JP2002270193A - Water added battery and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery capable of preventing leakage and evaporation of the electrolyte outside of a system and possible to be stored for a long time before using it and realized in the effective utilization of the used non-aqueous polymer obtained from the general plastic waste material. SOLUTION: A dry material of a polymer obtained by leading a hydrophilic polar group into a non-aqueous polymer and a dry material of the electrolyte are used to form a battery. The gel-type polymer electrolyte is formed by adding water to form the battery for operation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a process for producing a water-added battery, comprising a dried product of a water-insoluble polymer having a hydrophilic polar group introduced therein and a dried product of an electrolyte.
And the water-added battery.

[0002]

2. Description of the Related Art At present, a battery generally has an electrode immersed in an electrolyte, but in this case, the electrolyte leaks or evaporates out of the system, or the electrolyte is in direct contact with the electrode. There have been various problems that the storage period until actual use is shortened due to factors such as corrosion of the electrode portion. Therefore, the release of the electrolyte out of the system is small, and
A battery with a long storage period is desired.

On the other hand, general-purpose plastics, especially plastics having an aromatic ring or a conjugated diene in the molecule, for example,
The production volume of products using ABS (acrylonitrile-butadiene-styrene) polymer, SAN (styrene-acrylonitrile) polymer, polyacrylonitrile-butadiene, polyethylene terephthalate (PET), etc. has been increasing. The amount of waste materials generated also tends to increase, and interest in global environmental conservation has increased, and the need for effective use of the waste materials has also increased. Under such circumstances, the use of these materials is expected to be further expanded for reuse, and there is a demand for a study on reforming to a higher value-added material.

[0004] By the way, the above-mentioned waste materials of general-purpose plastics are roughly classified and treated by three kinds of methods of landfill, incineration and remelting. In Japan, landfill and incineration account for about 90% of the total,
Currently, most are not recycled. In addition, as a method for recycling such general-purpose plastic waste materials, a method of melting by heating and re-forming (however, only a thermoplastic polymer) is generally performed.
There are many problems such as deterioration of quality due to heat (for example, molecular weight reduction, oxidation of polymer, etc.), mixing of foreign matter such as dust, or mixing of polymers containing various coloring agents, which necessitates color matching. there were. As described above, when waste materials of general-purpose plastics are recycled by heating and melting, processing techniques and costs have been a major obstacle.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides a battery having a long storage period without leakage or evaporation of an electrolyte outside the system, and a method of manufacturing the same. The purpose is to provide. Further, the present invention further provides:
It is another object of the present invention to effectively use a used water-insoluble polymer obtained from general-purpose plastic waste materials and convert it to a high value-added product.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the achievement of the above-mentioned object, and as a result, have found that a polymer obtained by introducing a hydrophilic polar group into a water-insoluble polymer obtained from a versatile monomer. By using the dried material and the dried electrolyte as the constituent materials of the battery, we succeeded in creating a battery that has no leakage or evaporation of the electrolytic solution outside the system and has a long storage period before use, and further studies. Again, the present invention has been completed.

