JP2808822B2 - Manufacturing method of zinc alkaline battery - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a mercury-free technology for zinc-alkaline batteries using zinc as a negative electrode active material, an aqueous alkaline solution as an electrolyte, and manganese dioxide, silver oxide, oxygen, etc. as a positive electrode active material. The present invention provides a method for producing a zinc alkaline battery which is pollution-free and has excellent storage properties and discharge performance.

2. Description of the Related Art About ten years ago, there has been a strong concern that environmental pollution due to mercury in waste batteries has become a concern, and research has been conducted on reducing the amount of mercury in alkaline dry batteries. As a result, with the development of corrosion-resistant zinc alloys and the like, the amount of mercury contained in alkaline dry batteries is currently being reduced to 250 ppm based on the battery weight. However, today, there is a concern about environmental destruction caused by industrial products worldwide, as represented by the problem of ozone depletion due to chlorofluorocarbons, and there is a growing demand for completely eliminating mercury in alkaline dry batteries.

The approach to the technology of mercury-free alkaline batteries was made at the time when alkaline batteries containing mercury were developed, and many patents and Japanese documents have been filed and published on various materials related to zinc alloys, inorganic inhibitors and organic inhibitors. Has been made.

Indium is known as a material having a high hydrogen overvoltage and as an additive to a negative electrode of a secondary battery regardless of a primary battery. Numerous applications and publications have also been made on a method of using metal indium as an alloying additive element and a method of using an indium compound as an inorganic inhibitor.

For example, a method used as an alloy addition element (Japanese Patent Publication No.
-41576), a method using indium oxide and indium hydroxide as an inorganic inhibitor (JP-B-51-3645).
0, JP-A-49-93831, JP-A-49-112125, Proceedings of the 56th Electrification Conference: Publication No. 3G05; page 205), a method of adding indium oxide and cadmium oxide in a complex manner (Japanese Unexamined Patent Publication No.
−105466). Examples of addition as an additive to a negative electrode of a secondary battery (JP-A-61-96666, JP-A-61-10161)
955).

Further, as an organic inhibitor, diethanolamine, oleic acid, lauryl ether, amine, or ethylene oxide polymer has been proposed. Further, as an example of the composite addition of an inorganic inhibitor and an organic inhibitor, it has been proposed to compositely add indium hydroxide and an ethoxyfluoroalcohol polyfluorinated compound (Japanese Patent Laid-Open No. 2-79367).

Problems to be Solved by the Invention In a battery in which pure zinc is used as the active material of the negative electrode without mercury silver, a corrosion reaction accompanied by hydrogen generation of zinc occurs violently,
There is a problem that the internal pressure of the battery is increased and the electrolytic solution is pushed to the outside, and the resistance to liquid leakage is reduced.

In a partially discharged battery, the hydrogen generation rate of the zinc negative electrode is accelerated, and the leak resistance is further reduced. These are attributable to the fact that by increasing the hydrogen overpotential on the zinc surface, mercury that suppressed the corrosion reaction disappeared.

If the battery is made of mercury-free zinc alloy containing indium, aluminum and lead, for which the effect of corrosion resistance has been proved by reducing the mercury of the zinc negative electrode, it is not possible to secure the liquid leakage resistance of the battery after partial discharge.

Also, a battery formed by adding commercially available indium oxide or indium hydroxide to a gel negative electrode using pure zinc powder as an active material of the negative electrode is practically the same as a battery formed only of the above-described corrosion-resistant alloy. Battery leakage resistance cannot be ensured.

Furthermore, even if a battery is formed by adding an amine-based surfactant that is effective in reducing mercury as an organic inhibitor to a gel negative electrode using a corrosion-resistant zinc alloy containing indium, aluminum, and lead as an active material of the negative electrode, The liquid resistance of the battery after the partial discharge cannot be ensured.

As described above, each of the conventional sheaths does not have a perfect corrosion inhibiting effect, and cannot be said to be practical at least for sealed batteries.

In realizing the realization of mercury-free alkaline batteries, the present inventors have proposed a corrosion-resistant zinc alloy, a combined effect of an inorganic inhibitor and an organic inhibitor,
The materials that can exert the best effect and their optimal conditions and concentrations were studied.

