JP2002177747A - Permselective membrane and air cell using the same - Google Patents
Permselective membrane and air cell using the sameInfo
- Publication number
- JP2002177747A JP2002177747A JP2000376052A JP2000376052A JP2002177747A JP 2002177747 A JP2002177747 A JP 2002177747A JP 2000376052 A JP2000376052 A JP 2000376052A JP 2000376052 A JP2000376052 A JP 2000376052A JP 2002177747 A JP2002177747 A JP 2002177747A
- Authority
- JP
- Japan
- Prior art keywords
- permselective membrane
- water
- hydrophilic
- repellent
- porous film
- 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.)
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Classifications
-
- Y02E60/128—
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸素を透過して水
を遮断する選択透過膜と、当該選択透過膜を封止材とし
て用いた空気電池とに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permselective membrane for permeating oxygen to block water and an air battery using the permselective membrane as a sealing material.
【０００２】[0002]
【従来の技術】従来より、正極活物質（減極剤）として
大気中の酸素を用いる空気電池が知られている。この空
気電池は、正極活物質として大気中の酸素を用いるの
で、正極活物質及び負極活物質（電解液）の双方を電池
セル内に充填しなくてはならない通常の電池に比べて負
極活物質を多く充填することができ、容量の大幅な増加
が期待できる。また、この空気電池は、貯蔵中の容量劣
化が少なく、正極活物質として重金属酸化物を使用しな
いために無公害であるという特徴もある。2. Description of the Related Art Conventionally, an air battery using oxygen in the atmosphere as a positive electrode active material (depolarizer) has been known. Since this air battery uses oxygen in the air as the positive electrode active material, both the positive electrode active material and the negative electrode active material (electrolyte solution) must be filled in the battery cell. And a large increase in capacity can be expected. In addition, this air battery is characterized in that it has little capacity deterioration during storage and is pollution-free because it does not use a heavy metal oxide as a positive electrode active material.
【０００３】その反面、この空気電池には、放電機能を
発揮するために大気中から電池セル内に酸素を導入しな
くてはならず、しかも、放電使用中に負極活物質が乾燥
すると放電機能が劣化するという短所がある。On the other hand, in this air battery, oxygen must be introduced into the battery cell from the atmosphere in order to exhibit a discharge function. Has the disadvantage of deteriorating.
【０００４】したがって、大気中から電池セル内に酸素
を導入して空気電池に放電機能を発揮させ、かつ負極活
物質の乾燥を抑制して放電機能の劣化を防止するために
は、酸素を透過して水を遮断する封止材を空気取入口の
内側に配置する必要がある。従来より、この種の封止材
としては、ファインセラミクスなどの多孔質セラミック
や、多孔質の樹脂フィルムなどが用いられている。[0004] Therefore, in order to introduce oxygen into the battery cell from the atmosphere to cause the air battery to exhibit a discharge function, and to suppress drying of the negative electrode active material to prevent deterioration of the discharge function, oxygen must be transmitted. Therefore, it is necessary to arrange a sealant for blocking water inside the air intake. Conventionally, porous ceramics such as fine ceramics, porous resin films, and the like have been used as this type of sealing material.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
封止材は、分子サイズに大差がない酸素分子と水分子と
を封止材に形成された微細孔だけで弁別する構成である
ので、酸素分子と水分子とを高精度に弁別することが難
しく、酸素分子を取り込みやすいものは水分子を放出し
やすく、反対に、水分子の遮断効果が大きいものは酸素
分子を取り込みにくいことから、空気電池の性能を向上
することが難しいという問題がある。また、酸素分子と
水分子とを高精度に弁別可能な封止材は、必然的に微細
孔の孔径の調整が困難になって製造工程が複雑化するた
め、製品が高価になるという問題もある。However, the conventional sealing material has a structure in which oxygen molecules and water molecules having no large difference in molecular size are discriminated only by the fine holes formed in the sealing material. It is difficult to distinguish molecules from water molecules with high precision. There is a problem that it is difficult to improve the performance of the battery. In addition, a sealing material that can discriminate oxygen molecules and water molecules with high precision also has a problem in that the adjustment of the diameter of the micropores becomes inevitably difficult and the manufacturing process becomes complicated, so that the product becomes expensive. is there.
【０００６】本発明は、かかる従来技術の不備を解決す
るためになされたものであって、その課題は、安価にし
て酸素分子と水分子とを高精度に弁別することができ、
空気電池の封止材として適用可能な選択透過膜を提供す
ること、並びに放電特性及び耐久性に優れた空気電池を
提供することにある。The present invention has been made in order to solve the deficiencies of the prior art, and its object is to make it possible to discriminate oxygen molecules and water molecules with high accuracy at low cost.
An object of the present invention is to provide a permselective membrane applicable as a sealing material for an air battery, and to provide an air battery excellent in discharge characteristics and durability.
【０００７】[0007]
【課題を解決するための手段】本発明は、前記の課題を
解決するため、選択透過膜に関しては、片面に親水性を
もち、他の片面に撥水性をもつという構成にした。According to the present invention, in order to solve the above-mentioned problems, the permselective membrane is configured to have hydrophilicity on one side and water repellency on the other side.
