JPH0251874A - Alkaline zinc lead-acid battery - Google Patents
Alkaline zinc lead-acid batteryInfo
- Publication number
- JPH0251874A JPH0251874A JP63202580A JP20258088A JPH0251874A JP H0251874 A JPH0251874 A JP H0251874A JP 63202580 A JP63202580 A JP 63202580A JP 20258088 A JP20258088 A JP 20258088A JP H0251874 A JPH0251874 A JP H0251874A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- battery
- zinc oxide
- negative electrode
- current collector
- 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.)
- Pending
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 19
- 239000011701 zinc Substances 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011149 active material Substances 0.000 claims abstract description 38
- 239000011787 zinc oxide Substances 0.000 claims abstract description 27
- 239000002562 thickening agent Substances 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010419 fine particle Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 230000032683 aging Effects 0.000 abstract 1
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
簾呈上箆机几分互
本発明はニッケルー亜鉛蓄電池、銀−亜鉛蓄電池等、負
極活物質として亜鉛を用いるアルカリ亜鉛蓄電池に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkaline zinc storage batteries using zinc as a negative electrode active material, such as nickel-zinc storage batteries and silver-zinc storage batteries.
従来少肢困
最近の電気機器のコードレス化に伴い、軽量で高エネル
ギー密度の蓄電池が要求されるようになった。この中で
、負極容量の低減、換言すると、負極容量と正極容量と
の比が低下し、電池のサイクル寿命が制限されるという
問題が生じている。With the recent trend of cordless electrical equipment, there has been a demand for lightweight, high-energy-density storage batteries. Among these, a problem has arisen that the negative electrode capacity is reduced, in other words, the ratio between the negative electrode capacity and the positive electrode capacity is reduced, and the cycle life of the battery is limited.
そこで、単位重量あたりのエネルギー密度が太き（、安
価且つ無公害である亜鉛を負極活物質として用いる電池
の実用化研究が行われている。このように負極活物質と
して亜鉛を用いれば、活物質充填量が多く、且つ経時変
化が少ないという特徴を有する。Therefore, practical research is being conducted on batteries that use zinc, which has a high energy density per unit weight (and is inexpensive and non-polluting, as the negative electrode active material.) If zinc is used as the negative electrode active material, It is characterized by a large amount of substance filling and little change over time.
ところで、通常、負極の製造方法としては、焼結体や三
次元金属繊維体などに活物質を充填する焼結方式と、ペ
ースト方式とがある。活物質の利用率の向上という観点
からは焼結方式が優れているが、活物質の充填量の向上
という点ではペースト方式が優れ、且つペースト方式で
は製法自体も簡単であるという利点もある。上記ペース
ト方式は、結着剤を用いて作製した活物質ペーストを集
電体に塗布又は付着させて負極を作製するものであり、
活物質同士の付着力は上記結着剤により維持されている
。しかし、活物質と集電体との密着力が十分ではない。Incidentally, there are usually two methods for producing negative electrodes: a sintering method in which a sintered body, a three-dimensional metal fiber, or the like is filled with an active material, and a paste method. The sintering method is superior from the viewpoint of improving the utilization rate of the active material, but the paste method is superior from the viewpoint of improving the filling amount of the active material, and the paste method also has the advantage that the manufacturing method itself is simple. In the above paste method, a negative electrode is prepared by applying or adhering an active material paste prepared using a binder to a current collector,
Adhesion between the active materials is maintained by the binder. However, the adhesion between the active material and the current collector is not sufficient.