That is, the present invention provides (1) a water-added battery comprising a dried water-insoluble polymer having a hydrophilic polar group introduced therein and a dried electrolyte.
When the hydrophilic polar group forms a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group, or a salt. -PO (OH) ₂ groups, which may form a salt-
OPO (OH) ₂ groups, a hydroxyl group which may form a salt, and at least one or more hydrophilic polar groups selected from the group consisting of an amine base which may form a salt. (3) The water-added battery according to the above (1), wherein (3) the hydrophilic polar group accounts for 0.1 to 99 mol% of all monomer units in the water-insoluble polymer. (4) The water-added battery according to (1), wherein the water-insoluble polymer has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. (5) At least one of the aromatic ring and the conjugated diene contained in the water-insoluble polymer is 1 to 100 mol% based on all monomer units in the water-insoluble polymer. The water-added battery according to the above (4), A) a water-added battery comprising a dried product of a used water-insoluble polymer into which a hydrophilic polar group has been introduced and a dried product of an electrolyte; and (7) the hydrophilic polar group forms a salt. A sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group and a -PO (OH) ₂ group which may form a salt , Which may form a salt, -OPO
(OH) ₂ groups, a hydroxyl group which may form a salt, and at least one or more hydrophilic polar groups selected from the group consisting of an amine base which may form a salt. (6) The water-added battery according to (6), wherein (8) the hydrophilic polar group accounts for 0.1 to 99 mol% of all monomer units in the water-insoluble polymer. Water-added battery of (9) water-insoluble polymer,
(6) wherein the main chain and / or the side chain has at least one kind of an aromatic ring and a conjugated diene.
The water-added battery according to (10), wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble polymer is
1 to 1 for all monomer units in the water-insoluble polymer
The water-added battery according to the above (9), which is 100 mol%, and (11) a combination of a dried water-insoluble polymer having a hydrophilic polar group introduced and a dried electrolyte. (12)
When the hydrophilic polar group forms a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group, or a salt. -PO (OH) ₂ groups, which may form a salt-
OPO (OH) ₂ groups, a hydroxyl group which may form a salt, and at least one or more hydrophilic polar groups selected from the group consisting of an amine base which may form a salt. (13) The method for producing a water-added battery according to the above (11), wherein (13) the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble polymer. (11) The method for producing a water-added battery according to (11), wherein (14) the water-insoluble polymer has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. (15) The method for producing a water-added battery according to (11), wherein (15) at least one of an aromatic ring and a conjugated diene contained in the water-insoluble polymer is 1 to 1 with respect to all monomer units in the water-insoluble polymer. 100
(14) The method for producing a water-added battery according to the above (14), wherein (16) a dried product of a used water-insoluble polymer into which a hydrophilic polar group is introduced and a dried product of an electrolyte. (17) wherein the hydrophilic polar group forms a sulfo group which may form a salt, a sulfate group which may form a salt, or a salt. Carboxyl group, amide group, nitro group, -PO (OH) ₂ group which may form a salt, -OPO (OH) ₂ group which may form a salt, (16) The method for producing a water-added battery according to the above (16), which is at least one kind of hydrophilic polar group selected from the group consisting of a good hydroxyl group and an amine base which may form a salt. , (18) all the hydrophilic polar groups in the water-insoluble polymer 0.1 against Roh mer units
The method for producing a water-added battery according to (16), wherein the water-insoluble polymer is 99 mol%.
(1) The main chain and / or the side chain has at least one kind of an aromatic ring and a conjugated diene.
6) The method for producing a water-added battery according to the above, and (20) at least one of an aromatic ring and a conjugated diene contained in the water-insoluble polymer is 1 to 1 with respect to all monomer units in the water-insoluble polymer. (19) The method for producing a water-added battery according to the above (19), wherein the content is 100 mol%.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In order to manufacture a target battery, in the present invention, a dried polymer obtained by introducing a hydrophilic polar group into a water-insoluble polymer is used as one of the raw materials. Specifically, for example, ABS (acrylonitrile-butadiene-styrene) polymer, high impact polystyrene (HIPS), styrene-butadiene elastomer (S
BC), SAN (styrene-acrylonitrile) polymer, polyacrylonitrile polymer (PAN), polyacrylonitrile-butadiene (nitrile rubber), polystyrene (PS), nylon polymer, polyolefin (eg, polyethylene, polypropylene, polyisoprene, etc.) polymer, poly Vinyl chloride (PVC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polysulfone, polyallyl sulfone, polyether sulfone, polythioether sulfone, Polyetherketone, polyetherimide, polyetheretherketone, polyamide (nylon), polyamideimide, polyimide Polyarylate, aromatic polyester, polyurethane, polyvinyl chloride, chlorinated polyether, polychloromethylstyrene, polyacrylate, polymethacrylate, celluloid, various liquid crystal polymers, methacryl polymer (PMMA), amber polymer, terpene polymer , An epoxy polymer, a phenol-formalin polymer, a melamine polymer, and the like. Among these, an aromatic ring or a conjugated diene structure in which a hydrophilic polar group described later is easily introduced,
Those having a main chain and / or a side chain of the water-insoluble polymer are more preferable. The content of the aromatic ring and / or conjugated diene unit in the water-insoluble polymer is desirably about 1 to 100 mol% based on all monomer units in the water-insoluble polymer. The content is preferably about 1% or more in order to avoid a decrease in the number of hydrophilic polar groups introduced into the water-insoluble polymer and a decrease in the absorption effect on the electrolytic solution.

