JPH047066B2 - - Google Patents
Info
- Publication number
- JPH047066B2 JPH047066B2 JP58075613A JP7561383A JPH047066B2 JP H047066 B2 JPH047066 B2 JP H047066B2 JP 58075613 A JP58075613 A JP 58075613A JP 7561383 A JP7561383 A JP 7561383A JP H047066 B2 JPH047066 B2 JP H047066B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- polypropylene
- separator
- polyamide
- mixed
- 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 53
- 239000002131 composite material Substances 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 22
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 229920006122 polyamide resin Polymers 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 description 17
- 229920002647 polyamide Polymers 0.000 description 17
- 239000007788 liquid Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004660 morphological change Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 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
- H01M50/423—Polyamide resins
-
- 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)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Description
本発明は密閉型アルカリ電池、特にニツケルカ
ドミウム蓄電池に用いるアルカリ電池用セパレー
ターの構成に関するものである。
従来、アルカリ電池用セパレーターにはポリア
ミド繊維の持つ吸水性、吸液性等の特性を利用し
たポリアミド繊維のみよりなる不織布が一般に用
いられている。また、ポリアミド繊維の吸液性、
吸水性をより向上させる為に無機塩類により繊維
を溶出して繊維表面に多数の微細な孔を有する多
孔質の構造にしたものが見られる。このように繊
維を多孔性としたことにより、電解液の保液量は
均一となり、それがため放電容量が大きくなると
いう特徴がある。然るに、アルカリ電池は高温時
或は連続的に過充電が行われる様な条件下では、
電解液の温度上昇や電気化学変化が大きい為に、
上記ポリアミド製不織布セパレーターでは劣化が
著しく、長期の使用に耐え難いという欠点があ
る。
また、ポリアミド繊維に電解液に対し耐性のあ
るポリプロピレン繊維を混入した不織布よりなる
セパレーターも見られるが、ポリプロピレン繊維
の熱溶着により繊維相互を接着するため、加熱溶
着時にポリプロピレン繊維の収縮が著しく、厳密
な工程管理を必要とし、均一な製品を大量、かつ
安価に製造することが困難である等の問題点があ
る。
更に、ポリプロピレン樹脂のメルトプロー方式
による不織布、ポリプロピレン繊維の湿式法によ
る不織布をセパレーターとしたものがあるが、吸
液性、耐アルカリ性等の電池特性は満足しうるも
のの、セパレーターの機械的強度が弱い為、電池
製造工程に於てセパレーターの伸び、切断等の問
題が発生することによりラインアツプされていな
いのが現状である。
更に、ポリアミド繊維とポリプロピレン−ポリ
エチレン系複合繊維とを80〜50％：20〜50％の比
率で混合し形成したウエブを加熱、加圧してポリ
エチレン成分を溶融し、繊維相互間を一体に結合
したセパレーターも工夫されてはいる。しかし上
記ポリプロピレン−ポリエチレン系複合繊維の混
合割合が非常に限定されるという問題点がある。
即ち、上記複合繊維が20％以下では接着力が不足
となり、電池組立工程にかけられず、また強力を
付与するため複合繊維を20〜50％未満混合すると
ポリアミド繊維が50％以上含まれることになり、
前記アルカリ電池の高温時或は連続的過充電が行
われる様な条件下では電解液の温度上昇や電気化
学的変化が大きい為にポリアミド繊維の劣化が著
しくなり、繊維が分解されてセパレーターとして
の性能が低下することになり好ましくなく、又、
上記複合繊維を50％以上混入すると加熱・加圧時
に該複合繊維を形成する低融点樹脂成分（ポリエ
チレン）が溶融圧着時にフイルム化し易く、繊維
間隙の閉塞現象が発生し易くなり、セパレーター
としての性能に悪影響を及ぼす。この様にポリプ
ロピレン−ポリエチレン系複合繊維の混入割合が
非常に限定される上に、ポリアミド繊維が存在す
るため、劣化による形態変化が著しく、大巾な性
能低下をきたすことになる。
本発明は上記諸欠点を克服し、如何なる条件下
でも十分実用に供し得るアルカリ電池用セパレー
ターを提供するものである。
以下本発明の１実施例を詳細に説明する。
本発明のアルカリ電池用セパレーターを構成す
る繊維は剥離型複合紡糸法を利用し、放射型紡糸
口金と複数個の三角形状紡糸口金を使用し、上記
放射型紡糸口金よりポリアミド樹脂、三角形状紡
糸口金よりポリプロピレン樹脂を同時に紡糸して
形成した。繊維と、ポリプロピレン−ポリエチレ
ン系サイドバイサイド又は海島型複合繊維との混
合繊維が用いられている。例えばポリアミド樹脂
を10〜30％含有するポリプロピレン混合樹脂80％
の溶融樹脂液とポリアミド溶融樹脂液20％とを特
殊形状の紡糸口金より同時に紡糸して得られる放
射状貼合せ型海島複合繊維を70％とポリプロピレ
ン−ポリエチレン系複合繊維30％との混合繊維を
ランドウエバー機又はカード機により、目付90
ｇ／m3のランダムウエブ又はクロスウエブを形成
し、一対の加熱・加圧ロールを通過させて、ポリ
エチレン成分の溶融によりウエブ構成繊維相互を
一体に接着し、見掛密度0.2〜0.5ｇ／cm3のアルカ
リ電池用セパレーターを形成する。
尚、セパレーターの重量は40〜200ｇ／m2の間
で使用目的に応じて適宜変えて用いられる。また
見掛密度は0.20ｇ／cm2未満となるとセパレーター
の強度や吸液速度が低下しまた、0.5ｇ／cm2以上
になると間隙が詰まり過ぎて電解により発生した
酸素の通過が阻害されるので好ましくなく適宜の
空隙を保つ必要があり、好ましくは0.20〜0.50