【０００８】このように、選択透過膜を、片面に親水性
をもち、他の片面に撥水性をもつという構成にすると、
親水性をもつ面には大気中の水分が選択的に吸着されて
他方の面よりも蒸気圧が高くなるため、親水性をもつ面
側から撥水性をもつ面側への酸素の透過が促進され、か
つ、撥水性をもつ面側から親水性をもつ面側への水分子
の透過が抑制される。また、撥水性をもつ面側に存在す
る水分子は、選択透過膜の撥水性をもつ面で遮断される
ので、撥水性をもつ面側からの水分子の透過がより一層
効率的に抑制される。As described above, when the permselective membrane is configured to have hydrophilicity on one side and water repellency on the other side,
The moisture in the atmosphere is selectively adsorbed on the hydrophilic surface and the vapor pressure is higher than that of the other surface, which promotes the transmission of oxygen from the hydrophilic surface to the water-repellent surface. Further, permeation of water molecules from the water repellent surface to the hydrophilic surface is suppressed. In addition, since water molecules existing on the water-repellent surface side are blocked by the water-repellent surface of the permselective membrane, the permeation of water molecules from the water-repellent surface side is more efficiently suppressed. You.
【０００９】前記選択透過膜は、電気的に中性な多孔質
フィルムの片面に親水層を形成し、他の片面に撥水層を
形成すること、又は親水性の多孔質フィルムの片面に撥
水層を形成すること、若しくは撥水性の多孔質フィルム
の片面に親水層を形成することによって作成することが
できる。前記親水層は、シランカップリング剤、セルロ
ース樹脂、酸化チタン、酸化亜鉛又はゼオライトから選
択される１種又は複数種の物質をもって形成することが
でき、前記撥水層は、フッ素樹脂、ポリエチレン樹脂、
シリコーン樹脂、ダイヤモンドライクカーボン又はホワ
イトカーボンから選択される１種又は複数種の物質をも
って形成することができる。The permselective membrane is formed by forming a hydrophilic layer on one side of an electrically neutral porous film and forming a water-repellent layer on the other side, or repelling a hydrophilic layer on one side of a hydrophilic porous film. It can be prepared by forming an aqueous layer or forming a hydrophilic layer on one side of a water-repellent porous film. The hydrophilic layer can be formed of one or more substances selected from a silane coupling agent, a cellulose resin, titanium oxide, zinc oxide or zeolite, and the water-repellent layer is a fluororesin, a polyethylene resin,
It can be formed of one or more substances selected from silicone resin, diamond-like carbon, and white carbon.
【００１０】一方、空気電池に関しては、前記の課題を
解決するため、負極缶と、当該負極缶内に収納された正
極及び負極と、空気取入口が開口された正極キャップ
と、前記空気取入口の内側に配置された封止材とを備え
た空気電池において、前記封止材として、片面に親水性
をもち、他の片面に撥水性をもつ選択透過膜を用い、前
記親水性をもつ面を前記空気取入口側に向けると共に、
前記撥水性をもつ面を前記正極及び負極側に向けて、前
記選択透過膜を配置するという構成にした。On the other hand, with respect to the air battery, in order to solve the above-mentioned problems, a negative electrode can, a positive electrode and a negative electrode housed in the negative electrode can, a positive electrode cap having an open air inlet, and an air inlet. A sealing material disposed on the inside of the air cell, wherein the sealing material has a hydrophilicity on one side and a water-repellent permselective membrane on the other side, and the hydrophilic surface To the air intake side,
The permselective membrane is arranged with the water-repellent surface facing the positive and negative electrodes.
【００１１】このように、空気電池内に備えられる封止
材として、片面に親水性をもち、他の片面に撥水性をも
つ選択透過膜を用い、当該選択透過膜の親水性をもつ面
を空気取入口側に向け、撥水性をもつ面を正極及び負極
側に向けて配置すると、親水性をもつ面には大気中の水
分が選択的に吸着されて他方の面よりも蒸気圧が高くな
るため、親水性をもつ面側から撥水性をもつ面側への酸
素の透過が促進され、かつ、撥水性をもつ面側から親水
性をもつ面側への水分子の透過が抑制されると共に、撥
水性をもつ面側に存在する水分子は、選択透過膜の撥水
性をもつ面で遮断されるので、撥水性をもつ面側からの
水分子の透過がより一層効率的に抑制される。よって、
大気からの酸素の取り込みが十分に行われて高い放電性
能を発揮することができると共に、負極活物質の乾燥が
抑制されて放電機能の劣化が防止される。As described above, as the sealing material provided in the air battery, a permselective membrane having hydrophilicity on one side and water repellency on the other side is used, and the hydrophilic side of the permselective membrane is used. When the water-repellent surface is arranged toward the air intake side and toward the positive and negative electrodes, moisture in the atmosphere is selectively adsorbed on the hydrophilic surface and the vapor pressure is higher than that of the other surface. Therefore, permeation of oxygen from the hydrophilic side to the water-repellent side is promoted, and permeation of water molecules from the water-repellent side to the hydrophilic side is suppressed. At the same time, water molecules existing on the water-repellent surface side are blocked by the water-repellent surface of the permselective membrane, so that the permeation of water molecules from the water-repellent surface side is more efficiently suppressed. You. Therefore,
Oxygen from the atmosphere is sufficiently taken in, and high discharge performance can be exhibited. In addition, drying of the negative electrode active material is suppressed and deterioration of the discharge function is prevented.
【００１２】[0012]
【発明の実施の形態】まず、本発明に係る選択透過膜の
実施形態例を、図１乃至図３に基づいて説明する。図１
は第１実施形態例に係る選択透過膜の要部断面図、図２
は第２実施形態例に係る選択透過膜の要部断面図、図３
は第３実施形態例に係る選択透過膜の要部断面図であ
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an embodiment of a permselective membrane according to the present invention will be described with reference to FIGS. FIG.
FIG. 2 is a sectional view of a main part of the permselective membrane according to the first embodiment, FIG.
FIG. 3 is a sectional view of a main part of the permselective membrane according to the second embodiment, and FIG.
FIG. 7 is a sectional view of a main part of a permselective membrane according to a third embodiment.
