JPWO2020056275A5 - - Google Patents

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JPWO2020056275A5
JPWO2020056275A5 JP2021514050A JP2021514050A JPWO2020056275A5 JP WO2020056275 A5 JPWO2020056275 A5 JP WO2020056275A5 JP 2021514050 A JP2021514050 A JP 2021514050A JP 2021514050 A JP2021514050 A JP 2021514050A JP WO2020056275 A5 JPWO2020056275 A5 JP WO2020056275A5
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acid
flow battery
redox flow
membrane
aromatic
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Priority claimed from PCT/US2019/051036 external-priority patent/WO2020056275A1/en
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Figure 2020056275000004
Figure 2020056275000004

Figure 2020056275000005
Figure 2020056275000005

Figure 2020056275000006
Figure 2020056275000006

[0119]特定の用語を使用して開示された主題の幾つかの実施形態を説明したが、かかる記載は例示目的のみのためであり、主題の精神又は範囲から逸脱することなく、変更及び変形を行うことができることを理解すべきである。
以下に、出願時の特許請求の範囲の記載を示す。
［請求項１］
レドックスフロー電池膜を形成する方法であって、
ポリリン酸、芳香族又はヘテロ芳香族テトラアミノ化合物、及び芳香族又はヘテロ芳香族カルボン酸化合物を含む重合組成物であって、前記芳香族又はヘテロ芳香族カルボン酸化合物は、芳香族又はヘテロ芳香族ポリカルボン酸又はそのエステル、無水物、又は酸塩化物を含み、及び／又は芳香族又はヘテロ芳香族ジアミノカルボン酸を含む重合組成物を形成すること；
前記芳香族又はヘテロ芳香族テトラアミノ化合物を前記芳香族又はヘテロ芳香族カルボン酸化合物と重合して、前記ポリリン酸中に溶解したポリベンズイミダゾールを含むポリマー溶液を形成すること；
前記ポリマー溶液を成形して、前記ポリマー溶液を含む膜前駆体を形成すること；
前記膜前駆体のポリリン酸の少なくとも一部を加水分解してリン酸及び水を形成し、それにより、前記膜前駆体が、前記ポリベンズイミダゾールを含むゲル膜を形成すること、ここで、当該ゲル膜が、ポリベンズイミダゾールを含み、構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であり；及び
前記ゲル膜に、レドックスフロー電池支持電解質を吸収させること；
を含む、上記方法。
［請求項２］
前記重合組成物が、前記重合組成物の約１０重量％以下の濃度の前記芳香族又はヘテロ芳香族テトラアミノ化合物及び前記芳香族又はヘテロ芳香族カルボン酸化合物を含む、請求項１に記載の方法。
［請求項３］
前記芳香族又はヘテロ芳香族テトラアミノ化合物が、２，３，５，６－テトラアミノピリジン；３，３’，４，４’－テトラアミノジフェニルスルホン；３，３’，４，４’－テトラアミノジフェニルエーテル；３，３’，４，４’－テトラアミノビフェニル；１，２，４，５－テトラアミノベンゼン；３，３’，４，４’－テトラアミノベンゾフェノン；３，３’，４，４’－テトラアミノジフェニルメタン；及び３，３’，４，４’－テトラアミノジフェニルジメチルメタン、又はそれらの塩、或いはそれらの任意の組合せを含む、請求項１又は２に記載の方法。
［請求項４］
前記芳香族又はヘテロ芳香族カルボン酸化合物が、ピリジン－２，５－ジカルボン酸；ピリジン－３，５－ジカルボン酸；ピリジン－２，６－ジカルボン酸；ピリジン－２，４－ジカルボン酸；４－フェニル－２，５－ピリジンジカルボン酸；３，５－ピラゾールジカルボン酸；２，６－ピリミジンジカルボン酸；２，５－ピラジンジカルボン酸；２，４，６－ピリジントリカルボン酸；ベンズイミダゾール－５，６－ジカルボン酸；５－ヒドロキシイソフタル酸；４－ヒドロキシイソフタル酸；２－ヒドロキシテレフタル酸；５－アミノイソフタル酸；５－Ｎ，Ｎ－ジメチルアミノイソフタル酸；５－Ｎ，Ｎ－ジエチルアミノイソフタル酸；２，５－ジヒドロキシテレフタル酸；２，６－ジヒドロキシイソフタル酸；４，６－ジヒドロキシイソフタル酸；２，３－ジヒドロキシフタル酸；２，４－ジヒドロキシフタル酸；３，４－ジヒドロキシフタル酸；１，８－ジヒドロキシナフタレン－３，６－ジカルボン酸；ジフェニルスルホン－４，４’－ジカルボン酸；イソフタル酸；テレフタル酸；フタル酸；３－フルオロフタル酸；５－フルオロイソフタル酸；２－フルオロテレフタル酸；テトラフルオロフタル酸；テトラフルオロイソフタル酸；テトラフルオロテレフタル酸；３－スルホフタル酸；５－スルホイソフタル酸；２－スルホテレフタル酸；テトラスルホフタル酸；テトラスルホイソフタル酸；テトラスルホテレフタル酸；１，４－ナフタレンジカルボン酸；１，５－ナフタレンジカルボン酸；２，６－ナフタレンジカルボン酸；２，７－ナフタレンジカルボン酸；ジフェン酸；ジフェニルエーテル ４，４’－ジカルボン酸；ベンゾフェノン－４，４’－ジカルボン酸；ビフェニル－４，４’－ジカルボン酸；４－トリフルオロメチルフタル酸；２，２－ビス（４－カルボ
キシフェニル）ヘキサフルオロプロパン；４，４’－スチルベンジカルボン酸；及び４－カルボキシ桂皮酸、又はそれらの任意の組み合わせを含む、請求項１～３のいずれかに記載の方法。
［請求項５］
前記膜前駆体が２０μｍ～約４，０００μｍの厚さを有する、請求項１～４のいずれかに記載の方法。
［請求項６］
前記加水分解を、約０℃～約１５０℃の温度及び約２０％～１００％の相対湿度において行う、請求項１～５のいずれかに記載の方法。
［請求項７］
前記ゲル膜を架橋することを更に含む、請求項１～６のいずれかに記載の方法。
［請求項８］
レドックスフロー電池膜であって、
構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であるポリベンズイミダゾールゲル膜；及び
前記ポリベンズイミダゾールゲル膜内に吸収されたレドックスフロー電池支持電解質；を含み；
前記レドックスフロー電池膜は、約１００ｍＳ／ｃｍ２以上の２．６Ｍ硫酸溶液中における面内イオン伝導率を示す、上記レドックスフロー電池膜。
［請求項９］
前記ゲル膜の前記ポリベンズイミダゾールが、次の繰り返し単位：