そこで、通常、集電体としてパンチングメタルを用いて
いる。ところが、このよな構成としても、パンチング穴
を介した活物質ペースト同士の密着性の向上がみられる
だけで、活物質ペーストと集電体との密着性は余り向上
しない、そして、このような負極と正極とをセパレータ
を介して巻回すると、活物質層とパンチングメタルとの
剥離が生じる。このため、活物質層の脱落が生じたり、
巻き終り方向にずれたり、さらに集電体と密着していな
い活物質層でクラックが生じたりする。この結果、電池
缶底でショートや、電極巻き終り部でのショートが生じ
、電池の特性が劣化する。加えて、活物質層とパンチン
グメタルとの密着性が不均一であるということから、負
極での反応が不均一化し、負極の経時変化が促進されて
電池性能が劣化するという問題がある。Therefore, punched metal is usually used as the current collector. However, even with this configuration, the adhesion between the active material pastes is only improved through the punched holes, and the adhesion between the active material paste and the current collector is not improved much. When the negative electrode and the positive electrode are wound with a separator in between, the active material layer and the punching metal separate. This may cause the active material layer to fall off or
It may shift toward the end of the winding, and cracks may occur in the active material layer that is not in close contact with the current collector. As a result, a short circuit occurs at the bottom of the battery can or at the end of the electrode winding, resulting in deterioration of battery characteristics. In addition, since the adhesion between the active material layer and the punching metal is non-uniform, there is a problem that the reaction at the negative electrode becomes non-uniform, accelerating deterioration of the negative electrode over time and deteriorating battery performance.
そこで、集電体と活物質ペースト層との間粘剤等の結着
性に優れた層を設けることが提案されている。Therefore, it has been proposed to provide a layer with excellent binding properties, such as an adhesive, between the current collector and the active material paste layer.
しよ゛と る
しかしながら上記従来の構造では、圧着時の加圧によっ
て上記増粘剤が散逸し、増粘剤の効果が発揮されなくな
るため、やはり活物質層と集電体層との密着性が低下す
る。この結果、サイクル特性と信頬性とを十分に向上さ
せることができないという課題を有していた。However, in the above conventional structure, the thickener is dissipated by the pressure applied during crimping, and the effect of the thickener is no longer exhibited, so the adhesion between the active material layer and the current collector layer is still affected. decreases. As a result, there was a problem in that cycle characteristics and reliability could not be sufficiently improved.
そこで本発明は、集電体と活物質層との密着性を向上さ
せることにより、電池内部でのショートを防止すると共
に、負極の電極反応を均一化させることにより、サイク
ル特性と信顧性とを飛躍的に向上させうるアルカリ亜鉛
蓄電池の提供を目的とするものである。Therefore, the present invention prevents short circuits inside the battery by improving the adhesion between the current collector and the active material layer, and also improves cycle characteristics and reliability by uniformizing the electrode reaction of the negative electrode. The purpose is to provide an alkaline zinc storage battery that can dramatically improve the
量 るための
本発明は上記目的を達成するために、集電体及び活物質
層を有する負極と、正極とを備えたアルカリ亜鉛蓄電池
において、前記集電体と活物質層との間に、酸化亜鉛を
含む増粘剤層を設けたことを特徴とする。In order to achieve the above object, the present invention provides an alkaline zinc storage battery comprising a negative electrode having a current collector and an active material layer, and a positive electrode, wherein between the current collector and the active material layer, It is characterized by having a thickener layer containing zinc oxide.
立−Ｕ
上記構成であれば、圧着時の増粘剤の散逸が酸化亜鉛と
いう微粒子の抵抗体により抑制される。Stand-U With the above configuration, the dissipation of the thickener during pressure bonding is suppressed by the resistor made of fine particles of zinc oxide.
加えて、酸化亜鉛を含む増粘剤層は酸化亜鉛水溶液の粘
性と増粘剤の粘性との相乗効果によって、増粘剤単独の
場合と比べて集電体との密着性が向上する。加えて、集
電体上の酸化亜鉛により活物質ペーストと集電体との接
触面積が増大する。これらのことから、集電体と活物質
層との密着性を向上させることができる。In addition, the thickener layer containing zinc oxide has improved adhesion to the current collector due to the synergistic effect of the viscosity of the zinc oxide aqueous solution and the viscosity of the thickener, compared to the case of using only the thickener. In addition, the zinc oxide on the current collector increases the contact area between the active material paste and the current collector. For these reasons, it is possible to improve the adhesion between the current collector and the active material layer.
