JP2007115701A - Alkaline battery - Google Patents
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- JP2007115701A JP2007115701A JP2006306377A JP2006306377A JP2007115701A JP 2007115701 A JP2007115701 A JP 2007115701A JP 2006306377 A JP2006306377 A JP 2006306377A JP 2006306377 A JP2006306377 A JP 2006306377A JP 2007115701 A JP2007115701 A JP 2007115701A
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- potassium hydroxide
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 134
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 37
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 29
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003349 gelling agent Substances 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 150000003752 zinc compounds Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 9
- 230000005856 abnormality Effects 0.000 abstract description 7
- 239000004020 conductor Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000011149 active material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- -1 zinc oxide Chemical class 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 206010000117 Abnormal behaviour Diseases 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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- Y02E60/12—
Abstract
Description
本発明は、アルカリ電池に関し、より詳しくは、負荷特性に優れる一方で、異常発生時の発熱挙動を抑制したアルカリ電池に関する。 The present invention relates to an alkaline battery. More specifically, the present invention relates to an alkaline battery that has excellent load characteristics while suppressing heat generation behavior when an abnormality occurs.
亜鉛を負極活物質とするアルカリ電池は、各種電子機器の電源として用いられ、その用途に応じて種々の特性が要求されている。特に、近年普及が著しいデジタルカメラにおいては、撮影可能枚数をできるだけ多くするためには、電池の高容量化と大電流放電特性などの負荷特性のさらなる向上が必要であり、その要求を満たすことのできる電池設計が検討されている。 An alkaline battery using zinc as a negative electrode active material is used as a power source for various electronic devices, and various characteristics are required depending on its use. In particular, in digital cameras that have been widely used in recent years, in order to maximize the number of images that can be taken, it is necessary to increase the battery capacity and further improve the load characteristics such as the large current discharge characteristics. Possible battery designs are being studied.
電池の高容量化のためには、活物質の充填量の増加が必要であるが、活物質が放電に有効に利用されなければ容量増に結びつかないため、単に、活物質の充填量を多くするのみでは目的を達することはできない。放電容量は活物質の利用率との兼ね合いで決定されるものであるから、活物質相互の良好な導電性の確保と均質な充填が重要となる。 In order to increase the capacity of the battery, it is necessary to increase the filling amount of the active material. However, if the active material is not effectively used for discharging, the capacity cannot be increased. Therefore, simply increasing the filling amount of the active material. You can't achieve your goal by just doing it. Since the discharge capacity is determined in view of the utilization factor of the active material, it is important to ensure good conductivity between the active materials and to perform uniform filling.
また、負荷特性の向上には、活物質の反応面積の増加や導電性の向上などが必要となるが、活物質の反応面積の増加に伴い、電解液との反応によるガス発生が生じやすくなるため、負極においては、負極活物質である亜鉛とガス発生を抑制できる添加元素とを合金化させるのが一般的である。 Moreover, to improve the load characteristics, it is necessary to increase the reaction area of the active material and improve the conductivity, but as the reaction area of the active material increases, gas generation due to reaction with the electrolyte tends to occur. Therefore, in the negative electrode, it is common to alloy zinc, which is a negative electrode active material, with an additive element that can suppress gas generation.
しかしながら、添加元素の含有量の増加により、導電性が低下しやすくなるため、ガス発生の抑制と負荷特性を両立させることは困難である。しかも、自己放電の抑制のために、電解液には亜鉛化合物、特に、酸化亜鉛を含有させるのが一般的であるが、これによっても負荷特性は低下してしまう。 However, since the conductivity tends to decrease due to an increase in the content of the additive element, it is difficult to achieve both suppression of gas generation and load characteristics. Moreover, in order to suppress self-discharge, the electrolyte solution generally contains a zinc compound, particularly zinc oxide, but this also deteriorates the load characteristics.
また、たとえ負荷特性に優れる電池を設計できたとしても、以下に示す別の問題が生じるため、実用的な電池とするには解決すべき課題が残されている。すなわち、高温で貯蔵した場合の貯蔵性が悪かったり、電子機器の誤作動や誤って電池を短絡させるなどして電池に過大な電流が流れた際に、電池内で発生する熱により電池が高温となり、電解液の漏出や電池の破裂などの危険性が生じることが問題となる。特に、電池が高容量化、高負荷対応となるほど反応性が高まり、かつ発熱量が大きくなるため、上記問題の解決はより重要となる。 Even if a battery having excellent load characteristics can be designed, another problem shown below arises. Therefore, there remains a problem to be solved for a practical battery. In other words, when the battery is stored at a high temperature, the battery becomes hot due to heat generated in the battery when an excessive current flows through the battery due to malfunction of the electronic device or accidental short circuit of the battery. Thus, there arises a problem that dangers such as leakage of the electrolyte and rupture of the battery occur. In particular, the higher the capacity of the battery and the higher the load, the higher the reactivity and the greater the amount of heat generated. Therefore, the solution of the above problem becomes more important.
従って、高容量で負荷特性に優れる一方で、貯蔵性に優れ、短絡などの異常発生時には、発熱による急激な温度上昇などの異常挙動が生じにくいアルカリ電池を設計することが求められているのである。 Therefore, it is required to design an alkaline battery that has high capacity and excellent load characteristics, but also has excellent storability and is unlikely to cause abnormal behavior such as rapid temperature rise due to heat generation when an abnormality such as a short circuit occurs. .