The molecular weight of the water-insoluble polymer material (M
The weight average molecular weight (M) is not particularly limited as w).
In general, w) is about 1,000 to 20,000,000, and more preferably about 10,000 to 1,000,000. When the molecular weight is higher than 1,000, it is possible to avoid the disadvantage that the introduction of the hydrophilic polar group completely dissolves in the electrolyte solution and makes it impossible to maintain the gel state after absorption. When the molecular weight is lower than 20,000,000, introduction of a hydrophilic polar group is facilitated, which is more practical.

[0010] These water-insoluble polymers may be freshly produced virgin granular polymers (virgin pellets), or may be used water-insoluble polymers or waste materials molded for specific applications. There may be. Examples of the waste materials include waste products (semi-finished products) in the production process of resin raw materials and molded products, housings and various component materials already used for electric products and automobiles, or tubes, hoses, and various cushioning materials. And the like. The used water-insoluble polymer refers to a water-insoluble polymer recovered from the above waste materials and the like. The place where the waste material is discharged may be from a factory, a store, a household, or the like. However, a waste collected from a factory, a store, or the like (for example, odd ) Are more desirable because they often have relatively uniform compositions.

The water-insoluble polymer may be an alloy with another polymer, such as a facial dye, a stabilizer,
It may be a waste material or a used water-insoluble polymer containing additives such as a flame retardant, a plasticizer, a filler, a curable adhesive, and other auxiliary agents. Alternatively, it may be a used water-insoluble polymer or a mixture of waste material and virgin material.

The present invention aims at conversion to an electrolyte-absorbing polymer by introducing a hydrophilic polar group into the water-insoluble polymer described above. At this time, the hydrophilic polar group has an effect of increasing the absorbability to the electrolytic solution, while the hydrophobic portion (the main chain, the aromatic ring and the portion where the hydrophilic polar group is not introduced) in the water-insoluble polymer is This has the effect of preventing the polymer from dissolving in various electrolyte solutions.

The hydrophilic polar group includes a polar group such as an acidic group or a basic group. The acidic group or the basic group may form a salt. Specifically, such a hydrophilic polar group forms a salt represented by the formula —SO ₃ M (where M represents a hydrogen atom or a cation such as a metal such as sodium and potassium). An optionally present sulfo group, formula-
A sulfate group which may form a salt represented by OSO ₃ M (where M is as defined above), a compound of the formula —PO (OM ₁ ) (OM
₂ ) or a formula -OPO (OM ₁ ) (OM ₂ ) wherein
M ₁ and M ₂ are the same or different, and are the same as M above. Good phospho group which may form a salt represented by), wherein -OM 3 _(wherein, M ₃ is like hydroxyl group which may form a salt represented by as defined M.), Salts And an acidic group which may be formed. Also, for example, an amino group,
An amine base which may form a salt such as a secondary amino group (for example, methylamino group), a tertiary amino group (for example, dimethylamino group), for example, a quaternary ammonium group (for example, trimethylammonium chloride group), or the like, And an amide group, a nitro group and the like.

A method for introducing a sulfo group and / or a sulfo group forming a salt into the water-insoluble polymer is as follows.
Preferably, the water-insoluble polymer having an aromatic ring is directly reacted with a sulfuric acid such as concentrated sulfuric acid (more preferably about 70% by weight or more), sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid and the like. Alternatively, the polymer is dissolved or dispersed in an organic solvent and reacted with a sulfonating agent to introduce a sulfo group. Subsequently, the polymer is converted to a basic substance (for example, sodium hydroxide or potassium hydroxide, etc.). ), It is possible to convert to a sulfonate. The reaction temperature at the time of sulfo group introduction greatly differs depending on whether or not an organic solvent is used.
To about 200 ° C., preferably about 30 to 120 ° C. When the temperature is about 0 ° C. or higher, the reaction rate becomes sufficiently high, and an electrolytic solution-absorbing polymer having better performance can be obtained. On the other hand, when the temperature is lower than about 200 ° C., the molecular chains in the polymer are hardly cut, and the polymer is hardly dissolved in water or a solvent. The reaction time varies greatly depending on the reaction temperature, but is generally about 1 minute to 40 hours, preferably 5 minutes to 2 hours. Under these conditions, the reaction proceeds more sufficiently and the production efficiency is good.

