JP2013246958A - Alkaline dry battery - Google Patents
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- JP2013246958A JP2013246958A JP2012119675A JP2012119675A JP2013246958A JP 2013246958 A JP2013246958 A JP 2013246958A JP 2012119675 A JP2012119675 A JP 2012119675A JP 2012119675 A JP2012119675 A JP 2012119675A JP 2013246958 A JP2013246958 A JP 2013246958A
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- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052729 chemical element Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 229910052742 iron Inorganic materials 0.000 description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
本発明はアルカリ乾電池、特にその導電性被膜に関する。 The present invention relates to an alkaline dry battery, and particularly to a conductive film thereof.
従来より、アルカリ乾電池では、正極活物質としての二酸化マンガンおよび導電剤としての黒鉛を含む正極を収納する電池ケースの内面に、その内面の導電性を上げることによって内部抵抗を低減するために、黒鉛等の炭素系材料を含む導電性被膜が形成されている（例えば、特許文献１）。 Conventionally, in an alkaline battery, in order to reduce the internal resistance by increasing the conductivity of the inner surface of a battery case containing a positive electrode containing manganese dioxide as a positive electrode active material and graphite as a conductive agent, A conductive film containing a carbon-based material such as is formed (for example, Patent Document 1).
一方、通常、電池ケースは鉄製であり、その表面に鉄の腐食を防止するためにニッケルメッキが施されている。しかし、電池ケースの加工時にニッケルメッキの微細なクラックが生じ、母材の鉄が露出する場合がある。このような電池ケースを用いた電池では、二酸化マンガンと鉄との間に局部電池が構成されて、母材の鉄が腐食し易くなる。そして、鉄の腐食が進行すると、電池ケースと正極との接触抵抗が増大し、保存後の強負荷放電性能が低下するという問題がある。 On the other hand, the battery case is usually made of iron, and the surface thereof is nickel-plated to prevent iron corrosion. However, when the battery case is processed, fine cracks in the nickel plating may occur, and the base iron may be exposed. In a battery using such a battery case, a local battery is formed between manganese dioxide and iron, and the base iron is easily corroded. And when corrosion of iron advances, there exists a problem that the contact resistance of a battery case and a positive electrode will increase, and the heavy load discharge performance after a storage will fall.
このような電池ケースの腐食の発生を抑制する方法としては、正極中の黒鉛の含有量を増やすことが考えられる。電池ケース内面と二酸化マンガンが接触する確率が低下し、錆の発生が抑制され、保存後の強負荷放電性能が改善されるが、正極中の二酸化マンガンの量が減少するために、軽負荷放電性能が低下してしまう。 As a method for suppressing the occurrence of such corrosion of the battery case, it is conceivable to increase the content of graphite in the positive electrode. The probability of contact between the inner surface of the battery case and manganese dioxide is reduced, the generation of rust is suppressed, and the heavy load discharge performance after storage is improved, but the amount of manganese dioxide in the positive electrode is reduced, so light load discharge Performance will be degraded.
さらに、ニッケルメッキを施した電池ケースの内面に黒鉛を含む導電性被膜を形成したとしても、塗膜によりニッケルメッキに生じた微細なクラックを完全に覆うことは困難である。 Furthermore, even if a conductive film containing graphite is formed on the inner surface of a nickel-plated battery case, it is difficult to completely cover fine cracks generated in the nickel plating by the coating film.
電池ケースの錆の発生を抑制する別の方法としては、二酸化マンガンの酸化力を弱める方法があるが、二酸化マンガンの活性度が低下し、強負荷放電性能が低下してしまう。 As another method for suppressing the occurrence of rust in the battery case, there is a method of weakening the oxidizing power of manganese dioxide, but the activity of manganese dioxide is lowered and the heavy load discharge performance is lowered.