ここで、増粘剤層の含有物として酸化亜鉛を用いたのは
、酸化亜鉛は活物質であるので負極活物質の充填量が増
大すること、及び、蓄電池では電池組立後に活物質の活
性化を図るために化成処理を行なうが、酸化亜鉛を用い
れば化成処理における初充電時に集電体に接触している
酸化亜鉛が還元されて集電体上に電着されるので、集電
体表面に電気化学的に活性な亜鉛が均一に形成され、こ
の結果負極の反応が均一となるという理由によるもので
ある。Here, zinc oxide was used as a content in the thickener layer because zinc oxide is an active material, so the filling amount of the negative electrode active material increases, and in a storage battery, the active material is activated after battery assembly. Chemical conversion treatment is performed to achieve this, but if zinc oxide is used, the zinc oxide that is in contact with the current collector during the first charge in the chemical conversion treatment will be reduced and electrodeposited on the current collector, so the surface of the current collector will be reduced. This is because electrochemically active zinc is uniformly formed in the oxide layer, and as a result, the reaction at the negative electrode becomes uniform.
尚、増粘剤層の含有物として酸化亜鉛の代わりに金属亜
鉛を用いれば、化成時に集電体上の亜鉛は還元されない
ため、集電体と亜鉛とは密着せず、逆に水素発生により
密着性が低下するという問題がある。したがって、増粘
剤層の含有物としては酸化亜鉛を用いることが望ましい
。Furthermore, if metal zinc is used instead of zinc oxide as the content of the thickener layer, the zinc on the current collector will not be reduced during formation, so the current collector and zinc will not come into close contact with each other, and on the contrary, hydrogen generation will cause There is a problem that adhesion deteriorates. Therefore, it is desirable to use zinc oxide as the content of the thickener layer.
皇−血−■
〔実施例〕
本発明の一実施例を、第１図及び第２図に基づいて、以
下に説明する。[Embodiment] An embodiment of the present invention will be described below based on FIGS. 1 and 2.
第１図は単三型の二ンケルー亜鉛蓄電池の断面図であり
、公知の焼結式ニッケルから成る正極１と、亜鉛を活物
質とする負極２と、これら正負両極ｌ・２間に介挿され
たセパレータ３とから成る電極群４は渦巻状に巻回され
ている。この電極群４は熱収縮チューブ５に内包され、
この熱収縮チューブ５を介して上記負極２は負極端子兼
用の外装縁６に接触するように配置されている。この外
装縁６の上部開口にはパフキング７を介して封口体８が
装着されており、この封口体８の内部にはコイルスプリ
ング９が設けられている。このコイルスプリング９は電
池内部の内圧が異常上昇したときに矢印Ａ方向に押圧さ
れて内部のガスが大気中に開放されるように構成されて
いる。また、上記封口体８と前記正極１とは正極用導電
タブＩＯにて接続されており、前記外装罐６と負極２と
は負極用導電タブ１１にて接続されている。Figure 1 is a cross-sectional view of an AA-type two-layer zinc storage battery, showing a positive electrode 1 made of known sintered nickel, a negative electrode 2 made of zinc as an active material, and an electrode inserted between these positive and negative electrodes 1 and 2. The electrode group 4 consisting of the separated separator 3 is spirally wound. This electrode group 4 is enclosed in a heat shrink tube 5,
The negative electrode 2 is placed in contact with an exterior edge 6 which also serves as a negative electrode terminal via the heat-shrinkable tube 5. A sealing body 8 is attached to the upper opening of the exterior edge 6 via a puff king 7, and a coil spring 9 is provided inside the sealing body 8. This coil spring 9 is configured so that when the internal pressure inside the battery rises abnormally, it is pressed in the direction of arrow A and the gas inside is released to the atmosphere. Further, the sealing body 8 and the positive electrode 1 are connected by a conductive tab IO for the positive electrode, and the exterior can 6 and the negative electrode 2 are connected by a conductive tab 11 for the negative electrode.