本発明は、上記課題を解決するためになされたもので、負荷特性に優れ、電解液との反応によるガス発生や貯蔵性の低下を防止する一方で、異常発生時の発熱挙動を抑制したアルカリ電池を提供するものである。 The present invention has been made in order to solve the above-described problems, and has an excellent load characteristic, an alkali that suppresses heat generation behavior at the time of occurrence of an abnormality while preventing gas generation and storage deterioration due to reaction with an electrolytic solution. A battery is provided.
本発明のアルカリ電池は、二酸化マンガンおよびニッケル酸化物の少なくとも一方と導電剤と水酸化カリウムを溶解したアルカリ電解液(A)とを含有する正極合剤、セパレータ、亜鉛合金粉末とゲル化剤と水酸化カリウムを溶解したアルカリ電解液(B)とを含有する負極合剤、および水酸化カリウムを溶解したアルカリ電解液(C)を外装体内部に封入することにより作製されるアルカリ電池であって、アルカリ電解液(C)は電池組み立て時に外装体内部に注入してセパレータに吸収させたものであり、電池組み立て後に、電池系内のアルカリ電解液の水酸化カリウム濃度が平均して30〜37質量%となるように、アルカリ電解液(A)、アルカリ電解液(B)およびアルカリ電解液(C)それぞれの水酸化カリウム濃度を調整してあり、負極の亜鉛合金粉末として、200メッシュのふるい目を通過する粉末の割合が4〜40質量%である亜鉛合金粉末を用いたことを特徴とするものである。 The alkaline battery of the present invention comprises a positive electrode mixture, a separator, a zinc alloy powder and a gelling agent containing at least one of manganese dioxide and nickel oxide, a conductive agent and an alkaline electrolyte (A) in which potassium hydroxide is dissolved. A negative electrode mixture containing an alkaline electrolyte (B) in which potassium hydroxide is dissolved, and an alkaline battery produced by enclosing an alkaline electrolyte (C) in which potassium hydroxide is dissolved inside an exterior body. The alkaline electrolyte (C) is injected into the exterior body during battery assembly and absorbed by the separator. After the battery is assembled, the average potassium hydroxide concentration of the alkaline electrolyte in the battery system is 30 to 37. Adjust the potassium hydroxide concentration of each of the alkaline electrolyte (A), alkaline electrolyte (B) and alkaline electrolyte (C) so as to be mass%. Ri, as zinc alloy powder of the negative electrode, in which the proportion of the powder passing through a sieve of 200 mesh is characterized by using a zinc alloy powder is 4-40 weight%.
本発明によれば、負荷特性に優れ、電解液との反応によるガス発生や貯蔵性の低下を防止する一方で、異常発生時の発熱挙動を抑制したアルカリ電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in load characteristics and preventing the gas generation | occurrence | production and storage property fall by reaction with electrolyte solution, the alkaline battery which suppressed the heat-generation behavior at the time of abnormality generation can be provided.
本発明は、電池組み立て後に、電池系内のアルカリ電解液の水酸化カリウム濃度が平均して30〜37質量%となるように、アルカリ電解液(A)、アルカリ電解液(B)およびアルカリ電解液(C)それぞれの水酸化カリウム濃度を調整してあることを第1の特徴とする。 The present invention provides an alkaline electrolyte (A), alkaline electrolyte (B), and alkaline electrolysis so that the average potassium hydroxide concentration of the alkaline electrolyte in the battery system is 30 to 37% by mass after battery assembly. The first characteristic is that the potassium hydroxide concentration of each liquid (C) is adjusted.
本発明のアルカリ電池は、上記正極合剤および負極合剤をセパレータと共に外装体内部に封入することにより作製される。正極合剤は、活物質と導電剤とアルカリ電解液(A)とを混合することにより形成され、負極合剤は、亜鉛合金粉末とゲル化剤と水酸化カリウムを溶解したアルカリ電解液(B)とを混合し、ゲル状の混合体として形成されるが、正極合剤および負極合剤に含有されるアルカリ電解液のみでは液量が不足する場合が多いため、さらにアルカリ電解液(C)を注入してセパレータに吸収させる。 The alkaline battery of the present invention is produced by enclosing the positive electrode mixture and the negative electrode mixture together with a separator in the exterior body. The positive electrode mixture is formed by mixing an active material, a conductive agent and an alkaline electrolyte (A), and the negative electrode mixture is an alkaline electrolyte (B) in which zinc alloy powder, a gelling agent and potassium hydroxide are dissolved. ) And is formed as a gel-like mixture. However, since the amount of the liquid is often insufficient only with the alkaline electrolyte contained in the positive electrode mixture and the negative electrode mixture, the alkaline electrolyte (C) Is injected and absorbed by the separator.
そして、電池組み立て後に、電池系内のアルカリ電解液(A)〜(C)は拡散して混じりあい、徐々に一様な電解液に近づいていくが、このとき、アルカリ電解液全体の水酸化カリウムの平均濃度が30〜37質量%となるように、アルカリ電解液(A)〜(C)のそれぞれの水酸化カリウム濃度を調整しておく。水酸化カリウム濃度を30質量%以上とすることにより高温で貯蔵した際の貯蔵性が向上し、33.5質量%以上であればより優れた特性が得られる。 Then, after the battery is assembled, the alkaline electrolytes (A) to (C) in the battery system are diffused and mixed, and gradually approach a uniform electrolyte. At this time, hydroxylation of the entire alkaline electrolyte is performed. The potassium hydroxide concentration of each of the alkaline electrolytes (A) to (C) is adjusted so that the average concentration of potassium is 30 to 37% by mass. When the potassium hydroxide concentration is 30% by mass or more, the storage property when stored at a high temperature is improved, and if it is 33.5% by mass or more, more excellent characteristics are obtained.
