JPH0461462B2 - - Google Patents
Info
- Publication number
- JPH0461462B2 JPH0461462B2 JP58087222A JP8722283A JPH0461462B2 JP H0461462 B2 JPH0461462 B2 JP H0461462B2 JP 58087222 A JP58087222 A JP 58087222A JP 8722283 A JP8722283 A JP 8722283A JP H0461462 B2 JPH0461462 B2 JP H0461462B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- oil
- batteries
- impregnated
- water
- 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
- 239000000839 emulsion Substances 0.000 claims description 6
- 229920005594 polymer fiber Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 22
- -1 polyethylene Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 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
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M2300/0005—Acid 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)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Description
本発明は鉛蓄電池用セパレータの製造方法に係
るもので、特にMF（保守不要）電池に使用する
エンベロープ用に好適なセパレーターを提供する
ものである。
近年、自動車用電池は小形、軽量化、MF化が
急速に進み、格子合金は従来のPb−Sb系から低
Sbへ、更にSbフリー（Pb−Ca系）になつてき
た。
Pb−Ca系合金は、従来のPb−Sb系合金に比べ
ると、電気抵抗が小さく、耐蝕性が勝れ、電池で
の自己放電が少ないので、MF電池用に好適であ
るが、使用中に正極格子が著しく伸びる欠点があ
る。
このような欠点を補うために、MF電池では正
または負極板をセパレーターでエンベロープして
格子の伸びによるシヨートを防止する設計構造が
一般的に適用されている。
MF電池用セパレーターは、エンベロープが可
能であり、極板が使用中に変形しても破れないも
のであることは勿論、低抵抗薄形で、耐酸化性が
勝れ、しかも溶出不純物が少ないことが要求され
るので、従来品をそのまま使用することは、電池
性能面での問題が多い。
また前記したような特性を備えたセパレーター
としては、押出成形による微孔性の超高分子量の
ポリオレフインやシンターPVC（ポリ塩化ビニ
ル）がある。しかし、前者は高価であり、後者は
特性面から必ずしも十分なものであるとは言えな
い。
本発明はポリエチレン、ポリプロピレン、ポリ
スチロール、ポリアクリロニトリル、ポリアクリ
ル酸エステル系或いはポリエステル系などの親油
性のポリマー繊維を含む抄造体に水溶性のオイル
エマルジヨンを吹付け、塗着あるいは含浸して乾
燥することにより、上述のエンベロープ用セパレ
ーターとしての特性を満足する安価なセパレータ
ーを提供するものである。
以下、本発明について実施例により説明する。
実施例 １
ポリエチレン（SWP）繊維45wt％、ポリアク
リロニトリル繊維10wt％、6〓μｍＣガラス繊維
7wt％、シリカ微粉末38wt％よりなる抄造体に水
溶性のオイルエマルジヨン（オイル10％水溶液）
を等量含浸し、110℃で乾燥して水分を蒸発させ、
オイルを付着したセパレーターＡを得た。なお、
ここで使用したオイルエマルジヨンは、パラフイ
ン系の精製鉱油95部に石油系アニオン活性剤５部
を混合して作製した水溶性のオイルを水で希釈し
て調整した。またSWPとはポリエチレン合成パ
ルプの商品名である。
実施例 ２
ナフテン系の精製鉱油95部に石油系アニオン活
性剤５部を混合して作製した水溶性のオイルを使
つた以外は実施例１と同様にしてセパレーターＢ
を得た。
実施例 ３
ポリエチレン（SWP）繊維40wt％、太さ6dの
ポリエステル繊維15wt％、珪藻土45wt％よりな
る抄造体に実施例１で述べたオイルの20％水溶液
を塗着し、150℃で乾燥してセパレーターＣを得
た。
実施例 ４
ポリプロピレン繊維80wt％、シリカ微粉末
20wt％よりなる抄造体に実施例１で述べたオイ
ルの50％水溶液を吹付け、140℃で乾燥してセパ
レーターＤを得た。
表１に上記実施例で作製したセパレーターの特
性とNS40Z・MF電池（正極板をエンベロープ）
での性能を示す。なお、比較のために従来例とし
て実施例１に記載の抄造体（実施例１においてオ
イルを含浸させる前のもの）をセパレーターＥと
して作製した。
The present invention relates to a method for manufacturing a separator for lead-acid batteries, and in particular provides a separator suitable for envelopes used in MF (maintenance-free) batteries. In recent years, automotive batteries have rapidly become smaller, lighter, and more MF-based, and lattice alloys have changed from the conventional Pb-Sb system to lower
It has become more and more Sb-free (Pb-Ca type). Compared to conventional Pb-Sb alloys, Pb-Ca alloys have lower electrical resistance, better corrosion resistance, and less self-discharge in batteries, so they are suitable for MF batteries, but during use, The disadvantage is that the positive electrode lattice is significantly elongated. To compensate for these shortcomings, MF batteries generally have a design structure in which the positive or negative electrode plate is enveloped with a separator to prevent shortening due to grid elongation. Separators for MF batteries are capable of enveloping and do not break even if the electrode plates are deformed during use, as well as being thin with low resistance, having excellent oxidation resistance, and containing little eluted impurities. Therefore, using conventional products as is will cause many problems in terms of battery performance. Further, examples of separators having