Means for Solving the Problems First, the configuration of the present invention regarding the combined use of a corrosion-resistant zinc alloy and an inorganic inhibitor will be described. The gelled negative electrode in the present invention is an active material composed of a corrosion-resistant zinc alloy powder obtained by adding an appropriate amount of indium, lead, bismuth, calcium, and aluminum in a proper combination and to zinc, and an inorganic inhibitor. It is composed of a gel alkaline electrolyte in which indium sulfide powder having appropriate properties is dispersed at an appropriate concentration.

The above-mentioned corrosion-resistant zinc alloy contains 0.01 to 1 wt% of indium.
%, One or two of lead and bismuth in total 0.005
0.5% by weight of zinc alloy or indium
1 to 1 wt%, one or two types of lead and bismuth in total
It is a zinc alloy containing 0.005 to 0.5 wt% and one or two kinds of calcium and aluminum in total of 0.005 to 0.2 wt%. Also, the appropriate addition amount of the above indium sulfide,
0.005 to 0.5 wt% based on the zinc alloy.

Next, the configuration of the present invention regarding the combined use of a zinc alloy, an inorganic inhibitor and an organic inhibitor will be described.
The gelled negative electrode of the present invention is obtained by mixing indium, lead, bismuth, calcium, and aluminum in a proper combination with a corrosion-resistant zinc alloy powder to which a proper amount is added, and an indium sulfide powder having a proper property at a proper concentration. Disperse in
Further, it comprises a gel-like alkaline electrolyte to which an appropriate amount of a surfactant having polyethylene oxide as a hydrophilic part and having a fluorinated alkyl group as a lipophilic part is added as an organic inhibitor.

The above surfactants are 0.001-0.1wt% based on zinc alloy
It is effective to include it in the alkaline electrolyte.

The corrosion-resistant zinc alloy contains 0.01 to 1 wt% of indium,
0.005 to 0.5 in total of one or two of lead and bismuth
wt% containing zinc alloy or indium 0.01-1w
t%, one or two of lead and bismuth in total 0.005
It is a zinc alloy containing about 0.5 wt% and one or two kinds of calcium and aluminum in total of 0.005 to 0.2 wt%. Further, an appropriate addition amount of indium sulfide is 0.005 to 0.5% by weight based on the zinc alloy.

It is preferable to use indium sulfide synthesized by reacting with hydrogen sulfide in an aqueous solution in which an indium salt such as indium chloride is dissolved.

The indium sulfide has a particle diameter of 0.5 to 8 μm.
It is effective to use a powder composed of a powder containing 60% by weight or more, preferably 70% by weight or more of the total amount of particles in the range described above.

Also, the surfactant is represented by the following structural formula _{(X) -C n F 2n -} (Y) - (CH 2 CH 2 O) m - (Z) X: -H or -F Y: -CONH- or -SO ₂ NR- ｛R is an alkyl group｝ Z: —CH ₃ , —PO ₃ W ₂ or —SO ₃ W ｛W is an alkali metal｝ n: 4 to 10 m: 20 to 100 or (X) —C _n F _{2n - (CH 2 CH 2)} - (CH 2 CH 2 O) m - (Z) X: -H or _{-F Z: -CH 3, -PO 3} W 2 or -SO ₃ W {W is an alkali metal} n: 4 to 10 m: 40 to 100 are effective.

The corrosion-resistant zinc alloy of the present invention, the inorganic inhibitor, the material of the organic inhibitor, and the combination and composition in the composite thereof have been found as a result of intensive research so that each of them can exert the composite effect to the maximum. . Although the elucidation of its mechanism of action is unclear at present,
It is inferred as follows.

First, the functions and effects of the additive elements of the alloy, the inorganic inhibitor, and the organic inhibitor alone are as follows.

Among the additional elements in the alloy, indium, lead and bismuth have a high hydrogen overpotential of these elements themselves, and have an effect of being added to zinc to increase the hydrogen overpotential on the surface. If they are added uniformly into the alloy, this effect is retained even if a new zinc surface appears due to the discharge, since the added elements are present at every depth of the powder. Also, aluminum and calcium have the effect of spheroidizing zinc particles, and reduce the amount of corrosion per unit weight of zinc powder to reduce the true specific surface area.