一方、アルカリ電解液全体の水酸化カリウムの平均濃度を37質量%以下とすることにより負荷特性が向上し、また、短絡時の異常発熱の抑制効果が得られる。すなわち、電池が短絡した場合は、短絡発生直後の段階では過大な短絡電流が流れるが、このときに生じる負極の亜鉛合金粉末の急激な放電反応により、反応を抑制する酸化物層が亜鉛合金粉末表面に一気に形成されることになり、短時間のうちに短絡電流は減少する。このため、放電に伴う発熱は比較的少なくなり、電池の温度上昇が抑制されて、電解液の漏出や電池の破裂などの異常な挙動が生じるのを防ぐことができると考えられる。 On the other hand, when the average concentration of potassium hydroxide in the entire alkaline electrolyte is 37% by mass or less, load characteristics are improved, and an effect of suppressing abnormal heat generation at the time of a short circuit is obtained. That is, when the battery is short-circuited, an excessive short-circuit current flows immediately after the occurrence of the short-circuit, but the oxide layer that suppresses the reaction due to the rapid discharge reaction of the zinc alloy powder of the negative electrode generated at this time It will be formed on the surface at once, and the short circuit current will decrease in a short time. For this reason, it is considered that the heat generated by the discharge is relatively small, the battery temperature rise is suppressed, and abnormal behavior such as leakage of the electrolytic solution or battery rupture can be prevented.
アルカリ電解液(C)は、20〜40質量%の濃度で水酸化カリウムを溶解させたものが好ましく用いられる。すなわち、前述した短絡時の異常発熱を抑制する効果は、アルカリ電解液(C)の水酸化カリウム濃度にも依存するのであり、できるだけ低い濃度の電解液を用いることが望ましく、35質量%未満であればより好ましい結果が得られる。 As the alkaline electrolyte (C), a solution in which potassium hydroxide is dissolved at a concentration of 20 to 40% by mass is preferably used. That is, the effect of suppressing the abnormal heat generation at the time of short circuit described above also depends on the potassium hydroxide concentration of the alkaline electrolyte (C), and it is desirable to use an electrolyte having a concentration as low as possible, less than 35% by mass. If so, more favorable results can be obtained.
本発明は、負極合剤の形成において、亜鉛合金粉末として、200メッシュのふるい目を通過する粉末の割合が4〜40質量%である亜鉛合金粉末を用いることを第2の特徴とする。負極合剤は、亜鉛合金粉末とゲル化剤と水酸化カリウムを溶解したアルカリ電解液(B)とを混合し、ゲル状の混合体として形成されるが、亜鉛合金粉末において、200メッシュのふるい目を通過する粉末の割合が4質量%以上であれば、大電流のパルス放電での特性が向上する。亜鉛合金粉末における200メッシュのふるい目を通過する粉末の割合は、15質量%以上がより望ましく、一方、均質で流動性の良好な負極合剤を形成するためには40質量%以下にすることが望ましい。 The present invention is characterized in that, in the formation of the negative electrode mixture, a zinc alloy powder having a ratio of powder passing through a 200 mesh sieve is 4 to 40% by mass as the zinc alloy powder. The negative electrode mixture is formed by mixing a zinc alloy powder, a gelling agent, and an alkaline electrolyte (B) in which potassium hydroxide is dissolved, and is formed as a gel-like mixture. When the proportion of the powder passing through the eye is 4% by mass or more, the characteristics in a large current pulse discharge are improved. The proportion of the powder passing through the 200 mesh sieve in the zinc alloy powder is more preferably 15% by mass or more, while it is 40% by mass or less in order to form a negative electrode mixture having a uniform and good fluidity. Is desirable.
また、亜鉛合金粉末の合金元素としてインジウム、ビスマスおよびアルミニウムを含有していることが望ましい。亜鉛合金粉末の表面状態をより好適なものとすることができ、負荷特性や異常発熱の抑制効果に影響をおよぼすだけでなく、亜鉛合金粉末の反応面積を増加させるために微小粒子の割合を多くする場合でも、電解液との反応を抑制しガス発生を防ぐことができるからである。これら元素の含有量としては、インジウム、ビスマスおよびアルミニウムが、それぞれ0.03〜0.07質量%、0.007〜0.025質量%および0.001〜0.004質量%であるのが望ましい。 Moreover, it is desirable to contain indium, bismuth and aluminum as alloy elements of the zinc alloy powder. The surface condition of the zinc alloy powder can be made more suitable, not only affecting the load characteristics and the effect of suppressing abnormal heat generation, but also increasing the proportion of fine particles to increase the reaction area of the zinc alloy powder. This is because the reaction with the electrolytic solution can be suppressed and gas generation can be prevented. As contents of these elements, indium, bismuth and aluminum are preferably 0.03 to 0.07% by mass, 0.007 to 0.025% by mass and 0.001 to 0.004% by mass, respectively. .