【００１３】図１に示すように、第１実施形態例に係る
選択透過膜１Ａは、電気的に中性な多孔質フィルム１１
の片面に親水層１２を形成し、他の片面に撥水層１３を
形成したことを特徴とする。As shown in FIG. 1, the permselective membrane 1A according to the first embodiment comprises an electrically neutral porous film 11A.
Is characterized in that a hydrophilic layer 12 is formed on one side and a water-repellent layer 13 is formed on the other side.
【００１４】前記多孔質フィルム１１としては、多孔質
ポリエステルフィルムを用いることができる。また、前
記親水層１２は、シランカップリング剤、セルロース樹
脂、酸化チタン、酸化亜鉛又はゼオライトから選択され
る１種又は複数種の物質をもって形成することができ、
前記撥水層１３は、フッ素樹脂、ポリエチレン樹脂、シ
リコーン樹脂、ダイヤモンドライクカーボン又はホワイ
トカーボンから選択される１種又は複数種の物質をもっ
て形成することができる。As the porous film 11, a porous polyester film can be used. Further, the hydrophilic layer 12 can be formed of one or more kinds of substances selected from a silane coupling agent, a cellulose resin, titanium oxide, zinc oxide or zeolite,
The water-repellent layer 13 can be formed of one or more substances selected from a fluorocarbon resin, a polyethylene resin, a silicone resin, diamond-like carbon, and white carbon.
【００１５】前記多孔質フィルム１１の厚さ及び平均孔
径は、当該選択透過膜１Ａの適用対象によって種々変更
することができるが、一般的には、前記多孔質フィルム
１１の厚さについては３０μｍ乃至１００μｍ、当該多
孔質フィルム１１の平均孔径については０．１ｎｍ乃至
０．５ｎｍとすることができる。また、親水層１２及び
撥水層１３の層厚についても、当該選択透過膜１Ａの適
用対象によって種々変更することができるが、一般的に
は、親水層１２及び撥水層１３とも、１０ｎｍ乃至５０
ｎｍにすることができる。また、親水層１２及び撥水層
１３の形成方法としては、スパッタリングやプラズマＣ
ＶＤ等の真空成膜手段を用いることができる。なお、前
記多孔質フィルム１１に開設される微細孔１１ａの形成
は、親水層１２及び撥水層１３の形成前に行うこともで
きるし、親水層１２及び撥水層１３の形成後に行うこと
もできる。The thickness and the average pore diameter of the porous film 11 can be variously changed depending on the application target of the permselective membrane 1A. Generally, the thickness of the porous film 11 is 30 μm to 30 μm. The average pore size of the porous film 11 can be set to 0.1 nm to 0.5 nm. The thickness of the hydrophilic layer 12 and the water-repellent layer 13 can also be variously changed depending on the application target of the permselective membrane 1A. In general, both the hydrophilic layer 12 and the water-repellent layer 13 have a thickness of 10 nm or less. 50
nm. As a method for forming the hydrophilic layer 12 and the water-repellent layer 13, sputtering or plasma C
Vacuum film forming means such as VD can be used. The formation of the fine holes 11a formed in the porous film 11 can be performed before the formation of the hydrophilic layer 12 and the water-repellent layer 13, or can be performed after the formation of the hydrophilic layer 12 and the water-repellent layer 13. it can.
【００１６】本例の選択透過膜１Ａは、電気的に中性な
多孔質フィルム１１の片面に親水層１２を形成し、他の
片面に撥水層１３を形成したので、親水層１２に大気中
の水分が選択的に吸着される。このため、選択透過膜１
Ａの親水層形成面側の蒸気圧が撥水層形成面側の蒸気圧
よりも高くなり、親水層形成面側から撥水層形成面側へ
の酸素の透過が促進されると共に、撥水層形成面側から
親水層形成面側への水分子の透過が抑制される。また、
撥水層１３によっても、撥水層形成面側から親水層形成
面側への水分子の透過が抑制される。したがって、親水
層形成面側から撥水層形成面側に酸素を透過できて、撥
水層形成面側から親水層形成面側に水分子が透過されな
い選択透過膜とすることができる。In the permselective membrane 1A of this embodiment, the hydrophilic layer 12 is formed on one side of the electrically neutral porous film 11 and the water-repellent layer 13 is formed on the other side. The moisture inside is selectively adsorbed. Therefore, the permselective membrane 1
The vapor pressure on the hydrophilic layer forming surface side of A becomes higher than the vapor pressure on the water repellent layer forming surface side, so that the transmission of oxygen from the hydrophilic layer forming surface side to the water repellent layer forming surface side is promoted, and Permeation of water molecules from the layer forming surface side to the hydrophilic layer forming surface side is suppressed. Also,
The water-repellent layer 13 also suppresses the transmission of water molecules from the water-repellent layer forming surface side to the hydrophilic layer forming surface side. Therefore, it is possible to form a permselective membrane in which oxygen can pass from the hydrophilic layer forming surface side to the water repellent layer forming surface side, and water molecules do not pass from the water repellent layer forming surface side to the hydrophilic layer forming surface side.
【００１７】図２に示すように、第２実施形態例に係る
選択透過膜１Ｂは、撥水性の多孔質フィルム１４の片面
に親水層１２を形成したことを特徴とする。As shown in FIG. 2, the permselective membrane 1B according to the second embodiment is characterized in that a hydrophilic layer 12 is formed on one surface of a water-repellent porous film 14.
【００１８】前記多孔質フィルム１４としては、多孔質
フッ素樹脂フィルムなどを用いることができる。その他
については、撥水層１３を有しない点を除いて前記第１
実施形態例に係る選択透過膜１Ａと同じであるので、重
複を避けるために説明を省略する。本例の選択透過膜１
Ｂも、前記第１実施形態例に係る選択透過膜１Ａと同様
の効果を有する。As the porous film 14, a porous fluororesin film or the like can be used. Other than the above, except for not having the water repellent layer 13, the first
Since it is the same as the permselective membrane 1A according to the embodiment, the description is omitted to avoid duplication. Permselective membrane 1 of this example
B has the same effect as the permselective membrane 1A according to the first embodiment.
