JPH0481305B2 - - Google Patents
Info
- Publication number
- JPH0481305B2 JPH0481305B2 JP60237138A JP23713885A JPH0481305B2 JP H0481305 B2 JPH0481305 B2 JP H0481305B2 JP 60237138 A JP60237138 A JP 60237138A JP 23713885 A JP23713885 A JP 23713885A JP H0481305 B2 JPH0481305 B2 JP H0481305B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- fiber diameter
- liquid
- nonwoven fabric
- average fiber
- 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.)
- Expired - Lifetime
Links
- 239000000835 fiber Substances 0.000 claims description 21
- -1 polypropylene Polymers 0.000 claims description 12
- 239000004745 nonwoven fabric Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 230000035699 permeability Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver 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
-
- 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)
- Nonwoven Fabrics (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は可搬用或は電気自動車用の電源として
用いられる密閉形ニツケル・亜鉛蓄電池に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a sealed nickel-zinc storage battery used as a power source for portable or electric vehicles.
従来技術とその問題点
ニツケル・亜鉛蓄電池は高エネルギー密度、高
出力特性を有している。Conventional technology and its problems Nickel-zinc storage batteries have high energy density and high output characteristics.
しかしながらZnの溶解度が高いために、充電
時Znのデンドライトが成長し、セパレータの貫
通シヨートを起し、或は形状変化のために利用率
の低下を招き、これらによりサイクル寿命が低下
した。 However, due to the high solubility of Zn, dendrites of Zn grow during charging, causing shoot-through of the separator or a change in shape, leading to a decrease in utilization rate, resulting in a decrease in cycle life.
従来この形状変化の軽減のためZn極へのBi2O3
等種々の金属酸化物の添加、或は保液紙の材質、
厚み等の検討がなされ、種々の提案がなされてい
る。 Conventionally, Bi 2 O 3 was added to the Zn electrode to reduce this shape change.
Addition of various metal oxides, etc., or the material of liquid-retaining paper,
Studies have been made on the thickness, etc., and various proposals have been made.
この内、金属酸化物の添加は、物により効果が
見られるものの、その効果の程度は無添加と比較
して数割程度の改善にすぎず又、反面自己放電量
を大きくする欠点を有していた。 Among these, the addition of metal oxides is effective depending on the material, but the degree of effect is only a few tenths of an improvement compared to no addition, and on the other hand, it has the disadvantage of increasing the amount of self-discharge. was.
ポリプロピレンの従来の繊維径を有するもの
は、電解液の保持率が弱く、形状変化を軽減する
程度が小さく、寿命特性改良も少なかつた。 Polypropylene fibers with conventional fiber diameters had a weak electrolyte retention rate, a small degree of reduction in shape change, and little improvement in life characteristics.
発明の目的
本発明は上記に鑑みなされたものであり、その
目的とするところは、サイクル寿命を改良した密
閉形ニツケル・亜鉛蓄電池を提供することであ
る。OBJECTS OF THE INVENTION The present invention has been made in view of the above, and its object is to provide a sealed nickel-zinc storage battery with improved cycle life.
発明の構成
即、本発明は上記の目的を達成するべく、保液
紙として平均繊維径0.5〜5μmのポリプロピレン
不織布を用いたものである。これにより保液紙中
の電解液量を多く保持し、かつ充電末期に正極か
ら発生する酸素ガスを不織布の面方向に沿つて、
極板中央付近まで拡散することが出来るので、
Znの酸素ガス吸収を極板の全面において可能と
した。Structure of the Invention Namely, in order to achieve the above object, the present invention uses a polypropylene nonwoven fabric having an average fiber diameter of 0.5 to 5 μm as a liquid-retaining paper. This allows a large amount of electrolyte to be retained in the liquid-retaining paper, and at the same time directs oxygen gas generated from the positive electrode at the end of charging along the surface direction of the nonwoven fabric.
It can be diffused to near the center of the electrode plate, so
This allows Zn to absorb oxygen gas over the entire surface of the electrode plate.
従来のZn極では周縁部のみにガス吸収が起り、
生じたジンケートイオンがその元の位置よりも少
し内側にZnとして析出し、形状変化を増大させ
ていたのに比べて、形状変化を大巾に緩和するこ
とが出来る。 In conventional Zn electrodes, gas absorption occurs only at the periphery,
Compared to the case where the generated zincate ions precipitate as Zn slightly inside the original position and increase the shape change, the shape change can be greatly alleviated.