負極合剤の形成において用いるアルカリ電解液(B)は、水酸化カリウムを35質量%以下の濃度で含有することが好ましい。アルカリ電解液(B)の水酸化カリウム濃度を35質量%以下とすることにより、亜鉛合金粉末表面の酸化物被膜の状態を適切なものとすることができ、アルカリ電解液の伝導度を上げて負荷特性をより向上させ、また、短絡時の初期段階で放電反応が容易に進行するため、前述した異常発熱の抑制効果が得られやすくなると思われる。 The alkaline electrolyte (B) used in the formation of the negative electrode mixture preferably contains potassium hydroxide at a concentration of 35% by mass or less. By setting the potassium hydroxide concentration of the alkaline electrolyte (B) to 35% by mass or less, the state of the oxide coating on the surface of the zinc alloy powder can be made appropriate, and the conductivity of the alkaline electrolyte is increased. It seems that the load characteristics are further improved and the discharge reaction easily proceeds in the initial stage at the time of a short circuit, so that the above-described effect of suppressing abnormal heat generation is likely to be obtained.
また、アルカリ電解液(B)に亜鉛化合物を含有させることによっても、亜鉛合金粉末の表面状態をより好適なものとすることができる。亜鉛化合物としては、酸化亜鉛、ケイ酸亜鉛、チタン酸亜鉛、モリブデン酸亜鉛などを用いることができ、酸化亜鉛が好適に用いられる。亜鉛化合物の溶解度を高めるためには、アルカリ電解液(B)の水酸化カリウム濃度を20質量%以上とすることが望ましい。なお、後述する正極合剤のアルカリ電解液(A)あるいは上記のアルカリ電解液(C)に亜鉛化合物を含有させることもできる。 Moreover, the surface state of a zinc alloy powder can be made more suitable also by making an alkaline electrolyte (B) contain a zinc compound. As the zinc compound, zinc oxide, zinc silicate, zinc titanate, zinc molybdate and the like can be used, and zinc oxide is preferably used. In order to increase the solubility of the zinc compound, the potassium hydroxide concentration of the alkaline electrolyte (B) is desirably 20% by mass or more. In addition, a zinc compound can be contained in an alkaline electrolyte (A) of the positive electrode mixture described later or the alkaline electrolyte (C) described above.
上記以外の構成要素として、負極合剤に酸化インジウムなどのインジウム化合物、酸化ビスマスなどのビスマス化合物を少量含有させることもできる。これらの化合物を含有させた場合、亜鉛合金粉末と電解液との反応によるガス発生をより効果的に防ぐことができるが、負荷特性を低下させるおそれがあるので、必要に応じて含有量が決定される。 As constituent elements other than the above, the negative electrode mixture may contain a small amount of an indium compound such as indium oxide or a bismuth compound such as bismuth oxide. When these compounds are contained, gas generation due to the reaction between the zinc alloy powder and the electrolytic solution can be prevented more effectively, but the load characteristics may be reduced, so the content is determined as necessary. Is done.
本発明において、正極合剤は、上記の通り、二酸化マンガンおよびニッケル酸化物の少なくとも一方と導電剤と上記アルカリ電解液(A)とを混合することにより形成されるが、アルカリ電解液(A)の水酸化カリウム濃度を45質量%以上とすることが好ましく、これにより均質な混合体が形成され、合剤の高密度での充填や合剤全体の導電性向上を可能とする。従って、電池の高容量設計を実現することができるとともに、負荷特性を向上させることも可能となる。 In the present invention, the positive electrode mixture is formed by mixing at least one of manganese dioxide and nickel oxide, a conductive agent and the alkaline electrolyte (A) as described above. The potassium hydroxide concentration is preferably 45% by mass or more, whereby a homogeneous mixture is formed, and the mixture can be filled at a high density and the conductivity of the entire mixture can be improved. Therefore, it is possible to realize a high capacity design of the battery and to improve load characteristics.
ここで、上記電解液(A)として50質量%を超える濃度で水酸化カリウムを含有したアルカリ電解液を用いれば、上記効果がより得られやすくなる他、上述の負極合剤のアルカリ電解液(B)として、より水酸化カリウム濃度の低いものを使用することができるので、本発明においては特に望ましい結果が得られる。 Here, if the alkaline electrolyte containing potassium hydroxide at a concentration exceeding 50% by mass is used as the electrolytic solution (A), the above effect can be obtained more easily, and the alkaline electrolyte of the negative electrode mixture ( Since B) having a lower potassium hydroxide concentration can be used, a particularly desirable result can be obtained in the present invention.