the above-mentioned characteristics include extrusion-molded microporous ultra-high molecular weight polyolefins and sintered PVC (polyvinyl chloride). However, the former is expensive, and the latter cannot necessarily be said to have sufficient characteristics. The present invention involves spraying, coating, or impregnating a water-soluble oil emulsion on a paper product containing lipophilic polymer fibers such as polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyacrylic acid ester, or polyester, and then drying it. By doing so, it is possible to provide an inexpensive separator that satisfies the above characteristics as an envelope separator. The present invention will be explained below with reference to Examples. Example 1 45wt% polyethylene (SWP) fiber, 10wt% polyacrylonitrile fiber, 6〓μmC glass fiber
Water-soluble oil emulsion (10% aqueous oil solution) in a paper structure consisting of 7wt% and 38wt% silica fine powder.
Impregnated with equal amount of
Separator A with oil attached was obtained. In addition,
The oil emulsion used here was prepared by diluting with water a water-soluble oil prepared by mixing 95 parts of paraffin-based refined mineral oil with 5 parts of a petroleum-based anion activator. SWP is the trade name for polyethylene synthetic pulp. Example 2 Separator B was prepared in the same manner as in Example 1, except that a water-soluble oil prepared by mixing 95 parts of naphthenic refined mineral oil with 5 parts of a petroleum-based anion activator was used.
I got it. Example 3 A 20% aqueous solution of the oil described in Example 1 was applied to a paper product consisting of 40 wt% polyethylene (SWP) fibers, 15 wt% polyester fibers with a thickness of 6 d, and 45 wt% diatomaceous earth, and dried at 150°C. Separator C was obtained. Example 4 80wt% polypropylene fiber, fine silica powder
A 50% aqueous solution of the oil described in Example 1 was sprayed onto a paper product consisting of 20 wt% and dried at 140°C to obtain Separator D. Table 1 shows the characteristics of the separator produced in the above example and the NS40Z・MF battery (positive electrode plate is enveloped)
The performance is shown below. For comparison, the paper article described in Example 1 (before being impregnated with oil in Example 1) was prepared as Separator E as a conventional example.
【表】
表１の結果より明らかな如く、本発明のオイル
を含浸したセパレーターを使用した電池での寿命
性能は、オイル含浸なしの従来品に比べて勝れて
いた。
パラフイン系オイルを含浸したセパレーターＡ
は、ナフテン系オイルを含浸したセパレーターＢ
に比べると電気抵抗では僅かに高くなつている
が、寿命性能が勝れていた。
寿命試験終了後のそれぞれのセパレーターにつ
いて、オイルの残存量をソツクスレー抽出器で分
析して調べたところ、パラフイン系のものは93
％、ナフテン系のものは89％であつた。
本発明のセパレーターに付着するオイルの最適
量は、セパレーターに使用されている親油性ポリ
マー繊維の種類、形状や量により異なるが、通常
の場合、親油性ポリマー繊維量の1/10以上で、1/
２以下である。1/10未満ではオイル付着の効果が
顕著でなく、また1/2より多く付着すると電気抵
抗が著しく高くなつたり、オイルが電池での使用
中に遊離してくるので好ましくない。
本発明で使用する界面活性剤は、オイルに混合
して均一なオイルエマルジヨンを形成するもの
で、実施例で述べたアニオン系のものの外、ノニ
オン系でもカチオン系でもいずれでもよく、使用
するオイルに対して通常5/1000〜1/10の割合で混
合する。
本発明では界面活性剤を含む水溶性のオイルエ
マルジヨンを抄造体に吹付け、塗着あるいは含浸
して乾燥するので、水に蒸発させた後、界面活性
剤がセパレーター中に残存する結果、浸造剤処理
が不要である特徴を有する。
一方、セパレーターに吹付け、塗着あるいは含
浸したオイルは、親油性ポリマー繊維に選択的に
吸着し、ポリマーの電気化学的な酸化による劣化
を防止するものである。しかも、このオイルは電
池での使用中にほとんど分解することがないので
有害不純物に変化しない。
以上の如く本発明の製造方法により得たセパレ
ーターは、抄造法により大量且つ安価に得られる
従来のセパレーターの特性を大幅に改良してエン
ベロープ用セパレーターとしての特性を満足した
ものであり、特に耐酸化性が勝れ、必ずしもエン
ベロープ用に限定されるものではなく、従来の
Pb−Sb系格子を使つた電池にも適用できるもの
であり、その工業的価値は大きい。[Table] As is clear from the results in Table 1, the life performance of the battery using the oil-impregnated separator of the present invention was superior to that of the conventional product not impregnated with oil. Separator A impregnated with paraffin oil
is separator B impregnated with naphthenic oil.
