JPH0426062A - Manufacture of zinc-alkali battery - Google Patents
Manufacture of zinc-alkali batteryInfo
- Publication number
- JPH0426062A JPH0426062A JP12848090A JP12848090A JPH0426062A JP H0426062 A JPH0426062 A JP H0426062A JP 12848090 A JP12848090 A JP 12848090A JP 12848090 A JP12848090 A JP 12848090A JP H0426062 A JPH0426062 A JP H0426062A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- indium
- zinc alloy
- sulfide
- alkaline battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003513 alkali Substances 0.000 title description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 73
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052738 indium Inorganic materials 0.000 claims abstract description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000007858 starting material Substances 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 150000002471 indium Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 30
- 239000003112 inhibitor Substances 0.000 abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000002301 combined effect Effects 0.000 description 4
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZOMNDSJRWSNDFL-UHFFFAOYSA-N sulfanylidene(sulfanylideneindiganylsulfanyl)indigane Chemical compound S=[In]S[In]=S ZOMNDSJRWSNDFL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000344 soap 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
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産メも利用分野
本発明は、負極活物質として亜鉛、電解液としてアルカ
リ水溶液、正極活物質として二酸化マンガン、酸化銀、
酸素等を用いる亜鉛アルカリ電池の無水銀化技術に関わ
り、無公害でかつ貯蔵性、放電性能に優れた亜鉛アルカ
リ電池の製造法を提供するものである。[Detailed Description of the Invention] Fields of Application The present invention uses zinc as a negative electrode active material, alkaline aqueous solution as an electrolyte, manganese dioxide, silver oxide,
The present invention relates to mercury-free technology for zinc-alkaline batteries using oxygen, etc., and provides a method for producing zinc-alkaline batteries that are pollution-free and have excellent storage and discharge performance.
従来の技術
約十年前から廃電池の水銀による環境汚染が強く懸念さ
れるようになり、アルカリ乾電池中の水銀量の低減の研
究がなされた。その結果、耐食性亜鉛合金等の開発によ
り、現状ではアルカリ乾電池中に含まれる水銀量は電池
重量に対し250ppmに低減されようとしている。と
ころが、フロンによるオゾン層破壊の問題に代表される
ように、世界的な工業製品による環境破壊問題が懸念さ
れている今日、さらにアルカリ乾電池中の水銀を完全に
なくす要望が高まってきている。Conventional Technology Approximately ten years ago, there was a strong concern about environmental pollution caused by mercury in waste batteries, and research was conducted into reducing the amount of mercury in alkaline batteries. As a result, with the development of corrosion-resistant zinc alloys, etc., the amount of mercury contained in alkaline dry batteries is currently being reduced to 250 ppm relative to the battery weight. However, now that there is worldwide concern about environmental destruction caused by industrial products, as exemplified by the problem of ozone layer depletion caused by fluorocarbons, there is an increasing demand for the complete elimination of mercury in alkaline batteries.
アルカリ乾電池の無水銀化技術に関するアプローチは、
水銀を含有したアルカリ乾電池が開発されていた当時か
らなされ、特許や邦文に亜鉛合金、無機系インヒビター
および有機系インヒビターに関する様々な材料について
、多数出願や発表がなされている。The approach to mercury-free alkaline batteries is as follows:
This has been done since the time when mercury-containing alkaline batteries were being developed, and numerous applications and publications have been made in patents and Japanese literature regarding various materials related to zinc alloys, inorganic inhibitors, and organic inhibitors.
インジウムは水素過電圧の高い材料として、次電池にか
かわらず二次電池の負極への添加剤として知られている
。そして金属インジウムを合金添加元素として用いる方
法や、インジウム化合物を無機系インヒビターとして用
いる方法についても多数出願、発表がなされている。Indium is a material with a high hydrogen overvoltage and is known as an additive to the negative electrode of secondary batteries, regardless of the type of battery. Many applications and publications have also been made regarding methods of using metallic indium as an alloy additive element and methods of using indium compounds as inorganic inhibitors.
たとえば、合金添加元素として用いる方法(特公平1−
41576)、無機系インヒビターとして酸化インジウ
ムおよび水酸化インジウムを用いる方法(特公昭51−
36450、特開昭49−93831、特開昭49−1
12125、第56回電化大会講演要旨集・発表番号3
GO5; 205ページ)、酸化インジウムと酸化カド
ミウムとを複合添加する方法(特開平1−105466
)などがある。また、二次電池の負極への添加剤として
添加する例(特開昭61−96666、特開昭6l−1
01955)もある。For example, the method of using it as an alloy additive element (Japanese Patent Publication No. 1-
41576), a method using indium oxide and indium hydroxide as inorganic inhibitors (Japanese Patent Publication No. 1973-
36450, JP-A-49-93831, JP-A-49-1
12125, 56th Electrification Conference Lecture Abstracts/Presentation Number 3
GO5; page 205), method of adding indium oxide and cadmium oxide in combination (JP-A-1-105466)
)and so on. In addition, examples of adding it as an additive to the negative electrode of a secondary battery (JP-A-61-96666, JP-A-6L-1
01955) is also available.
また、有機系インヒビターとてはジェタノールアミン、
オレイン酸、ラウリルエーテル、アミン、あるいはエチ
レンオキサイド重合体か提案されている。また、無機系
インヒビターと有機系インヒビターの複合添加の例とし
て、水酸化インジウムとエトキシルフルオロアルコール
系ポリフッ化化合物を複合添加する提案されている(特
開平2−79367)。In addition, organic inhibitors include jetanolamine,
Oleic acid, lauryl ether, amines, or ethylene oxide polymers have been proposed. Moreover, as an example of the combined addition of an inorganic inhibitor and an organic inhibitor, the combined addition of indium hydroxide and an ethoxylfluoroalcohol-based polyfluoride compound has been proposed (Japanese Unexamined Patent Publication No. 2-79367).
発明が解決しようとする課題
純亜鉛を無水銀のまま負極の活物質に用いた電池では、
亜鉛の水素発生を伴った腐食反応か激しく起こり、電池
内圧が増加して電解液を外部へ押し出し、耐漏液性の低
下という問題がある。Problems to be Solved by the Invention In batteries that use pure zinc without mercury as the active material of the negative electrode,
A corrosion reaction of zinc accompanied by hydrogen generation occurs violently, increasing the internal pressure of the battery and pushing the electrolyte to the outside, resulting in a problem of reduced leakage resistance.
また部分的に放電した電池では亜鉛負極の水素発生速度
が加速され、耐漏液性はさらに低下する。Additionally, in a partially discharged battery, the rate of hydrogen generation in the zinc negative electrode is accelerated, further reducing leakage resistance.
