JP3776790B2 - Polymer electrolyte - Google Patents

Description

ここで、Ｘ，Ｙ，Ｚはそれぞれ二置換、三置換、四置換の芳香環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、ナフタレン環、ビフェニル、ジフェニルメタン、ジフェニルエーテル、ジフェニルサルフォン、ジフェニルアミン、Ｎ，Ｎ‘−ジフェニルパラフェニレンジアミン、ピロール、ピロリジン、シクロ環、ピペリジン、ピペラジンなどの骨格を指す。
【００１４】
第二番目の発明は、第一番目の発明において、上記ポリアミン化合物が、パラフェニレンジアミン、メタフェニレンジアミン、ベンゼントリアミン、オルソフェニレンジアミン、キシリレンジアミン、ビスアミノメチルシクロヘキサン、トリアミノジフェニルエーテル、ジアミノジフェニルエーテル、ジアミノジフェニルメタン、ジアミノジフェニルサルフォン、ジアミノビベンジル、ジアリルメラミン、メラミン、トリアミノピリミジン、トリアムテレン、テトラアミノビフェニル、テトラアミノベンゼン、テトラアミノピリミジンのいずれか一種であることを特徴とする高分子電解質にある。
【００１７】
第三番目の発明は、第一番目又は第二番目の発明の高分子電解質をフィルム化した電解質膜と、該電解質膜を挟む１対の電極とを備えたことを特徴とする高分子電解質燃料電池にある。
【００１８】
第四番目の発明は、第三番目の発明において、作動温度が２００℃以下室温の範囲であることを特徴とする高分子電解質燃料電池にある。
【００１９】
【発明の実施の形態】
本発明による高分子電解質の実施の形態を以下に説明するが、本発明はこれらの実施の形態に限定されるものではない。
【００２０】
本発明の高分子電解質は、上記「化２」に示す一般式（１）で表されるポリアミン化合物を少なくとも原料の一成分として重合した重合体を含有するものである。
【００２１】
本発明において、上記ポリアミン化合物の具体的な例としてはパラフェニレンジアミン、メタフェニレンジアミン、ベンゼントリアミン、オルソフェニレンジアミン、キシリレンジアミン、ビスアミノメチルシクロヘキサン、トリアミノジフェニルエーテル、ジアミノジフェニルエーテル、ジアミノジフェニルメタン、ジアミノジフェニルサルフォン、ジアミノビベンジル、ジアリルメラミン、メラミン、トリアミノピリミジン、トリアムテレン、テトラアミノビフェニル、テトラアミノベンゼン、テトラアミノピリミジン等を挙げることができる。
【００２２】
上記ポリアミン化合物において、特に骨格のモビリティが高く、プロトンの動き易い化合物が好ましく、例えばパラフェニレンジアミン、メタフェニレンジアミン、ベンゼントリアミン、トリアミノジフェニルエーテルが特に好ましい。
【００２３】
これらのポリアミン化合物は単独で、あるいは複数のポリアミン化合物や他の重合性化合物と組み合わせても本発明の高分子電解質に用いることができる。
【００２４】
ここで、上記他の重合性化合物としては、例えば、アニリン、ピロール、アミノピラジン、アミノピリジン、トルエンジイソシアネート、フタル酸クロライド、テトラカルボン酸無水物、ホルムアルデヒド等を挙げることができる。
【００２５】
また、上記ポリアミン化合物や他の重合性化合物としてはアミノ基以外の置換基を含んでいても良い。
【００２６】
上記アミノ基以外の置換基としては、例えば水酸基、メチル基やエチル基などの飽和アルキル基、ビニル基などの不飽和アルキル基、スルホン酸基、りん酸基、カルボン酸基等を挙げることができる。
【００２７】
これらのポリアミン化合物は重合用溶媒中で酸化剤を添加することにより容易に本発明の高分子電解質の母体となる塩基性高分子を得ることができる。
【００２８】
ここで、重合に使用される溶媒としては、例えばＮ−メチル２ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、メチルエチルケトンなどの有機溶剤や硫酸、塩酸、硝酸、過塩素酸、りん酸などの酸性水溶液および両者の混合溶媒が用いられる。これらの溶媒の中で好ましくはＮ−メチル２ピロリドン、希塩酸、希硫酸等を挙げることができる。
【００２９】
ここで、上記酸化剤としては過硫酸アンモニウム、塩化鉄（ＩＩＩ）、二酸化マンガン、過酸化水素などが用いられる。これらの酸化剤の中で好ましくは過硫酸アンモニウムを挙げることができる。
【００３０】
上記重合温度は溶媒の凝固点以上、１００℃以下の範囲から選択される。
ここで、好ましい重合体を得る温度としては、例えば０℃から３０℃の範囲とするのがよい。
【００３１】
また、重合時間は使用する原料モノマーの種類や配合、重合温度や重合する規模、攪拌の激しさなどにも依るが数時間から数十時間の範囲から選択される。
【００３２】
