JPH03108258A - Battery - Google Patents
BatteryInfo
- Publication number
- JPH03108258A JPH03108258A JP24681389A JP24681389A JPH03108258A JP H03108258 A JPH03108258 A JP H03108258A JP 24681389 A JP24681389 A JP 24681389A JP 24681389 A JP24681389 A JP 24681389A JP H03108258 A JPH03108258 A JP H03108258A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- glassine paper
- oxygen
- gas diffusion
- air
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 24
- 239000011086 glassine Substances 0.000 claims abstract description 23
- 238000009792 diffusion process Methods 0.000 claims abstract description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 5
- 239000012982 microporous membrane Substances 0.000 claims 2
- 239000011148 porous material Substances 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 12
- 230000035515 penetration Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 25
- 239000003792 electrolyte Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007774 longterm Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- 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】
産業上の利用分野
本発明は、酸素を活物質に用いるガス拡散電極と、アル
カリ水溶液からなる電解液と、亜鉛、マグネシウム、ア
ルミニウム等の金属、もしくはアルコール、ヒドラジン
、水素等の負極活物質とを備えた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 gas diffusion electrode using oxygen as an active material, an electrolytic solution consisting of an alkaline aqueous solution, and a metal such as zinc, magnesium, or aluminum, or alcohol, hydrazine, or hydrogen. The present invention relates to a battery equipped with a negative electrode active material such as.
従来の技術
ガス拡散電極を備え、酸素を活物質とする電池としては
、空気電池、燃料電池等がある。特にアルカリ水溶液、
中性塩水溶液を電解質として使用する電池においては、
ガス拡散電極（酸素極）より内部の蒸気圧に応じて水蒸
気の出入りがあり、電池内電解液の濃度変化１体積変化
が起こり、これが電池の諸特性に影響を与えていた。ボ
タン型空気電池を例にとり、第２図を用いてその状況を
説明する。１は酸素極（空気極）、２はガス拡散性はあ
るが液体は阻止するポリテトラフルオロエチレン（ＰＴ
ＦＥ）よりなり酸素極１を支持する多孔性撥水膜である
。３は外部からの空気取入れ孔、４は空気の拡散を行う
多孔体、５．６はセパレータ、７は負極亜鉛で、これら
に含浸保持されるアルカリ電解液には水酸化カリウム水
溶液を使用し、その濃度は３０〜３５重量％とじている
。BACKGROUND OF THE INVENTION BACKGROUND ART Batteries equipped with gas diffusion electrodes and using oxygen as an active material include air cells, fuel cells, and the like. Especially alkaline aqueous solution,
In batteries that use a neutral salt aqueous solution as the electrolyte,
Water vapor flows in and out from the gas diffusion electrode (oxygen electrode) depending on the internal vapor pressure, and a change in concentration and volume of the electrolyte in the battery occurs, which affects various characteristics of the battery. Taking a button-type air battery as an example, the situation will be explained using FIG. 2. 1 is an oxygen electrode (air electrode), 2 is a polytetrafluoroethylene (PT) that has gas diffusion properties but blocks liquids.
This is a porous water-repellent membrane made of FE) that supports the oxygen electrode 1. 3 is an air intake hole from the outside, 4 is a porous body for air diffusion, 5.6 is a separator, 7 is a negative electrode zinc, and the alkaline electrolyte impregnated and retained in these is a potassium hydroxide aqueous solution, Its concentration is 30-35% by weight.
このため相対湿度が４７〜５９％より高いと外部の湿気
を取り込み、電解液濃度の低下と体積膨張とが起こり、
放電性能の低下、電解液の漏液を生じていた。一方、相
対湿度が前記以下の場合には電解液の蒸発が起こり、内
部抵抗の増大や放電性能の低下をもたらしていた。従っ
て、環境雰囲気による影響を受は易いため、長期間保存
後の電池特性に問題が生じ、これが空気電池や燃料電池
を特定の分野での使用に制約し、その汎用化を図る上で
大きな課題を有していた。なお、図中８は負極亜鉛７を
収容した負極容器、９は絶縁ガスケット、１０は正極容
器である。For this reason, if the relative humidity is higher than 47-59%, external moisture will be taken in, causing a decrease in the electrolyte concentration and volume expansion.
