JPH0195466A - Separator for metal halide battery - Google Patents
Separator for metal halide batteryInfo
- Publication number
- JPH0195466A JPH0195466A JP62251566A JP25156687A JPH0195466A JP H0195466 A JPH0195466 A JP H0195466A JP 62251566 A JP62251566 A JP 62251566A JP 25156687 A JP25156687 A JP 25156687A JP H0195466 A JPH0195466 A JP H0195466A
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- film
- fibers
- barrier property
- separator
- 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.)
- Granted
Links
- 229910001507 metal halide Inorganic materials 0.000 title abstract 2
- 150000005309 metal halides Chemical class 0.000 title abstract 2
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 19
- 239000004698 Polyethylene Substances 0.000 claims abstract description 13
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- -1 polyethylene Polymers 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000012982 microporous membrane Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 34
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052794 bromium Inorganic materials 0.000 abstract description 34
- 230000004888 barrier function Effects 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 6
- 230000003028 elevating effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 29
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
この発明は、金属ハロゲン電池において正極電解液と負
極電解液を隔離するために使用するセパレークに関する
ものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application This invention relates to a separator used to separate a positive electrode electrolyte and a negative electrode electrolyte in a metal halogen battery.
Ｂ０発明の概要
この発明は、ポリエチレン繊維とガラス繊維を用いて、
抄紙状微細多孔質膜とすることことによって、膜の電気
抵抗が低く、且つ、臭素バリアー性の高い金属ハロゲン
電池用セパレータを提供するものである。B0 Summary of the invention This invention uses polyethylene fibers and glass fibers to
By forming a paper-like microporous membrane, the present invention provides a separator for metal halogen batteries that has low electrical resistance and high bromine barrier properties.
Ｃ０従来の技術
金属ハロゲン電池の一例として、例えば、亜鉛臭素電池
においては、充電時に正極において臭素が発生し、この
臭素が負極に析出した亜鉛と反応すると自己放電を引き
起こすため、正極電解液と負極電解液を隔離する臭素バ
リアー性の高いセパレータが必要不可欠である。C0 Conventional Technology As an example of a metal halogen battery, for example, in a zinc-bromine battery, bromine is generated at the positive electrode during charging, and when this bromine reacts with zinc deposited on the negative electrode, it causes self-discharge. A separator with high bromine barrier properties is essential to isolate the electrolyte.
また、このセパレータは臭素バリアー性に優れるととも
に、セパレータ自体の電気抵抗が低いことが望まれるも
のである。Further, it is desired that this separator has excellent bromine barrier properties and that the separator itself has low electrical resistance.
従来、このような亜鉛臭素電池のセパレータとしては、
各種の微細多孔質膜から適宜選択して用いられているが
、これらの微細多孔質膜は、素材となるｖＩ４ＩＩ＆粉
体に、各種無機微粉体および有機液状体を加えて、混合
、成形し、しかる後に空孔形成成分である有Ｐｌｉ？ｒ
ｌ状体を抽出することによって作られている。Conventionally, as a separator for such zinc bromine batteries,
Various fine porous membranes are selected and used as appropriate, and these fine porous membranes are made by adding various inorganic fine powders and organic liquids to the raw material vI4II & powder, mixing and shaping the mixture. After that, the pore-forming component Pli? r
It is made by extracting l-shaped bodies.
Ｄ０発明が解決しようとする問題点
上記のような従来のセパレータにおいては、例えば、絶
縁物である素材樹脂の相対的な割合を低下させると膜の
電気抵抗は減少するが、臭素バリアー性は低下してしま
うというように膜の電気抵抗と臭素バリアー性とは相反
する性質のものであった０
すなわち、従来のセパレータにおいては、膜の電気抵抗
と臭素バリアー性は、膜の電気抵抗が比較的低ければ臭
素バリアー性が劣り、逆に臭素バリアー性に優れていれ
ば膜の電気抵抗が高くなるというように、反比例的な相
関があり、求められる２つの特性の両立が困難であると
いう問題点があった。D0 Problems to be Solved by the Invention In the conventional separators as described above, for example, if the relative proportion of the resin material, which is an insulator, is reduced, the electrical resistance of the film is reduced, but the bromine barrier property is reduced. In other words, in conventional separators, the electrical resistance and bromine barrier properties of the membrane are relatively contradictory. If the bromine barrier property is low, the bromine barrier property will be poor, and conversely, if the bromine barrier property is excellent, the electrical resistance of the membrane will be high.There is an inversely proportional correlation, and it is difficult to achieve both of the required properties. was there.