そこで、本発明は、上記の問題を解決するものであり、電池ケースの腐食を抑制することにより保存後の放電性能に優れたアルカリ乾電池を提供することを目的とする。 Therefore, the present invention solves the above-described problems, and an object of the present invention is to provide an alkaline dry battery excellent in discharge performance after storage by suppressing corrosion of the battery case.
上記目的を達成するために本発明は、ニッケルメッキ鋼板からなる電池ケースの内表面に形成された炭素系材料を含む導電性被膜と、前記導電性被膜を介して前記電池ケース内に配置された中空円筒状の正極と、前記正極の中空部にセパレータを介して配置された負極とを備えたアルカリ乾電池において、前記導電性被膜が、添加物として、カルシウム、ビスマス、ストロンチウム、及びマグネシウムからなる群から選択された少なくとも１種類の元素を含む化合物、またはリン酸塩を含ませた構成にしている。 In order to achieve the above object, the present invention provides a conductive film containing a carbon-based material formed on the inner surface of a battery case made of a nickel-plated steel sheet, and is disposed in the battery case via the conductive film. In an alkaline dry battery comprising a hollow cylindrical positive electrode and a negative electrode disposed in a hollow part of the positive electrode via a separator, the conductive coating is a group consisting of calcium, bismuth, strontium, and magnesium as additives A compound containing at least one element selected from the above, or a phosphate.
本発明によれば、電池ケースの母材である鉄の腐食を防止することにより、保存性能に優れたアルカリ乾電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the alkaline dry battery excellent in the preservation | save performance can be provided by preventing the corrosion of iron which is a base material of a battery case.
本発明によれば、ニッケルメッキ鋼板からなる電池ケースの内表面に形成された炭素系材料を含む導電性被膜と、前記導電性被膜を介して前記電池ケース内に配置された中空円筒状の正極と、前記正極の中空部にセパレータを介して配置された負極とを備えたアルカリ乾電池において、前記導電性被膜が、添加物として、カルシウム、ビスマス、ストロンチウム、及びマグネシウムからなる群から選択された少なくとも１種類の元素を含む化合物、またはリン酸塩を含ませることによって、電池ケースの腐食を抑制して保存後の放電性能に優れるという効果を奏するものである。 According to the present invention, a conductive coating containing a carbon-based material formed on the inner surface of a battery case made of a nickel-plated steel plate, and a hollow cylindrical positive electrode disposed in the battery case via the conductive coating And an alkaline dry battery comprising a negative electrode disposed in a hollow portion of the positive electrode via a separator, wherein the conductive coating is at least selected from the group consisting of calcium, bismuth, strontium, and magnesium as an additive By including a compound containing one kind of element or a phosphate, corrosion of the battery case is suppressed and the discharge performance after storage is excellent.
一般に有底円筒形の電池ケースは鉄製であり、その内面には鉄の腐食を防止するために、ニッケルメッキが施されている。本発明は、このニッケルメッキが施された電池ケースの内面に添加物を含む導電性被膜を形成することにより、電池ケースの内面に施されたニッケルメッキの微細なクラックにより生じる鉄の腐食を抑制するものである。 In general, a bottomed cylindrical battery case is made of iron, and its inner surface is nickel-plated to prevent iron corrosion. The present invention suppresses iron corrosion caused by minute cracks in the nickel plating applied to the inner surface of the battery case by forming a conductive film containing an additive on the inner surface of the nickel plated battery case. To do.
二酸化マンガンと鉄との間に局部電池が構成されて鉄が腐食された際に、即座に上記添加物と反応することで複合酸化物の被膜が形成される。この被膜が鉄の露出面を覆うことにより、電池ケースの母材である鉄の腐食を抑制することができると考えられる。 When a local battery is formed between manganese dioxide and iron and the iron is corroded, the composite oxide film is formed by immediately reacting with the additive. It is considered that corrosion of iron, which is the base material of the battery case, can be suppressed by covering this exposed surface of iron.