ここで、上記負極２は以下のようにして作製される。Here, the negative electrode 2 is manufactured as follows.
先ず始めに、銅よりなるパンチングメタル〔開孔率：約
２０％〕を用いた集電体に、酸化亜鉛を３００ ｇ ／
１の濃度で含んだ増粘剤であるＨＰＣ（ヒドロキシプ
ロピルセルロース）２％水溶液を塗着した後、これを乾
燥させて集電体上に増粘剤層を形成する。次に、酸化亜
鉛を６０重量％と、金属亜鉛３０重量％とに、添加剤と
して水酸化インジウム５重量％と結着剤としてフッ素樹
脂５重量％とを混合させて混合粉末を作成した後、この
混合粉末に水を加える。次いで、これらを混練した後、
ローラにより活！７Ｉ質シートを作製する。しかる後、
この活物質シートを前記増粘剤層上に付着させ加圧成型
した後、活物質シートを乾燥させることにより作製した
。First, 300 g of zinc oxide was added to a current collector made of punched metal made of copper [porosity: about 20%].
A 2% aqueous solution of HPC (hydroxypropyl cellulose), which is a thickener containing a concentration of 1%, is applied and then dried to form a thickener layer on the current collector. Next, a mixed powder was created by mixing 60% by weight of zinc oxide, 30% by weight of zinc metal, 5% by weight of indium hydroxide as an additive, and 5% by weight of a fluororesin as a binder. Add water to this mixed powder. Next, after kneading these,
Lively by Laura! 7I quality sheet is produced. After that,
This active material sheet was adhered onto the thickener layer and pressure molded, and then the active material sheet was dried.
このようにして作製した電池を、以下（Ａ）電池と称す
る。The battery thus produced is hereinafter referred to as the (A) battery.
集電体に酸化亜鉛２０％水溶液を塗着した後これを乾燥
させて、集電体上に酸化亜鉛層を形成した。このような
集電体を用いた以外は前記実施例と同様に負極２を作製
し、更に公知のニッケル極と組合せて電池を作製した。A 20% zinc oxide aqueous solution was applied to the current collector and then dried to form a zinc oxide layer on the current collector. A negative electrode 2 was produced in the same manner as in the above example except that such a current collector was used, and a battery was produced by combining it with a known nickel electrode.
このようにして作製した電池を、以下（Ｂ）電池と称す
る。The battery thus produced is hereinafter referred to as the (B) battery.
集電体にＲＰＣ２％水溶液を塗着した後、これを乾燥さ
せて集電体上に増粘剤層を形成した。このような集電体
を用いた以外は前記実施例と同様に負極２を作製し、更
に公知のニッケル極と組合せて電池を作製した。After applying a 2% RPC aqueous solution to the current collector, this was dried to form a thickener layer on the current collector. A negative electrode 2 was produced in the same manner as in the above example except that such a current collector was used, and a battery was produced by combining it with a known nickel electrode.
このようにして作製した電池を、以下（Ｃ）電池と称す
る。The battery thus produced is hereinafter referred to as the (C) battery.
表面処理を全く行わない集電体を用いた以外は前記実施
例と同様に負極２を作製し、更に公知のニッケル極を組
合せて電池を作製した。A negative electrode 2 was produced in the same manner as in the above example except that a current collector without any surface treatment was used, and a battery was produced by combining it with a known nickel electrode.
このようにして作製した電池を、以下（Ｄ）電池と称す
る。The battery thus produced is hereinafter referred to as (D) battery.
上記（Ａ）電池〜（Ｄ）電池を用いて、’ＡＣの電流で
５時間充電した後、％Ｃの電流で放電し、放電終止電圧
を１．０■とするサイクル条件にてサイクル試験を行っ
たので、その結果を第２図に示す。そして、電池容量が
初期容量の５０％以下になった時点で電池寿命とした。Using the above (A) batteries to (D) batteries, a cycle test was carried out under the cycle conditions of charging with an AC current for 5 hours, discharging with a current of %C, and setting the discharge end voltage to 1.0 ■. The results are shown in Figure 2. The battery life was determined when the battery capacity became 50% or less of the initial capacity.