この発明は、係る問題点を解決し、電気抵抗が低く、且
つ、臭素バリアー性に優れた金属ハロゲン電池用セパレ
ータを提供することを目的とするものである。The object of the present invention is to solve these problems and provide a separator for metal halogen batteries that has low electrical resistance and excellent bromine barrier properties.
Ｅ０問題点を解決するための手段
この発明においては、ポリエチレン繊維を素材とし、ガ
ラス繊維を分散させて、抄紙状の微細多孔質膜とするこ
とにより、臭素バリアー性を低下させることなく、膜の
電気抵抗を引き下げて、上記の問題を解決したものであ
る。Means for solving the E0 problem In this invention, by using polyethylene fibers as a material and dispersing glass fibers to form a paper-like microporous membrane, the bromine barrier properties of the membrane can be improved. This solves the above problem by lowering the electrical resistance.
Ｆ０作用
この発明において、ガラスｍ維は、その添加により、膜
の電気抵抗を引下げるとともに、素材であるポリエチレ
ンｍ維の間隙を充たして、適当な′ 微細孔を形成する
ことにより、臭素バリアー性を高める点においても有利
に働くものである。F0 effect In this invention, the addition of glass m-fibers lowers the electrical resistance of the membrane, and also fills the gaps between the polyethylene m-fibers, which are the raw material, and forms appropriate micropores, thereby improving bromine barrier properties. It also works advantageously in terms of increasing the
また、このガラス繊維は添加量が同じであれば、その直
径が小さいほうがより膜が緻密になり、臭素バリアー性
がさらに向上する。Furthermore, if the amount of glass fibers added is the same, the smaller the diameter, the denser the film, and the further improved the bromine barrier properties.
Ｇ、実施例 以下、実施例によってこの考案をより詳細に説明する。G. Example Hereinafter, this invention will be explained in more detail with reference to examples.
実施例１：
直径約１０〜１５μｍ１長さ約ｌｌ１１１Ｉのポリエチ
レン繊維と直径約ｌＯμ■のガラス繊維を用いて、ポリ
エチレン繊維とガラス繊維の重量比を変化させ、５種類
の抄紙状微細多孔質（Ａ−Ｅ）を作製した。Example 1: Using polyethylene fibers with a diameter of approximately 10 to 15 μm and a length of approximately 111I and glass fibers with a diameter of approximately 10 μμ, five types of paper-like microporous materials (A -E) was produced.
この内、膜Ａは、ポリエチレン繊維のみからなる比較サ
ンプルである。Among these, membrane A is a comparison sample consisting only of polyethylene fibers.
また、抄紙状とする方法は、各ｍ維を所定の割合に混合
したものを、水に分散させ、この分散液を抄紙機に入れ
て、紙層ミ説水、乾燥の工程を経て抄紙とするというも
のであるが、各繊維の結合を強固なものにする上で、脱
水後、抄紙を加熱加圧することが望ましい。In addition, the method for making paper is to mix each m-fiber in a predetermined ratio and disperse it in water, put this dispersion into a paper machine, and pass through the steps of watering and drying the paper layer to make paper. However, in order to strengthen the bond between each fiber, it is desirable to heat and press the paper after dehydration.
この実施例においては、成形する際に、１２０°Ｃに昇
温した２本ロールに通してヒートプレスすることによっ
て、ポリエチレン樹脂の密着を向上させた。In this example, when molding, the adhesion of the polyethylene resin was improved by heat pressing it through two rolls heated to 120°C.
以上のようにして作製した膜サンプルＡ−Ｅについて、
膜の電気抵抗の測定と臭素バリアー性試験を行った。Regarding membrane samples A-E prepared as above,
The electrical resistance of the membrane was measured and a bromine barrier property test was conducted.
膜の電気抵抗の測定はＪＩＳ Ｃ−２３１３に従って
行い、その結果は、第１表および第１図に示されるよう
であった。The electrical resistance of the film was measured according to JIS C-2313, and the results were as shown in Table 1 and FIG.
第１図から明らかなように、ポリエチレン繊維のみから
なろ膜Ａに比べて、ガラス繊維を添加した膜（Ｂ−Ｅ）
は、いずれも膜の電気抵抗が著しく低下している。As is clear from Figure 1, compared to Nafila membrane A made only of polyethylene fibers, the membrane added with glass fibers (B-E)
In both cases, the electrical resistance of the membrane is significantly reduced.