これらは亜鉛表面の水素過電圧を高めることで、腐食反
応を抑制していた水銀がなくなったことに起因している
。These results are due to the disappearance of mercury, which was suppressing corrosion reactions, by increasing the hydrogen overvoltage on the zinc surface.
亜鉛負極の低水銀化で耐食性の効果が証明されているイ
ンジウム、アルミニウムおよび鉛を含む耐食性亜鉛合金
でも無水銀のまま電池を構成すれば、部分放電後の電池
の耐漏液性は確保できない。Even with a corrosion-resistant zinc alloy containing indium, aluminum, and lead, which has been proven to have a corrosion-resistant effect by reducing mercury in the zinc negative electrode, if a battery is constructed without mercury, the leakage resistance of the battery after partial discharge cannot be ensured.
また、純亜鉛粉末を負極の活物質としたゲル負極に通常
市販されている酸化インジウムあるいは水酸化インジウ
ムを添加して構成した電池でも、上述の耐食性合金のみ
で構成した電池と同様に実用的な電池の耐漏液性は確保
できない。In addition, a battery constructed by adding commercially available indium oxide or indium hydroxide to a gel negative electrode using pure zinc powder as the negative electrode active material is as practical as a battery constructed only of the above-mentioned corrosion-resistant alloy. The leakage resistance of the battery cannot be ensured.
サラにインジウム、アルミニウム、鉛を含む耐食性亜鉛
合金を、負極の活物質としたゲル負極に有機系インヒビ
ターとして、低水銀化で効果のあるアミン系界面活性剤
を添加して電池を構成しても、部分放電後の電池の耐漏
液性は確保できない。A battery can be constructed by using a corrosion-resistant zinc alloy containing indium, aluminum, and lead as the active material for the negative electrode, and adding an organic inhibitor to the gel negative electrode and an amine surfactant that is effective in reducing mercury. , leakage resistance of the battery after partial discharge cannot be ensured.
以上のように、今までのシーズはそれぞれ腐食抑制効果
が完全でなく、少なくとも密閉系の電池には実用的なも
のとはいえない。As described above, the conventional seeds do not have a complete corrosion inhibiting effect, and cannot be said to be practical at least for sealed batteries.
アルカリ乾電池の無水銀化の実現を可能にするにあたり
、本発明者等は耐食性亜鉛合金、無機系インヒビターや
有機系インヒビターのそれぞれの複合効果において、最
高に効果を発揮できる材料およびその最適な状態や濃度
について検討した。In order to make alkaline dry batteries mercury-free, the present inventors have developed materials that can exhibit the best combined effects of corrosion-resistant zinc alloys, inorganic inhibitors, and organic inhibitors, as well as their optimal conditions. The concentration was investigated.
課題を解決するための手段
まず、耐食性亜鉛合金と無機系インヒビターの複合使用
についての本発明の詳細な説明する。本発明におけるゲ
ル状負極は、インジウム、鉛、ビスマス、カルシウム、
およびアルミニウムの群のうちいずれかを適正な組合せ
でかつ亜鉛に適正量添加した耐食性亜鉛合金粉末からな
る活物質と、無機系インヒビターとして適切な性質を持
った硫化インジウム粉末を適正な濃度で分散させたゲル
状アルカリ電解液により構成される。Means for Solving the Problems First, the present invention will be described in detail regarding the combined use of a corrosion-resistant zinc alloy and an inorganic inhibitor. The gelled negative electrode in the present invention includes indium, lead, bismuth, calcium,
An active material consisting of a corrosion-resistant zinc alloy powder containing an appropriate combination of zinc and aluminum in an appropriate amount, and an indium sulfide powder having appropriate properties as an inorganic inhibitor are dispersed at an appropriate concentration. It is composed of a gel-like alkaline electrolyte.
上記の耐食性亜鉛合金は、インジウムを0.01〜1w
t%、鉛およびビスマスの一種または二種を合計で0.
005〜0.5wt%含有した亜鉛合金、あるいはイン
ジウムを0,01〜1wt%、鉛およびビスマスの一種
または二種を合計で0.005〜0.5wt%、カルシ
ウムおよびアルミニウムの一種または二種を合計で00
05〜0.2 w t%金含有た亜鉛合金である。また
、上記の硫化インジウムの適切な添加量は、亜鉛合金に
対して0.005〜0.5wt%である。The above corrosion-resistant zinc alloy contains 0.01 to 1 w of indium.
t%, one or both of lead and bismuth in total of 0.
Zinc alloy containing 0.05 to 0.5 wt%, or 0.01 to 1 wt% of indium, a total of 0.005 to 0.5 wt% of one or both of lead and bismuth, and one or two of calcium and aluminum. 00 in total
It is a zinc alloy containing 0.05 to 0.2 wt% gold. Further, the appropriate amount of indium sulfide added is 0.005 to 0.5 wt% based on the zinc alloy.
次に、亜鉛合金、無機系インヒビターと有機系インヒビ
ターの複合使用についての本発明の詳細な説明する。本
発明のゲル状負極は、インジウム、鉛、ビスマス、カル
シウム、および、アルミニウムを適正な組合せで適正な
量だけ添加された耐食性亜鉛合金粉末と、適正な性質を
持った硫化インジウム粉末を適正な濃度で分散させ、さ
らに有機系インヒビターとしてポリエチレンオキサイド
を親水部に持ち、フッ化アルキル基を親油部に持った界
面活性剤の適正量を添加したゲル状アルカリ電解液とに
より構成される。Next, the present invention will be described in detail regarding the combined use of a zinc alloy, an inorganic inhibitor, and an organic inhibitor. The gel-like negative electrode of the present invention is made by combining corrosion-resistant zinc alloy powder to which an appropriate amount of indium, lead, bismuth, calcium, and aluminum is added in an appropriate combination, and indium sulfide powder with appropriate properties at an appropriate concentration. and a gel-like alkaline electrolyte to which an appropriate amount of a surfactant having polyethylene oxide as an organic inhibitor in its hydrophilic part and a fluorinated alkyl group in its lipophilic part is added.
上記の界面活性剤は亜鉛合金に対して0,001〜0.
1wt%アルカリ電解液中に含有させることで効果があ
る。The above surfactant is 0.001 to 0.00% for zinc alloy.
It is effective to include it in the alkaline electrolyte at 1 wt%.
また、耐食性亜鉛合金はインジウムを001〜1 w
t%、鉛およびビスマスの一種または二種を合計で0.