ｇ／cm2に調整する。
本発明に用いるポリプロピレン樹脂とポリアミ
ド樹脂との混合溶融樹脂と、ポリアミド樹脂より
紡糸された放射状貼合せ型海島複合繊維は第１図
に示す如く、略三角形状のポリプロピレン樹脂成
分１中に、島状にポリアミド樹脂成分２の点存す
るものが軸芯より多数放射状に配列して円柱体を
なし、上記三角柱形状のポリプロピレン樹脂成分
１の相隣りあう面を板状のポリアミド樹脂成分３
で接合した構造となつており、この放射状貼合せ
型海島複合繊維４と第２図に示す様に耐アルカリ
性にすぐれたサイドバイサイド型ポリプロピレン
−ポリエチレン複合繊維６とのポリエチレン成分
５との融着によつてウエブ構成繊維相互を一体に
接着してセパレーターを構成する。
従つて、セパレーターの主構成繊維であるポリ
アミド混合ポリプロピレン−ポリアミド放射状貼
合せ型海島複合繊維は三角柱形状のポリプロピレ
ン樹脂成分を相互に接合するポリアミド樹脂成分
は電解液により劣化・脱落し、ポリプロピレン樹
脂成分の分割と毛細管現象とにより、更にはポリ
プロピレン樹脂成分に島成分として混合されたポ
リアミド成分の劣化・脱落により多孔質化し吸液
特性は向上する。
次に、上記本発明のアルカリ電池用セパレータ
ーＡと比較例として従来のポリアミド繊維セパレ
ーターＢ、ポリプロピレン繊維セパレーターＣ、
ポリアミド、ポリプロピレン混合繊維セパレータ
ーＤの物性を下表に示した。
The present invention relates to the structure of an alkaline battery separator used in sealed alkaline batteries, particularly nickel-cadmium storage batteries. Conventionally, nonwoven fabrics made only of polyamide fibers have been generally used for separators for alkaline batteries, taking advantage of the properties of polyamide fibers such as water absorption and liquid absorption. In addition, the liquid absorption properties of polyamide fibers,
In order to further improve water absorption, fibers are eluted with inorganic salts to create a porous structure with many fine pores on the fiber surface. By making the fibers porous in this manner, the amount of electrolyte solution retained is uniform, and as a result, the discharge capacity is increased. However, under high temperature conditions or conditions where alkaline batteries are continuously overcharged,
Due to the large temperature rise and electrochemical changes in the electrolyte,
The polyamide nonwoven fabric separator described above has the disadvantage that it deteriorates significantly and cannot withstand long-term use. In addition, there are separators made of nonwoven fabric made of polyamide fibers mixed with polypropylene fibers that are resistant to electrolyte solutions, but since the fibers are bonded together by heat welding, the polypropylene fibers shrink significantly during heat welding, making it difficult to There are problems such as the need for detailed process control and the difficulty of manufacturing uniform products in large quantities at low cost. Furthermore, there are separators made of non-woven fabric made of polypropylene resin made by the melt-blown process, and non-woven fabric made of polypropylene fiber made by the wet process, but although they can satisfy battery properties such as liquid absorption and alkali resistance, the mechanical strength of the separator is weak. Currently, this product is not available in the lineup due to problems such as elongation and cutting of the separator during the battery manufacturing process. Furthermore, a web formed by mixing polyamide fibers and polypropylene-polyethylene composite fibers at a ratio of 80 to 50%: 20 to 50% was heated and pressurized to melt the polyethylene component and bond the fibers together. The separator has also been devised. However, there is a problem in that the mixing ratio of the polypropylene-polyethylene composite fibers is very limited.