このように錆の発生が抑制されることにより、電池ケースと、電池ケースに収納される正極活物質を含む正極との間の接触抵抗の増大を抑制することができる。このように正極の集電効果が低下しないため、保存後の放電性能が向上し、特に保存後の強負荷放電性能が大幅に向上する。さらに、この集電効果の改善により、正極中の正極活物質の量を増やし、黒鉛の量を低減することができるため、軽負荷放電性能の向上も可能となる。 Thus, by suppressing generation | occurrence | production of rust, the increase in the contact resistance between a battery case and the positive electrode containing the positive electrode active material accommodated in a battery case can be suppressed. Thus, since the current collecting effect of the positive electrode does not decrease, the discharge performance after storage is improved, and particularly the heavy load discharge performance after storage is greatly improved. Furthermore, the improvement in the current collecting effect can increase the amount of the positive electrode active material in the positive electrode and reduce the amount of graphite, so that the light load discharge performance can be improved.
この導電性被膜中の添加物の含有量は、炭素系材料に対して０．５〜２０質量％であることが好ましい。０．５質量％以上で、充分な防食効果が得られる。一方、２０質量％以上の添加は、添加量の増大に見合う効果は得られにくい。 The content of the additive in the conductive film is preferably 0.5 to 20% by mass with respect to the carbon-based material. A sufficient anticorrosive effect can be obtained at 0.5% by mass or more. On the other hand, the addition of 20% by mass or more is difficult to obtain an effect commensurate with the increase of the addition amount.
前記カルシウムを含む化合物としては、Ｃａ（ＯＨ）２、ＣａＯなどが挙げられる。
前記ビスマスを含む化合物としては、Ｂｉ２Ｏ３、Ｂｉ（ＯＨ）２などが挙げられる。
前記ストロンチウムを含む酸化物としては、Ｓｒ（ＯＨ）２・８Ｈ２Ｏ、ＳｒＯなどが挙げられる。
前記マグネシウムを含む化合物としては、Ｍｇ（ＯＨ）２、ＭｇＯなどが挙げられる。
前記リン酸塩としては、ＫＨ２ＰＯ４、Ｋ３ＰＯ４などが挙げられる。
Examples of the compound containing calcium include Ca (OH) 2 and CaO.
Examples of the compound containing bismuth include Bi 2 O 3 and Bi (OH) 2 .
Examples of the oxide containing strontium include Sr (OH) 2 .8H 2 O, SrO, and the like.
Examples of the compound containing magnesium include Mg (OH) 2 and MgO.
Examples of the phosphate include KH 2 PO 4 and K 3 PO 4 .
前記炭素系材料としては、黒鉛、カーボンブラックまたは炭素繊維を用いるのが好ましい。例えば黒鉛とカーボンブラックを併用し、それらの配合比率（質量比）を、６０〜７５：４０〜２５とすることによって、導電性被膜自体の電気抵抗の増加を抑制することができる。 As the carbon material, graphite, carbon black or carbon fiber is preferably used. For example, when graphite and carbon black are used in combination and the blending ratio (mass ratio) thereof is set to 60 to 75:40 to 25, an increase in electrical resistance of the conductive coating itself can be suppressed.
本発明の導電性被膜は、例えば、次のような方法により得られる。炭素系材料、バインダー、溶剤、添加物を混合し、被膜用混合物を得る。このとき、炭素系材料に対して添加物を０．５〜２０質量％含むことが好ましい。また、炭素系材料、バインダー、および溶剤の混合質量比は、２５〜３５：５〜１０：７０〜５５であるのが好ましい。 The conductive film of the present invention can be obtained, for example, by the following method. A carbon-based material, a binder, a solvent, and additives are mixed to obtain a coating mixture. At this time, it is preferable to contain 0.5-20 mass% of additives with respect to carbonaceous material. Moreover, it is preferable that the mixing mass ratio of a carbonaceous material, a binder, and a solvent is 25-35: 5-10: 70-55.