第２図に示すように、比較例の（Ｂ）電池〜（Ｄ）電池
では略３００サイクル以下でサイクル寿命となるのに対
して、本発明の（Ａ）電池では３００サイクルでも余り
電池容量が低下していないことが認められる。これによ
り、本発明の（Ａ）電池は比較例の（Ｂ）電池〜（Ｄ）
電池と比べてサイクル特性が大幅に改善されているのが
わかる。As shown in Figure 2, the battery (B) to (D) of the comparative examples reach their cycle life after about 300 cycles or less, whereas the battery (A) of the present invention has a residual battery capacity even after 300 cycles. It can be seen that there has been no decline. As a result, the battery (A) of the present invention is the battery (B) of the comparative example ~ (D)
It can be seen that the cycle characteristics are significantly improved compared to batteries.
これは、以下に示す理由によるものと考えられる。This is considered to be due to the following reasons.
即ち、（Ｂ）電池では、集電体上に酸化亜鉛層があるの
で集電体と活物質層との接触面積は増大するが、酸化亜
鉛と集電体との結着力が低いため活物質層と集電体との
密着性が低下する。この密着性の不均一により電極反応
の不均一化が生じ、負極２の反応面積が低下することに
よるものと考えられる。That is, in the battery (B), since there is a zinc oxide layer on the current collector, the contact area between the current collector and the active material layer increases, but since the binding force between the zinc oxide and the current collector is low, the active material Adhesion between the layer and the current collector decreases. It is thought that this non-uniform adhesion causes non-uniform electrode reactions and a decrease in the reaction area of the negative electrode 2.
次に（Ｃ）電池では、負極２の作製後、集電体と活物質
界面との間に殆ど増粘剤が残ってないため、上記（Ｂ）
電池と同様、活物質層と集電体との密着性の低下及び不
均一化が生じることによるものと考えられる。Next, in the (C) battery, since there is almost no thickener remaining between the current collector and the active material interface after the negative electrode 2 is produced, the above (B)
This is thought to be due to a decrease in adhesion and non-uniformity between the active material layer and the current collector, similar to batteries.
更に（Ｄ）電池では、活物質層と集電体との密着性がフ
ッ素樹脂の繊維化（フィブリル化）による結合だけであ
るため、やはり活物質と集電体との密着性の低下及び不
均一性が生が生じることによるものと考えられる。Furthermore, in (D) batteries, the adhesion between the active material layer and the current collector is only due to the fiberization (fibrillation) of the fluororesin, so the adhesion between the active material and the current collector may decrease or fail. It is thought that the uniformity is due to the occurrence of raw material.
一方、これに対して本発明の（Ａ）電池では、活物質層
と集電体との間に、増粘剤と酸化亜鉛とからなる増結剤
層が存在する。したがって、増粘剤の結着効果、及び酸
化亜鉛による活物質層と集電体との接触面積の向上によ
って負極２の作製時における密着性が向上する。加えて
、充放電反応により集電体表面の酸化亜鉛が金属亜鉛に
還元されるので、導電性マトリックスが形成される。し
たがって、電極反応が均一化して、負極２の経時変化が
抑制される。これらのことより、サイクル寿命が改善さ
れたものと考えられる。On the other hand, in the battery (A) of the present invention, a binder layer made of a thickener and zinc oxide is present between the active material layer and the current collector. Therefore, the adhesion during fabrication of the negative electrode 2 is improved due to the binding effect of the thickener and the improvement in the contact area between the active material layer and the current collector due to zinc oxide. In addition, the charge/discharge reaction reduces zinc oxide on the surface of the current collector to metallic zinc, thereby forming a conductive matrix. Therefore, the electrode reaction becomes uniform, and deterioration of the negative electrode 2 over time is suppressed. It is considered that the cycle life was improved from these facts.
