JPH02216757A - Alkaline zinc storage battery - Google Patents
Alkaline zinc storage batteryInfo
- Publication number
- JPH02216757A JPH02216757A JP1038731A JP3873189A JPH02216757A JP H02216757 A JPH02216757 A JP H02216757A JP 1038731 A JP1038731 A JP 1038731A JP 3873189 A JP3873189 A JP 3873189A JP H02216757 A JPH02216757 A JP H02216757A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- electrode
- surface active
- anionic surface
- zinc
- 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 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 34
- 239000011701 zinc Substances 0.000 title claims abstract description 34
- -1 polypropylene Polymers 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 239000004677 Nylon Substances 0.000 abstract description 4
- 238000003411 electrode reaction Methods 0.000 abstract description 4
- 239000004745 nonwoven fabric Substances 0.000 abstract description 4
- 229920001778 nylon Polymers 0.000 abstract description 4
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 2
- 229940077388 benzenesulfonate Drugs 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 5
- 239000003513 alkali Substances 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000009736 wetting Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 206010024769 Local reaction Diseases 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、銀−亜鉛蓄電池、ニッケルー亜ｊ９蓄電池等
のアルカリ亜鉛蓄電池に係り、特にそのセパレータの改
良に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to alkaline zinc storage batteries such as silver-zinc storage batteries and nickel-AJ9 storage batteries, and particularly to improvements in separators thereof.
（ロ）従来の技術
負極活物質としての亜鉛は、単位重量あたりのエネルギ
ー密度が高く、安価であり、且つ無公害であることから
、数多くの実用化研究が行なわれてきているが、未だ満
足な性能を有するものが得られていない。(b) Conventional technology Since zinc as a negative electrode active material has a high energy density per unit weight, is inexpensive, and is non-polluting, many studies have been conducted to put it into practical use, but the results are still unsatisfactory. However, we have not yet obtained a product with excellent performance.
これは、亜鉛極が可溶性であることに起因している。即
ち、放電時に、亜鉛がアルカリ電解液中に溶解し、充電
時に溶解時と異なる部分に電着するので、充放電を繰り
返すと、電極の形状変形が生じ、反応面積が減少し、電
池の容量低下を招来する。また、アルカリ電解液中に溶
出した亜鉛酸イオンが亜鉛極表面に、デンドライト亜鉛
として析出し、充放電サイクルの進行と共にデンドライ
ト亜鉛が生長し、正極と内部短絡を生じ、サイクルが命
となってしまうためである。This is due to the fact that the zinc electrode is soluble. That is, during discharging, zinc dissolves in the alkaline electrolyte, and during charging, it is electrodeposited in a different part from when it was dissolved. Therefore, when charging and discharging are repeated, the electrode shape deforms, the reaction area decreases, and the battery capacity decreases. cause a decline. In addition, zincate ions eluted into the alkaline electrolyte precipitate on the surface of the zinc electrode as dendrite zinc, and as the charge/discharge cycle progresses, the dendrite zinc grows, causing an internal short circuit with the positive electrode, and ending the cycle. It's for a reason.
このような欠点を解消するため、例えば遊離の電解液が
存在しないよう電池内における電解液量を規制して、亜
鉛酸イオンの拡散を抑制したつ、されている、しかしな
がら、これらの手法でデンドライトの析出、生長を防止
することはほとんどは、負極に接するセパレータの電解
液量を正極に接するセパレータの電解液量より小となる
ように構成することが提案されているが、この方法であ
ってもデンドライトの発生及び生長を完全に抑制するこ
とは難しい。In order to overcome these drawbacks, for example, the amount of electrolyte in the battery is regulated so that no free electrolyte exists, and the diffusion of zincate ions is suppressed. It has been proposed that most of the methods for preventing the precipitation and growth of electrolyte are to configure the amount of electrolyte in the separator in contact with the negative electrode to be smaller than the amount of electrolyte in the separator in contact with the positive electrode. However, it is difficult to completely suppress the occurrence and growth of dendrites.
そこで、特開昭５３−２１１５４１号公報等に記載され
た如く、亜鉛極に近接するセパレータとして微孔性セパ
レータを使用することで、亜鉛極表面に電析したデンド
ライト亜鉛がセパレータを貫通するのを物理的に抑制す
る技術が知られている。Therefore, as described in JP-A-53-211541, etc., by using a microporous separator as a separator close to the zinc electrode, it is possible to prevent the dendrite zinc electrodeposited on the surface of the zinc electrode from penetrating the separator. Techniques for physically suppressing it are known.