また、酸化剤の添加は一度に加えても重合体が得られるが、反応溶液の温度が異常に上昇しない程度に徐々に加えるのが好ましい。
【００３３】
例えば一般式（１）に示したポリアミン化合物としてパラフェニレンジアミンを原料として用い、重合溶媒としてＮ−メチル２ピロリドンを用い、酸化剤として過硫酸アンモニウムを添加して重合した場合、下記「化３」に示す一般式（２）で表される重合体が得られる。
【化３】

【００３４】
この重合体にりん酸化合物を反応させることにより本発明の高分子電解質が得られる。
【００３５】
ここで、りん酸化合物としては亜りん酸、オルトりん酸、ピロりん酸、三りん酸、メタりん酸、フェニルりん酸などが挙げられる。これらのりん酸化合物の中で好ましくはオルトりん酸である。
【００３６】
上記りん酸化合物の混合量は、上記ポリアミン化合物のアミンに対して当量以下とするのが好ましい。これは、当量以上混合しても発電により生成する水分の増加によりりん酸化合物が脱落し、好ましくないからである。
【００３７】
上記重合体とりん酸化合物との反応は室温で単に両者を混合するだけで達成されるが、さらに溶媒中で反応させることもできる。
ここで、上記溶媒としては水、メタノール、エタノール、テトラヒドロフラン、ジオキサンなどが挙げられる。これらの溶媒の中で特に水を用いるのが好ましい。
【００３８】
一例として示した上記「化３」に示す一般式（２）にりん酸化合物の一例としてオルトりん酸を反応させた場合、下記「化４」に示す一般式（３）で表される高分子電解質を得ることができる。
【化４】

【００３９】
上記一般式（３）で表される本発明の高分子電解質の一例を示すように、本発明の高分子電解質はりん酸化合物を高い割合で混合できる特徴があり、高いイオン伝導率が得られると共にりん酸化合物の保持能が高まり、発電に生成する水分の増加によるりん酸化合物の脱落を抑制することが可能となる。
【００４０】
【実施例】
以下、本発明による高分子電解質の好適な一実施例を以下に説明するが、本発明はこれらの実施例に何等限定されるものではない。
【００４１】
［第１実施例］
窒素パージした３００ｍLの四つ口フラスコにパラフェニレンジアミン２ｇを入れ、Ｎ−メチル２ピロリドン１９８ｇを加えて溶解させた。溶液を０℃に冷却し、攪拌しながら過硫酸アンモニウム８．４ｇを徐々に加えて反応させた。反応による発熱が止まってから更に１２時間攪拌を続けた。１Lビーカーに蒸留水８００ｍLを入れ、反応溶液を注いで重合物を沈殿させた。ガラスフィルターを用いて重合物を吸引濾過し、蒸留水で３回、アセトンで３回重合物を洗浄した。重合物をシャーレに移し減圧乾燥機に入れて１００℃で１２時間減圧乾燥した。重合物は黒色の粉末状で乾燥後の収量は１．７ｇであった。
【００４２】
上記得られた重合物の赤外スペクトルを図１に示す。
【００４３】
また、メノウ乳鉢に上記得られた重合物０．５ｇを入れ、８５％オルトりん酸水溶液１．１ｇを加えて混合すると、粘調なペーストが得られた。
上記得られたペーストの赤外スペクトルを図２に示す。
【００４４】
上記得られたペーストをガラス板にキャストし、１００℃で１２時間減圧乾燥してフィルムを得た。
【００４５】
交流インピーダンス法によりフィルムの８０℃、相対湿度４％環境に於けるイオン伝導率を測定した結果、２．２×１０^-3Ｓ／ｃｍであった。
【００４６】
上記フィルムのイオン伝導率の温度と相対湿度による変化を図３に示す。なお、比較として従来技術にかかるパーフロロスルフォン酸系高分子から得られたフィルムのそれを示す。
図３に示すように、本実施例にかかる８０℃で相対湿度４％におけるイオン伝導率は２．２×１０^-3Ｓ／ｃｍであるのに対し、従来技術のイオン伝導率は２×１０^-4Ｓ／ｃｍであった。
【００４７】
［第２実施例］
窒素パージした３００ｍLの四つ口フラスコに３，４，４‘−トリアミノジフェニルエーテル５ｇを入れ、Ｎ−メチル２ピロリドン１００ｇを加えて溶解させた。溶液を０℃に冷却し、攪拌しながら過硫酸アンモニウム１５．９ｇを徐々に加えて反応させた。反応による発熱が止まってから更に１２時間攪拌を続けた。２Lビーカーに蒸留水１５００ｍLを入れ、反応溶液を注いで重合物を沈殿させた。ガラスフィルターを用いて重合物を吸引濾過し、蒸留水で３回、アセトンで３回重合物を洗浄した。重合物をシャーレに移し減圧乾燥機に入れて１００℃で１２時間減圧乾燥した。黒色の粉末状の重合物を得た。
【００４８】
メノウ乳鉢に重合物１ｇを入れ８５％オルトりん酸水溶液２．６ｇを加えて混合すると、粘調なペーストが得られた。ペーストをガラス板にキャストし、１００℃で１２時間減圧乾燥してフィルムを得た。
【００４９】
交流インピーダンス法によりフィルムの８０℃、相対湿度４％環境に於けるイオン伝導率を測定した結果、１．８×１０^-3Ｓ／ｃｍであった。
【００５０】