In other words, if the composite fiber is less than 20%, the adhesive strength will be insufficient and it cannot be used in the battery assembly process, and if less than 20 to 50% of the composite fiber is mixed to give strength, it will contain more than 50% polyamide fiber. ,
When the alkaline battery is subjected to high temperatures or continuous overcharging, the temperature rise and electrochemical changes in the electrolyte are large, resulting in significant deterioration of the polyamide fibers, causing the fibers to decompose and fail to function as a separator. This is undesirable because the performance will deteriorate, and
If 50% or more of the above composite fibers are mixed, the low melting point resin component (polyethylene) that forms the composite fibers during heating and pressurization tends to form a film during melt-pressing, and fiber gap clogging phenomenon tends to occur, resulting in poor performance as a separator. have a negative impact on As described above, since the mixing ratio of polypropylene-polyethylene composite fibers is extremely limited, and in addition to the presence of polyamide fibers, morphological changes due to deterioration are significant, resulting in a large drop in performance. The present invention overcomes the above-mentioned drawbacks and provides a separator for alkaline batteries that can be put to practical use under any conditions. One embodiment of the present invention will be described in detail below. The fiber constituting the separator for alkaline batteries of the present invention is produced using a peel-type composite spinning method using a radial spinneret and a plurality of triangular spinnerets. It was formed by simultaneously spinning polypropylene resin. Mixed fibers of fibers and polypropylene-polyethylene side-by-side or sea-island composite fibers are used. For example, 80% polypropylene mixed resin containing 10-30% polyamide resin
A mixed fiber of 70% radially laminated sea-island composite fiber and 30% polypropylene-polyethylene composite fiber obtained by simultaneously spinning 20% molten resin liquid and 20% polyamide molten resin liquid using a specially shaped spinneret. Fabric weight: 90 by Weber machine or card machine
A random web or cross web of g/m 3 is formed, passed through a pair of heated and pressurized rolls, and the web constituent fibers are bonded together by melting the polyethylene component, resulting in an apparent density of 0.2 to 0.5 g/cm. 3 to form a separator for alkaline batteries. The weight of the separator may be varied between 40 and 200 g/m 2 depending on the purpose of use. Furthermore, if the apparent density is less than 0.20 g/cm 2 , the strength and liquid absorption rate of the separator will decrease, and if it is more than 0.5 g/cm 2 , the gaps will become too clogged and the passage of oxygen generated by electrolysis will be inhibited. It is necessary to maintain an appropriate gap, preferably 0.20 to 0.50.
Adjust to g/ cm2 . As shown in FIG. 1, the radially laminated sea-island composite fiber spun from the mixed molten resin of polypropylene resin and polyamide resin used in the present invention and the polyamide resin has an island shape in the approximately triangular polypropylene resin component 1. A large number of dotted polyamide resin components 2 are arranged radially from the axis to form a cylindrical body, and adjacent surfaces of the triangular prism-shaped polypropylene resin component 1 are formed into a plate-shaped polyamide resin component 3.
As shown in Fig. 2, this radially laminated sea-island composite fiber 4 is bonded to a side-by-side type polypropylene-polyethylene composite fiber 6 with excellent alkali resistance by fusion with the polyethylene component 5. The fibers constituting the web are then bonded together to form a separator. Therefore, in the polyamide mixed polypropylene-polyamide radially laminated sea-island composite fiber, which is the main constituent fiber of the separator, the polyamide resin component that connects the triangular prism-shaped polypropylene resin components to each other deteriorates and falls off due to the electrolyte, and the polypropylene resin component Due to the splitting and capillary phenomenon, and further due to deterioration and shedding of the polyamide component mixed as an island component with the polypropylene resin component, it becomes porous and the liquid absorption properties are improved. Next, the separator A for alkaline batteries of the present invention, conventional polyamide fiber separator B, polypropylene fiber separator C as comparative examples,
The physical properties of polyamide and polypropylene mixed fiber separator D are shown in the table below.
