind selected from the group consisting of carboxylic acid (COOH), sulfonic acid (SO3H), hydroxyl group (OH), and nitro group (NO2) Examples include acids (organic acids) containing functional groups and salts, anhydrides, esters, ions and derivatives thereof.
[0049]
More specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, phenol, glycerin, glycolic acid, ethylene glycol, formic acid, acetic acid, propionic acid, oxalic acid, salicylic acid, Sulfosalicylic acid, malic acid, tartaric acid, succinic acid, fumaric acid, phthalic acid, malonic acid, citric acid, maleic acid, lactic acid, butyric acid, pyruvic acid, benzoic acid, sulfobenzoic acid, nitromethane, sulfoaniline, nitrobenzenesulfonyl, polyvinyl alcohol , Vinyl acetate, vinyl sulfonate, poly (styrene sulfonic acid), poly (vinyl acetate), methyl acetate, acetic anhydride, maleic anhydride, phthalic anhydride, diethyl malonate, sodium benzoate, sodium sulfobenzoate, Sulfoaniline chloride, ethyl chloroacetate, dichloroacetate Le, poly (vinyl acetate potassium salt), poly (lithium styrenesulfonate), poly acrylic acid, poly lithium acrylic acid. For a polymer, a copolymer containing one of these may be used.
[0050]
The concentration of the additive in the electrolyte is preferably in the range of 0.0001 to 40% by weight. This is due to the following reasons. If the concentration of the additive is less than 0.0001% by weight, the effect of the additive on the negative electrode surface may not be sufficiently obtained, and the corrosion reaction may not be sufficiently suppressed. On the other hand, if the concentration of the additive exceeds 40% by weight, the ionic conductivity of the electrolyte / electrolyte solution may decrease, and a high voltage may not be obtained. A more preferable range of the concentration is 0.001 to 30% by weight.
[0051]
Further, by adjusting the concentration of the additive within such a range, the amount of the additive component present on the electrode surface is desirably about 1.0 × 10 −20 g / cm 2 to 1.0 g / cm 2. If the amount is less than 1.0 × 10−20 g / cm 2, it is difficult to sufficiently suppress the corrosion of the negative electrode. If the amount is more than 1.0 g / cm 2, ion conductivity may be reduced.
[0052]
The amount of the additive forming the film can be measured by an electrochemical quartz crystal microbalance method.
[0053]
In addition, the effect of the present invention is sufficiently exerted if the amount is such that the presence of the additive can be confirmed by various spectroscopic measurements such as infrared spectroscopy, nuclear magnetic resonance spectrum, and ultraviolet / visible absorption spectrum.
[0054]
Further, it is preferable that the electrolyte contains halogen ions in addition to the additives and the electrolyte. By containing halogen ions, the ionic conductivity of the electrolytic solution can be improved. In addition, the addition of halogen ions increases the amount of the additive dissolved in the electrolytic solution. As a result, it becomes possible to form a thin film of the additive formed on the surface of the negative electrode, thereby improving the voltage of the battery.
[0055]
It is preferable that the concentration of halogen ions in the electrolytic solution be in the range of 0.01 to 6 M / L. If the concentration is less than 0.01 M / L, the effect of adding the halogen ions described above cannot be sufficiently obtained. On the other hand, if the concentration of the halogen ions exceeds 6 M / L, the progress of self-discharge due to the corrosion of the negative electrode. May increase. A more preferred range is from 0.05 to 4 M / L.
[0056]
In the electrolytic solution, as a solvent for dissolving the electrolyte and the like, for example, water, methyl ethyl carbonate, or the like may be used.
[0057]
According to the battery using such aluminum for the negative electrode, it is possible to provide a primary battery in which self-discharge and gas generation are suppressed.
[0058]
In addition, it has been confirmed that a battery using aluminum as a negative electrode causes liquid leakage during discharge. The liquid leakage phenomenon is caused by a product generated by oxidation of aluminum. This is because the aluminum discharge product generated near the negative electrode is hardly diffused and becomes very high in concentration, and the electrolytic solution located elsewhere (for example, the electrolytic solution near the positive electrode and the separator disposed on the opposite side of the separator) It is considered that the electrolyte held by the separator moves to the vicinity of the negative electrode due to the osmotic pressure effect, and the one that exceeds the amount that can be held between the separator and the negative electrode is discharged outside the battery.
[0059]
As a result of intensive studies by the inventor, they have found that the above phenomenon can be suppressed by adding barium ions to the electrolyte or adding barium to the negative electrode. This is presumably because the product generated by the oxidation of aluminum produces a different product different from the product resulting from the leakage due to the presence of barium ions, and the different product is easily diffused.
[0060]
【Example】
In the following example, a battery using the components of the battery described in the above embodiment of the present invention was prepared, and its characteristics were evaluated.
(Example 1)
FIG. 1 shows a cross-sectional view of the battery used. In FIG. 1, 1 is an exterior body (a heat-shrinkable tube made of Teflon (R)), 2 is brim paper (kraft paper), 4 is a positive electrode, 5 is a separator (kraft paper), 6 is a negative electrode, and 7 is a negative electrode terminal. (Made of stainless steel), 8 is a sealing plate (made of polypropylene), 9 is a positive electrode current collector (made of graphite).