［第３実施例］
窒素パージした３００ｍLの四つ口フラスコに１，２，４，５−ベンゼンテトラミン塩酸塩５ｇを入れ、１N塩酸１００ｇを加えて溶解させた。溶液を０℃に冷却し、攪拌しながら過硫酸アンモニウム１６．１ｇを徐々に加えて反応させた。反応による発熱が止まってから更に１２時間攪拌を続けた。２Lビーカーに蒸留水１５００ｍLを入れ、反応溶液を注いで重合物を沈殿させた。ガラスフィルターを用いて重合物を吸引濾過し、蒸留水で３回、アセトンで３回重合物を洗浄した。重合物をシャーレに移し減圧乾燥機に入れて１００℃で１２時間減圧乾燥した。黒色の粉末状の重合物を得た。
【００５１】
メノウ乳鉢に重合物１ｇを入れ８５％オルトりん酸水溶液３．２ｇを加えて混合すると、粘調なペーストが得られた。ペーストをガラス板にキャストし、１００℃で１２時間減圧乾燥してフィルムを得た。
交流インピーダンス法によりフィルムの８０℃、相対湿度４％環境に於けるイオン伝導率を測定した結果、１．９×１０^-3Ｓ／ｃｍであった。
【００５２】
［第４実施例］
窒素パージした３００ｍLの四つ口フラスコにメタフェニレンジアミン２ｇを入れ、１N硫酸２００ｍＬを加えて溶解させた。溶液を０℃に冷却し、攪拌しながら過硫酸アンモニウム８．４ｇを徐々に加えて反応させた。反応による発熱が止まってから更に１２時間攪拌を続けた。１Lビーカーに蒸留水８００ｍLを入れ、反応溶液を注いで重合物を沈殿させた。ガラスフィルターを用いて重合物を吸引濾過し、蒸留水で３回、アセトンで３回重合物を洗浄した。重合物をシャーレに移し減圧乾燥機に入れて１００℃で１２時間減圧乾燥した。黒色の粉末状の重合物を得た。
【００５３】
メノウ乳鉢に重合物０．５ｇを入れ８５％オルトりん酸水溶液１．１ｇを加えて混合すると、粘調なペーストが得られた。ペーストをガラス板にキャストし、１００℃で１２時間減圧乾燥してフィルムを得た。
交流インピーダンス法によりフィルムの８０℃、相対湿度４％環境に於けるイオン伝導率を測定した結果、２．１×１０^-3Ｓ／ｃｍであった。
【００５４】
【発明の効果】
以上の説明したように、本発明による高分子電解質は、例えば相対湿度１０％以下の低湿度環境で従来のパーフロロスルフォン酸系高分子よりも優れたイオン伝導性を有している。
【００５５】
よって、本発明の高分子電解質は低湿度条件下でも高いイオン伝導性を示し、従来のパーフロロスルフォン酸系高分子膜を用いた燃料電池、二次電池、表示素子及び太陽電池等の電解質膜の代替膜として用いて特に有用である。
【図面の簡単な説明】
【図１】第一実施例で得られた塩基性高分子の赤外スペクトル図である。
【図２】第一実施例で得られた塩基性高分子とりん酸との混合物の赤外スペクトル図である。
【図３】第一実施例で得られた塩基性高分子のイオン伝導率図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer electrolyte used for, for example, a fuel cell, a secondary battery, a display element, a solar cell and the like.
[0002]
[Background]
In general, a polymer electrolyte fuel cell (hereinafter referred to as “PEFC”) has a different power generation principle from a conventional internal combustion engine generator, and the chemical energy of the fuel is electrochemically oxidized and directly converted into electrical energy for extraction. For this reason, it has a small size, high efficiency, quietness, and clean characteristics, and has recently been applied in various fields.
[0003]
Various compounds have been proposed as polymer electrolytes, which are the core parts of the PEFC. Typical examples are “Nafion (trade name)”, “Flemion (trade name)”, “Aciplex (trade name). ) "And other perfluororosulphonic acid polymers.
[0004]