実施例
以下に本発明の詳細につき、一実施例により説
明する。EXAMPLE The details of the present invention will be explained below using an example.
本発明の電池は、焼結式又はベースト式正極
板、シート式又はペースト式負極板よりなる公称
容量10Ahの密閉形ニツケル・亜鉛蓄電池である。
第１図は本発明の電池の水平断面図である。 The battery of the present invention is a sealed nickel-zinc storage battery having a nominal capacity of 10 Ah and comprising a sintered or base type positive electrode plate and a sheet type or paste type negative electrode plate.
FIG. 1 is a horizontal sectional view of the battery of the present invention.
１はニツケルシンター極板或は、ニツケルペー
スト式極板からなる正極板、２は亜鉛極で亜鉛粉
末及び酸化亜鉛粉末をポリ四弗化エチレン樹脂で
シート化したもの、或はペースト化したものを銅
又銀集電体に付着させたものであり、３はセパレ
ータとしての微孔ポリプロピレン膜、或はグラフ
トポリエチレン膜であり、各１〜３重又は組合せ
たものであり、４は正極板又は負極板に接した本
発明に係わる保液紙であり、５は電槽である。 1 is a positive electrode plate made of a nickel sinter electrode plate or a nickel paste type electrode plate, and 2 is a zinc electrode made of zinc powder and zinc oxide powder made into a sheet or paste with polytetrafluoroethylene resin. It is attached to a copper or silver current collector, 3 is a microporous polypropylene membrane or grafted polyethylene membrane as a separator, and 1 to 3 layers each or a combination, 4 is a positive electrode plate or a negative electrode. This is the liquid retaining paper according to the present invention that is in contact with the board, and 5 is a battery case.
電解液は比重1.30〜1.40の水酸化カリウムを主
体とする水溶液であり、正極、負極、セパレー
タ、保液紙の全空隙の90〜95％を満たす液量を注
入する。 The electrolyte is an aqueous solution mainly composed of potassium hydroxide with a specific gravity of 1.30 to 1.40, and is injected in an amount that fills 90 to 95% of the total voids in the positive electrode, negative electrode, separator, and liquid-retaining paper.
第２図にポリプロピレン不織布の平均繊維径と
電解液保持率とその時の通気度の実測値の関係を
示した。目付量40g／m2のポリプロピレン不織布
の平均繊維径について測定した。5μmより太い繊
維径では保液率が極端に悪くなる。 FIG. 2 shows the relationship between the average fiber diameter of the polypropylene nonwoven fabric, the electrolyte retention rate, and the measured value of air permeability at that time. The average fiber diameter of a polypropylene nonwoven fabric with a basis weight of 40 g/m 2 was measured. If the fiber diameter is thicker than 5 μm, the liquid retention rate will be extremely poor.
一方、形状変化に影響する原因である酸素ガス
通気度は、0.5μmより細い繊維径では５c.c.／cm2．
sec以下となる。この通気度測定は、電解液保液
率90％においての測定値であり、実用電池におけ
る通気性のそのものではないが、傾向としては一
致するものである。保液率、通気度の両者よりポ
リプロピレン不織布の繊維径は0.5μmより5μmま
での間が適切である。 On the other hand, the oxygen gas permeability, which is a factor that affects shape change, is 5 c.c./cm 2 for fibers with a diameter smaller than 0.5 μm.
sec or less. This air permeability measurement is a value measured at an electrolyte retention rate of 90%, and although it is not the same as the air permeability of a practical battery, it does match the tendency. In view of both liquid retention rate and air permeability, the fiber diameter of the polypropylene nonwoven fabric is suitably between 0.5 μm and 5 μm.
第３図に各々繊維径のポリプロプレン不織布の
Ａは平均繊維径1.0μm，Ｂは平均繊維径5μm，Ｃ
は平均繊維径10μm，Ｄは平均繊維径30μmを用い
た電池の放電深度100％におけるサイクル寿命特
性を示した。尚、Ｅは繊維径が30μmのセルロー
ス系不織布を用いた電池である。繊維径の細い方
がサイクル寿命特性が良好であり、すなわち形状
変化は少ない。Ｅのセルロース系不織布を用いた
電池は、電解液により膨潤し酸素ガス透過性が極
端に悪くなるのでサイクル寿命が短い。Ｅは同一
目付量、同一平均繊維径でも形状変化が大きくな
ることが分り、酸素ガス透過性の重要性を示して
いる。 Figure 3 shows polypropylene nonwoven fabrics with different fiber diameters: A is 1.0 μm in average fiber diameter, B is 5 μm in average fiber diameter, and C is 5 μm in average fiber diameter.