ただし、室温での水酸化カリウムの飽和濃度がおよそ50質量%であることから、これより高い濃度のアルカリ電解液を用いる場合は、合剤の温度管理を行うことが望ましい。すなわち、アルカリ電解液の調製は、通常、水酸化カリウムが溶解しやすいように加温された条件下で行われるため、50質量%を超える濃度の水酸化カリウム水溶液を作製することは容易であるが、合剤の作製を室温付近かそれ以下で行う場合は、その温度での飽和量を超えた水酸化カリウムが析出し、均質な合剤の形成が損なわれる可能性が高い。そのため、電解液が飽和濃度に達しないよう加温雰囲気下で合剤構成物を混合し、正極合剤を作製することが望ましい。温度条件としては、水酸化カリウムの飽和溶解量を高めるため、35℃以上で行うことが望ましく、水分の蒸発により電解液組成が変化するのを防ぐため、70℃以下の温度で行うことが望ましい。また、水酸化カリウム濃度が45〜50質量%である場合も、加温雰囲気下で合剤構成物を混合することにより、構成物の分散性が向上して均質な合剤が形成されやすくなる。 However, since the saturated concentration of potassium hydroxide at room temperature is approximately 50% by mass, it is desirable to control the temperature of the mixture when using an alkaline electrolyte having a higher concentration. That is, since the preparation of the alkaline electrolyte is usually performed under conditions that are heated so that potassium hydroxide is easily dissolved, it is easy to produce a potassium hydroxide aqueous solution having a concentration exceeding 50% by mass. However, when the mixture is produced at or near room temperature, it is highly possible that potassium hydroxide exceeding the saturation amount at that temperature precipitates and the formation of a homogeneous mixture is impaired. Therefore, it is desirable to mix the mixture composition in a heated atmosphere so that the electrolytic solution does not reach a saturated concentration to produce a positive electrode mixture. As the temperature condition, it is desirable to carry out at 35 ° C. or higher in order to increase the saturated dissolution amount of potassium hydroxide. . In addition, even when the potassium hydroxide concentration is 45 to 50% by mass, the dispersibility of the composition is improved and a homogeneous mixture is easily formed by mixing the mixture composition in a heated atmosphere. .
また、上記導電剤としては、黒鉛、アセチレンブラック、カーボンブラック、繊維状炭素などの炭素材料を主として用いることができるが、中でも黒鉛が好ましく用いられる。本発明においては、正極の活物質として、二酸化マンガン、あるいは、オキシ水酸化ニッケルやそのニッケルの一部が他の元素で置換された化合物に代表されるニッケル酸化物のいずれか一方かあるいはそれらを混合して用いるが、正極活物質である二酸化マンガンおよびニッケル酸化物の合計量100質量部に対し、6質量部以上の割合で黒鉛を混合することが望ましい。これは、前述した短絡時の異常発熱を抑制する効果が一段と発揮されやすくなるからである。一方、活物質充填量の低下は好ましくないため、黒鉛の割合は、正極活物質である二酸化マンガンおよびニッケル酸化物の合計量100質量部に対し、8.5質量部以下にすることが望ましい。 Moreover, as said electrically conductive agent, carbon materials, such as graphite, acetylene black, carbon black, and fibrous carbon, can be mainly used, However, Among these, graphite is used preferably. In the present invention, as the active material of the positive electrode, manganese dioxide, nickel oxyhydroxide, nickel oxide represented by a compound in which part of nickel is substituted with another element, or any of them is used. Although mixed and used, it is desirable to mix graphite at a ratio of 6 parts by mass or more with respect to 100 parts by mass of the total amount of manganese dioxide and nickel oxide as positive electrode active materials. This is because the effect of suppressing the abnormal heat generation at the time of the short circuit is more easily exhibited. On the other hand, since the reduction of the active material filling amount is not preferable, the proportion of graphite is desirably 8.5 parts by mass or less with respect to 100 parts by mass of the total amount of manganese dioxide and nickel oxide as the positive electrode active material.
上記以外の構成要素として、正極合剤にカルボキシメチルセルロース、メチルセルロース、ポリアクリル酸塩、ポリテトラフルオロエチレン、ポリエチレンなどのバインダを少量含有させることもできる。添加量が多いと導電性が低下するなどの弊害が生じるが、少量であれば導電剤と活物質との接触を良好にするので却って好都合である。 As a constituent element other than the above, a small amount of a binder such as carboxymethyl cellulose, methyl cellulose, polyacrylate, polytetrafluoroethylene, and polyethylene can be contained in the positive electrode mixture. If the added amount is large, adverse effects such as a decrease in conductivity occur, but if the added amount is small, the contact between the conductive agent and the active material is improved, which is advantageous.
また、アルカリ電解液(B)だけでなく(A)および(C)にも亜鉛化合物を含有させれば、電池を高温で貯蔵したときの特性劣化を低減する効果が大きくなる。アルカリ電解液(C)の水酸化カリウム濃度を20質量%以上にしておけば、亜鉛化合物の溶解度が高まるため、亜鉛化合物の添加の面からも好都合である。 Further, if the zinc compound is contained not only in the alkaline electrolyte (B) but also in (A) and (C), the effect of reducing characteristic deterioration when the battery is stored at a high temperature is increased. If the potassium hydroxide concentration of the alkaline electrolyte (C) is set to 20% by mass or more, the solubility of the zinc compound increases, which is advantageous from the viewpoint of adding the zinc compound.