The chemical structure of the above-mentioned perfluororosphonic acid-based polymer has a main chain of an ethylene tetrafluoride skeleton known as “Teflon (trade name)” and a side chain having a sulfonic acid group at the end via an ether bond. It is represented by the structure.
[0005]
The perfluoro sulfonic acid polymer has a hydrophobic tetrafluoroethylene main chain moiety and a hydrophilic sulfonic acid group side chain moiety in the molecule, so microphase separation into hydrophobic and hydrophilic moieties. Then, proton conduction is performed through the hydrated sulfonic acid group which is a hydrophilic portion.
For this reason, the ionic conductivity of the perfluorosulfonic acid-based polymer depends on the water content, and it is necessary to keep the water content of the electrolyte high in order to obtain high ionic conductivity.
As a result, PEFC using a perfluorosulfonic acid polymer as an electrolyte generally has a humidification mechanism, and the reaction temperature is generally limited to a range of 0 ° C to 90 ° C.
[0006]
[Problems to be solved by the invention]
On the other hand, in the power generation operation of PEFC, there is a problem that water is generated by a power generation reaction together with moisture added to the fuel gas or oxygen gas by the humidifying mechanism, and the aggregated moisture closes the gas flow path, thereby reducing the performance.
For this reason, in the power generation operation of PEFC, it is important to control the mechanism and operating conditions for appropriately maintaining the moisture of the electrolyte, and appropriate moisture management according to the structure of the electrode stack and the operating conditions is required.
[0007]
Thus, while the conventional perfluoro sulfonic acid polymer has excellent characteristics as an electrolyte, there is a problem that proper moisture management is required for the operation of PEFC.
[0008]
Because of these problems, the development of electrolytes exhibiting high ionic conductivity even under non-humidified conditions is being promoted.