When indium sulfide is dispersed as a powder in a gel alkaline electrolyte in the coexistence state with a zinc alloy, part of it is electrodeposited as metal indium on the zinc alloy surface by the principle of displacement plating, increasing the hydrogen overvoltage on the surface . The remaining portion remains as a solid in the electrolytic solution, and when a new zinc alloy surface appears due to discharge, it is electrodeposited on the new surface to exhibit an anticorrosion effect. The working efficiency of sulfides after discharge is higher than that of hydroxides because of their poor solubility.

When a surfactant coexists with a zinc alloy in a gelled alkaline electrolyte, it chemically adsorbs on the surface of the zinc alloy based on the principle of metallic soap to form a hydrophobic monolayer and exhibits an anticorrosion effect. In particular, surfactants having polyethylene oxide in the hydrophilic part have high solubility as micelles in the alkaline electrolyte, and when introduced into the electrolyte, transfer to the zinc alloy surface,
The anticorrosion effect is high because adsorption occurs quickly. In addition, if the fluorinated alkyl group is held in the lipophilic portion, when it is adsorbed on the surface of the zinc alloy, it has high electrical insulation, effectively alienates the electron transfer of the corrosion reaction, and its effect is strong because of its strong alkali resistance. continue.

Next, the combined effect of the zinc alloy and indium sulfide will be described. Since indium sulfide deposits and acts on the surface of the zinc alloy, it must be deposited smoothly and uniformly. Since significant hydrogen gas is generated on the surface of the zinc alloy having no corrosion resistance, indium electrodeposition is alienated, and the state of electrodeposition becomes non-uniform. However, the generation of hydrogen gas is suppressed on the zinc alloy surface with good corrosion resistance,
Since electrodeposition occurs smoothly and uniformly, a combined effect can be obtained. This is the same in the state after the partial discharge. In the case of sulfide, electrodeposition is slow due to its poor solubility, and the effect is larger than that of hydroxide. However, on the other hand, it is easily affected by the corrosion resistance of the zinc alloy.

Next, the combined effect of the corrosion-resistant zinc alloy, indium sulfide and the surfactant will be described. The mechanism of action of indium sulfide is as described above. However, if all of them are electrodeposited, there will be no action after partial discharge. It is considered that the surfactant acts not only on its own, but also on suppressing unnecessary indium electrodeposition and securing an amount of action after partial discharge.

Next, the meaning of limiting the properties of indium sulfide will be described. The finer the particle size, the better the dispersibility in the gel electrolyte, and the uniform effect can be exerted on the gel negative electrode. However, if it is too fine, it will be melted at once, and it will not be possible to secure a sufficient amount to act after partial discharge.

Next, the meaning of limiting the method for synthesizing indium sulfide will be described. The properties of indium sulfide differ depending on the synthesis method. In the dry method, non-stoichiometric indium sulfide is formed and the effect is unstable, but indium sulfide synthesized by the wet method has a stoichiometric and excellent anticorrosive action of excellent crystallinity and particle shape.

Next, the meaning of limiting the molecular structure of the surfactant will be described. Surfactant having polyethylene oxide in the hydrophilic part has high solubility as a micelle in the alkaline electrolyte, and when injected into the electrolyte, migration and adsorption to the zinc alloy surface occur quickly, resulting in high anticorrosion effect . Also,
If the terminal of the polyethylene oxide is a hydroxyl group, that is, an alcohol, the terminal is liable to be hydrolyzed in an alkaline electrolytic solution. Therefore, the terminal group is preferably a methyl group, a sulfone group, or a phosphate group having strong alkali resistance. When a fluorinated alkyl group is held in the lipophilic portion, when it is adsorbed on the surface of the zinc alloy, it has a high electrical insulation property and effectively eliminates the electron transfer of the corrosion reaction. If the bonding group between the hydrophilic part and the lipophilic part is a hydrophilic amide group or a sulfoamide group than the water-repellent alkyl group, chemical adsorption with zinc occurs at this part, and high corrosion protection appears.

Examples Hereinafter, details and effects of the present invention will be described with reference to examples.

First, the method of preparing a corrosion-resistant zinc alloy, the method of synthesizing indium sulfide, the structure of the LR6 type alkaline manganese battery used in the examples, and the method of comparative evaluation of leakage resistance are described to show the effects of the production method of the present invention. I do.