ここで、ガラス繊維の添加量が多い程、膜の電気抵抗は
低くなっているが、添加量が一定量に達すると、それ以
上添加量を増しても、膜の電気抵抗の低下が少なくなる
のは、膜がある程度の緻密さに達するとそれ以上は膜の
電気抵抗が低下しにくくなるためと考えられる。Here, the electrical resistance of the membrane decreases as the amount of glass fiber added increases, but once the amount added reaches a certain amount, even if the amount added is further increased, the decrease in the electrical resistance of the membrane becomes smaller. This is thought to be because once the film reaches a certain degree of density, the electrical resistance of the film becomes difficult to decrease beyond that point.
また、臭素バリアー性試験については、第４図に示され
るようなＵ字管２を用いて行い、微細多孔質膜１を介し
て一方には３ｍｏｌ／ｌ臭化亜鉛水溶液、他方に３ｍｏ
Ｉ ／ ｌ臭化亜鉛水溶液と０．３ｍｏｌ／ｌ臭素の
混合液を入れ、４時間後の臭素透過量を測定した。In addition, the bromine barrier property test was conducted using a U-shaped tube 2 as shown in FIG.
A mixed solution of I/l zinc bromide aqueous solution and 0.3 mol/l bromine was added, and the amount of bromine permeated after 4 hours was measured.
第１表及び第２図は臭素バリアー性試験の結果を示すも
のであるが、ポリエチレン繊維のみからなる膜Ａに比較
して、ガラス繊維を添加した膜Ｂ〜Ｅはいずれも臭素の
透過量が大きく減少しており、ガラス繊維の添加量の多
いもの程、臭素バリアー性の向上が著しい。Table 1 and Figure 2 show the results of the bromine barrier property test. Compared to membrane A made only of polyethylene fibers, all membranes B to E containing glass fibers had a lower amount of bromine permeation. The bromine barrier properties are significantly improved as the amount of glass fiber added increases.
以上の結果は、ポリエチレン繊維にガラス繊維を添加し
て、抄紙状の微細多孔質膜とすることが膜の電気抵抗を
低下させる上でも、臭素バリアー性を向上させる上でも
、非常に有効であることを示している。The above results demonstrate that adding glass fiber to polyethylene fibers to create paper-like microporous membranes is very effective in lowering the membrane's electrical resistance and improving its bromine barrier properties. It is shown that.
第１表
実施例： ２
実施例１で最も好ましい結果を得た膜サンプルＥと同じ
組成比で、ガラス繊維の直径を変化させて、抄紙状微細
多孔質膜（Ｅ−１，Ｅ−２，Ｅ−３，Ｅ−４）を作製し
、実施例１と同様に膜の電気抵抗を測定し、臭素バリア
ー性試験を行った。Table 1 Examples: 2 Paper-like microporous membranes (E-1, E-2, E-3 and E-4) were prepared, and the electrical resistance of the film was measured in the same manner as in Example 1, and a bromine barrier property test was conducted.
膜の電気抵抗については、第２表に示されるるように、
ガラスｔａ雑の直径によって大差はなく、いずれも０．
０００２Ω−一／枚前後であった。Regarding the electrical resistance of the membrane, as shown in Table 2,
There is no big difference depending on the diameter of the glass ta.
It was around 0002Ω-1/piece.
しかし、従来この種のセパレータとして用いられている
微細多孔質膜の膜抵抗は、例えばポリオレフィン系のも
ので約０．００５Ω−ｄ／枚程度であるから、この発明
に係るセパレータの電気抵抗は従来のものの約２０分の
１以下と、極めて低いものである。However, since the membrane resistance of microporous membranes conventionally used as this type of separator is about 0.005 Ω-d/sheet, for example, polyolefin-based membranes, the electrical resistance of the separator according to the present invention is lower than that of the conventional separator. It is extremely low, about 1/20th of that of the average.
また、臭素バリアー性については、第２表および第３図
に示されろように、Ｅ−１＞ Ｅ−２＞ Ｅ−３＞ Ｅ
−４とガラス繊維の直径が順に小さくなる程、臭素透過
量が少な（、臭素バリアー性が向上していることが明確
である。Regarding the bromine barrier property, as shown in Table 2 and Figure 3, E-1>E-2>E-3>E
-4 and the smaller the diameter of the glass fiber, the smaller the amount of bromine permeation (it is clear that the bromine barrier property is improved).