[0009]
For example, a technique for mixing and moisturizing perfluorosulfonic acid polymers with a moisturizing agent such as molecular sieves, silica gel, polyethylene oxide, or a technique for mixing and moisturizing a catalyst such as platinum-supported titania or a low molecular weight sulfonic acid group-containing compound. , A method using an electrolyte membrane in which a basic polymer is mixed with a phosphoric acid compound, a method using an electrolyte membrane in which tin dioxide hydrate, zinc dioxide hydrate, tungsten trioxide hydrate, etc. are mixed in a polymer, A technique using an inorganic electrolyte membrane such as phosphosilicate gel has been proposed.
[0010]
Among these, the method using an electrolyte membrane in which a basic polymer is mixed with a phosphoric acid compound, etc. is characterized by relatively high ionic conductivity even under non-aqueous conditions because the mixed phosphoric acid compound is responsible for proton conduction. However, there is a problem that an electrolyte that can be used as an electrolyte membrane of a fuel cell or the like has not been obtained in an environment with low humidity (for example, relative humidity of 10% or less). is there.
[0011]
In view of the above problems, the present invention provides a secondary battery, a display element, a solar battery, and the like having ion conductivity superior to that of a conventional perfluorosulfonic acid polymer in a low humidity environment with a relative humidity of 10% or less. It is an object of the present invention to provide a polymer electrolyte to be used in the manufacturing process.
[0012]
[Means for Solving the Problems]
As a result of intensive studies on the basic polymer mixed with the phosphoric acid compound, the present inventors have polymerized a polyamine compound represented by the general formula (1) represented by the following “chemical formula 2” as at least one component as a raw material. The present inventors have found that a polyelectrolyte complexed with a phosphoric acid compound exhibits high ionic conductivity in a low humidity environment, and have reached the present invention.
[0013]
A first invention for solving the above-described problems based on such knowledge includes a polymer obtained by polymerizing a polyamine compound represented by the following general formula (1) as at least one component of a raw material, and the phosphate compound is The polymer electrolyte is characterized in that the polymer and the phosphoric acid compound are mixed so that the amount of the polymer is equal to or less than the equivalent of the amine of the polyamine compound .
[Chemical 2]

Here, X, Y, and Z are disubstituted, trisubstituted, and tetrasubstituted aromatic rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, naphthalene rings, biphenyl, diphenylmethane, diphenyl ether, diphenylsulfone, diphenylamine, N , N′-diphenylparaphenylenediamine, pyrrole, pyrrolidine, cyclocycle, piperidine, piperazine and the like.
[0014]
A second invention is the first invention, wherein the polyamine compound is paraphenylenediamine, metaphenylenediamine, benzenetriamine, orthophenylenediamine, xylylenediamine, bisaminomethylcyclohexane, triaminodiphenyl ether, diaminodiphenyl ether, It is a polymer electrolyte characterized by being one of diaminodiphenylmethane, diaminodiphenylsulfone, diaminobibenzyl, diallylmelamine, melamine, triaminopyrimidine, triamterene, tetraaminobiphenyl, tetraaminobenzene, and tetraaminopyrimidine .
[0017]
According to a third aspect of the invention, there is provided a polymer electrolyte fuel comprising an electrolyte membrane formed by filming the polymer electrolyte of the first or second invention, and a pair of electrodes sandwiching the electrolyte membrane. In the battery.
[0018]
A fourth invention is the polymer electrolyte fuel cell according to the third invention, wherein the operating temperature is in the range of 200 ° C. or lower and room temperature.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the polymer electrolyte according to the present invention will be described below, but the present invention is not limited to these embodiments.
[0020]
The polymer electrolyte of the present invention contains a polymer obtained by polymerizing a polyamine compound represented by the general formula (1) represented by the above “chemical formula 2” as at least one component of a raw material.
[0021]
In the present invention, specific examples of the polyamine compound include paraphenylenediamine, metaphenylenediamine, benzenetriamine, orthophenylenediamine, xylylenediamine, bisaminomethylcyclohexane, triaminodiphenyl ether, diaminodiphenyl ether, diaminodiphenylmethane, and diaminodiphenyl. Examples include sulfone, diaminobibenzyl, diallyl melamine, melamine, triaminopyrimidine, triamterene, tetraaminobiphenyl, tetraaminobenzene, tetraaminopyrimidine and the like.