As a method for introducing a sulfate group which may form a salt, preferably, a sulfate group is first introduced by reacting a water-insoluble polymer having an unsaturated bond with a high-temperature sulfuric acid aqueous solution, and thereafter, By reacting with a basic compound (eg, sodium hydroxide or potassium hydroxide), a sulfate can be obtained. As a method for introducing a carboxyl group which may form a salt, preferably, n-butyllithium is added to a water-insoluble polymer having an aromatic ring, and then the carboxyl group is first reacted with dry ice. A group can be introduced, and then a carboxylic acid salt can be obtained by reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide).

As a method for introducing an amide group, for example, the water-insoluble polymer having a nitrile group is hydrolyzed with a heated concentrated sulfuric acid or a heated alkali such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. Can be obtained. The method for introducing a nitro group is preferably achieved by reacting a water-insoluble polymer having an aromatic ring with fuming nitric acid or a mixture of nitric acid and sulfuric acid. -PO (OH) which may form a salt
_As a method for introducing _two groups, preferably, -PO (OH) ₂ group is first introduced by adding phosphorus trichloride to a water-insoluble polymer having an aromatic ring, followed by hydrolysis, and thereafter, a basic compound is added. (E.g., sodium hydroxide or potassium hydroxide) to form the same salt. -OPO (OH) _{2 which} may form a salt
As a method for introducing a group, preferably, -OPO (OH) ₂ group is first introduced by adding phosphorus trioxide to a water-insoluble polymer having an unsaturated bond, followed by hydrolysis, and thereafter, a basic compound ( (E.g., sodium hydroxide or potassium hydroxide) to give the same salt.

As a method for introducing a hydroxyl group which may form a salt, preferably, a hydroxyl group can be introduced first by reacting a water-insoluble polymer having an unsaturated bond with an aqueous sulfuric acid solution, and then a basic group is added. The salt can be obtained by reacting with a compound (for example, sodium hydroxide or potassium hydroxide). Level 3 and / or
Alternatively, as a method for introducing a quaternary amine base, preferably, a water-insoluble polymer having an aromatic ring is subjected to chloromethylation by a Friedel-Crafts reaction, and then reacted with ammonia or various amine compounds. Tertiary and quaternary amine salts can be introduced as ionic groups.
Introduction of a primary amino group or a secondary amino group, and conversion of these amino groups into salts may be carried out according to a method known per se.

The hydrophilic polar group-introducing agent or basic substance may be a virgin agent, a waste liquid discharged from a factory, or a recycled product. From the viewpoint of effective utilization of resources, it is more preferable that the waste liquid is used as a raw material of the electrolyte absorbing polymer. In addition, only one type of these hydrophilic polar groups may be introduced into the water-insoluble polymer, or two or more types may be introduced. Further, the amount of these hydrophilic polar groups introduced into the water-insoluble polymer is preferably about 0.1 to 99 mol% with respect to all units in the polymer. The above range is preferable in order to prevent the polymer after the introduction of the hydrophilic polar group from being dissolved in water, and to have a good absorbability to the electrolytic solution. The electrolyte is not particularly limited, and for example, sodium hydroxide, sodium chloride, copper chloride, sulfuric acid and the like can be applied to all electrolytes used in factories or laboratories.

The electrolyte-absorbing polymer obtained by the above-described method may be further subjected to a treatment known per se.
According to a preferred embodiment, the reaction product, which is usually a gel, obtained by the above-described hydrophilic polar group introduction reaction is preferably filtered, washed with water, and then dried or dehydrated to obtain various types of excellent electrolysis. A polymer having a liquid absorbing ability is obtained. In addition, the electrolyte absorbing polymer of the present invention,
Needless to say, it may be produced by polymerizing a monomer having the above-mentioned hydrophilic polar group introduced into the main chain and / or side chain according to a means known per se.