Corrosion-resistant zinc alloy powder melts 99.97% pure zinc, adds a predetermined amount of added elements, and uniformly dissolves it.
The powder was prepared by a so-called atomizing method in which powder was sprayed with compressed air, and this was classified by a sieve and adjusted to a particle size range of 45 to 150 mesh. For indium sulfide, a saturated amount of indium chloride or sulfate is added to an aqueous acetic acid solution,
Hydrogen sulfide was reacted while stirring the aqueous solution with a screw stirrer. The precipitate is washed on a filter having a coarseness of 0.5μ with ion-exchanged water until the pH of the solution becomes 6, and vacuum is pulled from under the filter to separate water, and vacuum dried at 60 ° C. And synthesized.

The gelled negative electrode was prepared as follows. First, 3% by weight of sodium polyacrylate and 1% by weight of carboxymethylcellulose are added to a 40% by weight potassium hydroxide solution (containing 3% by weight of ZnO) to gel. Next, a predetermined amount of indium sulfide powder is gradually added and dissolved while stirring the gel electrolyte, and the mixture is aged for 2 to 3 hours. Further, zinc alloy powder was added in a weight ratio twice that of the gel electrolyte and mixed. In addition, when adding the organic inhibitor, a step of adding a predetermined amount of this to the gel electrolyte and aging it for 2 to 3 hours before adding indium sulfide in the above-mentioned adjustment step was added.

FIG. 1 shows the alkaline manganese battery LR6 used in this embodiment.
FIG. In FIG. 1, 1 is a positive electrode mixture,
2 is a gelled negative electrode characterized by the present invention, 3 is a separator, and 4 is a current collector of the gelled negative electrode. 5 is a positive electrode terminal cap, 6 is a metal case, 7 is a battery outer can, 8 is a case 6
A resin sealing body made of polyethylene for closing the opening of No. 9 is a bottom plate forming a negative electrode terminal.

The method of comparative evaluation of the leak resistance is as follows: 100 alkaline manganese batteries as shown in Fig. 1 were prototyped at a time, and partial discharge was performed to a depth of 20% of the theoretical capacity at a constant current of 1A, which is the most severe condition for LR6 The number of batteries that leaked after storage at 60 ° C. was evaluated as a leak index (%). 60 ° C under these severe conditions
It is practical if the leak index is 0% after 30 days of storage,
It is desirable that the performance relating to reliability such as liquid leakage resistance can be maintained for as long as possible.

Example 1 The present invention in the case where a zinc alloy and an inorganic inhibitor are combined is described.

First, zinc alloys were examined in advance by changing the composition of various additive elements in various ways. As a result, a zinc alloy containing indium as an essential alloy component and further containing lead and bismuth individually or in combination, or indium as an essential component, and lead and bismuth each alone or in combination with calcium It has been found that a zinc alloy containing aluminum alone or in combination with aluminum is good alone. Table 1 shows the best alloy composition group among them.

Table 2 shows the results of a liquid leakage test after storage at 60 ° C. for 60 days for batteries prepared by changing the amount of indium sulfide added to the various zinc alloys shown in Table 1 above.

As shown in Table 2, even a zinc alloy having excellent corrosion resistance cannot secure a very practical liquid leakage resistance by itself. However, it is understood that leakage resistance can be secured by adding an appropriate amount of indium sulfide. The addition amount of indium sulfide is preferably in the range of 0.005 to 0.5 wt% for each zinc alloy.

In Table 3, the amount of indium sulfide added was fixed at 0.1 wt%.
60 ℃ of battery made by changing the amount of alloying element added
The results of the liquid leakage test after storage for 60 days are shown.

From Table 3, the amount of indium added to the zinc alloy is from 0.01 to
1 wt%, lead and bismuth each alone or in total 0.005-0.5 wt%, or calcium and aluminum each alone or in total 0.005-0.2 wt%
Is suitable.

In this embodiment, indium sulfide synthesized by reacting an aqueous solution thereof with hydrogen sulfide using a sulfate as a starting material is used. However, an effect can be obtained by using indium sulfide using a chloride or a nitrate as a starting material. The degree of the effect was higher in the order of those using chloride as a starting material, those using sulfate as a starting material, and those using nitrate as a starting material.

Example 2 The present invention relating to the limitation of starting materials in the synthesis of indium sulfide when a zinc alloy and an inorganic inhibitor are combined is described.