【００１９】図３に示すように、第３実施形態例に係る
選択透過膜１Ｃは、親水性の多孔質フィルム１５の片面
に撥水層１３を形成したことを特徴とする。As shown in FIG. 3, the permselective membrane 1C according to the third embodiment is characterized in that a water-repellent layer 13 is formed on one surface of a hydrophilic porous film 15.
【００２０】前記多孔質フィルム１５としては、セロハ
ン紙などを用いることができる。その他については、親
水層１２を有しない点を除いて前記第１実施形態例に係
る選択透過膜１Ａと同じであるので、重複を避けるため
に説明を省略する。本例の選択透過膜１Ｂも、前記第１
実施形態例に係る選択透過膜１Ａと同様の効果を有す
る。As the porous film 15, cellophane paper or the like can be used. Others are the same as the permselective membrane 1A according to the first embodiment except that the hydrophilic layer 12 is not provided, and thus the description is omitted to avoid duplication. The permselective membrane 1B of this example is also the first
It has the same effect as the permselective membrane 1A according to the embodiment.
【００２１】以下に、空気電池の封止材として適用可能
な各実施形態例に係る選択透過膜の実施例と、その比較
例とを示す。Examples of the permselective membrane according to each embodiment applicable as a sealing material of an air battery and comparative examples are shown below.
【００２２】〈実施例１〉厚さが６０μｍで平均孔径が
０．３ｎｍの多孔質ポリエステルフィルムの片面に、厚
さが３０ｎｍの酸化チタン層からなる親水層１１をプラ
ズマＣＶＤ法により形成すると共に、前記多孔質ポリエ
ステルフィルムの他の片面に、厚さが１０ｎｍのダイヤ
モンドライクカーボン層からなる撥水層１２をプラズマ
ＣＶＤ法により形成して、第１実施形態例に係る選択透
過膜１Ａを形成した。Example 1 A hydrophilic layer 11 composed of a titanium oxide layer having a thickness of 30 nm was formed on one surface of a porous polyester film having a thickness of 60 μm and an average pore diameter of 0.3 nm by a plasma CVD method. A water-repellent layer 12 composed of a diamond-like carbon layer having a thickness of 10 nm was formed on the other surface of the porous polyester film by a plasma CVD method to form a permselective film 1A according to the first embodiment.
【００２３】〈実施例２〉厚さが１００μｍで平均孔径
が０．３ｎｍの撥水性を有する多孔質フッ素樹脂フィル
ムの片面に、厚さが５０ｎｍの酸化亜鉛層からなる親水
層１１をスパッタ法により形成して、第２実施形態例に
係る選択透過膜１Ｂを形成した。Example 2 A hydrophilic layer 11 made of a zinc oxide layer having a thickness of 50 nm was formed on one side of a water-repellent porous fluororesin film having a thickness of 100 μm and an average pore diameter of 0.3 nm by a sputtering method. Then, the permselective membrane 1B according to the second embodiment was formed.
【００２４】〈実施例３〉厚さが１００μｍの親水性を
有するセロハンの片面に、厚さが２０ｎｍのホワイトカ
ーボン層からなる撥水層１２をカーボン−フッ素共スパ
ッタ法により形成して、第３実施形態例に係る選択透過
膜１Ｃを形成した。Example 3 A water-repellent layer 12 composed of a white carbon layer having a thickness of 20 nm was formed on one side of hydrophilic cellophane having a thickness of 100 μm by a carbon-fluorine co-sputtering method. The permselective membrane 1C according to the embodiment was formed.
【００２５】〈比較例〉厚さが１００μｍで平均孔径が
０．１５ｎｍの撥水性を有する多孔質フッ素樹脂フィル
ムのみをもって比較例に係る選択透過膜１Ｘを形成し
た。Comparative Example A permselective membrane 1X according to a comparative example was formed using only a water-repellent porous fluororesin film having a thickness of 100 μm and an average pore diameter of 0.15 nm.
【００２６】次に、本発明に係る空気電池の実施形態例
を、図４乃至図１０に基づいて説明する。図４は実施形
態例に係る空気電池の断面図であり、図５乃至図１０は
本発明に係る空気電池の効果を示すグラフである。Next, an embodiment of an air battery according to the present invention will be described with reference to FIGS. FIG. 4 is a cross-sectional view of the air battery according to the embodiment, and FIGS. 5 to 10 are graphs showing the effects of the air battery according to the present invention.
【００２７】図４に示すように、本例の空気電池は、有
底円筒形の負極缶２１と、当該負極缶２１の底面に配置
された底部絶縁リング２２と、前記負極缶２１の内周面
に配置された側部絶縁筒２３と、前記負極缶２１の上面
に配置された上部絶縁リング２４と、前記負極缶２１内
に収納された正極２５、負極２６、セパレータ２７及び
これら各部材２５〜２７を巻回する心棒２８と、空気取
入口２９ａが開口された正極キャップ２９と、前記負極
缶２１と前記正極キャップ２９とを封止する封止リング
３０と、前記空気取入口２６ａの内側に配置された封止
材３１と、前記負極缶２１と前記負極２６とを接続する
負極引出線３２と、前記正極キャップ２９と前記正極２
５とを接続する正極引出線３３とから構成されている。As shown in FIG. 4, the air battery of the present embodiment has a cylindrical negative electrode can 21 having a bottom, a bottom insulating ring 22 disposed on the bottom surface of the negative electrode can 21, and an inner periphery of the negative electrode can 21. Side insulating cylinder 23 disposed on the surface, an upper insulating ring 24 disposed on the upper surface of the negative electrode can 21, a positive electrode 25, a negative electrode 26, a separator 27 contained in the negative electrode can 21, and these members 25 27, a positive electrode cap 29 having an open air inlet 29a, a sealing ring 30 for sealing the negative electrode can 21 and the positive electrode cap 29, and an inner side of the air inlet 26a. , A negative electrode lead 32 connecting the negative electrode can 21 and the negative electrode 26, the positive electrode cap 29 and the positive electrode 2.