This caused a decline in discharge performance and electrolyte leakage. On the other hand, when the relative humidity is below the above range, evaporation of the electrolytic solution occurs, resulting in an increase in internal resistance and a decrease in discharge performance. Therefore, since they are easily affected by the environmental atmosphere, problems arise with battery characteristics after long-term storage.This restricts the use of air cells and fuel cells in specific fields, and poses a major challenge in making them more versatile. It had In the figure, 8 is a negative electrode container containing the negative electrode zinc 7, 9 is an insulating gasket, and 10 is a positive electrode container.
発明が解決しようとする課題
これらの課題を改善するため、従来より種々の提案がな
されてきた。例えば、空気孔周辺の一部に電解液と反応
する物質を挿入し、電池外部への電解液漏出を防止する
。あるいは紙または高分子材料よりなる不織布等の電解
液吸収材を設けて、電池外部への電解液漏出を防止する
。さらには空気孔を極端に小さくして酸素の供給量を制
限してまでも、水蒸気や炭酸ガスの電池内部への進入を
防止する等の提案がなされている。しかし、いずれの方
法も漏液防止や放電性能、特に長時間放電での性能に大
きな問題を残していた。これらの主要原因は空気中の水
蒸気の電池内への進入によるアルカリ電解液の希釈と体
積膨張、及び炭酸ガスの進入による炭酸塩の生成に基づ
く放電反応の阻害と空気流通経路の閉塞によるもので、
外気が低湿度の場合には逆に電解液中の水分の逸散が性
能低下の原因となっていた。この原因を取り除くため、
近年では、水蒸気や炭酸ガスの透過量を制御し、選択的
に酸素を優先して透過させる膜を介して空気を酸素極に
供給する方法、例えばオルガノポリシロキサン系の無孔
性の均一な薄膜や金属酸化物、あるいは金属元素を含有
する有機化合物の薄膜と適宜な多孔性膜とを一体化させ
た膜を用いる方法が提案されている。Problems to be Solved by the Invention Various proposals have been made in the past in order to improve these problems. For example, a substance that reacts with the electrolyte is inserted into a portion around the air hole to prevent the electrolyte from leaking to the outside of the battery. Alternatively, an electrolyte absorbing material such as a nonwoven fabric made of paper or a polymeric material is provided to prevent leakage of the electrolyte to the outside of the battery. Furthermore, proposals have been made to prevent water vapor and carbon dioxide from entering the inside of the battery, even by making the air holes extremely small to limit the amount of oxygen supplied. However, both methods had major problems in preventing liquid leakage and discharge performance, especially in long-term discharge performance. The main causes of these are dilution and volume expansion of the alkaline electrolyte due to the entry of water vapor from the air into the battery, and inhibition of the discharge reaction due to the formation of carbonates due to the entry of carbon dioxide gas and blockage of the air circulation path. ,
Conversely, when the outside air has low humidity, the loss of moisture in the electrolyte causes a decline in performance. In order to eliminate this cause,
In recent years, methods have been developed to supply air to the oxygen electrode through a membrane that controls the amount of permeation of water vapor and carbon dioxide and selectively allows oxygen to permeate, such as a non-porous, uniform thin film made of organopolysiloxane. A method using a film in which a thin film of an organic compound containing a metal element, metal oxide, or metal element is integrated with a suitable porous film has been proposed.
しかしながら、現在までのところ、十分に有効な酸素選
択透過性が得られないことから、満足な放電性能は得ら
れず、電池として長期の使用や貯蔵に耐えられないので
、その実用化に至っていないという技術課題を持ってい
た。However, to date, it has not been put to practical use because it has not been possible to obtain sufficient oxygen selective permeability, and therefore it has not been possible to obtain satisfactory discharge performance, and it has not been possible to withstand long-term use or storage as a battery. There was a technical problem.
そこで本発明は上記の電池の貯蔵性、長期使用における
性能を改善すると共に、軽負荷から重負荷に至る広い放
電条件で満足な放電性能を得るために、大気中の酸素を
選択的に十分な速度で電池内に取り入れると共に、水蒸
気の電池への出入りと、大気中の炭酸ガスの電池内への
進入を長期にわたり防止する有効な手段を提供すること
を目的とするものである。Therefore, the present invention improves the storability and long-term use performance of the above-mentioned battery, and also selectively removes enough oxygen from the atmosphere in order to obtain satisfactory discharge performance under a wide range of discharge conditions from light loads to heavy loads. The object of the present invention is to provide an effective means to introduce water vapor into the battery at a high speed and prevent water vapor from entering and exiting the battery, and carbon dioxide from the atmosphere from entering the battery for a long period of time.