Table 4 shows the results of a liquid leakage test after storage at 60 ° C. for 60 days of a battery in which indium sulfide having a different starting material was added to each zinc alloy at 0.1 wt%.

From Table 4, it can be seen that nitrates synthesized in the presence of chloride ions are suitable. By the way, even when nitrate was used as the starting material, the leak index was 0% at 45 days at 60 ° C.
Although it is at a sufficiently practicable level, a battery using a chloride or a sulfate as a starting material may not leak until 60 ° C. and 75 days.

Example 3 An example of limiting the particle size range of indium sulfide in the case where a zinc alloy and an inorganic inhibitor are combined will be described.

Table 5 shows the results of a liquid leakage test at 60 ° C. for 60 days after adding 0.1 wt% of indium sulfide having different particle size distributions to each zinc alloy.

According to Table 5, 60% by weight of particles having a particle diameter in the range of 0.5 to 8 μm.
(Because the substance remaining on the filter having a roughness of 0.5 μm in the synthetic washing step is used, the remaining particles are particles of 8 μm or more).
If those particles contain 70 wt% or more, there is a case that the liquid does not leak even at 75 days at 60 ° C.

As the indium sulfide having a different particle size distribution used in this example, a nitrate was used as a starting material, and those having a large particle diameter were classified and adjusted by a wet sedimentation method.

Example 4 An example in which a zinc alloy is combined with an inorganic inhibitor and an organic inhibitor will be described.

Table 6 shows that the amount of indium sulfide added to each zinc alloy was fixed at the optimal 0.1 wt%, and the amount of the surfactant, which is an organic inhibitor, was changed. The results of the liquid leakage test are shown.

From this, the amount of surfactant added was 0.00 for each zinc alloy.
It turns out that 1 to 0.1 wt% is appropriate.

Even when an organic inhibitor is added, the composition of the zinc alloy is 0.01 to 1 wt% of indium, and lead and bismuth are used alone or in a total of 0.005 to 0.5 in total, similarly to the case where the zinc alloy and the inorganic inhibitor are added in combination. wt
% Or calcium and aluminum alone or in a total amount of 0.005 to 0.2 wt% was appropriate.

Surfactant used in Example 4 the following structural formula _{(X) -C n F 2n -} (Y) - (CH 2 CH 2 O) m - (Z) X: -H Y: -CONH- Z: —CH ₃ , n: 9, m: 60 were used.

Following structural formula _{(X) -C n F 2n -} (Y) - (CH 2 CH 2 O) m - (Z) X: -H or -F Y: -CONH- or -SO ₂ NR- {R is Alkyl group｝ Z: —CH ₃ , —PO ₃ W ₂ or —SO ₃ W ｛W is an alkali metal｝ n: 4 to 10 m: 20 to 100 or (X) —C ₂ F _2n — (CH ₂ CH _{2) - (CH 2 CH 2} O) m - (Z) X: -H or _{-F Z: -CH 3, -PO 3} W 2 or -SO ₃ W {W is an alkali metal} n: 4 to 10 m : 40 to 100, a similar or better effect can be obtained. In addition, among the above surfactants, a phosphoric acid-based surfactant may be a mixture of primary and secondary phosphates.

Indium sulfide is a powder containing, as a starting material, a sulfate and having a particle diameter of at least 80 wt% in the range of 0.5 to 8 μm, which is the same as that shown in Examples 2, 3 and 4. It has been confirmed that sufficient starting material and indium sulfide having the same properties can provide sufficient or higher leakage resistance.

By the way, in all the embodiments, the effect of the present invention has been explained by using a non-melted zinc alloy. However, the effect is sufficient even when the amount of added mercury is extremely low, such as several ppm to several tens of PPM.