005〜0.5wt%含有した亜鉛合金、あるいはイン
ジウムを0.01〜1wt%、鉛およびビスマスの一種
または二種を合計で0゜005〜0.5wt%、カルシ
ウムおよびアルミニウムの一種または二種を合計で00
05〜0゜2 w t%金含有た亜鉛合金である。また
、硫化インジウムの適切な添加量は亜鉛合金に対して0
゜005〜0.5wt%である。In addition, corrosion-resistant zinc alloy contains indium of 001 to 1 w
t%, one or both of lead and bismuth in total of 0.
Zinc alloy containing 0.005 to 0.5 wt%, or 0.01 to 1 wt% of indium, a total of 0.005 to 0.5 wt% of one or both of lead and bismuth, and one or two of calcium and aluminum. 00 in total
It is a zinc alloy containing 0.05 to 0.02 wt% gold. In addition, the appropriate amount of indium sulfide added is 0 to zinc alloy.
It is 0.005 to 0.5 wt%.
さらに、電池の製造法上から硫化インジウムはインジウ
ム塩を出発物質とし、その水溶液中で硫化水素との反応
で合成した水酸化インジウムを用いることが望ましい。Further, from the viewpoint of the battery manufacturing method, it is desirable to use indium hydroxide synthesized by using an indium salt as a starting material and reacting it with hydrogen sulfide in an aqueous solution of the indium sulfide.
また、上記の硫化インジウムは、粒子径が0゜5〜8μ
の範囲の粒子を総量の60wt%以上、好ましくは70
wt%以上含む粉末で構成されているものが効果的であ
る。In addition, the above indium sulfide has a particle size of 0°5 to 8μ.
of the total amount of particles in the range of 60 wt% or more, preferably 70 wt% of the total amount.
It is effective to use a powder containing at least % by weight.
また、界面活性剤は下記の構造式
(X)
XニーHあるいは−F
Y・−CONH−あるいは−8O2NR−(Rはアルキ
ル基)
Z : −CH3−PO3W2
アルいは一5O3W(Wはアルカリ金属)n: 4〜1
0
m:20〜100
または、
(X)−C,F 2n(C)12 CH= ’)−(C
H2CH20)−−(Z)XニーHあるいは−F
Z : CH3、−PO3W2
あるいは一5O3W(Wはアルカリ金属)n: 4〜1
0
m:40〜100
で表されるものが効果的である。In addition, the surfactant has the following structural formula (X) )n: 4-1
0 m: 20-100 or (X)-C,F2n(C)12CH=')-(C
H2CH20) --(Z)
0 m: 40 to 100 is effective.
作用
本発明の耐食性亜鉛合金、無機系インヒビター有機系イ
ンヒビターの材料、およびそれらの複合における組合せ
や組成については、それぞれが複合効果を最高に発揮で
きるように鋭意研究した結果、見出したものである。そ
の作用機構の解明は今のところ不明確であるが、以下の
ように推察される。Function: The materials of the corrosion-resistant zinc alloy, inorganic inhibitor, and organic inhibitor of the present invention, as well as the combination and composition of their composites, were discovered as a result of intensive research to maximize the combined effects of each. Although the elucidation of its mechanism of action is currently unclear, it is inferred as follows.
まず、合金の添加元素、無機系インヒビター有機系イン
ヒビターそれぞれの単独での作用効果は次のようである
。First, the effects of each of the additive elements of the alloy, the inorganic inhibitor, and the organic inhibitor are as follows.
合金中の添加元素のうちインジウム、鉛およびビスマス
はそれらの元素自身の水素過電圧か高く、亜鉛に添加さ
れて、その表面の水素過電圧を高める作用がある。これ
らが均一に合金中に添加した場合、粉末のどの深さにも
添加元素が存在するため、この作用は放電により新しい
亜鉛表面が現れたとしても保持される。また、アルミニ
ウムやカルシウムは亜鉛粒子を球形化させる作用があり
、真の比表面積を少なくさせるため亜鉛粉末の単位重量
当たりの腐食量を低下させる。Among the additive elements in the alloy, indium, lead, and bismuth have high hydrogen overpotentials themselves, and when added to zinc, they have the effect of increasing the hydrogen overvoltage on the surface. If they are added uniformly into the alloy, this effect will be retained even if a new zinc surface appears due to the discharge, since the added elements are present at every depth in the powder. Furthermore, aluminum and calcium have the effect of making zinc particles spherical, reducing the true specific surface area, thereby reducing the amount of corrosion per unit weight of zinc powder.
硫化インジウムは粉末としてゲル状アルカリ電解液中に
亜鉛合金と共存状態で分散された場合、その一部は置換
メツキの原理で亜鉛合金表面に金属インジウムとして電
析し、その表面の水素過電圧を高める。残りの部分は電
解液中に固体のまま残留し、放電により新しい亜鉛合金
表面が現れたとき、その新しい表面に電析して防食効果
を示す。When indium sulfide is dispersed as a powder in a gel-like alkaline electrolyte in coexistence with a zinc alloy, a portion of it is deposited as metallic indium on the surface of the zinc alloy using the principle of displacement plating, increasing the hydrogen overvoltage on the surface. . The remaining part remains as a solid in the electrolyte, and when a new zinc alloy surface appears due to discharge, it is electrodeposited on the new surface and exhibits a corrosion-preventing effect.
硫化物の放電後の作用効果は、それ自身の難溶解性のた
め、水酸化物に比べ高くなる。The effect of sulfide after discharge is higher than that of hydroxide due to its own low solubility.
界面活性剤はゲル状アルカリ電解液中に亜鉛合金と共存
すると、金属石けんの原理で亜鉛合金表面に化学吸着し
て疎水性の単分子層を形成し、防食効果を示す。特に、
ポリエチレンオキサイドを親水部に持つ界面活性剤は、
アルカリ電解液に対しミセルとしての溶解性か高く、電
解液に投入させた場合、亜鉛合金表面への移動、吸着が
速やかに起こるため防食効果が高い。さらに、フッ化ア
ルキル基を親油部に持てば、これが亜鉛合金表面に吸着
した場合、電気絶縁性が高いため腐食反応の電子授受を
効果的に疎外し、また耐アルカリ性か強いためその効果
は持続する。When a surfactant coexists with a zinc alloy in a gel-like alkaline electrolyte, it chemically adsorbs onto the surface of the zinc alloy based on the principle of metal soap, forming a hydrophobic monomolecular layer, which exhibits an anticorrosion effect. especially,
Surfactants with polyethylene oxide in the hydrophilic part are
It has high solubility as a micelle in an alkaline electrolyte, and when added to the electrolyte, it quickly migrates and adsorbs to the surface of the zinc alloy, so it has a high anticorrosion effect. Furthermore, if the oleophilic moiety has a fluorinated alkyl group, when it is adsorbed onto the surface of the zinc alloy, it has high electrical insulation properties, effectively eliminating electron transfer during corrosion reactions, and has strong alkali resistance, so its effect is negligible. last.