5 and a positive electrode lead wire 33 connecting the positive electrode 5 and the negative electrode 5.
【００２８】前記正極２５、負極２６及びセパレータ２
７はリボン状に形成されており、この順に重ね合わせ
て、心棒２８に巻回されている。セパレータ２７には、
電解液である負極活物質が含浸されている。The positive electrode 25, the negative electrode 26 and the separator 2
Numeral 7 is formed in a ribbon shape, and is wound on a mandrel 28 while being superposed in this order. In the separator 27,
A negative electrode active material as an electrolyte is impregnated.
【００２９】前記封止材３１としては、前記実施例１乃
至実施例３に係る選択透過膜１Ａ〜１Ｃのいずれかが用
いられており、親水性をもつ面を前記空気取入口２９ａ
側に向けると共に、撥水性をもつ面を前記正極２５及び
負極２６側に向けて配置されている。As the sealing material 31, any one of the permselective membranes 1A to 1C according to the first to third embodiments is used, and the hydrophilic surface is formed by the air inlet 29a.
And the water-repellent surface is directed toward the positive electrode 25 and the negative electrode 26.
【００３０】図５に、前記実施例１に係る選択透過膜１
Ａを封止材３１として用いた空気電池と前記比較例に係
る選択透過膜１Ｘを封止材３１として用いた空気電池
を、気温が６０℃で相対湿度が３０％ＲＨの環境下に放
置したときの重量減少特性を示す。また、図６に、前記
実施例１に係る選択透過膜１Ａを封止材３１として用い
た空気電池と前記比較例に係る選択透過膜１Ｘを封止材
３１として用いた空気電池を１０００ｍＡｈで放電させ
たときの電圧降下特性を示す。FIG. 5 shows the permselective membrane 1 according to the first embodiment.
The air battery using A as the sealing material 31 and the air battery using the selective permeable membrane 1X according to the comparative example as the sealing material 31 were left in an environment at an air temperature of 60 ° C. and a relative humidity of 30% RH. The weight loss characteristics at the time are shown. FIG. 6 shows that the air battery using the permselective membrane 1A according to the first embodiment as the sealing material 31 and the air battery using the permselective membrane 1X according to the comparative example as the sealing material 31 are discharged at 1000 mAh. 4 shows the voltage drop characteristics at the time of this.
【００３１】図５から明らかなように、前記比較例に係
る選択透過膜１Ｘを封止材３１として用いた空気電池
は、試験開始から約１００時間で重量が１０％低下し、
試験開始から約４００時間で重量が５５％にまで低下し
たのに対し、前記実施例１に係る選択透過膜１Ａを封止
材３１として用いた空気電池は、重量が１０％低下する
のに試験開始から約１１００時間かかっており、電解液
である負極活物質の乾燥防止に顕著な効果があることが
わかった。また、図６から明らかなように、前記比較例
に係る選択透過膜１Ｘを封止材３１として用いた空気電
池は、１０００ｍＡｈで放電させたとき、試験開始から
約１０分間で電圧が１．７Ｖから１．４Ｖに降下したの
に対し、前記実施例１に係る選択透過膜１Ａを封止材３
１として用いた空気電池は、１０００ｍＡｈで放電させ
たとき、電圧が１．７Ｖから１．４Ｖに降下するのに約
１７分間かかっており、放電特性も改善されていること
が判った。As is apparent from FIG. 5, the air cell using the selective permeable membrane 1X according to the comparative example as the sealing material 31 lost 10% in weight in about 100 hours from the start of the test.
While the weight was reduced to 55% in about 400 hours from the start of the test, the air battery using the permselective membrane 1A according to Example 1 as the sealing material 31 was tested even though the weight was reduced by 10%. It took about 1100 hours from the start, and it was found that there was a remarkable effect on the prevention of drying of the negative electrode active material as the electrolytic solution. As is clear from FIG. 6, when the air battery using the selective permeable membrane 1X according to the comparative example as the sealing material 31 was discharged at 1000 mAh, the voltage was 1.7 V in about 10 minutes from the start of the test. To 1.4 V, the selective permeable membrane 1A according to the first embodiment is
In the air battery used as No. 1, it took about 17 minutes for the voltage to drop from 1.7 V to 1.4 V when discharged at 1000 mAh, and it was found that the discharge characteristics were also improved.
【００３２】図７に、前記実施例２に係る選択透過膜１
Ｂを封止材３１として用いた空気電池を、気温が６０℃
で相対湿度が３０％ＲＨの環境下に放置したときの重量
減少特性を示す。また、図８に、前記実施例２に係る選
択透過膜１Ｂを封止材３１として用いた空気電池を１０
００ｍＡｈで放電させたときの電圧降下特性を示す。FIG. 7 shows a permselective membrane 1 according to the second embodiment.
An air battery using B as the sealing material 31 is heated at a temperature of 60 ° C.
Shows the weight reduction characteristics when left in an environment where the relative humidity is 30% RH. FIG. 8 shows an air battery using the permselective membrane 1B according to the second embodiment as a sealing material 31.
5 shows a voltage drop characteristic when discharged at 00 mAh.