Further, the electrolyte-absorbing polymer of the present invention may optionally contain other components, for example, a conventionally known electrolyte-absorbing polymer (for example, a polymer obtained by adding a crosslinkable monomer), a stabilizer, a hygroscopic agent, a curable type. An adhesive or the like may be further added. Regardless of the method, preferably by introducing a hydrophilic polar group into the water-insoluble polymer according to the method described above, it becomes possible to obtain a polymer capable of absorbing various electrolytic solutions at a high concentration.

Examples of the dried electrolyte used in the present invention include various inorganic salts and organic salts, for example, sulfates (alkali metal sulfate, alkaline earth metal sulfate, copper sulfate, etc.), hydrochloride, nitrate, phosphoric acid Salts, carbonates, fluorides, ammonium salts, various amine salts, acetates, formates, and mixtures of at least two or more of these.

Since both a dried polymer and a dried electrolyte in which a hydrophilic polar group is introduced into the water-insoluble polymer described above are contained as constituent materials in a battery,
By adding water, the electrolyte becomes an electrolyte, while the polymer absorbs the electrolyte, resulting in the formation of an electrolyte gel. This allows
For example, if electrodes having different ionization tendencies are present in the same gel, current will flow between the electrodes. That is,
Until water is added, the dried polymer and the dried electrolyte and the electrodes are present, so that the electrolyte does not leak out of the system or evaporate. Also, the electrodes are not corroded. In fact, it can be generated only by adding water when a battery is needed. According to the above technology, it is possible to manufacture a battery that has no leakage or evaporation of the electrolytic solution outside the system and has a long storage period until use.

[0023]

EXAMPLES Here, samples of Examples 1 to 5 and Comparative Example were actually prepared and evaluated as batteries according to the present invention, but the present invention is not limited to these.

Example 1 A commercially available pulverized SAN polymer (styrene; 73 mol%, acrylonitrile; 27 mol%) (classified from 16 to 32 mesh) was heated to 96% by weight with hot sulfuric acid at 100 ° C. for 30 minutes. Reacted. After the reaction,
The gel in the system was filtered with a glass filter, washed with water, and filtered again. This was dried at 115 ° C. for 2 hours using a circulating drier. From the elemental analysis result of sulfur of the obtained dried product,
It was confirmed that sulfonic acid groups accounted for 42 mol% of all monomer units. In addition, it was confirmed from the result of FT-IR measurement that the nitrile group in the polymer was converted to an amide group. Next, the dried product was immersed in a 1% saline solution for 30 minutes, and then the water-absorbing gel was again heated at 115 ° C. for 2 minutes.
Drying was performed for hours.

Example 2 A commercially available ABS polymer (styrene; 65 mol%, acrylonitrile; 25 mol%, butadiene; 10 mol%) was crushed at 90% by weight at 100 ° C. at 90% by weight. The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out with hot sulfuric acid for 30 minutes. From the elemental analysis result of sulfur, it was confirmed that the sulfonic acid group in the product was 48 mol% in all monomer units. In addition, it was confirmed from the result of FT-IR measurement that the nitrile group in the polymer was converted to an amide group. Next, the dried product was immersed in a 1% aqueous solution of copper chloride for 30 minutes, and then the water-absorbing gel was dried again at 115 ° C. for 2 hours.

Example 3 A transparent portion of a used 8 mm video cassette (SAN polymer, styrene;
Mol%, acrylonitrile; 40 mol%)
6-32 mesh) were reacted under the same conditions as in Example 1. From the elemental analysis result of sulfur, it was confirmed that the sulfonic acid group in the product was 37 mol% in all the monomer units. In addition, it was confirmed from the result of FT-IR measurement that the nitrile group in the polymer was converted to an amide group. Next, the dried product was immersed in a 1% aqueous sodium sulfate solution for 30 minutes, and then the water-absorbing gel was again heated to 115 ° C.
For 2 hours.