本発明の導電性被膜は、ニッケルメッキを施した鉄製の電池ケースの内面にこの被膜用混合物を塗布した後、乾燥して、溶剤を蒸発させる。このようにして、電池ケースの内面に添加物および炭素系材料を含む導電性被膜を形成する。 The conductive coating of the present invention is applied to the inner surface of a nickel-plated iron battery case and then dried to evaporate the solvent. In this way, a conductive film containing an additive and a carbon-based material is formed on the inner surface of the battery case.
以下、本発明の実施例を詳細に説明する。以下に示す手順で、図１に示す構造のアルカリ乾電池を作製した。図１は、アルカリ乾電池の一部を断面とした正面図である。 Hereinafter, embodiments of the present invention will be described in detail. The alkaline dry battery having the structure shown in FIG. 1 was produced by the following procedure. FIG. 1 is a front view of a cross section of a part of an alkaline battery.
《実施例１〜５および比較例１》
（１）電池ケース内面における導電性被膜の形成
黒鉛、カーボンブラック、バインダーとしてＰＶＢ（ポリビニルブチラール）、溶剤としてメチルエチルケトン、および添加物としてＣａ（ＯＨ）２を混合し、被膜用混合物を得た。このとき、炭素系材料に対してＣａ（ＯＨ）２の含有量が表１に示す割合となるように、Ｃａ（ＯＨ）２の添加量を種々に変えた。なお、黒鉛、カーボンブラック、バインダー、および溶剤の混合質量比は、１８：８：４：７０とした。
<< Examples 1 to 5 and Comparative Example 1 >>
(1) Formation of conductive film on inner surface of battery case Graphite, carbon black, PVB (polyvinyl butyral) as a binder, methyl ethyl ketone as a solvent, and Ca (OH) 2 as an additive were mixed to obtain a coating mixture. At this time, the addition amount of Ca (OH) 2 was variously changed so that the content of Ca (OH) 2 with respect to the carbon-based material became a ratio shown in Table 1. The mixing mass ratio of graphite, carbon black, binder, and solvent was 18: 8: 4: 70.
内面にニッケルメッキを施した有底円筒形の鉄製の電池ケースを回転させながら、この被膜用混合物を電池ケース１の内面に塗布した後、２００℃で３０秒間乾燥し、溶剤を蒸発させて電池ケースの内面にＣａ（ＯＨ）２および黒鉛を含む導電性被膜１０を形成した。このときの塗布量は０．５ｍｇ／ｃｍ２とした。 The coating mixture was applied to the inner surface of the battery case 1 while rotating the bottomed cylindrical iron battery case with nickel plating on the inner surface, and then dried at 200 ° C. for 30 seconds to evaporate the solvent and remove the battery. A conductive coating 10 containing Ca (OH) 2 and graphite was formed on the inner surface of the case. The coating amount at this time was 0.5 mg / cm 2 .
（２）正極の作製
正極活物質として二酸化マンガンおよび導電剤として黒鉛を９３．４：６．６の割合で混合し、得られた混合物に対し１．５％のアルカリ電解液を添加し、充分に攪拌した後、フレーク状に圧縮成形した。このとき、アルカリ電解液には、３４．５質量％の水酸化カリウム水溶液を用いた。ついでフレーク状の混合物を粉砕して顆粒状とし、これを篩によって分級し、１０〜１００メッシュのものを中空円筒状に加圧成形して正極ペレットを得た。
(2) Production of positive electrode Manganese dioxide as a positive electrode active material and graphite as a conductive agent were mixed in a ratio of 93.4: 6.6, and 1.5% alkaline electrolyte was added to the resulting mixture, and And then compression-molded into flakes. At this time, 34.5 mass% potassium hydroxide aqueous solution was used for the alkaline electrolyte. Subsequently, the flaky mixture was pulverized into granules, which were classified by a sieve, and those having a 10 to 100 mesh were pressed into a hollow cylinder to obtain a positive electrode pellet.