課題を解決するための手段
上記の目的を達成するため、本発明は酸素を活物質とす
るガス拡散電極と、外気に通じる空気取入れ孔を有する
電池容器を備えた電池のガス゛拡散電極の空気取入れ側
と電池容器内面との間に、グラシン紙を介在させたもの
である。Means for Solving the Problems In order to achieve the above object, the present invention provides an air intake system for a gas diffusion electrode of a battery comprising a gas diffusion electrode containing oxygen as an active material and a battery container having an air intake hole communicating with the outside air. Glassine paper is interposed between the side and the inner surface of the battery container.
本発明は、グラシン紙の大きい酸素選択性透過能に着目
したものである。The present invention focuses on the high oxygen selective permeability of glassine paper.
この膜が、重負荷での満足な放電性を得るために必要な
酸素透過速度と、長期保存や低湿度下あるいは、高湿度
雰囲気下での長期放電に耐えるだけの水蒸気及び炭酸ガ
スに対する透過−阻止能を持ち、この膜を適用した電池
の性能が極めて優れていることを見い出し、完成させた
ものである。This membrane has the oxygen permeation rate necessary to obtain satisfactory discharge performance under heavy loads, and the water vapor and carbon dioxide permeability sufficient to withstand long-term storage and long-term discharge under low humidity or high humidity atmospheres. They discovered that this membrane has a blocking ability and that the performance of the battery to which this membrane is applied is extremely excellent.
作用
この構成による複合膜は、後述の実施例における電池試
験の結果からも明らかなように、電池用としての良好な
酸素透過速度と、空気中の水蒸気や炭酸ガスの電池内へ
の進入を遮断する効果を共に満足すべき状態に保て、実
用的な電池に要求される重負荷放電性能と、高湿度や低
湿度の雰囲気下で長時間放電した場合の性能も共に満足
することとなる。Function: As is clear from the results of the battery test in the Examples described later, the composite membrane with this configuration has a good oxygen permeation rate for batteries and blocks water vapor and carbon dioxide from entering the battery. Both the heavy load discharge performance required of a practical battery and the performance when discharged for a long time in an atmosphere of high humidity or low humidity can be maintained in a satisfactory state.
実施例
酸素選択性透過膜として、厚さ９０μｍ１坪量９３ｇ／
ｒｒ１．密度１ｇ／ｃｊのグラシン紙を用いたもの。Example: As an oxygen selective permeable membrane, the thickness is 90 μm and the basis weight is 93 g/
rr1. Made of glassine paper with a density of 1 g/cj.
（比較例１）
酸素選択性透過膜として、補強用のポリプロピレン製不
織布上に、厚さ５０μｍでポリジメチルシロキサン膜を
製膜した酸素富化膜を用いたもの。(Comparative Example 1) As the oxygen-selective permeable membrane, an oxygen enrichment membrane was used in which a polydimethylsiloxane membrane was formed to a thickness of 50 μm on a reinforcing polypropylene nonwoven fabric.
（比較例２）
多孔性撥水膜は使用するが、酸素選択性透過膜を用いな
いもの。(Comparative Example 2) A porous water-repellent membrane is used, but an oxygen-selective permeable membrane is not used.
本発明は効果を確認するために、実施例のグラシン紙、
及び比較例１の複合膜を使用した電池と、酸素選択性透
過膜を使用していない電池を試作評価して検討した。ま
ず、酸素選択性透過膜を用いない比較例２の場合は第２
図と全く同一の構成とした。次に、酸素選択性透過膜を
使用した電池は、第１図に示すようにＰＴＦＥの多孔膜
２と、酸素の流れを分散しかつ均一化させる多孔体４と
の間にそれぞれの複合膜が介在した構成である。In order to confirm the effect of the present invention, glassine paper as an example,
A battery using the composite membrane of Comparative Example 1 and a battery not using an oxygen-selective permeable membrane were prototyped and evaluated. First, in the case of Comparative Example 2, which does not use an oxygen-selective permeable membrane, the second
The configuration was exactly the same as in the figure. Next, in a battery using an oxygen selective permeable membrane, as shown in Fig. 1, each composite membrane is placed between a porous PTFE membrane 2 and a porous body 4 that disperses and equalizes the flow of oxygen. This is an intervening configuration.