[0061]
Water is used as a solvent for the electrolytic solution, and the solvent contains 0.5 mol / l of aluminum chloride and 1 mol / l of barium chloride. Manganese dioxide was used as the positive electrode active material, 10% by weight of acetylene black was used as the positive electrode conductive agent, and 40% by weight of the electrolytic solution was stirred to obtain a positive electrode. On the other hand, as the negative electrode, one obtained by processing 99.999% aluminum into a cylindrical shape with a bottom was used. The inner circumference of the cylinder had a diameter of 2 cm and a height of 5 cm. A non-woven fabric made of polypropylene was laid inside the negative electrode, the positive electrode was filled therein, and a rod made of graphite was inserted into the positive electrode as a current collector. The cap was made of paper or polypropylene so as to cover the positive electrode, but it was not completely shut off from outside air because of the gap.
[0062]
Discharge was performed at a constant current of 1 A, and discharge was performed to 0.3 V.
The utilization rate of the positive electrode was 308 mAh / g, where the reaction of manganese dioxide was a one-electron reaction, and the utilization rate was 100%. The liquid leakage at the time of discharge was indicated by the number out of ten. The results are shown in Table 1 below. The evaluation item of the frequency of occurrence of liquid leakage was defined as follows. When the number of leaked liquids is within 0-5% of the number of experiments, it is especially A. When it is within 5% -10%, it is A. When it is 10% -25%, it is B. When C is 40% or more, it is described as D.
(Examples 2 to 7, Comparative Example 1)
The same test as in Example 1 was performed by changing the positive electrode active material, the positive electrode conductive agent, the negative electrode metal, the electrolyte, and the solvent. The results are shown in Tables 1, 2 and 5 described below.
(Example 8)
In Example 8, the battery having the cross-sectional structure shown in FIG. 2 was used. In FIG. 2, 21 is a positive electrode current collector (made of tungsten), 22 is a negative electrode brim paper (made of polypropylene), 23 is a positive electrode brim paper (Mr. Kraft), 24 is a positive electrode, 25 is a separator (made of nylon), 26 is a negative electrode , 27 are a negative electrode terminal (made of stainless steel), 28 is a negative electrode current collector (made of tungsten), and 29 is a positive electrode terminal (made of tungsten).
[0063]
For the positive electrode, 10% by weight of graphite and a positive electrode active material were mixed, and the mixture was formed into a hollow cylindrical shape by pressing and used. The negative electrode was prepared by mixing the negative electrode active material with 1% by weight of polyvinyl alcohol and then mixing with 50% by weight of an electrolytic solution to form a gel. Water is used as a solvent for the electrolytic solution, and the solvent contains 0.5 mol / l of aluminum chloride and 1 mol / l of barium chloride. A 95% aluminum-5% barium alloy was used for the negative electrode.
[0064]
The discharge experiment conditions were the same as in Example 1. The size of the entire battery is a cylinder having a diameter of 2 cm and a height of 5 cm.
(Examples 9 to 14, Comparative Example 2)
In Examples 9 to 14 and Comparative Example 2, an experiment similar to that of Example 10 was performed, and a similar test was performed by changing the positive electrode active material, the positive electrode conductive agent, the negative electrode metal, the electrolyte, and the solvent. The results are shown in Tables 2, 3, and 5 described below.
[0065]
The barium ion concentration in the negative electrode oxide film is a value separately measured by ICP emission analysis using the same material as the negative electrode at the time of battery preparation. Specifically, working electrode was oxidized with a barium chloride solution to store barium in the oxide.
(Example 15)
In Example 15, a battery having the cross-sectional structure shown in FIG. 3 was used. In FIG. In FIG. 3, 31 is a sealing body (made of polypropylene), 33 is an insulator (made of styrene-butadiene rubber), 34 is a positive electrode, 35 is a separator (polyethylene porous body), 36 is a negative electrode, and 37 is a negative electrode serving also as a negative electrode current collector. A terminal (made of molybdenum) 39 is a positive electrode terminal (made of tungsten) which also serves as a positive electrode current collector.
[0066]
For the positive electrode, 10% by weight of graphite and a positive electrode active material were mixed, pressed and molded. The negative electrode was prepared by mixing 1% of methyl methacrylate and 99.99% of a negative electrode active material and a barium alloy of 0.01%, and mixing 40% by weight of an electrolytic solution to form a gel.
[0067]
The discharge experiment conditions were the same as in Example 1. The overall size of the battery is a disk having a diameter of 2 cm and a height of 0.5 cm. The results are shown in Table 4.
(Examples 16 to 21, Comparative Example 3)
In Examples 16 to 21 and Comparative Example 3, the same experiment as in Example 10 was performed, and the same test was performed by changing the positive electrode active material, the positive electrode conductive agent, the negative electrode metal, the electrolyte, and the solvent. The results are shown in Tables 4 and 5 below.
[0068]
The barium ion concentration in the negative electrode oxide film is a value separately measured by ICP emission analysis using the same material as the negative electrode at the time of battery preparation. Specifically, working electrode was oxidized with a barium chloride solution to store barium in the oxide.
[0069]
[Table 1]