次に亜鉛合金と硫化インジウムとの複合効果について説
明する。硫化インジウムは亜鉛合金表面に電析して作用
するので、電析がスムーズにかつ均−に起こる必要があ
る。耐食性のない亜鉛合金の表面では著しい水素ガスの
発生が起こっているため、インジウムの電析か疎外され
、電析の状態が不均一となる。しかし、耐食性の良好な
亜鉛合金表面では水素ガスの発生が抑制されており、電
析がスムーズにかつ、均一に起こるために複合効果が得
られる。これは部分放電後の状態でも同様である。硫化
物の場合、それ自身の難溶解性のため、電析が遅く水酸
化物に比べ作用効果は大きい。Next, the combined effect of zinc alloy and indium sulfide will be explained. Since indium sulfide acts by being electrodeposited on the surface of the zinc alloy, the electrodeposition must occur smoothly and uniformly. Since a significant amount of hydrogen gas is generated on the surface of the zinc alloy, which has no corrosion resistance, the electrodeposition of indium is inhibited, and the state of the electrodeposition becomes non-uniform. However, on the surface of a zinc alloy with good corrosion resistance, the generation of hydrogen gas is suppressed, and electrodeposition occurs smoothly and uniformly, resulting in a compound effect. This also applies to the state after partial discharge. In the case of sulfides, because of their low solubility, electrodeposition is slow and the effect is greater than that of hydroxides.
しかし、その反面、亜鉛合金の耐食性の影響を受けやす
い。However, on the other hand, it is susceptible to the corrosion resistance of zinc alloys.
次に耐食性亜鉛合金、硫化インジウムおよび界面活性剤
の複合効果について説明する。硫化インジウムの作用機
構は先に記したとうりであるが、すべてが電析してしま
えば部分放電後に作用する物がなくなってしまう。界面
活性剤はそれ単独の作用に加え、必要以上のインジウム
の電析を抑え、部分放電後に作用する量を確保する作用
を果たすと考えられる。Next, the combined effect of the corrosion-resistant zinc alloy, indium sulfide, and surfactant will be explained. The mechanism of action of indium sulfide is as described above, but if all of the indium sulfide is electrodeposited, there will be nothing left to act on after partial discharge. In addition to its own effect, the surfactant is thought to have the effect of suppressing the electrodeposition of more indium than necessary and ensuring the amount of indium that is available after partial discharge.
次に硫化インジウムの性状を限定する意味について説明
する。その粒度は細かい方かゲル状電解液への分散性か
良くなり、ゲル負極で均一に効果を発揮できる。しかし
細かすぎては一度に溶解してしまい、部分放電後に作用
するための量が確保できなくなる。Next, the meaning of limiting the properties of indium sulfide will be explained. The finer the particle size, the better the dispersibility in the gel electrolyte, and the gel negative electrode can exhibit a uniform effect. However, if it is too fine, it will dissolve all at once, making it impossible to secure enough amount to act after partial discharge.
次に硫化インジウムの合成方法を限定する意味について
説明する。合成方法により、硫化インジウムの性状が違
ってくる。乾式法では非化学量論的な硫化インジウムが
できて、作用効果が不安定であるが、湿式で合成した硫
化インジウムは化学量論的で防食作用の優れた結晶性、
粒子形状となる。Next, the meaning of limiting the method of synthesizing indium sulfide will be explained. The properties of indium sulfide vary depending on the synthesis method. The dry method produces non-stoichiometric indium sulfide, which has unstable effects, but indium sulfide synthesized by the wet method is stoichiometric, crystalline, and has excellent anti-corrosion properties.
It becomes a particle shape.
次に界面活性剤の分子構造を限定する意味について説明
する。ポリエチレンオキサイドを親水部に持つ界面活性
剤は、アルカリ電解液に対しミセルとしての溶解性が高
く、電解液に投入させた場合、亜鉛合金表面への移動、
吸着が速やかに起こるため防食効果が高い。また、ポリ
エチレンオキサイドの末端が水酸基つまりアルコールで
あると、アルカリ電解液中で加水分解を受けやすいので
、末端基は耐アルカリ性が強いメチル基、スルホン基、
燐酸基がよい。フッ化アルキル基を親油部に持てば、こ
れが亜鉛合金表面に吸着した場合、電気絶縁性が高いた
め腐食反応の電子授受を効果的に疎外する。親水部と親
油部の間の結合基は撥水性のアルキル基より、親水性の
アミド基、スルホアミド基であればこの部分での亜鉛と
の化学吸着が起こり、高い防食性が現われる。Next, the meaning of limiting the molecular structure of the surfactant will be explained. Surfactants with polyethylene oxide as their hydrophilic part have high solubility as micelles in alkaline electrolytes, and when added to electrolytes, they migrate to the zinc alloy surface,
It has a high corrosion prevention effect because adsorption occurs quickly. In addition, if the terminal end of polyethylene oxide is a hydroxyl group, that is, an alcohol, it is easily hydrolyzed in an alkaline electrolyte.
Phosphoric acid groups are preferred. If a fluorinated alkyl group is present in the lipophilic moiety, when it is adsorbed on the surface of a zinc alloy, it has high electrical insulation properties and effectively eliminates the transfer of electrons in the corrosion reaction. If the bonding group between the hydrophilic part and the lipophilic part is a hydrophilic amide group or sulfoamide group rather than a water-repellent alkyl group, chemical adsorption with zinc will occur at this part, resulting in high corrosion resistance.
実施例
以下、実施例によって、本発明の詳細ならびに効果を説
明する。EXAMPLES The details and effects of the present invention will be explained below using examples.
まず、耐食性亜鉛合金の作成方法、硫化インジウムの合
成方法、本発明の製造法の効果を示すため、実施例に用
いたLRe型アルカリマンガン電池の構造、および耐漏
液性の比較評価の方法について説明する。First, in order to demonstrate the effects of the method of creating a corrosion-resistant zinc alloy, the method of synthesizing indium sulfide, and the manufacturing method of the present invention, we will explain the structure of the LRe-type alkaline manganese battery used in the examples and the method of comparative evaluation of leakage resistance. do.