試作した電池の寸法はいずれも直径１１．６ｍｍ。The dimensions of the prototype batteries were 11.6 mm in diameter.
総高５．４閣であり、比較的重負荷（７５Ω）で２０℃
、常湿（６０％ＲＨ）での連続放電により電池内への空
気中の酸素取り込み速度の充足性を評価し、比較的軽負
荷（３にΩ）で２０℃、高湿度（９０％ＲＨ）、及び低
湿度（２０％ＲＨ）での長時間連続放電により、長期の
放電期間中における雰囲気からの水蒸気の電池内への取
り込みや電池内の水分の蒸発、及び炭酸ガスの取り込み
など電池性能への影響度を評価した。The total height is 5.4 cm, and the temperature is 20℃ under relatively heavy load (75Ω).
, the sufficiency of the rate of oxygen uptake into the battery was evaluated by continuous discharge at normal humidity (60% RH), and the sufficiency of the rate of oxygen uptake into the battery was evaluated at 20°C and high humidity (90% RH) under a relatively light load (3Ω). , and long-term continuous discharge at low humidity (20% RH), the battery performance may be affected by the incorporation of water vapor from the atmosphere into the battery, evaporation of moisture within the battery, and incorporation of carbon dioxide gas during the long-term discharge period. The degree of influence was evaluated.
試作した電池の内訳は第１表に示す通りである。ここで
、比較例１は、酸素と窒素のガス透過速度比は、１以上
であるが、酸素と水蒸気のガス透過速度比は、１以下で
あり、電池用の膜としては、酸素選択性透過膜とはいえ
ない。しかし、実施例では、８以上であり、本発明のグ
ラシン紙は優れた酸素選択性透過能を有していることが
わかる。The details of the prototype battery are shown in Table 1. Here, in Comparative Example 1, the gas permeation rate ratio of oxygen and nitrogen is 1 or more, but the gas permeation rate ratio of oxygen and water vapor is 1 or less. It cannot be called a membrane. However, in the examples, it is 8 or more, which shows that the glassine paper of the present invention has excellent oxygen selective permeability.
また第°２表に試作電池の性能試験結果を示す。Table 2 shows the performance test results of the prototype battery.
（以 下 余 白）
第２表において、放電終止電圧はいずれも０．９ｖであ
り、重量変化は放電試験前後の増減を示しており、主と
して放電中の水分の取り込み、あるいは蒸発の多少を示
唆する数値である。(Margin below) In Table 2, the end-of-discharge voltage is 0.9V in each case, and the weight change indicates an increase or decrease before and after the discharge test, which mainly suggests the amount of moisture taken in or evaporated during discharge. This is the numerical value.
これらの電池の特性を、複合膜を使用していない比較例
２と対比すると最も端的に本発明の詳細な説明できる。The present invention can be most clearly explained in detail by comparing the characteristics of these batteries with Comparative Example 2, which does not use a composite membrane.
まず２０℃、常湿での重負荷試験では放電時間が短く、
水分の取り込みや蒸発の影響や炭酸ガスの影響が少ない
ので、電池の性能は酸素の供給速度が充分であれば水分
や炭酸ガスの透過阻止はあまり考慮する必要がない。従
って、このような条件下では比較例２でも優れた特性が
得られる。これに対し、前述の実施例は比較例２と同等
の放電特性が得られており、複合膜を酸素が透過する速
度が放電反応で酸素が消費される速度に十分追随してい
ることを示している。しかしながら、比較例１は、酸素
透過速度が全く不足していることがわかる。First, in a heavy load test at 20℃ and normal humidity, the discharge time was short.
Since the influence of moisture uptake and evaporation and the influence of carbon dioxide gas are small, there is no need to consider blocking the permeation of moisture and carbon dioxide gas as long as the oxygen supply rate is sufficient for battery performance. Therefore, under such conditions, excellent characteristics can be obtained even in Comparative Example 2. On the other hand, the above-mentioned example obtained the same discharge characteristics as Comparative Example 2, indicating that the rate at which oxygen permeates through the composite membrane sufficiently follows the rate at which oxygen is consumed in the discharge reaction. ing. However, it can be seen that Comparative Example 1 is completely insufficient in oxygen permeation rate.