本発明では、電池の形状などは特に限定されないが、外装体として円筒形の金属製外装缶を用いる場合は、リング状に成形された前記正極合剤を外装缶内部に配置し、その内側にコップ状のセパレータを配置し、次いで、アルカリ電解液(C)を注入してセパレータに吸収させ、さらに前記負極合剤をセパレータの内側の空隙に充填し、これら構成要素を外装缶内部に封入することにより電池が組み立てられる。図2に示されるように、円筒形のアルカリ電池においては、外装缶1の開口端部1aを内方に折り曲げて封口を行った際に、負極端子板207の変形を防ぎ、かつ封口体6を内側から支える指示手段として金属ワッシャ9(円板状の金属板)を用いることが一般に行われているが、封口部分10の占める体積が大きくなってしまうという問題がある。
In the present invention, the shape of the battery is not particularly limited. However, when a cylindrical metal outer can is used as the outer casing, the positive electrode mixture formed in a ring shape is disposed inside the outer can, and inside the outer casing can. A cup-shaped separator is placed, and then the alkaline electrolyte (C) is injected and absorbed by the separator. Further, the negative electrode mixture is filled in the gap inside the separator, and these components are sealed inside the outer can. As a result, the battery is assembled. As shown in FIG. 2, in the cylindrical alkaline battery, when the opening
一方、金属ワッシャをなくし、封口体6を内側から支える指示手段として負極端子板7を利用した図1の電池では、封口部分10の占める体積を減少させることができるので、正極2および負極4の合剤の充填量をより高めることができる反面、電池の高容量化に伴い、短絡時の発熱は一層大きくなる。しかし、このような高容量設計の電池においても、本発明を用いることにより、電池の異常発熱挙動を防ぐことができるので、電池の実用性を高めることができる。
On the other hand, in the battery of FIG. 1 in which the metal washer is eliminated and the negative electrode terminal plate 7 is used as an instruction means for supporting the sealing
以下において本発明の実施例を説明するが、もちろん本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below. Of course, the present invention is not limited to these examples.
(参考例1)
電解二酸化マンガン、黒鉛、ポリテトラフルオロエチレン粉末およびアルカリ電解液(A)(酸化亜鉛を2.9質量%含有した56質量%水酸化カリウム水溶液)を87.6:6.7:0.2:5.5の質量比で混合し、正極合剤を作製した。この正極合剤の作製は50℃の温度下で行った。また、上記正極合剤中、二酸化マンガン100質量部に対する黒鉛の割合は7.6質量部であった。
(Reference Example 1)
Electrolytic manganese dioxide, graphite, polytetrafluoroethylene powder and alkaline electrolyte (A) (56% by mass aqueous potassium hydroxide solution containing 2.9% by mass of zinc oxide) 87.6: 6.7: 0.2: The mixture was mixed at a mass ratio of 5.5 to prepare a positive electrode mixture. The positive electrode mixture was produced at a temperature of 50 ° C. Moreover, the ratio of the graphite with respect to 100 mass parts of manganese dioxides in the said positive electrode mixture was 7.6 mass parts.
また、インジウム、ビスマスおよびアルミニウムをそれぞれ0.05質量%、0.05質量%および0.005質量%の割合で含有する亜鉛合金粉末、ポリアクリル酸ソーダ、ポリアクリル酸およびアルカリ電解液(B)(酸化亜鉛を2.2質量%含有した32質量%水酸化カリウム水溶液)を39:0.2:0.2:18の質量比で混合し、ゲル状の負極合剤を作製した。なお、上記亜鉛合金粉末は、平均粒径が122μmで、80メッシュのふるい目を全て通過し、かつ200メッシュのふるい目を通過しない亜鉛合金粉末であって、その見掛け密度は2.65g/cm3であった。 Also, zinc alloy powder, polyacrylic acid soda, polyacrylic acid, and alkaline electrolyte (B) containing 0.05% by mass, 0.05% by mass, and 0.005% by mass of indium, bismuth, and aluminum, respectively. (A 32% by mass aqueous potassium hydroxide solution containing 2.2% by mass of zinc oxide) was mixed at a mass ratio of 39: 0.2: 0.2: 18 to prepare a gelled negative electrode mixture. The zinc alloy powder is a zinc alloy powder having an average particle size of 122 μm, passing through all 80 mesh screens and not passing through 200 mesh screens, and has an apparent density of 2.65 g / cm. 3 .
外装体として、封口部分10の厚みが0.25mmで、胴部分20の厚みが0.16mmに加工され、また、電池を落下させたときに正極端子1bのへこみを防ぐために、正極端子部分の缶厚を胴部分20より多少厚くしたキルド鋼板製の単三形アルカリ乾電池用外装缶1を用い、以下のようにしてアルカリ電池を作製した。
As the exterior body, the sealing
上記正極合剤11gを、内径9.1mm、外径13.7mm、高さ41.7mmの円筒状に加圧成形して正極とし、これを上記外装缶1に挿入した。その後、外装缶1の開口端から高さ方向において3.5mmの位置にグルーブを施し、外装缶1と封口体6との密着性を向上させるために、このグルーブ位置まで外装缶1の内側にピッチを塗布した。
11 g of the positive electrode mixture was press-molded into a cylindrical shape having an inner diameter of 9.1 mm, an outer diameter of 13.7 mm, and a height of 41.7 mm to form a positive electrode, which was inserted into the
次に、厚みが100μmで目付が30g/m2のアセタール化ビニロンとテンセルからなる不織布を三重に重ねて筒状に巻き、底部になる部分を折り曲げてこの部分を熱融着し、一端が閉じられたコップ状のセパレータ3とした。このセパレータ3を、外装缶内に挿入された正極1の内側に装填し、さらに、アルカリ電解液(C)(酸化亜鉛を2.2質量%含有した32質量%水酸化カリウム水溶液)1.35gを外装缶内に注入してセパレータ3にしみこませた。次いで、上記負極合剤5.74gをセパレータ3の内側に充填して負極4とし、さらに、ナイロン6−6製の封口体6と組み合わされ、かつ打ち抜き・プレス加工により形成された厚さ0.4mmの負極端子板7(ニッケルメッキ鋼板製)に溶接により取り付けられた負極集電棒5(表面がスズメッキされた真鍮製)を上記負極中央部に差し込み、外装缶1の開口端部1aの外側からスピニング方式によりかしめることにより、図1に示す単3形アルカリ電池を作製した。なお、外装缶1の開口端と負極端子板7との間には、短絡防止のために絶縁板8を装着した。
Next, a nonwoven fabric made of acetalized vinylon having a thickness of 100 μm and a basis weight of 30 g / m 2 and tencel is overlapped in a cylinder, wound into a cylindrical shape, the bottom portion is bent, this portion is heat-sealed, and one end is closed The cup-shaped
上記電池において、組み立て後の電池系内のアルカリ電解液は、平均して35質量%の水酸化カリウムを含有していた。 In the above battery, the alkaline electrolyte in the assembled battery system contained 35% by mass of potassium hydroxide on average.