（ハ） 発明が解決しようとする課題
−成功に、微孔性セパレータとしてはポリオレフィン系
、例えばポリプロピレン又はポリエチレンなどが用いら
れている。しかしながら、ポリオレフィン系微孔性膜は
、疎水性なので電解液に漏れにくく、微孔性薄膜に濡れ
の不均一が生じ、亜鉛極においてそれに対応して局部反
応が生じるので、デンドライト発生、生長が観察される
という問題点があった。(c) Problems to be Solved by the Invention - Polyolefins, such as polypropylene or polyethylene, have been successfully used as microporous separators. However, since polyolefin microporous membranes are hydrophobic, they do not easily leak into the electrolyte, resulting in uneven wetting of the microporous thin membrane and a corresponding local reaction at the zinc electrode, resulting in dendrite formation and growth. There was a problem that
そこで、本発明は前記問題点に鑑みてなされたものであ
って、アルカリ亜鉛蓄電池のセパレータとして用いられ
るポリオレフィン系微孔性薄膜の濡れ性を改善し、嵩れ
を均一化させるものである。このようにすることで、亜
鉛極における局部反応が抑えられ、デンドライト発生、
生長が抑制されるので、サイクル寿命の長いアルカリ亜
鉛蓄電池が提供できる。The present invention has been made in view of the above-mentioned problems, and is intended to improve the wettability of a polyolefin microporous thin film used as a separator for alkaline zinc storage batteries and to make the bulk uniform. By doing this, local reactions at the zinc electrode are suppressed, dendrite formation,
Since growth is suppressed, an alkaline zinc storage battery with a long cycle life can be provided.
（ニ）課題を解決するための手段
本発明のアルカリ亜鉛蓄電池は、正極と、亜鉛極と、セ
パレータとしてのポリオレフィン系微孔性薄膜と、アル
カリ電解液とからなり、前記ポリオレフィン系微孔性薄
膜に、スルホン酸基を有するアニオン界面活性剤を付着
させたことを特徴とするものである。(d) Means for Solving the Problems The alkaline zinc storage battery of the present invention comprises a positive electrode, a zinc electrode, a polyolefin microporous thin film as a separator, and an alkaline electrolyte. It is characterized by having an anionic surfactant having a sulfonic acid group attached thereto.
また、前記スルホン酸基を有するアニオン界面活性剤と
しては、アルキルベンゼンスルホン酸塩、アルキルスル
ホン酸塩、アルキルスルホン酸エステルからなる群より
選ばれた、少なくとも１つを用いることが好ましい。Further, as the anionic surfactant having a sulfonic acid group, it is preferable to use at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfonates, and alkyl sulfonate esters.
また前記ポリオレフィン系微孔性薄膜として、ポリプロ
ピレンフィルムもしくはポリエチレンフィルムを用いる
ことができる。Moreover, a polypropylene film or a polyethylene film can be used as the polyolefin microporous thin film.
（ホ）作 用
電池電解液のアルカリ濃度が２０％以上という過酷な条
件下において、アニオン界面活性剤の中でも特にスルホ
ン酸基を有するものが、安定であることを見い出し、本
発明を完成するに至ったものである。(E) Function It has been discovered that among anionic surfactants, those having a sulfonic acid group are particularly stable under severe conditions where the alkaline concentration of the battery electrolyte is 20% or more, and in order to complete the present invention. This is what we have come to.
ポリオレフィン系、例えばポリプロピレン、ポリエチレ
ン等の微孔性薄膜を、スルホン酸基を有するアニオン界
面活性剤で処理することにより、微孔性薄膜の濡れが十
分となり、濡れの均一化が計られ、その結果、電極反応
が均一化される。そして、亜鉛極における電流集中が防
止されるので、亜鉛極においてデンドライト析出、生長
が抑制される。By treating a microporous thin film made of polyolefin, such as polypropylene or polyethylene, with an anionic surfactant having a sulfonic acid group, the wetting of the microporous thin film becomes sufficient and uniform wetting is achieved. , the electrode reaction is homogenized. Since current concentration at the zinc electrode is prevented, dendrite precipitation and growth at the zinc electrode are suppressed.
また、充放電サイクルを繰り返し行っても、前記界面活
性剤が安定に保持され、界面活性剤の分解に起因せる電
解液のイオン伝導性の低下も観察されないので５前記添
加効果が十分に発揮される。In addition, even after repeated charging and discharging cycles, the surfactant is stably retained, and no decrease in the ionic conductivity of the electrolytic solution due to decomposition of the surfactant is observed, so the effects of the addition mentioned above are fully exhibited. Ru.