[0022]
Among the polyamine compounds, compounds having particularly high skeletal mobility and easy proton movement are preferable. For example, paraphenylenediamine, metaphenylenediamine, benzenetriamine, and triaminodiphenyl ether are particularly preferable.
[0023]
These polyamine compounds can be used in the polymer electrolyte of the present invention alone or in combination with a plurality of polyamine compounds or other polymerizable compounds.
[0024]
Here, examples of the other polymerizable compounds include aniline, pyrrole, aminopyrazine, aminopyridine, toluene diisocyanate, phthalic acid chloride, tetracarboxylic acid anhydride, and formaldehyde.
[0025]
The polyamine compound and other polymerizable compounds may contain a substituent other than an amino group.
[0026]
Examples of the substituent other than the amino group include a hydroxyl group, a saturated alkyl group such as a methyl group and an ethyl group, an unsaturated alkyl group such as a vinyl group, a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group. .
[0027]
These polyamine compounds can easily obtain a basic polymer as a base material of the polymer electrolyte of the present invention by adding an oxidizing agent in a polymerization solvent.
[0028]
Here, examples of the solvent used for the polymerization include organic solvents such as N-methyl 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, sulfuric acid, hydrochloric acid, nitric acid, perchlorine. An acidic aqueous solution such as acid and phosphoric acid and a mixed solvent of both are used. Among these solvents, N-methyl 2-pyrrolidone, dilute hydrochloric acid, dilute sulfuric acid and the like are preferable.
[0029]
Here, ammonium persulfate, iron (III) chloride, manganese dioxide, hydrogen peroxide, or the like is used as the oxidizing agent. Among these oxidizing agents, ammonium persulfate is preferable.
[0030]
The polymerization temperature is selected from the range from the freezing point of the solvent to 100 ° C.
Here, the temperature for obtaining a preferable polymer is, for example, preferably in the range of 0 ° C to 30 ° C.
[0031]
The polymerization time is selected from the range of several hours to several tens of hours, although it depends on the type and blending of the raw material monomers used, the polymerization temperature, the scale of polymerization, and the intensity of stirring.
[0032]
Moreover, although the polymer can be obtained by adding the oxidizing agent all at once, it is preferable to add gradually so that the temperature of the reaction solution does not rise abnormally.
[0033]
For example, when paraphenylenediamine is used as a raw material as a polyamine compound represented by the general formula (1), N-methyl-2-pyrrolidone is used as a polymerization solvent, and ammonium persulfate is added as an oxidizing agent, polymerization is performed. A polymer represented by the general formula (2) shown is obtained.
[Chemical 3]

[0034]
The polymer electrolyte of the present invention can be obtained by reacting this polymer with a phosphoric acid compound.
[0035]
Here, examples of the phosphoric acid compound include phosphorous acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, and phenylphosphoric acid. Of these phosphoric acid compounds, orthophosphoric acid is preferred.
[0036]
The mixing amount of the phosphoric acid compound is preferably less than or equal to the amine of the polyamine compound. This is because even if the equivalent amount or more is mixed, the phosphoric acid compound falls off due to an increase in water generated by power generation, which is not preferable.
[0037]
The reaction between the polymer and the phosphoric acid compound can be achieved by simply mixing both at room temperature, but it can also be reacted in a solvent.
Here, examples of the solvent include water, methanol, ethanol, tetrahydrofuran, and dioxane. Among these solvents, it is particularly preferable to use water.
[0038]
When orthophosphoric acid is reacted as an example of a phosphoric acid compound with the general formula (2) represented by the above “chemical formula 3” shown as an example, a polymer represented by the general formula (3) represented by the following “chemical formula 4” An electrolyte can be obtained.
[Formula 4]

[0039]
As shown in the example of the polymer electrolyte of the present invention represented by the general formula (3), the polymer electrolyte of the present invention has a feature that a phosphoric acid compound can be mixed at a high ratio, and a high ionic conductivity is obtained. At the same time, the retention ability of the phosphoric acid compound is enhanced, and it becomes possible to suppress the dropping of the phosphoric acid compound due to an increase in moisture generated during power generation.