(参考例2)
電解二酸化マンガン、黒鉛、ポリテトラフルオロエチレン粉末およびアルカリ電解液(A)を89.3:5.1:0.2:5.6の質量比で混合し、正極合剤を作製した以外は参考例1と同様にして、単3形アルカリ電池を作製した。この正極合剤において、二酸化マンガン100質量部に対する黒鉛の割合は5.7質量部であった。
(Reference Example 2)
Reference was made except that electrolytic manganese dioxide, graphite, polytetrafluoroethylene powder and alkaline electrolyte (A) were mixed at a mass ratio of 89.3: 5.1: 0.2: 5.6 to prepare a positive electrode mixture. In the same manner as in Example 1, an AA alkaline battery was produced. In this positive electrode mixture, the ratio of graphite to 100 parts by mass of manganese dioxide was 5.7 parts by mass.
(参考例3)
アルカリ電解液(B)および(C)として、酸化亜鉛を2.0質量%含有した30質量%水酸化カリウム水溶液を用いた以外は参考例1と同様にして、単3形アルカリ電池を作製した。組み立て後の電池系内のアルカリ電解液は、平均して33質量%の水酸化カリウムを含有していた。
(Reference Example 3)
AA alkaline batteries were produced in the same manner as in Reference Example 1 except that 30% by mass potassium hydroxide aqueous solution containing 2.0% by mass of zinc oxide was used as the alkaline electrolytes (B) and (C). . The alkaline electrolyte in the assembled battery system contained 33% by mass of potassium hydroxide on average.
(実施例1)
負極の亜鉛合金粉末としてインジウム、ビスマスおよびアルミニウムをそれぞれ0.05質量%、0.015質量%および0.003質量%の割合で含有し、平均粒径が200μmで、35メッシュのふるい目を全て通過し、かつ200メッシュのふるい目を通過するものの割合が6質量%であって、見掛け密度が2.9g/cm3である亜鉛合金粉末を用いた以外は参考例1と同様にして、単3形アルカリ電池を作製した。
Example 1
Indium, bismuth and aluminum are contained in the proportions of 0.05% by mass, 0.015% by mass and 0.003% by mass, respectively, as the zinc alloy powder of the negative electrode, the average particle size is 200 μm, and all 35 mesh sieves Similar to Reference Example 1, except that a zinc alloy powder that passes through and passes through a 200-mesh sieve is 6% by mass and the apparent density is 2.9 g / cm 3. A three-type alkaline battery was produced.
(実施例2)
負極の亜鉛合金粉末として、平均粒径が135μmで、35メッシュのふるい目を全て通過し、かつ200メッシュのふるい目を通過するものの割合が20質量%であって、見掛け密度が2.9g/cm3である亜鉛合金粉末を用いた以外は参考例1と同様にして、単3形アルカリ電池を作製した。
(Example 2)
The proportion of the negative electrode zinc alloy powder having an average particle diameter of 135 μm, passing through all 35 mesh sieves and passing through 200 mesh sieves is 20% by mass, and the apparent density is 2.9 g / AA alkaline batteries were produced in the same manner as in Reference Example 1 except that the zinc alloy powder of cm 3 was used.
以上のようにして作製した実施例および参考例に係る電池各々12個に対し、ベース放電電流を0.5Aとし、30秒間隔で2Aのパルス電流を2秒間流すパルス放電試験を行い、2Aのパルス電流が流れた時点の電圧が1.0V以下に低下するまでに要するパルス放電の回数を測定して平均値を求め、負荷特性を評価した。 For each of the 12 batteries according to the example and the reference example manufactured as described above, a pulse discharge test was performed in which a base discharge current was 0.5 A and a pulse current of 2 A was supplied for 2 seconds at 30 second intervals. The number of pulse discharges required until the voltage at the time when the pulse current flowed decreased to 1.0 V or less was measured to obtain an average value, and the load characteristics were evaluated.
また、上記とは別の電池各々12個に対し、電池の外装缶側面の中央部にアルミニウム製のテープで熱伝対を固定し、電池を短絡させたときの外装缶表面温度を測定して平均値を求め、異常発生時の発熱挙動を評価した。このとき、参考例3の電池については電流値の時間変化も測定した。参考例3の電池の短絡電流および外装缶表面温度の短絡開始からの変化を図3に示した。 In addition, for each of 12 batteries different from the above, a thermocouple is fixed with an aluminum tape at the center of the side surface of the battery outer can, and the surface temperature of the outer can when the battery is short-circuited is measured. The average value was obtained and the heat generation behavior when an abnormality occurred was evaluated. At this time, the time change of the current value was also measured for the battery of Reference Example 3. The change from the short-circuit start of the short-circuit current of the battery of Reference Example 3 and the outer can surface is shown in FIG.