（へ）実施例
以下に、本発明の実施例を詳述し、比較例との対比に言
及する。(f) Examples Below, examples of the present invention will be described in detail, and comparisons with comparative examples will be mentioned.
実施例１゜
ポリプロピレン（ポリオレフィン系）微孔性薄膜を、前
記薄膜重量に対して１０重量％のアルキルベンゼンスル
ホン酸塩からなるアニオン界面活性剤を付着、保持させ
た。この操作は前記薄膜をアルキルベンゼンスルホン酸
塩の溶液に浸漬するというものである。そしてこのポリ
プロピレン微孔性薄膜とナイロン不織布（厚み１１２０
μｍ）とを用い、多層セパレータ３とした。尚、ここで
用いる薄膜としては、厚さ２０〜３０μｍのものが好ま
しい。また、ナイロン不織布は、保液層として用いてお
り、厚さ１００〜２００μｍのものが好適する。Example 1 A microporous polypropylene (polyolefin) thin film was coated with an anionic surfactant consisting of an alkylbenzene sulfonate in an amount of 10% by weight based on the weight of the thin film. This operation involves immersing the thin film in a solution of alkylbenzene sulfonate. This polypropylene microporous thin film and nylon nonwoven fabric (thickness: 1120 mm)
A multilayer separator 3 was prepared by using .mu.m). Note that the thin film used here preferably has a thickness of 20 to 30 μm. Further, the nylon nonwoven fabric is used as a liquid retaining layer, and a thickness of 100 to 200 μm is suitable.
亜鉛極２は、以下のようにして作製した。活物質として
の酸化亜鉛６０重量％、及び金属亜鉛３０重量％と、添
加剤としての水酸化インジウム５重量％と、結着剤とし
てのフッ素樹脂５重量％とからなる混合粉末に、水を加
えて混練した後、ローラを用いて活物質シートを作製す
る。このシートを銅等よりなる集電体上に付着する。こ
れを加圧成型後、乾燥して亜鉛８ｉ！２を得る。Zinc electrode 2 was produced as follows. Water was added to a mixed powder consisting of 60% by weight of zinc oxide and 30% by weight of zinc metal as active materials, 5% by weight of indium hydroxide as an additive, and 5% by weight of fluororesin as a binder. After kneading, an active material sheet is produced using a roller. This sheet is attached onto a current collector made of copper or the like. After pressure molding this, it is dried and becomes Zinc 8i! Get 2.
これらセパレータ３及び亜鉛極２を用い、公称容量５０
０ｍＡｈの単玉サイズのニッケルー亜鉛蓄電池を作製し
、本発明電池Ａとした。Using these separators 3 and zinc electrodes 2, the nominal capacity is 50
A 0 mAh single-cell size nickel-zinc storage battery was produced and designated as a battery A of the present invention.
第１図は、この電池の断面図であり、水酸化ニッケルを
活物質とする焼結式正極１と、亜鉛極（負極）２と、こ
れら正負両ｆ！１．２間に介挿された多層セパレータ３
とからなる電極群４は渦巻状に巻回され構成されている
。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、上記亜鉛極２は負極端子兼
用の外装缶６に負極用導電タブ１１にて、電気接続され
るように構成されている。この外装缶６の上部開口には
、バッキング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。このコイルスブリ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８ｉ！１とは正極用導
電タブ１０にて接続されている。FIG. 1 is a cross-sectional view of this battery, showing a sintered positive electrode 1 made of nickel hydroxide as an active material, a zinc electrode (negative electrode) 2, and both positive and negative f! 1. Multilayer separator 3 inserted between 2
The electrode group 4 consisting of is spirally wound. This electrode group 4 is enclosed in a heat-shrinkable tube 5, and through the heat-shrinkable tube 5, the zinc electrode 2 is electrically connected to an external can 6 which also serves as a negative electrode terminal with a conductive tab 11 for the negative electrode. It is configured. A sealing body 8 is attached to the upper opening of the outer can 6 via a backing 7.
A coil spring 9 is provided inside the sealing body 8 . This coil is configured to be submerged. Moreover, the above-mentioned sealing body 8 and the above-mentioned positive 8i! 1 through a conductive tab 10 for the positive electrode.
実施例２゜
前記実施例１において用いたアルキルベンゼンスルホン
酸塩に代えて、アルキルスルホン酸塩を使用した以外は
同様にして１本発明電池Ｂを作製した。Example 2 A battery B according to the present invention was prepared in the same manner as in Example 1 except that an alkyl sulfonate was used instead of the alkylbenzene sulfonate used in Example 1.