As described above, according to the present invention, in a zinc alkaline battery, a zinc alloy having an appropriate composition in a gel alkaline electrolyte and indium sulfide having appropriate physical properties by an appropriate synthesis method are provided. By adding, even with mercury-free, it is possible to suppress and increase the internal pressure of the battery due to gas generation accompanying the corrosion of zinc, and to obtain and improve the anti-leakage property of the battery more than expected. Then, by adding an appropriate amount of an organic inhibitor having an appropriate structural formula, a pollution-free zinc-alkali battery having even better storability can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of an alkaline manganese battery according to an embodiment of the present invention. 1 ... positive electrode mixture, 2 ... gelled negative electrode, 3 ... separator

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C23F 11/18 C23F 11/18 H01M 4/06 H01M 4/06 U 4/12 4/12 E 4/62 4/62 C ( 72) Inventor Sachiko Sugihara 1006 Kazuma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) H01M 6/06 H01M 4/06-4/12 H01M 4/62 C23F 11/10

Claims (12)

(57) [Claims] In the preparation of a gelled negative electrode in which zinc alloy powder is mixed and dispersed in a gelled alkaline electrolyte, indium,
Using a zinc alloy containing at least one of a group of lead, bismuth, calcium and aluminum as an active material,
A method for producing a zinc-alkaline battery, characterized in that the alkaline electrolyte contains indium sulfide in an amount of 0.005 to 0.5% by weight based on the zinc alloy. 2. A negative electrode active material comprising a zinc alloy containing 0.01 to 1% by weight of indium and one or two types of lead and bismuth in total of 0.005 to 0.5% by weight. The method for producing a zinc alkaline battery according to the above item. 3. An indium content of 0.01 to 1 wt%, a total of 0.005 to 0.5 wt% of one or two of lead and bismuth, and a total of 0.005 to 0.5 wt% of one or two of calcium and aluminum.
The method for producing a zinc alkaline battery according to claim 1, wherein a zinc alloy containing 5 to 0.2 wt% is used as a negative electrode active material. 4. The zinc alkali according to claim 1, wherein the indium sulfide is indium sulfide synthesized by adding indium chloride or sulfate to an aqueous acetic acid solution and reacting with hydrogen sulfide in the aqueous solution. Battery manufacturing method. 5. The method according to claim 1, wherein the synthesized indium sulfide contains particles having a particle size of 0.5 to 8 μm in a total amount of 60 wt% or more. 6. A method for preparing a gelled negative electrode in which a zinc alloy powder is mixed and dispersed in a gelled alkaline electrolyte, wherein indium,
Using a zinc alloy containing at least one of a group of lead, bismuth, calcium and aluminum as an active material,
The alkaline electrolyte contains 0.005 to 0.5 wt% of indium sulfide based on the zinc alloy, and further contains 0.001 to 0.1 wt% of a surfactant having a polyethylene oxide in a hydrophilic part based on the zinc alloy. A method for producing a zinc alkaline battery, comprising: 7. A negative electrode active material comprising a zinc alloy containing 0.01 to 1% by weight of indium and 0.005 to 0.5% by weight of a total of one or two of lead and bismuth. The method for producing a zinc alkaline battery according to the above item. 8. Indium 0.01 to 1% by weight, one or two kinds of lead and bismuth in a total of 0.005 to 0.5% by weight, calcium and aluminum one or two in a total of 0.005%.
7. The method for producing a zinc alkaline battery according to claim 6, wherein a zinc alloy containing about 0.2 wt% is used as a negative electrode active material. 9. The zinc alkali according to claim 6, wherein the indium sulfide is indium sulfide synthesized by adding indium chloride or sulfate to an aqueous acetic acid solution and reacting with hydrogen sulfide in the aqueous solution. Battery manufacturing method. 10. The method according to claim 6, wherein the synthesized indium sulfide contains particles having a particle diameter of 0.5 to 8 μm in a total amount of 60 wt% or more. 11. surfactant having polyethylene oxide in the hydrophilic portion represented by the following structural formula _{(X) -C n F 2n -} (Y) - (CH 2 CH 2 O) m - (Z) X: -H or -F Y: -CONH- or -SO ₂ NR- ｛R is an alkyl group｝ Z: -CH ₃ , -PO ₃ W ₂ or -SO ₃ W ｛W is an alkali metal｝ n: 4 to 10 m: 20 to 7. The method for producing a zinc alkaline battery according to claim 6, represented by 100. 12. A surfactant having polyethylene oxide in a hydrophilic portion is represented by the following structural formula (X) —C ₂ F _2n — (CH ₂ CH ₂ ) — (CH ₂ CH ₂ O) _m — (Z) X: -H or _{-F Z: -CH 3, -PO 3} W 2 or -SO ₃ W {W is an alkali metal} n: 4~10 m: the claims represented by 40 to 100 range described paragraph 6 Manufacturing method of zinc alkaline battery.