耐食性亜鉛合金粉末は、純度99.97%の亜鉛を融解
し、所定の添加元素を所定量加え、均一溶解させた後、
圧縮空気で噴霧して粉末化する、いわゆるアトマイズ法
で作成し、これをふるいで分級して粒度範囲45〜15
0メーソンユに調整した。 硫化インジウムはインジウ
ムの塩化物、もしくは硫酸塩を酢酸酸性水溶液に飽和量
添加し、その水溶液をスクリユつ攪拌機で攪拌しながら
硫化水素を反応させた。沈殿物を0.5μの目の粗さを
もつフィルター上でイオン交換水で口演のpHが6にな
るまで水洗し、フィルターの下から真空で引いて水分の
分離を行い、60℃で真空乾燥することにより合成した
。Corrosion-resistant zinc alloy powder is produced by melting 99.97% pure zinc, adding specified amounts of specified additive elements, and uniformly dissolving it.
It is made by the so-called atomization method, which is sprayed with compressed air and pulverized, and then classified with a sieve to obtain particles in the particle size range of 45 to 15.
Adjusted to 0 maesongyu. Indium sulfide was obtained by adding a saturated amount of indium chloride or sulfate to an acetic acid aqueous solution, and stirring the aqueous solution with a screw stirrer to react with hydrogen sulfide. The precipitate was washed with ion-exchanged water on a filter with a mesh size of 0.5μ until the oral pH reached 6, the moisture was separated by drawing a vacuum from the bottom of the filter, and the water was vacuum dried at 60°C. It was synthesized by
ゲル状負極は以下のようにして調整した。まず、40重
量%の水酸化カリウム溶液(ZnOを3wt%含む)に
3重量%のポリアクリル酸ソーダと1重量%のカルボキ
シメチルセルロースを加えてゲル化する。ついで、この
ゲル状電解液を攪拌しながら所定量の硫化インジウムの
粉末を徐々に投入溶解させ、2〜3時間熟成する。さら
にゲル状電解液に対して重量比で2倍の亜鉛合金粉末を
加えて混合した。なお、を根糸インヒビターを添加する
場合は、上記の調整工程中の硫化インジウムの投入前に
、ゲル状電解液にこれを所定量を投入し、2〜3時間熟
成する工程を付加した。The gelled negative electrode was prepared as follows. First, 3% by weight of sodium polyacrylate and 1% by weight of carboxymethyl cellulose are added to a 40% by weight potassium hydroxide solution (containing 3% by weight of ZnO) to form a gel. Next, while stirring the gel electrolyte, a predetermined amount of indium sulfide powder is gradually added and dissolved, and the electrolyte is aged for 2 to 3 hours. Furthermore, twice the weight ratio of zinc alloy powder was added to the gel electrolyte and mixed. In addition, when adding the root filament inhibitor, a predetermined amount of this was added to the gel electrolytic solution and aged for 2 to 3 hours before adding indium sulfide in the above-mentioned adjustment step.
第1図は本実施例で用いたアルカリマンガン電池LR6
の構造断面図である。第1図において、1は正極合剤、
2は本発明で特徴付けられたゲル状負極、3はセパレー
タ、4はゲル負極の集電子である。5は正極端子キャッ
プ、6は金属ケース、7は電池の外装缶、8はケース6
の開口部を閉塞するポリエチレン製樹脂封口体、9は負
極端子をなす底板である。Figure 1 shows the alkaline manganese battery LR6 used in this example.
FIG. In FIG. 1, 1 is a positive electrode mixture;
2 is a gel negative electrode characterized by the present invention, 3 is a separator, and 4 is a current collector of the gel negative electrode. 5 is the positive terminal cap, 6 is the metal case, 7 is the battery exterior can, 8 is the case 6
A resin sealing body made of polyethylene closes the opening, and 9 is a bottom plate forming a negative electrode terminal.
耐漏液性の比較評価の方法は、第1図で示したアルカリ
マンガン電池を100個ずつ試作し、LR6で最も苛酷
な条件であるIAの定電流で理論容量の深度20%まで
部分放電を行い、60℃で保存後に漏液した電池数を漏
液指数(%)として評価した。この苛酷な条件下におい
て60℃保存30日で漏液指数が0%であれば実用可能
であるが、耐漏液性などの信頼性に関する性能はできる
だけ長期に性能を維持できることが望ましい。The method for comparative evaluation of leakage resistance was to prototype 100 alkaline manganese batteries as shown in Figure 1 and partially discharge them to a depth of 20% of the theoretical capacity at a constant current of IA, which is the most severe condition for LR6. The number of batteries that leaked after storage at 60°C was evaluated as a leakage index (%). Under these harsh conditions, if the leakage index is 0% after 30 days of storage at 60°C, it is practical, but it is desirable to be able to maintain reliability-related performance such as leakage resistance for as long as possible.
実施例1
亜鉛合金と無機系インヒビターを複合した場合の本発明
を説明する。Example 1 The present invention will be described in the case where a zinc alloy and an inorganic inhibitor are combined.
まず、亜鉛合金を事前に種々の添加元素を組成をさまざ
まに変化させて検討した。その結果、インジウムを必須
合金成分とし、これにさらに鉛およびビスマスをそれぞ
れ単独かもしくは複合で含有する亜鉛合金、あるいはイ
ンジウムを必須成分とし、これに鉛およびビスマスをそ
れぞれ単独かまたは複合で、さらにカルシウムおよびア
ルミニウムを単独または複合で含有する亜鉛合金系が単
独では良好であることがわかった。それらの中で最もよ
い合金組成群を表1に示す。First, we investigated zinc alloys by adding various additive elements and varying the composition. As a result, zinc alloys containing indium as an essential alloy component, and lead and bismuth, either singly or in combination, or indium as an essential component, lead and bismuth, either singly or in combination, and calcium. It was found that a zinc alloy system containing aluminum alone or in combination is good when used alone. Table 1 shows the best alloy composition group among them.
表1
アルカリ亜鉛電池の無水銀化用耐食性亜鉛合金く表中(
)内は合金成分の添加量〉
表2に先の表1の各種亜鉛合金に対し硫化インジウムの
添加量を変化させて作成した電池の60’C60日保存
後の漏液試験結果を示す。Table 1 Corrosion-resistant zinc alloy for mercury-free alkaline zinc batteries (
) indicates the amount of alloy components added> Table 2 shows the leakage test results after storage at 60'C for 60 days for batteries prepared by varying the amount of indium sulfide added to the various zinc alloys shown in Table 1 above.
表2より耐食性の優れた亜鉛合金でもそれ単独ではとて
も実用的な耐漏液性は確保できない。しかし硫化インジ
ウムを適切量加えることにより、耐漏液性は確保できる
ことがわかる。各々の亜鉛合金に対し硫化インジウムの
添加量は0.005〜0.5wt%の範囲が良好である
。As shown in Table 2, even zinc alloys with excellent corrosion resistance cannot ensure practical leakage resistance when used alone. However, it can be seen that leakage resistance can be ensured by adding an appropriate amount of indium sulfide. The amount of indium sulfide added to each zinc alloy is preferably in the range of 0.005 to 0.5 wt%.