実施例３゜
前記実施例１において用いたアルキルベンゼンスルホン
酸塩に代えて、アルキルスルホン酸エステルを使用した
以外は同様にして、本発明電池Ｃを作製した。Example 3 A battery C of the present invention was produced in the same manner as in Example 1 except that an alkyl sulfonic acid ester was used in place of the alkyl benzene sulfonate used in Example 1.
比較例１゜
前記実施例１において用いたアルキルベンゼンスルホン
酸塩に代えて、脂肪酸塩を使用した以外は同様にして、
比較電池りを作製した。Comparative Example 1゜Similarly except that a fatty acid salt was used in place of the alkylbenzene sulfonate used in Example 1,
A comparative battery was prepared.
比較例２゜
前記実施例１において用いたアルキルベンゼンスルホン
酸塩に代えて、アルキルリン酸エステルを使用した以外
は同様にして、比較電池Ｅを作製した。Comparative Example 2 Comparative battery E was produced in the same manner as in Example 1, except that an alkyl phosphoric acid ester was used in place of the alkylbenzene sulfonate used in Example 1.
尚、各種電池に用いた界面活性剤とその構造式を第１表
に示す。Table 1 shows the surfactants used in various batteries and their structural formulas.
第 １ 表
これら電池は、ポリプロピレン微孔性薄膜が亜鉛極と当
接し、この薄膜と正極との間にナイロン不織布が保液層
として介挿された構成となっている。Table 1 These batteries have a structure in which a polypropylene microporous thin film is in contact with a zinc electrode, and a nylon nonwoven fabric is interposed as a liquid retaining layer between this thin film and the positive electrode.
そして、これら電池を用い、電池のサイクル特性を比較
した。この時のサイクル試験の条件は電池を１ＡＣの電
流で５時間充電を行なった後、ｌへＣの電流で放電し、
電池電圧が１．ＯＶに達した時点で放電を終了すると０
うものであり、電池容量が初期容量の５０％以下になっ
た時点で充放電サイクルを停止した。Using these batteries, the cycle characteristics of the batteries were compared. The conditions for the cycle test at this time were to charge the battery with a current of 1 AC for 5 hours, then discharge it with a current of C to l.
Battery voltage is 1. If you stop discharging when it reaches OV, it will be 0.
The charge/discharge cycle was stopped when the battery capacity became 50% or less of the initial capacity.
この結果を、第２図に示す。第２図より明らかな如く、
本発明電池Ａ＝Ｂ、Ｃのサイクル特性が、比較電池り、
Ｅよりも、優れていることがわかる。The results are shown in FIG. As is clear from Figure 2,
The cycle characteristics of the batteries A=B and C of the present invention are as follows:
It can be seen that it is better than E.
これは比較電池り、Ｈの場合、界面活性剤処理により微
孔性薄膜の濡れが均一となるが、スルホン酸基を有する
界面活性剤ではないので、濃厚なアルカリ電解液中では
安定ではなく、充放電サイクルの進行に住い、界面活性
剤が電解液と反応し分解するので、電解液濃度が低下す
る。その結果、微孔性薄膜中における保液量が減少し、
イオン伝導性が低下し、電池性能が劣化したものと考え
られる。In the case of the comparative battery H, the microporous thin film becomes uniformly wetted by surfactant treatment, but since the surfactant does not have a sulfonic acid group, it is not stable in a concentrated alkaline electrolyte. As the charge/discharge cycle progresses, the surfactant reacts with the electrolyte and decomposes, resulting in a decrease in the electrolyte concentration. As a result, the amount of liquid retained in the microporous thin film decreases,
It is thought that the ionic conductivity decreased and the battery performance deteriorated.
一方、本発明電池Ａ、Ｂ、Ｃでは、界面活性剤処理によ
り微孔性薄膜の濡れが均一となり、更にスルホン酸基を
有する界面活性剤を用いているので濃厚なアルカリ電解
液中においても安定であって、経時変化がないので界面
活性剤の分解もなく、イオン伝導性の低下がなく、電池
のサイクル特性が向上したと考えられる。On the other hand, in the batteries A, B, and C of the present invention, the wetting of the microporous thin film becomes uniform due to the surfactant treatment, and since a surfactant having a sulfonic acid group is used, it is stable even in a concentrated alkaline electrolyte. Since there is no change over time, there is no decomposition of the surfactant, and there is no decrease in ionic conductivity, which is thought to improve the cycle characteristics of the battery.