[0040]
【Example】
Hereinafter, although the suitable one Example of the polymer electrolyte by this invention is described below, this invention is not limited to these Examples at all.
[0041]
[First embodiment]
To a 300 mL four-necked flask purged with nitrogen, 2 g of paraphenylenediamine was added, and 198 g of N-methyl 2-pyrrolidone was added and dissolved. The solution was cooled to 0 ° C., and 8.4 g of ammonium persulfate was gradually added to react with stirring. Stirring was continued for 12 hours after the exotherm due to the reaction stopped. Into a 1 L beaker, 800 mL of distilled water was put, and the reaction solution was poured to precipitate a polymer. The polymer was suction filtered using a glass filter, and the polymer was washed 3 times with distilled water and 3 times with acetone. The polymer was transferred to a petri dish, placed in a vacuum dryer and dried under reduced pressure at 100 ° C. for 12 hours. The polymer was a black powder and the yield after drying was 1.7 g.
[0042]
The infrared spectrum of the polymer obtained is shown in FIG.
[0043]
In addition, 0.5 g of the polymer obtained above was put into an agate mortar, and 1.1 g of 85% orthophosphoric acid aqueous solution was added and mixed to obtain a viscous paste.
The infrared spectrum of the obtained paste is shown in FIG.
[0044]
The obtained paste was cast on a glass plate and dried under reduced pressure at 100 ° C. for 12 hours to obtain a film.
[0045]
As a result of measuring the ionic conductivity of the film at 80 ° C. and 4% relative humidity by the AC impedance method, it was 2.2 × 10 ⁻³ S / cm.
[0046]
The change of the ionic conductivity of the film with temperature and relative humidity is shown in FIG. For comparison, a film obtained from a perfluorosulfonic acid-based polymer according to the prior art is shown.
As shown in FIG. 3, the ionic conductivity of this example at 80 ° C. and a relative humidity of 4% is 2.2 × 10 ⁻³ S / cm, whereas the ionic conductivity of the prior art is 2 × 10. ^-4 S / cm.
[0047]
[Second Embodiment]
To a 300 mL four-necked flask purged with nitrogen, 5 g of 3,4,4′-triaminodiphenyl ether was added, and 100 g of N-methyl 2-pyrrolidone was added and dissolved. The solution was cooled to 0 ° C., and 15.9 g of ammonium persulfate was gradually added to react with stirring. Stirring was continued for 12 hours after the exotherm due to the reaction stopped. Into a 2 L beaker, 1500 mL of distilled water was put, and the reaction solution was poured to precipitate the polymer. The polymer was suction filtered using a glass filter, and the polymer was washed 3 times with distilled water and 3 times with acetone. The polymer was transferred to a petri dish, placed in a vacuum dryer and dried under reduced pressure at 100 ° C. for 12 hours. A black powdery polymer was obtained.
[0048]
When 1 g of the polymer was placed in an agate mortar and 2.6 g of 85% orthophosphoric acid aqueous solution was added and mixed, a viscous paste was obtained. The paste was cast on a glass plate and dried under reduced pressure at 100 ° C. for 12 hours to obtain a film.
[0049]
As a result of measuring the ionic conductivity of the film in an environment of 80 ° C. and 4% relative humidity by the AC impedance method, it was 1.8 × 10 ⁻³ S / cm.
[0050]
[Third embodiment]
To a 300 mL four-necked flask purged with nitrogen, 5 g of 1,2,4,5-benzenetetramine hydrochloride was added and dissolved by adding 100 g of 1N hydrochloric acid. The solution was cooled to 0 ° C., and 16.1 g of ammonium persulfate was gradually added to react with stirring. Stirring was continued for 12 hours after the exotherm due to the reaction stopped. Into a 2 L beaker, 1500 mL of distilled water was put, and the reaction solution was poured to precipitate the polymer. The polymer was suction filtered using a glass filter, and the polymer was washed 3 times with distilled water and 3 times with acetone. The polymer was transferred to a petri dish, placed in a vacuum dryer and dried under reduced pressure at 100 ° C. for 12 hours. A black powdery polymer was obtained.