これは、ガラス繊維の直径が小さ（なることにより、よ
り膜の緻密化が図られているためと考えられる。This is thought to be because the diameter of the glass fibers is small, thereby making the membrane more dense.
第２表
膜厚： Ａ−Ｅ ０．３ｍ
組成比（ｗｔに）： ポリエチレン繊維 ＝ｆＪラス繊
維＝６０ ・ ４０１１、発明の効果
この発明は、以上説明したとおり、ポリエチレン系繊維
を素材として、ガラス繊維を分散させて、抄紙状微細多
孔質膜とすることにより、膜の臭素バリアー性を向上さ
せつつ、且つ、膜の電気抵抗も著しく低下させるという
効果を有するものである。Second surface film thickness: A-E 0.3m Composition ratio (wt): Polyethylene fiber = fJ lath fiber = 60 ・ 4011, Effects of the Invention As explained above, the present invention uses polyethylene fiber as a material to produce glass fibers. By dispersing fibers to form a paper-like microporous membrane, it has the effect of improving the bromine barrier properties of the membrane and significantly lowering the electrical resistance of the membrane.
係る特性を兼ね備えたセパレータは、金属ハロゲン電池
のセパレータとして、極めて優れたものである。A separator having such characteristics is extremely excellent as a separator for metal halogen batteries.
第１図は実施例における膜の電気抵抗を示すグラフ、第
２図は第１図と同じ実施例おける膜の臭素バリアー性試
験の結果を示すグラフ、第３図は別の実施例における膜
の臭素バリアー性試験の結果を示すグラフ、第４図は臭
素バリアー性試験に用いた装置の模式図である。
１・・・微細多孔質膜、２・・・０字管、３・・３ｍｏ
ｌ／Ｉ臭化亜鉛水溶液、４・・・３ａ＋ｏｌ／ｌ臭化亜
鉛水溶液と０．３畠ｏ１／１臭素の混合液。
代理人 弁理士 佐 藤 正 年
ザンアルＮｏ。
・第 ４ 図
腰
凭
腰
蒼Figure 1 is a graph showing the electrical resistance of the membrane in the example, Figure 2 is a graph showing the results of the bromine barrier test of the membrane in the same example as Figure 1, and Figure 3 is the graph of the membrane in another example. A graph showing the results of the bromine barrier property test, and FIG. 4 is a schematic diagram of the apparatus used in the bromine barrier property test. 1... Microporous membrane, 2... O-shaped tube, 3... 3mo
1/I zinc bromide aqueous solution, 4...3a+ol/l zinc bromide aqueous solution and 0.3 ha 1/1 bromine solution. Agent: Patent Attorney Masaru Sato, No.・Figure 4 Waist support
Claims (2)
させて、抄紙状微細多孔質膜としたことを特徴とする金
属ハロゲン電池用セパレータ。(1) A separator for metal halogen batteries, characterized in that it is made of polyethylene fibers and dispersed with glass fibers to form a paper-like microporous membrane.
り、且つ、ガラス繊維の直径が５〜０．５μｍである特
許請求の範囲第１項記載の金属ハロゲン電池用セパレー
タ。(2) The separator for a metal halogen battery according to claim 1, wherein the content of the glass fiber is 20 to 50 wt%, and the diameter of the glass fiber is 5 to 0.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251566A JPH0195466A (en) | 1987-10-07 | 1987-10-07 | Separator for metal halide battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251566A JPH0195466A (en) | 1987-10-07 | 1987-10-07 | Separator for metal halide battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0195466A true JPH0195466A (en) | 1989-04-13 |
| JPH0526303B2 JPH0526303B2 (en) | 1993-04-15 |
Family
ID=17224721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62251566A Granted JPH0195466A (en) | 1987-10-07 | 1987-10-07 | Separator for metal halide battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0195466A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5549868A (en) * | 1978-10-02 | 1980-04-10 | Asahi Chem Ind Co Ltd | Metal-halogen thin type battery |
| JPS58155651A (en) * | 1982-02-02 | 1983-09-16 | エムハート インダストリーズ インコーポレーテッド | Separator for battery |
-
1987
- 1987-10-07 JP JP62251566A patent/JPH0195466A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5549868A (en) * | 1978-10-02 | 1980-04-10 | Asahi Chem Ind Co Ltd | Metal-halogen thin type battery |
| JPS58155651A (en) * | 1982-02-02 | 1983-09-16 | エムハート インダストリーズ インコーポレーテッド | Separator for battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0526303B2 (en) | 1993-04-15 |
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