表3に硫化インジウムの添加量を0.1wt%に固定し
、合金成分元素の添加量を変化させて作成17た電池の
60℃60日保存後の漏液試験結果を示す。Table 3 shows the leakage test results after storage at 60° C. for 60 days for batteries prepared by fixing the amount of indium sulfide added at 0.1 wt% and varying the amount of alloy component elements added.
表3より亜鉛合金へのインジウムの添加量は、0.01
〜1wt%、鉛およびビスマスはそれぞれ単独かもしく
は合計で0005〜0.5wt%、あるいはカルシウム
およびアルミニウムはそれぞれ単独かもしくは合計で0
.005〜0.2wt%が適当であることがわかる。From Table 3, the amount of indium added to the zinc alloy is 0.01
~1 wt%, lead and bismuth each individually or in total 0005~0.5 wt%, or calcium and aluminum each individually or in total 0
.. It can be seen that 0.005 to 0.2 wt% is appropriate.
本実施例では硫酸塩を出発物質として、その水溶液を硫
化水素と反応することで合成した硫化インジウムを用い
たが、塩化物、硝酸塩を出発物質とした硫化インジウム
を用いても効果が得られる。In this example, indium sulfide synthesized by using sulfate as a starting material and reacting its aqueous solution with hydrogen sulfide was used, but the effect can also be obtained by using indium sulfide using chloride or nitrate as a starting material.
その効果の程度は、塩化物を出発物質としたもの、硫酸
塩を出発物質としたもの、硝酸塩を出発物質としたもの
の順に高かった。The degree of effectiveness was higher in the following order: those using chloride as a starting material, those using sulfate as a starting material, and those using nitrate as a starting material.
実施例2
亜鉛合金と無機系インヒビターを複合した場合で、硫化
インジウムの合成における出発物質の限定に関する本発
明を説明する。Example 2 The present invention regarding limitation of starting materials in the synthesis of indium sulfide is explained using a composite of a zinc alloy and an inorganic inhibitor.
表4に出発物質の異なる硫化インジウムを各亜鉛合金に
対し0.1wt%添加した電池の60℃60日保存後の
漏液試験結果を示す。Table 4 shows the leakage test results after storage at 60° C. for 60 days for batteries in which 0.1 wt % of indium sulfide, which is a different starting material, was added to each zinc alloy.
表4より、硝酸塩でも、塩素イオンの存在状態で合成し
たものか適当であることかわかる。ちなみに硝酸塩を出
発物質としたものでも漏液指数は60℃45日目では0
%であり、十分、実用可能なレベルにあるが、塩化物、
硫酸塩を出発物質としたものを用いた電池は60℃75
日目まで漏液しない場合がある。From Table 4, it can be seen that even nitrates are suitable if they are synthesized in the presence of chloride ions. By the way, even for products using nitrate as the starting material, the leakage index is 0 at 60℃ on the 45th day.
%, which is at a sufficiently practical level, but chloride,
Batteries using sulfate as a starting material are heated to 60°C and 75°C.
It may not leak until the next day.
実施例3
亜鉛合金と無機系インヒビターを複合した場合で、硫化
インジウムの粒度範囲の限定についての実施例を説明す
る。Example 3 An example of limiting the particle size range of indium sulfide will be described in the case where a zinc alloy and an inorganic inhibitor are combined.
表5に粒度分布の異なる硫化インジウムを各亜鉛合金に
対し0.1wt%添加した電池の60℃60日後の漏液
試験結果を示す。Table 5 shows the leakage test results after 60 days at 60°C for batteries in which 0.1 wt% of indium sulfide having different particle size distributions was added to each zinc alloy.
表5より、粒子径が0.5〜8μの範囲の粒子を60
w t%(合成の水洗工程で0.5μ目の粗さのフィル
ター上に残った物を用いているので残りの粒子は8μ以
上の粒子である)以上含む硫化インジウム粉末を用いる
のがよい。それらの粒子が70wt%以上含む場合、6
0℃75日目でも漏液しない場合がある。From Table 5, 60% of particles with particle diameters in the range of 0.5 to 8μ
It is preferable to use indium sulfide powder containing wt% or more (because the particles remaining on the filter with a coarseness of 0.5 μm in the water washing step of synthesis are used, the remaining particles are particles of 8 μm or more). If those particles contain 70 wt% or more, 6
There may be no leakage even after 75 days at 0°C.
この実施例で用いた粒度分布の異なる硫化インジウムは
硝酸塩を出発物質とし、粒子径の大きいものを湿式の沈
降法により分級調整したものを用いた。The indium sulfide having different particle size distributions used in this example used nitrate as a starting material, and those with large particle sizes were classified and adjusted by a wet sedimentation method.
実施例4
亜鉛合金と無機系インヒビターおよび 有機系インヒビ
ターを複合した場合についての実施例を説明する。Example 4 An example will be described in which a zinc alloy, an inorganic inhibitor, and an organic inhibitor are combined.
表6に各亜鉛合金に対し、硫化インジウムの添加量を最
適の0.1wt%に固定し、有機系インヒビターである
界面活性剤の添加量を変化させて作成した電池の60℃
60日保存後の漏液試験結果を示す。Table 6 shows the batteries prepared at 60℃ for each zinc alloy by fixing the amount of indium sulfide added to the optimal 0.1 wt% and varying the amount of surfactant, which is an organic inhibitor.
The results of a leakage test after 60 days of storage are shown.
これより界面活性剤の添加量は各亜鉛合金に対し0.0
01〜01W[%か適当であることがわかる。From this, the amount of surfactant added is 0.0 for each zinc alloy.
It can be seen that 01 to 01W [%] is appropriate.
有機系インヒビターを添加した場合でも、亜鉛合金と無
機系インヒビターを複合添加した場合と同様に、亜鉛合
金の組成はインジウムが、0.01〜1 w t%、鉛
およびビスマスがそれぞれ単独かもしくは合計で0.0
05〜0.5wt%、あるいはカルシウムおよびアルミ
ニウムかそれぞれ単独かもしくは合計で0.005〜0
.2wt%が適当であった。Even when an organic inhibitor is added, as in the case where a zinc alloy and an inorganic inhibitor are added in combination, the composition of the zinc alloy is that indium is 0.01 to 1 wt%, and lead and bismuth are contained individually or in total. at 0.0
05-0.5wt%, or calcium and aluminum, each alone or in total, 0.005-0
.. 2 wt% was appropriate.