【表】【table】
【表】
本発明は上記の様に構成したから、接着繊維と
なるポリプロピレン−ポリエチレン複合繊維が引
張強度と保液特性のみに機能が限定され、セパレ
ーターとして必要かつ十分な吸液速度及び吸液率
を維持し、且つ耐久性のある必要強度を得る最小
混合割合（30〜50％）に抑制することができる。
また電解液によるセパレーターの劣化による形態
変化はなくなり、電池寿命が大巾に延長する。更
に上表に示す如く電池特性としての吸液速度、吸
液量に優れ、短絡率、耐アルカリ性とも全般に良
好な結果を示す等のすぐれた効果を有する発明で
ある。[Table] Since the present invention is configured as described above, the function of the polypropylene-polyethylene composite fiber that serves as the adhesive fiber is limited only to tensile strength and liquid retention properties, and the liquid absorption rate and liquid absorption rate necessary and sufficient as a separator are obtained. can be suppressed to the minimum mixing ratio (30 to 50%) that maintains the required strength and durability.
In addition, the deterioration of the separator due to the electrolyte eliminates morphological changes, greatly extending battery life. Furthermore, as shown in the table above, this invention has excellent battery characteristics such as excellent liquid absorption speed and liquid absorption amount, and generally good results in terms of short circuit rate and alkali resistance.
第１図は本発明のアルカリ電池用セパレーター
に用いるポリアミド混合ポリプロピレン−ポリア
ミド放射状貼合せ型海島複合繊維の要部拡大図、
第２図は同上放射状貼合せ型海島複合繊維とポリ
プロピレン−ポリエチレン複合繊維の接着部の要
部拡大図である。
１…三角柱形状ポリプロピレン樹脂成分、２…
島状ポリアミド樹脂成分、３…板状ポリアミド樹
脂成分、４…放射状貼合せ型海島複合繊維、５…
ポリエチレン成分。
FIG. 1 is an enlarged view of the main parts of the polyamide mixed polypropylene-polyamide radially laminated sea-island composite fiber used in the alkaline battery separator of the present invention;
FIG. 2 is an enlarged view of the main part of the bonded portion between the radially laminated sea-island composite fiber and the polypropylene-polyethylene composite fiber. 1...Triangular prism-shaped polypropylene resin component, 2...
Island-shaped polyamide resin component, 3... Plate-shaped polyamide resin component, 4 ... Radial lamination type sea-island composite fiber, 5...
polyethylene component.
Claims (1)
の放射片の間〓に、断面形状が略三角柱形状のポ
リプロピレン樹脂とポリアミド樹脂との混合樹脂
片が配列した状態に複合紡糸した放射状貼合せ型
海島複合繊維とポリプロピレン−ポリエチレン複
合接着繊維との混合繊維からなるクロスウエブ又
はランダムウエブの繊維層で構成され、加熱・加
圧によりウエブ構成繊維相互がポリエチレン成分
の溶着により一体に接着してなることを特徴とす
るアルカリ電池用セパレーター。1. A radial lamination type sea island in which mixed resin pieces of polypropylene resin and polyamide resin, each having a substantially triangular prism cross-sectional shape, are arranged between the radial pieces of a polyamide resin core having a radial cross-sectional shape. It is composed of a cross web or random web fiber layer made of mixed fibers of composite fibers and polypropylene-polyethylene composite adhesive fibers, and the web constituent fibers are bonded together by welding of the polyethylene component by heating and pressure. A separator for alkaline batteries with special features.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58075613A JPS59201365A (en) | 1983-04-28 | 1983-04-28 | Separator for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58075613A JPS59201365A (en) | 1983-04-28 | 1983-04-28 | Separator for alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59201365A JPS59201365A (en) | 1984-11-14 |
| JPH047066B2 true JPH047066B2 (en) | 1992-02-07 |
Family
ID=13581233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58075613A Granted JPS59201365A (en) | 1983-04-28 | 1983-04-28 | Separator for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59201365A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2622744B2 (en) * | 1989-02-20 | 1997-06-18 | チッソ株式会社 | Water-retaining nonwoven |
-
1983
- 1983-04-28 JP JP58075613A patent/JPS59201365A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59201365A (en) | 1984-11-14 |
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