【００３３】図７から明らかなように、前記実施例２に
係る選択透過膜１Ｂを封止材３１として用いた空気電池
は、重量が１０％低下するのに試験開始から約６００時
間かかっており、前記比較例に係る選択透過膜１Ｘを封
止材３１として用いた空気電池に比べて、電解液である
負極活物質の乾燥防止特性に優れていることがわかっ
た。また、図８から明らかなように、前記実施例２に係
る選択透過膜１Ｂを封止材３１として用いた空気電池
は、１０００ｍＡｈで放電させたとき、電圧が１．７Ｖ
から１．４Ｖに降下するのに約１４分間かかっており、
前記比較例に係る選択透過膜１Ｘを封止材３１として用
いた空気電池に比べて放電特性も改善されていることが
判った。As is apparent from FIG. 7, in the air battery using the permselective membrane 1B according to the second embodiment as the sealing material 31, it took about 600 hours from the start of the test to reduce the weight by 10%. It was found that the negative electrode active material, which is an electrolytic solution, was superior in drying prevention characteristics as compared with an air battery using the permselective membrane 1X according to the comparative example as the sealing material 31. As is clear from FIG. 8, the air battery using the selective permeable membrane 1B according to Example 2 as the sealing material 31 has a voltage of 1.7 V when discharged at 1000 mAh.
It took about 14 minutes to fall to 1.4V from
It was found that the discharge characteristics were also improved as compared with the air battery using the permselective membrane 1X according to the comparative example as the sealing material 31.
【００３４】図９に、前記実施例３に係る選択透過膜１
Ｃを封止材３１として用いた空気電池を、気温が６０℃
で相対湿度が３０％ＲＨの環境下に放置したときの重量
減少特性を示す。また、図１０に、前記実施例３に係る
選択透過膜１Ｃを封止材３１として用いた空気電池を１
０００ｍＡｈで放電させたときの電圧降下特性を示す。FIG. 9 shows a selectively permeable membrane 1 according to the third embodiment.
An air battery using C as the sealing material 31 is heated at a temperature of 60 ° C.
Shows the weight reduction characteristics when left in an environment where the relative humidity is 30% RH. FIG. 10 shows an air battery using the permselective membrane 1C according to the third embodiment as a sealing material 31.
5 shows a voltage drop characteristic when discharging is performed at 000 mAh.
【００３５】図９から明らかなように、前記実施例３に
係る選択透過膜１Ｃを封止材３１として用いた空気電池
は、重量が１０％低下するのに試験開始から約６００時
間かかっており、前記比較例に係る選択透過膜１Ｘを封
止材３１として用いた空気電池に比べて、電解液である
負極活物質の乾燥防止特性に優れていることがわかっ
た。また、図１０から明らかなように、前記実施例３に
係る選択透過膜１Ｃを封止材３１として用いた空気電池
は、１０００ｍＡｈで放電させたとき、電圧が１．７Ｖ
から１．４Ｖに降下するのに約１４分間かかっており、
前記比較例に係る選択透過膜１Ｘを封止材３１として用
いた空気電池に比べて放電特性も改善されていることが
判った。As is clear from FIG. 9, in the air battery using the permselective membrane 1C according to the third embodiment as the sealing material 31, it took about 600 hours from the start of the test to reduce the weight by 10%. It was found that the negative electrode active material, which is an electrolytic solution, was superior in drying prevention characteristics as compared with an air battery using the permselective membrane 1X according to the comparative example as the sealing material 31. As is clear from FIG. 10, the air battery using the selective permeable membrane 1C according to the third embodiment as the sealing material 31 has a voltage of 1.7 V when discharged at 1000 mAh.
It took about 14 minutes to drop from 1.4V to 1.4V,
It was found that the discharge characteristics were also improved as compared with the air battery using the selective permeable membrane 1X according to the comparative example as the sealing material 31.
【００３６】[0036]
【発明の効果】本発明の選択透過膜は、片面に親水性を
もち、他の片面に撥水性をもつという構成にしたので、
親水性をもつ面に大気中の水分が選択的に吸着されて、
親水性をもつ面の方が撥水性をもつ他方の面側よりも蒸
気圧が高くなり、親水性をもつ面側から撥水性をもつ面
側への酸素の透過が促進されると共に、撥水性をもつ面
側から親水性をもつ面側への水分子の透過を抑制するこ
とができる。The permselective membrane of the present invention has a hydrophilic property on one side and a water repellency on the other side.
Atmospheric moisture is selectively adsorbed on the hydrophilic surface,
The vapor pressure of the hydrophilic surface is higher than that of the other surface having water repellency, which promotes the transmission of oxygen from the hydrophilic surface side to the water repellent surface and increases the water repellency. Of the water molecules from the surface having the surface to the surface having the hydrophilicity can be suppressed.
【００３７】本発明の空気電池は、封止材として、片面
に親水性をもち、他の片面に撥水性をもつ選択透過膜を
用い、当該選択透過膜の親水性をもつ面を空気取入口側
に向け、撥水性をもつ面を正極及び負極側に向けて配置
したので、大気からの酸素の取り込みが十分に行われて
高い放電性能が発揮されると共に、負極活物質の乾燥が
抑制されて放電機能の経時劣化を抑制することができ
る。The air battery of the present invention uses, as a sealing material, a permselective membrane having hydrophilicity on one side and water repellency on the other side, and uses the hydrophilic side of the permselective membrane as an air inlet. As the water-repellent surface is oriented toward the positive and negative electrodes, oxygen is taken in sufficiently from the atmosphere to achieve high discharge performance, and drying of the negative electrode active material is suppressed. As a result, the deterioration with time of the discharge function can be suppressed.