[Embodiment 4] Used video 8 mm
Black part of cassette (ABS polymer, styrene; 48
Mole%, acrylonitrile; 39 mole%, butadiene;
13 mol%) (16-32 mesh classified material)
At 100 ° C. using waste sulfuric acid recovered from a semiconductor factory (used for cleaning semiconductors: 88% by weight).
Allowed to react for minutes. After completion of the reaction, the gel substance in the system was filtered with a glass filter, and this was neutralized with a sodium hydroxide waste liquid (used for regenerating an ion-exchange polymer) recovered from a semiconductor factory, and then washed with water. Filtered.
This was dried at 115 ° C. for 2 hours using a circulating drier.
From the elemental analysis result of sulfur, it was confirmed that the sulfonic acid group in the product was 40 mol% in all the monomer units. In addition, it was confirmed from the result of FT-IR measurement that the nitrile group in the polymer was converted to an amide group. Next, the dried product was immersed in a 10% aqueous solution of copper chloride for 30 minutes, and then the water-absorbing gel was dried again at 115 ° C. for 2 hours.

Example 5 Instead of immersion in a 10% aqueous copper chloride solution in Example 4, 5% by weight of sodium sulfate powder was mixed with the polymer.

Comparative Example A comparative example of Example 5 to which sodium sulfate was not added was used. A battery was filled with the powder obtained by the above treatment together with zinc and copper electrodes in a container. Next, the electromotive force when water was added to the battery was confirmed by a tester. The results are shown in the table.

[0030]

[Table 1] From the above results, it can be confirmed that the battery according to the present invention has excellent electromotive force.

[0031]

According to the present invention, a battery having no leakage or evaporation of the electrolytic solution to the outside of the system and having a long storage period before use can be manufactured. In addition, since this battery can also be manufactured from used general-purpose polymers and waste liquids (such as waste sulfuric acid), it can lead to effective use of resources and contribute to global environmental conservation.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA031 AB021 AC111 BA001 BB211 BC121 BD171 BG071 BG101 BN151 CC031 CC181 CD001 CF061 CF071 CF161 CG001 CH071 CH091 CK021 CL001 CM041 CN011 CN031 DD036 DD046 DE216 DF0006 016 016 BB02 BB08 BB11 FF01 GG01 HH01 5H025 AA13 BB02 BB11 CC00 CC16 CC18 CC39 MM10

Claims (12)

[Claims] 1. A water-added battery comprising a dried water-insoluble polymer having a hydrophilic polar group introduced therein and a dried electrolyte. 2. The hydrophilic polar group includes a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group,
A salt-forming -PO (OH) ₂ group, a salt-forming -OPO (OH) ₂ group, a salt-forming hydroxyl group, and a salt-forming 2. The water-added battery according to claim 1, wherein the battery is at least one hydrophilic polar group selected from the group consisting of good amine bases. 3. The water-added battery according to claim 1, wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble polymer. 4. The water-added battery according to claim 1, wherein the water-insoluble polymer has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. 5. The method according to claim 1, wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble polymer is 1 to 100 mol% based on all monomer units in the water-insoluble polymer.
The water-added battery according to claim 4, wherein 6. A water-added battery comprising a dried water-insoluble polymer into which a hydrophilic polar group is introduced and a dried electrolyte. 7. A method for producing a water-added battery, comprising combining a dried product of a water-insoluble polymer having a hydrophilic polar group introduced therein and a dried product of an electrolyte. 8. The hydrophilic polar group may be a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group,
A salt-forming -PO (OH) ₂ group, a salt-forming -OPO (OH) ₂ group, a salt-forming hydroxyl group, and a salt-forming 8. The method for producing a water-added battery according to claim 7, wherein at least one kind of hydrophilic polar group selected from the group consisting of good amine bases is used. 9. The method for producing a water-added battery according to claim 7, wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble polymer. 10. The method for producing a water-added battery according to claim 7, wherein the water-insoluble polymer has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. . 11. The method according to claim 1, wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble polymer accounts for 1 to 100 mol% based on all monomer units in the water-insoluble polymer. A method for producing a water-added battery according to claim 10. 12. A method for producing a water-added battery, comprising combining a dried product of a used water-insoluble polymer into which a hydrophilic polar group is introduced and a dried product of an electrolyte.