[0070]
[Table 2]

[0071]
[Table 3]

[0072]
[Table 4]

[0073]
[Table 5]

[0074]
As is clear from Tables 1 to 5, this example can provide a negative electrode active material of a high capacity nonaqueous electrolyte secondary battery, and further provides a high capacity nonaqueous electrolyte secondary battery. can do.
[0075]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the aluminum battery which prevented the liquid leakage and improved the discharge capacity can be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an aluminum battery according to Examples 1 to 7 and Comparative Examples 1 and 2 of the present invention.
FIG. 2 is a sectional view of an aluminum battery according to Examples 8 to 14 and Comparative Examples 3 and 4 of the present invention.
FIG. 3 is a cross-sectional view of an aluminum battery according to Examples 15 to 21 and Comparative Examples 5 and 6 of the present invention.
[Explanation of symbols]
1 ... exterior body,
2 ... brim paper,
4 ... positive electrode,
5 ... separator
6 ... negative electrode,
7 ... negative electrode terminal,
8 ... sealing plate,
9 ... Positive electrode current collector,
21 ... Positive electrode current collector,
22 ... negative electrode brim paper,
23 ・ ・ ・ Positive electrode brim paper,
24 ・ ・ ・ Positive electrode,
25 ... separator,
26 ... negative electrode,
27 ... negative electrode terminal,
28 ... negative electrode current collector,
29 ・ ・ ・ Positive terminal,
31 ・ ・ ・ Sealing body,
33 ... insulator
34 ・ ・ ・ Positive electrode,
35 ... separator,
36 ... negative electrode,
37 ... negative electrode terminal also serving as negative electrode current collector
39 ... Positive electrode terminal also serving as positive electrode current collector

Claims (4)

In an aluminum battery having a positive electrode, a negative electrode containing aluminum or an aluminum alloy, and an electrolytic solution interposed between the positive electrode and the negative electrode, the electrolytic solution or the negative electrode contains barium ions or barium. Aluminum battery. The aluminum battery according to claim 1, wherein the electrolyte contains water. 2. The aluminum battery according to claim 1, wherein the electrolyte contains one or more ions selected from chloride ions, sulfate ions, and nitrate ions. 3. The aluminum battery according to claim 1, wherein the barium ion concentration is in the range of 0.0001 mol / l to 5 mol / l.

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