【図１】第１実施形態例に係る選択透過膜の要部断面図
である。FIG. 1 is a cross-sectional view of a main part of a permselective membrane according to a first embodiment.
【図２】第２実施形態例に係る選択透過膜の要部断面図
である。FIG. 2 is a cross-sectional view of a main part of a permselective membrane according to a second embodiment.
【図３】第３実施形態例に係る選択透過膜の要部断面図
である。FIG. 3 is a sectional view of a main part of a permselective membrane according to a third embodiment.
【図４】実施形態例に係る空気電池の断面図である。FIG. 4 is a cross-sectional view of the air battery according to the embodiment.
【図５】実施形態例に係る空気電池の効果を示すグラフ
図である。FIG. 5 is a graph showing the effect of the air battery according to the embodiment.
【図６】実施形態例に係る空気電池の効果を示すグラフ
図である。FIG. 6 is a graph showing the effect of the air battery according to the embodiment.
【図７】実施形態例に係る空気電池の効果を示すグラフ
図である。FIG. 7 is a graph showing the effect of the air battery according to the embodiment.
【図８】実施形態例に係る空気電池の効果を示すグラフ
図である。FIG. 8 is a graph showing the effect of the air battery according to the embodiment.
【図９】実施形態例に係る空気電池の効果を示すグラフ
図である。FIG. 9 is a graph showing the effect of the air battery according to the embodiment.
【図１０】実施形態例に係る空気電池の効果を示すグラ
フ図である。FIG. 10 is a graph showing the effect of the air battery according to the embodiment.
１Ａ〜１Ｃ 選択透過膜 １１ 電気的に中性な多孔質フィルム １２ 親水層 １３ 撥水層 １４ 撥水性の多孔質フィルム １５ 親水性の多孔質フィルム ２１ 負極缶 ２２ 底部絶縁リング ２３ 側部絶縁筒 ２４ 上部絶縁リング ２５ 正極 ２６ 負極 ２７ セパレータ ２８ 心棒 ２９ 正極キャップ ２９ａ 空気取入口 ３０ 封止リング ３１ 封止材 ３２ 負極引出線 ３３ 正極引出線 1A-1C Permselective membrane 11 Electrically neutral porous film 12 Hydrophilic layer 13 Water-repellent layer 14 Water-repellent porous film 15 Hydrophilic porous film 21 Negative electrode can 22 Bottom insulating ring 23 Side insulating cylinder 24 Upper insulating ring 25 Positive electrode 26 Negative electrode 27 Separator 28 Mandrel 29 Positive electrode cap 29a Air inlet 30 Sealing ring 31 Sealant 32 Negative electrode lead 33 Positive electrode lead
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｄ 71/26 Ｂ０１Ｄ 71/26 71/32 71/32 71/70 ５００ 71/70 ５００ Ｈ０１Ｍ 12/06 Ｈ０１Ｍ 12/06 Ｂ Ｚ (72)発明者 小山 栄二 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 (72)発明者 藤本 由紀枝 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 Ｆターム(参考） 4D006 GA41 JA70A MA03 MA07 MA08 MA22 MA31 MB04 MB09 MB10 MC01 MC03X MC05X MC12X MC22 MC28X MC48X MC65 NA31 NA45 PA02 PB17 PB62 PC80 5H032 AA01 CC02 CC07 EE01 EE02 EE04 EE05 EE09 EE13 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01D 71/26 B01D 71/26 71/32 71/32 71/70 500 71/70 500 H01M 12/06 H01M 12/06 BZ (72) Inventor Eiji Koyama 1-88 Ushitora, Ibaraki City, Osaka Prefecture Inside Hitachi Maxell Co., Ltd. (72) Inventor Yukie Fujimoto 1-1-88 Ushitora Ibaraki City, Osaka Prefecture Hitachi Maxell In-house F-term (reference) 4D006 GA41 JA70A MA03 MA07 MA08 MA22 MA31 MB04 MB09 MB10 MC01 MC03X MC05X MC12X MC22 MC28X MC48X MC65 NA31 NA45 PA02 PB17 PB62 PC80 5H032 AA01 CC02 CC07 EE01 EE02 EE04 EE05 EE09 EE13
Claims (7)
をもつことを特徴とする選択透過膜。1. A permselective membrane characterized in that one side has hydrophilicity and the other side has water repellency.
電気的に中性な多孔質フィルムの片面に親水層を形成
し、前記多孔質フィルムの他の片面に撥水層を形成した
ことを特徴とする選択透過膜。2. The permselective membrane according to claim 1, wherein
A permselective membrane characterized in that a hydrophilic layer is formed on one surface of an electrically neutral porous film, and a water-repellent layer is formed on another surface of the porous film.
親水性の多孔質フィルムの片面に撥水層を形成したこと
を特徴とする選択透過膜。3. The permselective membrane according to claim 1, wherein
A permselective membrane characterized in that a water-repellent layer is formed on one side of a hydrophilic porous film.
撥水性の多孔質フィルムの片面に親水層を形成したこと
を特徴とする選択透過膜。4. The permselective membrane according to claim 1, wherein
A permselective membrane comprising a hydrophilic layer formed on one surface of a water-repellent porous film.
いて、前記親水層が、シランカップリング剤、セルロー
ス樹脂、酸化チタン、酸化亜鉛又はゼオライトから選択
される１種又は複数種の物質で形成されていることを特
徴とする選択透過膜。5. The permselective membrane according to claim 2, wherein the hydrophilic layer is made of one or more substances selected from a silane coupling agent, a cellulose resin, titanium oxide, zinc oxide and zeolite. A permselective membrane characterized by being formed.