（ト）発明の効果
以上、上述した如く、本発明によればポリオレフィン系
微孔性薄膜にスルホン酸基を有するアニオン界面活性剤
を付着させ、これをセパレータに用いているので、前記
薄膜の濡れが均一となり、経時変化が少ないものが得ら
れる。その結果、電極反応が均一化され、亜鉛極におけ
るデンドライト発生、生長が抑制されるので、サイクル
特性に優れたアルカリ亜鉛蓄電池を提供できるものであ
り、その工業的価値は極めて大きい。(G) Effects of the Invention As described above, according to the present invention, an anionic surfactant having a sulfonic acid group is attached to a polyolefin microporous thin film and this is used as a separator, so that the wetting of the thin film is reduced. It is possible to obtain a product with uniformity and little change over time. As a result, the electrode reaction is made uniform and the generation and growth of dendrites in the zinc electrode are suppressed, so that an alkaline zinc storage battery with excellent cycle characteristics can be provided, and its industrial value is extremely large.
第１図は本発明電池の縦断面図、第２図は電池のサイク
ル特性図である。
Ａ、Ｂ、Ｃ・・・本発明電池、
Ｄ、Ｅ・・比較電池。FIG. 1 is a longitudinal sectional view of the battery of the present invention, and FIG. 2 is a cycle characteristic diagram of the battery. A, B, C... Batteries of the present invention, D, E... Comparative batteries.
Claims (3)
フィン系微孔性薄膜と、アルカリ電解液とからなる電池
であって、 前記ポリオレフィン系微孔性薄膜に、スルホン酸基を有
するアニオン界面活性剤を付着させたことを特徴とする
アルカリ亜鉛蓄電池。(1) A battery comprising a positive electrode, a zinc electrode, a polyolefin microporous thin film as a separator, and an alkaline electrolyte, wherein the polyolefin microporous thin film contains an anionic surfactant having a sulfonic acid group. An alkaline zinc storage battery characterized by adhering.
、アルキルベンゼンスルホン酸塩、アルキルスルホン酸
塩、アルキルスルホン酸エステルからなる群より選ばれ
た、少なくとも１つであることを特徴とする請求項（１
）記載のアルカリ亜鉛蓄電池。(2) The anionic surfactant having a sulfonic acid group is at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfonates, and alkyl sulfonate esters. 1
) described alkaline zinc storage battery.
ンフィルムもしくはポリエチレンフィルムであることを
特徴とする請求項（１）記載のアルカリ亜鉛蓄電池。(3) The alkaline zinc storage battery according to claim (1), wherein the polyolefin microporous thin film is a polypropylene film or a polyethylene film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038731A JPH02216757A (en) | 1989-02-17 | 1989-02-17 | Alkaline zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038731A JPH02216757A (en) | 1989-02-17 | 1989-02-17 | Alkaline zinc storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02216757A true JPH02216757A (en) | 1990-08-29 |
Family
ID=12533473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1038731A Pending JPH02216757A (en) | 1989-02-17 | 1989-02-17 | Alkaline zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02216757A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012544A1 (en) * | 1990-12-28 | 1992-07-23 | Yuasa Battery Co., Ltd. | Separator for alkali zinc battery |
| JP2009218047A (en) * | 2008-03-10 | 2009-09-24 | Nippon Kodoshi Corp | Separator for alkaline storage battery and manufacturing method thereof, and alkaline storage battery |
| JP2009218048A (en) * | 2008-03-10 | 2009-09-24 | Nippon Kodoshi Corp | Separator for alkaline storage battery and manufacturing method thereof, and alkaline storage battery |
-
1989
- 1989-02-17 JP JP1038731A patent/JPH02216757A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992012544A1 (en) * | 1990-12-28 | 1992-07-23 | Yuasa Battery Co., Ltd. | Separator for alkali zinc battery |
| US5320916A (en) * | 1990-12-28 | 1994-06-14 | Yuasa Corporation | Separator for alkali-zinc battery |
| US5547779A (en) * | 1990-12-28 | 1996-08-20 | Yuasa Corporation | Separator for alkali-zinc battery |
| JP2009218047A (en) * | 2008-03-10 | 2009-09-24 | Nippon Kodoshi Corp | Separator for alkaline storage battery and manufacturing method thereof, and alkaline storage battery |
| JP2009218048A (en) * | 2008-03-10 | 2009-09-24 | Nippon Kodoshi Corp | Separator for alkaline storage battery and manufacturing method thereof, and alkaline storage battery |
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