尚、本発明で増結剤としてＲＰＣを用いたが、同じく粘
性と結着力を有するＰ２Ｏ（ポリエチレンオキサイド）
、ＭＣ（メチルセルロース）、ＰＶＡ（ポリビニルアル
コール）、ＣＭＣ（カルボキシメチルセルロース）も用
いても、同様の効果が得られることを確認している。Although RPC was used as a binder in the present invention, P2O (polyethylene oxide), which also has viscosity and binding power,
, MC (methylcellulose), PVA (polyvinyl alcohol), and CMC (carboxymethylcellulose) have also been confirmed to produce similar effects.
発」Ｌ（２）」［果
以上のように本発明によれば、活物質層と集電体との間
に酸化亜鉛を含む増粘剤層が設けられているので、活物
質と集電体との密着性が向上し、電池内部でのショート
を防止しうると共に、電極反応を均一化させることがで
きる。この結果、負極の経時変化を抑制することができ
るので、このような負極を用いた電池のサイクル特性と
信鎖性とを飛躍的に向上させることができるという効果
を奏する。As described above, according to the present invention, since the thickener layer containing zinc oxide is provided between the active material layer and the current collector, the active material and the current collector are Adhesion to the body is improved, short circuits inside the battery can be prevented, and electrode reactions can be made more uniform. As a result, it is possible to suppress the deterioration of the negative electrode over time, resulting in the effect that the cycle characteristics and reliability of a battery using such a negative electrode can be dramatically improved.
第１図は本発明のアルカリ亜鉛蓄電池を示す断面図、第
２図は本発明の（Ａ）電池及び比較例の（Ｂ）電池〜（
Ｄ）電池のサイクル特性を示すグラフである。
■・・・正極、２・・・負極、３・・・セパレータ。
特許出願人：三洋電機 株式会社FIG. 1 is a sectional view showing the alkaline zinc storage battery of the present invention, and FIG. 2 is a sectional view showing the (A) battery of the present invention and the (B) battery of the comparative example.
D) It is a graph showing the cycle characteristics of the battery. ■...Positive electrode, 2...Negative electrode, 3...Separator. Patent applicant: Sanyo Electric Co., Ltd.
Claims (1)
えたアルカリ亜鉛蓄電池において、 前記集電体と活物質層との間に、酸化亜鉛を含む増粘剤
層を設けたことを特徴とするアルカリ亜鉛蓄電池。(1) In an alkaline zinc storage battery comprising a negative electrode having a current collector and an active material layer, and a positive electrode, a thickener layer containing zinc oxide is provided between the current collector and the active material layer. An alkaline zinc storage battery featuring:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202580A JPH0251874A (en) | 1988-08-12 | 1988-08-12 | Alkaline zinc lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202580A JPH0251874A (en) | 1988-08-12 | 1988-08-12 | Alkaline zinc lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0251874A true JPH0251874A (en) | 1990-02-21 |
Family
ID=16459842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63202580A Pending JPH0251874A (en) | 1988-08-12 | 1988-08-12 | Alkaline zinc lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0251874A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017188213A (en) * | 2016-04-01 | 2017-10-12 | 日立化成株式会社 | Method for producing zinc electrode mixture paste for nickel zinc battery, method for producing zinc electrode for nickel zinc battery, and method for producing nickel zinc battery |
| JP2017188212A (en) * | 2016-04-01 | 2017-10-12 | 日立化成株式会社 | Zinc electrode for nickel zinc storage battery, and method for manufacturing the same |
-
1988
- 1988-08-12 JP JP63202580A patent/JPH0251874A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017188213A (en) * | 2016-04-01 | 2017-10-12 | 日立化成株式会社 | Method for producing zinc electrode mixture paste for nickel zinc battery, method for producing zinc electrode for nickel zinc battery, and method for producing nickel zinc battery |
| JP2017188212A (en) * | 2016-04-01 | 2017-10-12 | 日立化成株式会社 | Zinc electrode for nickel zinc storage battery, and method for manufacturing the same |
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