（３）アルカリ乾電池の組み立て
上記で得られた電池ケース１内に、上記で得られた正極ペレットを４個挿入し、加圧治具により再成形して正極２とし、導電性被膜１０を形成した電池ケース１の内面に密着させた。そして、電池ケース１内に配置された正極２の中央に有底円筒形のセパレータ４を配置し、セパレータ４内へアルカリ電解液として３４．５質量％の水酸化カリウム水溶液を所定量注入した。所定時間経過した後、負極３をセパレータ４内へ充填した。
(3) Assembling of the alkaline dry battery In the battery case 1 obtained above, four positive electrode pellets obtained above are inserted and re-formed with a pressure jig to form the positive electrode 2 to form the conductive coating 10. The battery case 1 was brought into close contact with the inner surface. And the bottomed cylindrical separator 4 was arrange | positioned in the center of the positive electrode 2 arrange | positioned in the battery case 1, and 34.5 mass% potassium hydroxide aqueous solution was inject | poured into the separator 4 as alkaline electrolyte. After a predetermined time, the negative electrode 3 was filled into the separator 4.
なお、負極３には、ゲル化剤であるポリアクリル酸ナトリウム、アルカリ電解液である３４．５質量％の水酸化カリウム水溶液、ならびにＡｌ、Ｂｉ、およびＩｎをそれぞれ１５、１５０、および２００ｐｐｍ含む亜鉛合金粉末を質量比１：３５：６４の割合で混合したものを用いた。セパレータ４には、ポリビニルアルコール繊維とレーヨン繊維を主体として混抄した不織布を用いた。 In addition, the negative electrode 3 includes sodium polyacrylate as a gelling agent, 34.5 mass% potassium hydroxide aqueous solution as an alkaline electrolyte, and zinc containing 15, 150, and 200 ppm of Al, Bi, and In, respectively. A mixture of alloy powders at a mass ratio of 1:35:64 was used. For the separator 4, a non-woven fabric mainly composed of polyvinyl alcohol fiber and rayon fiber was used.
続いて、負極集電子６を負極３の中央に挿入した。なお、負極集電子６には、ガスケット５および負極端子を兼ねる底板７を一体化させ、組立封口体９とした。そして、電池ケース１内の開口端部を、ガスケット５の端部を介して、底板７の周縁部にかしめつけ、電池ケース１の開口部を封口した。最後に、外装ラベル８で電池ケース１の外表面を被覆して、アルカリ乾電池を得た。そして、以下に説明する（イ）および（ロ）の評価を行った。 Subsequently, the negative electrode current collector 6 was inserted into the center of the negative electrode 3. Note that the negative electrode current collector 6 was integrated with a gasket 5 and a bottom plate 7 that also served as a negative electrode terminal to form an assembly sealing body 9. And the opening edge part in the battery case 1 was crimped to the peripheral part of the baseplate 7 via the edge part of the gasket 5, and the opening part of the battery case 1 was sealed. Finally, the outer surface of the battery case 1 was covered with the exterior label 8 to obtain an alkaline dry battery. Then, the evaluations (A) and (B) described below were performed.
（イ）放電性能の評価
初期（電池の製造後１週間）および８０℃で３日間保存後（加速評価）のアルカリ乾電池を、１５００ｍＷで２秒間放電させ、その後６５０ｍＷで２８秒間放電させた。これを１セットとして１０回、合計５分間行い、その後５５分間休止した。この１時間の工程を１サイクルとして、電池の電圧が１．０５Ｖになるまで繰り返し行い、サイクル回数を評価した。放電は２０±１℃の環境で行った。
(A) Evaluation of discharge performance The alkaline dry battery at the initial stage (one week after the production of the battery) and after storage at 80 ° C. for 3 days (acceleration evaluation) was discharged at 1500 mW for 2 seconds and then discharged at 650 mW for 28 seconds. This was carried out 10 times for a total of 5 minutes, and then rested for 55 minutes. This one-hour process was defined as one cycle until the battery voltage reached 1.05 V, and the number of cycles was evaluated. Discharging was performed in an environment of 20 ± 1 ° C.