実施例4で用いた界面活性剤は下記の構造式(X) :60 であるものを用いた。The surfactant used in Example 4 has the following structural formula (X) :60 I used something that is.
下記の構造式
(X)
X −Hあるいは−F
Z −CH3
あるいは
n: 4〜
m:20〜1
または、
あるいは−8O2NR
(Rはアルキル基)
、−P(VJW2
SO3W (Wはアルカリ金属)
CON H
(X)−C2F 2n(CH2CH2)−(CH2CH
20)m−(Z)X −Hあるいは−F
Z l−CH3−pQ3W2
あるいは−8O3W+Wはアルカリ金属)n: 4〜1
0
m:40〜100
である界面活性剤であれば、同様あるいはそれ以上の効
果が得られる。なお、上記の界面活性剤のうち、燐酸系
のものは一級、二級燐酸塩の混合物でもかまわない。The following structural formula (X) H(X)-C2F 2n(CH2CH2)-(CH2CH
20) m-(Z)X -H or -F Z l-CH3-pQ3W2 or -8O3W+W is an alkali metal) n: 4-1
If the surfactant has a ratio of 0 m:40 to 100, similar or better effects can be obtained. Note that among the above-mentioned surfactants, the phosphoric acid type surfactants may be a mixture of primary and secondary phosphates.
また、硫化インジウムは硫酸塩を出発物質としたもので
、その粒子径は0.5〜8μの範囲の粒子を80wt%
以上含んだ粉末で、実施例2、実雄側3および実施例4
に示したと同様な出発物質で、同じ性状を持った硫化イ
ンジウムであれば充分、あるいはそれ以上の耐漏液性が
得られることは確認している。In addition, indium sulfide is made from sulfate as a starting material, and its particle size is 80wt% in the range of 0.5 to 8μ.
Example 2, real side 3 and example 4 with the powder containing the above
It has been confirmed that sufficient or better leakage resistance can be obtained using indium sulfide having the same properties as the starting material shown in .
ところで、全実施例では本発明の効果を無氷化亜鉛合金
で説明したが、水銀添加量が数PPM〜数十PPMの極
低氷化の場合でも効果は充分である。Incidentally, in all the examples, the effects of the present invention have been explained using a non-icing zinc alloy, but the effects are sufficient even in the case of extremely low icing, where the amount of mercury added is several PPM to several tens of PPM.
発明の効果
以上のように、本発明によれば、亜鉛アルカリ電池にお
いて、ゲル状アルカリ電解液中に適正な組成を有する亜
鉛合金と、適正な合成方法により適当な物性をもつよう
にした硫化インジウムを加えることで無水銀でも亜鉛の
腐食に伴うガス発生による電池内圧の上昇を抑制して電
池の耐漏液性を予測以上の複合効果が得られ、向上させ
ることができる。そして適切な構造式を有する有機イン
ヒビターを適正量これに加えることでさらに貯蔵性の良
好な、無公害の亜鉛アルカリ電池を提供することができ
る。Effects of the Invention 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 used. By adding mercury-free, it is possible to suppress the increase in battery internal pressure due to gas generation due to corrosion of zinc, thereby achieving a more complex effect than expected and improving the leakage resistance of the battery. By adding an appropriate amount of an organic inhibitor having an appropriate structural formula to this, a pollution-free zinc-alkaline battery with even better storage stability can be provided.
第1図は本発明の実施例におけるアルカリマンガン電池
の断面図である。
1・・・正極合剤、
2・・・ゲル状負極、
3・・
セパレ−FIG. 1 is a sectional view of an alkaline manganese battery in an embodiment of the present invention. 1... Positive electrode mixture, 2... Gel-like negative electrode, 3... Separate
Claims (12)
したゲル状負極の調整において、インジウム、鉛、ビス
マス、カルシウムおよびアルミニウムの群のうち少なく
とも1種以上を含む亜鉛合金を活物質に用い、前記アル
カリ電解液中には硫化インジウムを前記亜鉛合金に対し
て0.005〜0.5wt%含有させることを特徴とす
る亜鉛アルカリ電池の製造法。(1) In preparing a gel-like negative electrode in which zinc alloy powder is mixed and dispersed in a gel-like alkaline electrolyte, a zinc alloy containing at least one member from the group of indium, lead, bismuth, calcium, and aluminum is used as an active material, A method for manufacturing a zinc-alkaline battery, characterized in that the alkaline electrolyte contains indium sulfide in an amount of 0.005 to 0.5 wt% based on the zinc alloy.
マスの一種または二種を合計で0.005〜0.5wt
%含有する亜鉛合金を負極活物質に用いたことを特徴と
する特許請求の範囲第1項記載の亜鉛アルカリ電池の製
造法。(2) 0.01 to 1 wt% of indium and 0.005 to 0.5 wt of one or both of lead and bismuth in total
% of zinc alloy is used as a negative electrode active material.
マスの一種または二種を合計で0.005〜0.5wt
%、カルシウムおよびアルミニウムの一種または二種を
合計で0.005〜0.2wt%含有する亜鉛合金を負
極活物質に用いたことを特徴とする特許請求の範囲第1
項記載の亜鉛アルカリ電池の製造法。(3) 0.01 to 1 wt% of indium and 0.005 to 0.5 wt of one or both of lead and bismuth in total
Claim 1, characterized in that a zinc alloy containing a total of 0.005 to 0.2 wt% of one or both of calcium and aluminum is used as the negative electrode active material.
A method for producing a zinc-alkaline battery as described in Section 1.
その水溶液中で硫化水素を反応して合成した硫化インジ
ウムである特許請求の範囲第1項記載の亜鉛アルカリ電
池の製造法。(4) Indium sulfide uses indium salt as a starting material,
The method for manufacturing a zinc-alkaline battery according to claim 1, wherein indium sulfide is synthesized by reacting hydrogen sulfide in an aqueous solution of the indium sulfide.
5〜8μの粒子を総量の60wt%以上含むものである
特許請求の範囲第1項記載の亜鉛アルカリ電池の製造法
。(5) The synthesized indium sulfide has a particle size of 0.
2. The method for producing a zinc-alkaline battery according to claim 1, wherein the zinc-alkaline battery contains 60 wt% or more of the total amount of particles having a size of 5 to 8 μ.