Although the electrical resistance was slightly higher than that of , the life performance was superior. After the life test, we analyzed the remaining amount of oil in each separator using a Soxhlet extractor, and found that the paraffin type had 93.
%, and naphthenic ones were 89%. The optimal amount of oil that adheres to the separator of the present invention varies depending on the type, shape, and amount of the lipophilic polymer fibers used in the separator, but usually it is 1/10 or more of the amount of lipophilic polymer fibers, and 1/10 or more of the amount of lipophilic polymer fibers. /
2 or less. If it is less than 1/10, the effect of oil adhesion will not be noticeable, and if it is more than 1/2, the electrical resistance will become extremely high or the oil will be liberated during use in the battery, which is not preferable. The surfactant used in the present invention is one that is mixed with oil to form a uniform oil emulsion, and in addition to the anionic type mentioned in the examples, it may be nonionic or cationic, depending on the oil used. Usually mixed at a ratio of 5/1000 to 1/10. In the present invention, a water-soluble oil emulsion containing a surfactant is sprayed, applied, or impregnated onto a paper article and dried. It has the characteristic that no agent treatment is required. On the other hand, the oil sprayed, applied, or impregnated onto the separator is selectively adsorbed to the lipophilic polymer fibers, thereby preventing deterioration of the polymer due to electrochemical oxidation. Moreover, this oil hardly decomposes during use in batteries, so it does not turn into harmful impurities. As described above, the separator obtained by the manufacturing method of the present invention has greatly improved the characteristics of conventional separators that can be obtained in large quantities and at low cost by the papermaking method, and satisfies the characteristics as a separator for envelopes, and is particularly resistant to oxidation. It is superior in nature and is not necessarily limited to envelope use, but can be
It can also be applied to batteries using Pb-Sb grids, and has great industrial value.
Claims (1)
含む抄造体に、水溶性のオイルエマルジヨンを吹
付け、塗着あるいは含浸して乾燥することを特徴
とする鉛蓄電池用セパレータの製造方法。1. A method for producing a separator for a lead-acid battery, which comprises spraying, coating or impregnating a paper product containing lipophilic polymer fibers excluding a chlorine-containing polymer with a water-soluble oil emulsion, and drying the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58087222A JPS59211959A (en) | 1983-05-17 | 1983-05-17 | Manufacture of separator for lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58087222A JPS59211959A (en) | 1983-05-17 | 1983-05-17 | Manufacture of separator for lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59211959A JPS59211959A (en) | 1984-11-30 |
| JPH0461462B2 true JPH0461462B2 (en) | 1992-09-30 |
Family
ID=13908864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58087222A Granted JPS59211959A (en) | 1983-05-17 | 1983-05-17 | Manufacture of separator for lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59211959A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62139068U (en) * | 1986-02-26 | 1987-09-02 | ||
| JP4789801B2 (en) * | 2004-02-27 | 2011-10-12 | 日本板硝子株式会社 | Lead-acid battery separator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5553063A (en) * | 1978-10-11 | 1980-04-18 | Yuasa Battery Co Ltd | Separator for cell and manufacturing method thereof |
-
1983
- 1983-05-17 JP JP58087222A patent/JPS59211959A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5553063A (en) * | 1978-10-11 | 1980-04-18 | Yuasa Battery Co Ltd | Separator for cell and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59211959A (en) | 1984-11-30 |
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