（ロ）内部抵抗の測定
初期および８０℃で３日間保存後のアルカリ乾電池の内部抵抗を交流４端子法により測定した。これらの結果を表１に示す。なお、表１における放電性能指数は、それぞれ比較例１の電池の放電時間を１００とした指数で表した。
(B) Measurement of internal resistance The internal resistance of the alkaline battery was measured by the AC four-terminal method at the initial stage and after storage at 80 ° C. for 3 days. These results are shown in Table 1. In addition, the discharge performance index | exponent in Table 1 was represented by the index | exponent which set the discharge time of the battery of the comparative example 1 to 100, respectively.
実施例１〜５では、８０℃で３日間保存後において、鉄の腐食による内部抵抗の増大が抑えられ、保存後の放電性能が大幅に向上した。 In Examples 1 to 5, the increase in internal resistance due to corrosion of iron was suppressed after storage at 80 ° C. for 3 days, and the discharge performance after storage was greatly improved.
《実施例６〜９》
Ｃａ（ＯＨ）２の代わりに、表２に示す添加物を炭素系材料に対し５％となるように添加物種を変えた以外は、実施例１と同様の方法により電池ケースの内面に塗膜を形成した。この電池ケースを用いた以外は、実施例１と同様の方法によりアルカリ乾電池を作製し、同様の電池の評価を行った。その結果を表２に示す。なお、表２における放電性能指数は、それぞれ比較例１の放電時間を１００とした指数で表した。
<< Examples 6 to 9 >>
A coating film was formed on the inner surface of the battery case in the same manner as in Example 1 except that the additive type shown in Table 2 was changed to 5% based on the carbon-based material instead of Ca (OH) 2. Formed. Except for using this battery case, an alkaline battery was prepared in the same manner as in Example 1, and the same battery was evaluated. The results are shown in Table 2. In addition, the discharge performance index in Table 2 was expressed as an index with the discharge time of Comparative Example 1 as 100, respectively.
実施例６〜９では、８０℃で３日間保存後において、鉄の腐食による内部抵抗の増大が抑えられ、保存後の放電性能が大幅に向上した。なお、上記の実施例では、正極活物質に二酸化マンガンを用いたが、オキシ水酸化ニッケルを用いた場合でも上記と同様の効果が得られる。 In Examples 6 to 9, the increase in internal resistance due to iron corrosion was suppressed after storage at 80 ° C. for 3 days, and the discharge performance after storage was greatly improved. In the above embodiment, manganese dioxide is used as the positive electrode active material, but the same effect as described above can be obtained even when nickel oxyhydroxide is used.
以上のように、本発明のアルカリ乾電池は、保存後の放電性能に優れており、小型電子機器や携帯機器用の電源等として適用することができる。 As described above, the alkaline dry battery of the present invention has excellent discharge performance after storage, and can be applied as a power source for small electronic devices and portable devices.
１ 電池ケース
２ 正極
３ 負極
４ セパレータ
５ ガスケット
６ 負極集電子
７ 底板
８ 外装ラベル
９ 組立封口体
１０ 導電性被膜
DESCRIPTION OF SYMBOLS 1 Battery case 2 Positive electrode 3 Negative electrode 4 Separator 5 Gasket 6 Negative electrode current collector 7 Bottom plate 8 Exterior label 9 Assembly sealing body 10 Conductive film
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014103026A (en) * | 2012-11-21 | 2014-06-05 | Hitachi Vehicle Energy Ltd | Storage element |
| US20160268588A1 (en) * | 2013-11-15 | 2016-09-15 | Panasonic Intellectual Property Management Co. Ltd. | Alkaline dry cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014103026A (en) * | 2012-11-21 | 2014-06-05 | Hitachi Vehicle Energy Ltd | Storage element |
| US20160268588A1 (en) * | 2013-11-15 | 2016-09-15 | Panasonic Intellectual Property Management Co. Ltd. | Alkaline dry cell |
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