さらに、別の電池各々24個に対し、まず、12個を1Aの放電電流で放電させて0.9V以下になるまでの放電時間を測定し、その平均時間を保存前の放電時間とし、次に、残り12個を60℃の恒温槽中に20日間保存し、取り出してから1日室温で冷却後、同じく1Aの放電電流で放電させて0.9V以下になるまでの放電時間を測定し、その平均時間を保存後の放電時間とし、保存前の放電時間に対する保存後の放電時間の割合を容量保持率として求め、高温での電池の貯蔵性を評価した。上記パルス放電の回数、外装缶表面温度および容量保持率の測定結果を表1にまとめて示した。なお、ガス発生は特に問題にはならなかった。 Furthermore, for each of 24 batteries, first, 12 batteries were discharged with a discharge current of 1 A, and the discharge time until 0.9 V or less was measured. The average time was taken as the discharge time before storage. In addition, the remaining 12 pieces were stored in a constant temperature bath at 60 ° C. for 20 days, taken out, cooled at room temperature for 1 day, and then discharged at a discharge current of 1 A and measured for a discharge time of 0.9 V or less. The average time was taken as the discharge time after storage, the ratio of the discharge time after storage to the discharge time before storage was determined as the capacity retention, and the storability of the battery at high temperature was evaluated. Table 1 summarizes the measurement results of the number of pulse discharges, the outer can surface temperature, and the capacity retention. Gas generation was not a problem.
表1の結果より明らかなように、本発明の実施例の電池は、負荷特性が優れ、異常発生時の発熱挙動が抑制されており、高温での貯蔵性にも優れていた。 As is clear from the results in Table 1, the batteries of the examples of the present invention were excellent in load characteristics, suppressed the heat generation behavior when an abnormality occurred, and were excellent in storage at high temperatures.
1 外装缶
1a 外装缶の開口端部
2 正極
3 セパレータ
4 負極
5 負極集電棒
6 封口体
7、207 負極端子板
8 絶縁板
9 金属ワッシャ
10 封口部分
20 胴部分
DESCRIPTION OF
Claims (6)
アルカリ電解液(C)は電池組み立て時に外装体内部に注入してセパレータに吸収させたものであり、
電池組み立て後に、電池系内のアルカリ電解液の水酸化カリウム濃度が平均して30〜37質量%となるように、アルカリ電解液(A)、アルカリ電解液(B)およびアルカリ電解液(C)それぞれの水酸化カリウム濃度を調整してあり、
負極の亜鉛合金粉末として、200メッシュのふるい目を通過する粉末の割合が4〜40質量%である亜鉛合金粉末を用いたことを特徴とするアルカリ電池。 Positive electrode mixture containing at least one of manganese dioxide and nickel oxide, a conductive agent and an alkaline electrolyte (A) in which potassium hydroxide is dissolved, a separator, a zinc alloy powder, a gelling agent, and an alkali in which potassium hydroxide is dissolved An alkaline battery produced by enclosing a negative electrode mixture containing an electrolytic solution (B) and an alkaline electrolytic solution (C) in which potassium hydroxide is dissolved, inside the outer package,
The alkaline electrolyte (C) is injected into the exterior body during battery assembly and absorbed by the separator.
After battery assembly, the alkaline electrolyte (A), alkaline electrolyte (B), and alkaline electrolyte (C) so that the average potassium hydroxide concentration of the alkaline electrolyte in the battery system is 30 to 37% by mass. Each potassium hydroxide concentration is adjusted,
An alkaline battery using a zinc alloy powder having a ratio of powder passing through a 200 mesh sieve as 4 to 40% by mass as a zinc alloy powder for a negative electrode.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004139909A (en) * | 2002-10-18 | 2004-05-13 | Toshiba Battery Co Ltd | Sealed nickel-zinc primary battery |
JP2009151958A (en) * | 2007-12-19 | 2009-07-09 | Hitachi Maxell Ltd | Alkaline battery |
JP2009170157A (en) * | 2008-01-11 | 2009-07-30 | Panasonic Corp | Aa alkaline battery |
JP2015141889A (en) * | 2014-01-30 | 2015-08-03 | Fdkエナジー株式会社 | Alkali battery |
JP2015141888A (en) * | 2014-01-30 | 2015-08-03 | Fdkエナジー株式会社 | alkaline battery |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004139909A (en) * | 2002-10-18 | 2004-05-13 | Toshiba Battery Co Ltd | Sealed nickel-zinc primary battery |
JP2009151958A (en) * | 2007-12-19 | 2009-07-09 | Hitachi Maxell Ltd | Alkaline battery |
JP2009170157A (en) * | 2008-01-11 | 2009-07-30 | Panasonic Corp | Aa alkaline battery |
JP2015141889A (en) * | 2014-01-30 | 2015-08-03 | Fdkエナジー株式会社 | Alkali battery |
JP2015141888A (en) * | 2014-01-30 | 2015-08-03 | Fdkエナジー株式会社 | alkaline battery |
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