一方、軽負荷放電の場合は放電時間が長く、しかも外気
が高湿度あるいは低湿度の場合には酸素の供給速度より
も水分や炭酸ガス、特に水分の透過阻止が優れた電池特
性を得るために重要となり、水分や炭酸ガスの透過阻止
機構を持たない比較例２の電池は水分の枯渇、あるいは
逆に水分の過剰取入れによる漏液に起因した空気孔の閉
塞などにより、放電の途中で電圧が低下し、重負荷試験
で得られた放電容量の一部分に担当する容量が得られる
に過ぎない。また放電途中での漏液は実用面で致命的な
問題であることはいうまでもない。これに対して実施例
は極めて優れた性能を示し、これらは重負荷試験の放電
容量とほぼ等しい容量が得られている。これらは傾向は
試験雰囲気が高湿度、低湿度、いずれの場合とも同様で
ある。このことは、実施例の場合、グラシン紙の水分透
過阻止効果が十分に発揮されていることを示している。On the other hand, in the case of light load discharge, the discharge time is long, and in addition, when the outside air is high or low humidity, it is necessary to obtain battery characteristics that are superior in preventing the permeation of moisture and carbon dioxide gas, especially moisture, rather than the oxygen supply rate. The battery of Comparative Example 2, which does not have a mechanism to prevent the permeation of moisture and carbon dioxide gas, suffers from voltage drop during discharge due to water depletion or, conversely, air hole blockage caused by leakage due to excessive moisture intake. The capacity decreases and only a portion of the discharge capacity obtained in the heavy load test is obtained. Furthermore, it goes without saying that liquid leakage during discharge is a fatal problem in practical terms. On the other hand, the Examples showed extremely excellent performance, and a capacity almost equal to the discharge capacity in the heavy load test was obtained. These trends are the same whether the test atmosphere is high humidity or low humidity. This shows that in the case of the example, the water permeation blocking effect of the glassine paper was sufficiently exhibited.
以上を総合して、グラシン紙を用いた電池は、重負荷特
性、軽負荷特性とも優れ、外部雰囲気の変化にも安定し
た優れた電池を提供できることが結論できる。Taking all the above into account, it can be concluded that a battery using glassine paper has excellent heavy load characteristics and light load characteristics, and can provide an excellent battery that is stable even under changes in the external atmosphere.
しかしながら、坪量が、３０ ｇ ／ ｒｄ未満の場合
は、水蒸気等の透過スピードが大きすぎて保存特性が低
下し、１００ｇ／ｒｒ？より大きい場合は、重負荷特性
が低下するので、坪量としては、３０〜１００ ｇ ／
ｒｒｒの範囲が適当である。However, when the basis weight is less than 30 g/rr, the permeation speed of water vapor etc. is too high and the storage properties are deteriorated. If it is larger, the heavy load characteristics will deteriorate, so the basis weight should be 30 to 100 g/
A range of rrr is appropriate.
また、本発明の実施例ではグラシン紙を、上記実施例で
は電池容器との間に空気拡散用の多孔体を介して設置し
たが、本発明のグラシン紙の機械的強度が十分な場合は
、前記空気拡散用の多孔体を除いても電池特性に差異は
ない。さらに、上記実施例では、本発明のグラシン紙を
酸素極との間に酸素極を支持する多孔膜を介して設置し
たが、酸素極の強度が十分であれば前記多孔膜は不要に
でき、その場合にも電池特性は変わらない。また、塩化
アンモニウム、塩化亜鉛などの中性塩の水溶液を電解液
に用いた空気電池に対しても、実施例で示したアルカリ
性の電極液を用いた電池と同様の効果があることも確認
している。Furthermore, in the examples of the present invention, glassine paper was installed between the battery container and the battery container through a porous body for air diffusion, but if the glassine paper of the present invention has sufficient mechanical strength, There is no difference in battery characteristics even if the porous body for air diffusion is removed. Furthermore, in the above examples, the glassine paper of the present invention was placed between the oxygen electrode and the porous membrane that supported the oxygen electrode, but if the oxygen electrode had sufficient strength, the porous membrane could be omitted. Even in that case, the battery characteristics remain unchanged. We also confirmed that an air battery using an aqueous solution of neutral salts such as ammonium chloride or zinc chloride as the electrolyte has the same effect as the battery using an alkaline electrode solution shown in the example. ing.