したゲル状負極の調整において、インジウム、鉛、ビス
マス、カルシウムおよびアルミニウムの群のうち少なく
とも1種以上を含む亜鉛合金を活物質に用い、前記アル
カリ電解液中には硫化インジウムを前記亜鉛合金に対し
て0.005〜0.5wt%含有させ、さらに、ポリエ
チレンオキサイドを親水部に持つ界面活性剤を前記亜鉛
合金に対して0.001〜0.1wt%含有させること
を特徴とする亜鉛アルカリ電池の製造法。(6) In preparing a gelled negative electrode in which zinc alloy powder is mixed and dispersed in a gelled alkaline electrolyte, a zinc alloy containing at least one member from the group of indium, lead, bismuth, calcium, and aluminum is used as an active material, The alkaline electrolyte contains indium sulfide in an amount of 0.005 to 0.5 wt% based on the zinc alloy, and further contains a surfactant having polyethylene oxide in the hydrophilic part in an amount of 0.001 to 0.5 wt% based on the zinc alloy. A method for manufacturing a zinc-alkaline battery characterized by containing 0.1 wt%.
マスの一種または二種を合計で0.005〜0.5wt
%含有する亜鉛合金を負極活物質に用いたことを特徴と
する特許請求の範囲第6項記載の亜鉛アルカリ電池の製
造法。(7) 0.01 to 1 wt% of indium and 0.005 to 0.5 wt of one or both of lead and bismuth in total
7. The method for manufacturing a zinc-alkaline battery according to claim 6, characterized in that a zinc alloy containing % of zinc is used as a negative electrode active material.
マスの一種または二種を合計で0.005〜0.5wt
%、カルシウムおよびアルミニウムの一種または二種を
合計で0.005〜0.2wt%含有する亜鉛合金を負
極活物質に用いたことを特徴とする特許請求の範囲第6
項記載の亜鉛アルカリ電池の製造法。(8) 0.01 to 1 wt% of indium and 0.005 to 0.5 wt of one or both of lead and bismuth in total
Claim 6, characterized in that a zinc alloy containing a total of 0.005 to 0.2 wt% of one or both of calcium and aluminum is used as the negative electrode active material.
A method for producing a zinc-alkaline battery as described in Section 1.
その水溶液中で硫化水素を反応して合成した硫化インジ
ウムである特許請求の範囲第6項記載の亜鉛アルカリ電
池の製造法。(9) Indium sulfide uses indium salt as a starting material,
The method for manufacturing a zinc-alkaline battery according to claim 6, wherein the indium sulfide is synthesized by reacting hydrogen sulfide in the aqueous solution.
.5〜8μの粒子を総量の60wt%以上含むものであ
る特許請求の範囲第6項記載の亜鉛アルカリ電池の製造
法。(10) The synthesized indium sulfide has a particle size of 0
.. 7. The method for producing a zinc-alkaline battery according to claim 6, wherein the zinc-alkaline battery contains 60 wt% or more of the total amount of particles having a size of 5 to 8 μ.
性剤が下記の構造式 (X)−C_nF_2_n−(Y)−(CH_2CH_
2O)_m−(Z)X:−Hあるいは−F Y:−CONH−あるいは−SO_2NR−{Rはアル
キル基} Z:−CH_3、−PO_3W_2 あるいは−SO_3W{Wはアルカリ金属}n:4〜1
0 m:20〜100 で表される特許請求の範囲第6項記載の亜鉛アルカリ電
池の製造法。(11) The surfactant having polyethylene oxide in the hydrophilic part has the following structural formula (X)-C_nF_2_n-(Y)-(CH_2CH_
2O)_m-(Z)
0 m: 20 to 100. The method for producing a zinc-alkaline battery according to claim 6.
性剤が下記の構造式 (X)−C_2F_2_n−(CH_2CH_2)−(
CH_2CH_2O)_m−(Z)X:−Hあるいは−
F Z:−CH_3、−PO_3W_2 あるいは−SO_3W{Wはアルカリ金属}n:4〜1
0 m:40〜100 で表される特許請求の範囲第6項記載の亜鉛アルカリ電
池の製造法。(12) A surfactant having polyethylene oxide in its hydrophilic part has the following structural formula (X)-C_2F_2_n-(CH_2CH_2)-(
CH_2CH_2O)_m-(Z)X:-H or-
F Z: -CH_3, -PO_3W_2 or -SO_3W {W is an alkali metal} n: 4 to 1
0 m: 40-100 The method for manufacturing a zinc-alkaline battery according to claim 6.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12848090A JP2808822B2 (en) | 1990-05-17 | 1990-05-17 | Manufacturing method of zinc alkaline battery |
US07/698,912 US5168018A (en) | 1990-05-17 | 1991-05-13 | Method of manufacturing zinc-alkaline batteries |
CA002042549A CA2042549C (en) | 1990-05-17 | 1991-05-14 | Method of manufacturing zinc-alkaline batteries |
AU77017/91A AU622588B2 (en) | 1990-05-17 | 1991-05-14 | Method of manufacturing zinc-alkaline batteries |
KR1019910007939A KR940007633B1 (en) | 1990-05-17 | 1991-05-16 | Method of manufacturing zinc-alkali bettery |
EP91108064A EP0457354B1 (en) | 1990-05-17 | 1991-05-17 | Method of manufacturing zinc-alkaline batteries |
DE69111686T DE69111686T2 (en) | 1990-05-17 | 1991-05-17 | Process for the production of alkaline zinc batteries. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12848090A JP2808822B2 (en) | 1990-05-17 | 1990-05-17 | Manufacturing method of zinc alkaline battery |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0426062A true JPH0426062A (en) | 1992-01-29 |
JP2808822B2 JP2808822B2 (en) | 1998-10-08 |
Family
ID=14985781
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12848090A Expired - Lifetime JP2808822B2 (en) | 1990-05-17 | 1990-05-17 | Manufacturing method of zinc alkaline battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2808822B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08510010A (en) * | 1993-02-25 | 1996-10-22 | エン.ファウ.ユニオン ミニーレ エス.アー. | Zinc powder for alkaline batteries |
US6602629B1 (en) | 2000-05-24 | 2003-08-05 | Eveready Battery Company, Inc. | Zero mercury air cell |
US8283069B2 (en) | 2006-03-28 | 2012-10-09 | Panasonic Corporation | Zinc-alkaline battery |
-
1990
- 1990-05-17 JP JP12848090A patent/JP2808822B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08510010A (en) * | 1993-02-25 | 1996-10-22 | エン.ファウ.ユニオン ミニーレ エス.アー. | Zinc powder for alkaline batteries |
US6602629B1 (en) | 2000-05-24 | 2003-08-05 | Eveready Battery Company, Inc. | Zero mercury air cell |
US8283069B2 (en) | 2006-03-28 | 2012-10-09 | Panasonic Corporation | Zinc-alkaline battery |
Also Published As
Publication number | Publication date |
---|---|
JP2808822B2 (en) | 1998-10-08 |
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