shows the cycle life characteristics at a depth of discharge of 100% for a battery using an average fiber diameter of 10 μm and D a mean fiber diameter of 30 μm. Note that E is a battery using cellulose nonwoven fabric with a fiber diameter of 30 μm. The smaller the fiber diameter, the better the cycle life characteristics, that is, the smaller the change in shape. Batteries using cellulose nonwoven fabric E have a short cycle life because they swell with the electrolyte and have extremely poor oxygen gas permeability. It was found that the shape change of E becomes large even with the same basis weight and the same average fiber diameter, indicating the importance of oxygen gas permeability.
一方、繊維径が細かくなる程コストは高くな
り、又不織布自体の強度が弱くかつ表面の毛ば立
ちが多くなり取扱いが困難となる。 On the other hand, the finer the fiber diameter, the higher the cost, and the strength of the nonwoven fabric itself is weaker and the surface becomes more fluffy, making it difficult to handle.
上記を総合して、平均繊維径は0.5〜5μmが適
切である。 Taking the above into consideration, it is appropriate that the average fiber diameter is 0.5 to 5 μm.
発明の効果
上述した如く、本発明ではサイクル寿命を改良
したニツケル・亜鉛蓄電池を提供することができ
るので、その工業的価値は極めて大である。Effects of the Invention As described above, the present invention can provide a nickel-zinc storage battery with improved cycle life, and therefore has extremely great industrial value.
第１図は本発明の電池の水平断面図、第２図は
ポリプロピレン不織布の平均繊維径と電解液保持
率と通気度の関係を示した図、第３図は本発明電
池と従来品とのサイクル寿命特性図である。
１……正極板、２……亜鉛極、３……セパレー
タ、４……保液紙。
Figure 1 is a horizontal cross-sectional view of the battery of the present invention, Figure 2 is a diagram showing the relationship between the average fiber diameter of the polypropylene nonwoven fabric, electrolyte retention rate, and air permeability, and Figure 3 is a diagram showing the relationship between the battery of the present invention and a conventional product. It is a cycle life characteristic diagram. 1... Positive electrode plate, 2... Zinc electrode, 3... Separator, 4... Liquid retaining paper.
Claims (1)
液紙間にセパレータを配した密閉形ニツケル・亜
鉛蓄電池において、前記正極板、負極板、保液
紙、セパレータが水平になるように配置するとと
もに、前記保液紙が平均繊維径0.5〜5μmのポリ
プロピレン不織布からなることを特徴とする密閉
形ニツケル・亜鉛蓄電池。1. In a sealed nickel-zinc storage battery in which a liquid-retaining paper is arranged on each of the positive electrode plate and the negative electrode plate, and a separator is arranged between the liquid-retaining papers, the positive electrode plate, the negative electrode plate, the liquid-retaining paper, and the separator are horizontal. A sealed nickel-zinc storage battery characterized in that the liquid retaining paper is made of polypropylene nonwoven fabric with an average fiber diameter of 0.5 to 5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60237138A JPS6297258A (en) | 1985-10-23 | 1985-10-23 | Enclosed nickel-zinc battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60237138A JPS6297258A (en) | 1985-10-23 | 1985-10-23 | Enclosed nickel-zinc battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6297258A JPS6297258A (en) | 1987-05-06 |
| JPH0481305B2 true JPH0481305B2 (en) | 1992-12-22 |
Family
ID=17010965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60237138A Granted JPS6297258A (en) | 1985-10-23 | 1985-10-23 | Enclosed nickel-zinc battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6297258A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04179048A (en) * | 1990-11-09 | 1992-06-25 | Japan Storage Battery Co Ltd | Ni-zn battery |
| JP6456138B2 (en) * | 2014-12-26 | 2019-01-23 | 株式会社日本触媒 | Electrode and battery constructed using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5590078A (en) * | 1978-12-27 | 1980-07-08 | Matsushita Electric Ind Co Ltd | Ni-zn battery |
-
1985
- 1985-10-23 JP JP60237138A patent/JPS6297258A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6297258A (en) | 1987-05-06 |
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