発明の効果
以上の説明で明らかなように、本発明のグラシン紙によ
れば、中性もくしはアルカリ性の水溶液を電解液とする
電池の重負荷から軽負荷にわたる広い範囲で優れた実用
性能と、優れた耐漏液性。Effects of the Invention As is clear from the above explanation, the glassine paper of the present invention has excellent practical performance in a wide range from heavy loads to light loads of batteries using an alkaline aqueous solution as the electrolyte. , excellent leakage resistance.
長期貯蔵性を得ることができるという効果がある。It has the effect of being able to be stored for a long time.
第１図は本発明の実施例及び比較例１の検討に用いたボ
タン型空気亜鉛電池の断面図、第２図は酸素選択性透過
膜を使用していない従来のボタン型空気亜鉛電池の断面
図である。
１・・・・・・酸素極（空気極）、２・・・・・・撥水
膜、３・・・・・・空気取入れ孔、４・・・・・・多孔
体、５，６・・・・・・セパレータ、７・・・・・・負
極亜鉛、８・・・・・・負極容器、９・・・・・・絶縁
ガスケット、１０・・・・・・正極容器、１１・・・・
・・酸素選択性透過膜。Figure 1 is a cross-sectional view of a button-type zinc-air battery used in the study of Examples of the present invention and Comparative Example 1, and Figure 2 is a cross-sectional view of a conventional button-type zinc-air battery that does not use an oxygen-selective permeable membrane. It is a diagram. DESCRIPTION OF SYMBOLS 1... Oxygen electrode (air electrode), 2... Water-repellent film, 3... Air intake hole, 4... Porous body, 5, 6... ... Separator, 7 ... Negative electrode zinc, 8 ... Negative electrode container, 9 ... Insulating gasket, 10 ... Positive electrode container, 11 ...・・・
...Oxygen selective permeable membrane.
Claims (6)
る空気取入れ孔を有する電池容器を備え、前記ガス拡散
電極の空気取入れ側と前記電池容器内面との間に、グラ
シン紙を介在させた電池。(1) A gas diffusion electrode containing oxygen as an active material and a battery container having an air intake hole communicating with the outside air are provided, and glassine paper is interposed between the air intake side of the gas diffusion electrode and the inner surface of the battery container. battery.
２の範囲にある特許請求の範囲第１項記載の電池。(2) The basis weight of the glassine paper is 30 to 100 g/m^
2. The battery according to claim 1, which falls within the scope of claim 2.
池容器の内面と前記ガス拡散電極に直接接している特許
請求の範囲第１項または第２項記載の電池。(3) The battery according to claim 1 or 2, wherein the glassine paper is in direct contact with the inner surface of the battery container having an air intake hole and the gas diffusion electrode.
の空気拡散多孔体を介在させた特許請求の範囲第１項ま
たは第２項記載の電池。(4) The battery according to claim 1 or 2, wherein an air diffusion porous material such as a nonwoven fabric is interposed between the glassine paper and the battery container.
テトラフルオロエチレン（ＰＴＦＥ）等のフィルムより
なる酸素極を支持する微多孔膜を介在させた特許請求の
範囲第１項または第２項記載の電池。(5) Claim 1 or 2, wherein a microporous membrane supporting an oxygen electrode made of a film of polytetrafluoroethylene (PTFE) is interposed between the glassine paper and the gas diffusion electrode. Batteries listed.
の空気拡散多孔体を介在させ、かつ前記グラシン紙と前
記ガス拡散電極との間にはポリテトラフルオロエチレン
等のフィルムよりなり、前記ガス拡散電極を支持する微
多孔膜を介在させた特許請求の範囲第１項記載の電池。(6) An air diffusion porous material such as a nonwoven fabric is interposed between the glassine paper and the battery container, and a film of polytetrafluoroethylene or the like is provided between the glassine paper and the gas diffusion electrode; The battery according to claim 1, wherein a microporous membrane supporting the gas diffusion electrode is interposed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24681389A JPH03108258A (en) | 1989-09-22 | 1989-09-22 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24681389A JPH03108258A (en) | 1989-09-22 | 1989-09-22 | Battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03108258A true JPH03108258A (en) | 1991-05-08 |
Family
ID=17154071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24681389A Pending JPH03108258A (en) | 1989-09-22 | 1989-09-22 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03108258A (en) |
-
1989
- 1989-09-22 JP JP24681389A patent/JPH03108258A/en active Pending
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