[0051]
When 1 g of the polymer was placed in an agate mortar and 3.2 g of 85% orthophosphoric acid aqueous solution was added and mixed, a viscous paste was obtained. The paste was cast on a glass plate and dried under reduced pressure at 100 ° C. for 12 hours to obtain a film.
As a result of measuring the ionic conductivity of the film in an environment at 80 ° C. and a relative humidity of 4% by the AC impedance method, it was 1.9 × 10 ⁻³ S / cm.
[0052]
[Fourth embodiment]
2 g of metaphenylenediamine was put into a 300 mL four-necked flask purged with nitrogen, and 200 mL of 1N sulfuric acid was added and dissolved. The solution was cooled to 0 ° C., and 8.4 g of ammonium persulfate was gradually added to react with stirring. Stirring was continued for 12 hours after the exotherm due to the reaction stopped. Into a 1 L beaker, 800 mL of distilled water was put, and the reaction solution was poured to precipitate a polymer. The polymer was suction filtered using a glass filter, and the polymer was washed 3 times with distilled water and 3 times with acetone. The polymer was transferred to a petri dish, placed in a vacuum dryer and dried under reduced pressure at 100 ° C. for 12 hours. A black powdery polymer was obtained.
[0053]
When 0.5 g of the polymer was put in an agate mortar and 1.1 g of 85% orthophosphoric acid aqueous solution was added and mixed, a viscous paste was obtained. The paste was cast on a glass plate and dried under reduced pressure at 100 ° C. for 12 hours to obtain a film.
As a result of measuring the ionic conductivity of the film in an environment of 80 ° C. and a relative humidity of 4% by the AC impedance method, it was 2.1 × 10 ⁻³ S / cm.
[0054]
【The invention's effect】
As described above, the polymer electrolyte according to the present invention has ionic conductivity superior to that of the conventional perfluorosulfonic acid polymer in a low humidity environment having a relative humidity of 10% or less.
[0055]
Therefore, the polymer electrolyte of the present invention exhibits high ionic conductivity even under low humidity conditions, and is an electrolyte membrane such as a fuel cell, a secondary battery, a display element, and a solar cell using the conventional perfluorosulfonic acid polymer membrane. It is particularly useful as an alternative membrane.
[Brief description of the drawings]
FIG. 1 is an infrared spectrum diagram of a basic polymer obtained in a first example.
FIG. 2 is an infrared spectrum diagram of a mixture of the basic polymer and phosphoric acid obtained in the first example.
FIG. 3 is an ionic conductivity diagram of the basic polymer obtained in the first example.

Claims (4)

Containing a polymer obtained by polymerizing a polyamine compound represented by the following general formula (1) as at least one component of the raw material, so that the phosphoric acid compound is less than or equal to the amine of the polyamine compound of the polymer, A polymer electrolyte, wherein the polymer and the phosphoric acid compound are mixed .

Here, X, Y, and Z are disubstituted, trisubstituted, and tetrasubstituted aromatic rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, naphthalene rings, biphenyl, diphenylmethane, diphenyl ether, diphenylsulfone, diphenylamine, N , N′-diphenylparaphenylenediamine, pyrrole, pyrrolidine, cyclocycle, piperidine, piperazine and the like. In claim 1,
The polyamine compound is paraphenylenediamine, metaphenylenediamine, benzenetriamine, orthophenylenediamine, xylylenediamine, bisaminomethylcyclohexane, triaminodiphenyl ether, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylsulfone, diaminobibenzyl, diallyl melamine A polymer electrolyte, which is any one of melamine, triaminopyrimidine, triamterene, tetraaminobiphenyl, tetraaminobenzene, and tetraaminopyrimidine. An electrolyte membrane formed by filming the polymer electrolyte of claim 1 or claim 2 ;
A polymer electrolyte fuel cell, comprising: a pair of electrodes sandwiching the electrolyte membrane. In claim 3 ,
A polymer electrolyte fuel cell, characterized in that the operating temperature is in the range of 200 ° C. or lower and room temperature.

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