いて、前記撥水層が、フッ素樹脂、ポリエチレン樹脂、
シリコーン樹脂、ダイヤモンドライクカーボン又はホワ
イトカーボンから選択される１種又は複数種の物質で形
成されていることを特徴とする選択透過膜。6. The permselective membrane according to claim 2, wherein the water-repellent layer is made of a fluorine resin, a polyethylene resin,
A permselective membrane formed of one or more substances selected from silicone resin, diamond-like carbon and white carbon.
極及び負極と、空気取入口が開口された正極キャップ
と、前記空気取入口の内側に配置された封止材とを備え
た空気電池において、前記封止材として、片面に親水性
をもち、他の片面に撥水性をもつ選択透過膜を用い、前
記親水性をもつ面を前記空気取入口側に向けると共に、
前記撥水性をもつ面を前記正極及び負極側に向けて、前
記選択透過膜を配置したことを特徴とする空気電池。7. A negative electrode can, a positive electrode and a negative electrode housed in the negative electrode can, a positive electrode cap having an open air inlet, and a sealing material disposed inside the air inlet. In the air battery, the sealing material has hydrophilicity on one side, and uses a permselective membrane having water repellency on the other side, and directs the hydrophilic side toward the air intake side.
An air battery, wherein the permselective membrane is disposed with the water-repellent surface facing the positive and negative electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000376052A JP2002177747A (en) | 2000-12-11 | 2000-12-11 | Permselective membrane and air cell using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000376052A JP2002177747A (en) | 2000-12-11 | 2000-12-11 | Permselective membrane and air cell using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2002177747A true JP2002177747A (en) | 2002-06-25 |
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ID=18844969
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| Application Number | Title | Priority Date | Filing Date |
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| JP2000376052A Withdrawn JP2002177747A (en) | 2000-12-11 | 2000-12-11 | Permselective membrane and air cell using the same |
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| JP (1) | JP2002177747A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011087089A1 (en) * | 2010-01-18 | 2011-07-21 | 住友化学株式会社 | Air battery and air battery stack |
| JP2013020724A (en) * | 2011-07-07 | 2013-01-31 | Toyota Motor Corp | Metal-air-battery |
| WO2013046975A1 (en) * | 2011-09-30 | 2013-04-04 | 富士フイルム株式会社 | Gas separation membrane, manufacturing method for same, and gas separation membrane module using same |
| JP2013097968A (en) * | 2011-10-31 | 2013-05-20 | Showa Denko Packaging Co Ltd | Air secondary battery packaging material, air secondary battery packaging material manufacturing method, and air secondary battery |
| WO2013151147A1 (en) * | 2012-04-05 | 2013-10-10 | 東京エレクトロン株式会社 | Filtration filter |
| JP2015525457A (en) * | 2012-06-19 | 2015-09-03 | ザフ エナジー システムズ, インコーポレイテッドZAF Energy Systems, Incorporated | Metal-air battery and gas impermeable anode conductive matrix |
| US9276301B2 (en) | 2012-12-07 | 2016-03-01 | Samsung Electronics Co., Ltd. | Polymeric compound, oxygen permeable membrane, and electrochemical device |
| US9343786B2 (en) | 2012-12-10 | 2016-05-17 | Samsung Electronics Co., Ltd. | Electrochemical device |
| JPWO2015080259A1 (en) * | 2013-11-29 | 2017-03-16 | 国立研究開発法人物質・材料研究機構 | NF or RO membrane made of hard carbon membrane, filtration filter, two-layer bonded filtration filter, and production method thereof |
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- 2000-12-11 JP JP2000376052A patent/JP2002177747A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9680192B2 (en) | 2010-01-18 | 2017-06-13 | Sumitomo Chemical Company, Limited | Air battery and air battery stack |
| JP2011146339A (en) * | 2010-01-18 | 2011-07-28 | Sumitomo Chemical Co Ltd | Air battery, air battery stack |
| CN102714338A (en) * | 2010-01-18 | 2012-10-03 | 住友化学株式会社 | Air battery and air battery stack |
| WO2011087089A1 (en) * | 2010-01-18 | 2011-07-21 | 住友化学株式会社 | Air battery and air battery stack |
| JP2013020724A (en) * | 2011-07-07 | 2013-01-31 | Toyota Motor Corp | Metal-air-battery |
| WO2013046975A1 (en) * | 2011-09-30 | 2013-04-04 | 富士フイルム株式会社 | Gas separation membrane, manufacturing method for same, and gas separation membrane module using same |
| JP2013075264A (en) * | 2011-09-30 | 2013-04-25 | Fujifilm Corp | Gas separation membrane, manufacturing method for the same, and gas separation membrane module using the same |
| JP2013097968A (en) * | 2011-10-31 | 2013-05-20 | Showa Denko Packaging Co Ltd | Air secondary battery packaging material, air secondary battery packaging material manufacturing method, and air secondary battery |
| WO2013151147A1 (en) * | 2012-04-05 | 2013-10-10 | 東京エレクトロン株式会社 | Filtration filter |
| JP2015525457A (en) * | 2012-06-19 | 2015-09-03 | ザフ エナジー システムズ, インコーポレイテッドZAF Energy Systems, Incorporated | Metal-air battery and gas impermeable anode conductive matrix |
| US9276301B2 (en) | 2012-12-07 | 2016-03-01 | Samsung Electronics Co., Ltd. | Polymeric compound, oxygen permeable membrane, and electrochemical device |
| US9343786B2 (en) | 2012-12-10 | 2016-05-17 | Samsung Electronics Co., Ltd. | Electrochemical device |
| JPWO2015080259A1 (en) * | 2013-11-29 | 2017-03-16 | 国立研究開発法人物質・材料研究機構 | NF or RO membrane made of hard carbon membrane, filtration filter, two-layer bonded filtration filter, and production method thereof |
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Legal Events
| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20080304 |