Figure 2020056275000007
Figure 2020056275000008
Figure 2020056275000009
 （式中、ｎ及びｍは、それぞれ独立して、１以上、約１０以上、又は約１００以上である）
の１以上又はそれらの任意の組み合わせを含む、請求項８に記載のレドックスフロー電池膜。
［請求項１０］
前記支持電解質が、塩酸、硝酸、フルオロスルホン酸、又は硫酸、或いはそれらの混合物のような鉱酸；酢酸、ギ酸、ｐ－トルエンスルホン酸、又はトリフルオロメタンスルホン酸、或いはそれらの混合物のような強有機酸；或いは１以上の鉱酸及び／又は１以上の有機酸の組合せを含むか；或いは前記支持電解質が、塩化ナトリウム、塩化カリウム、水酸化ナトリウム、水酸化カリウム、硫化ナトリウム、硫化カリウム、又はそれらの任意の組合せを含むか、或いは前記支持電解質が、テトラアルキルアンモニウムカチオンを含む、請求項８又は９に記載のレドックスフロー電池膜。
［請求項１１］
前記レドックスフロー電池膜が架橋されている、請求項８～１０のいずれかに記載のレドックスフロー電池膜。
［請求項１２］
ポリベンズイミダゾールゲル膜、及び前記ポリベンズイミダゾールゲル膜内に吸収されているレドックスフロー電池支持電解質を含むレドックスフロー電池であって、前記ポリベンズイミダゾールゲル膜は、構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であり、前記レドックスフロー電池は、約１００ｍＡ／ｃｍ２以上の電流密度で作動させることができる、上記レドックスフロー電池。
［請求項１３］
前記レドックスフロー電池がバナジウムフロー電池である、請求項１２に記載のレドックスフロー電池。
［請求項１４］
前記レドックスフロー電池が、２４２ｍＡ／ｃｍ２の電流密度において、約９０％以上のクーロン効率及び／又は約７５％以上のエネルギー効率及び／又は約８０％以上の電圧効率を有する、請求項１２又は１３に記載のレドックスフロー電池。
［請求項１５］
前記レドックスフロー電池が、４８３ｍＡ／ｃｍ２の電流密度において、約９０％以上のクーロン効率及び／又は約６５％以上のエネルギー効率及び／又は約６５％以上の電圧効率を有する、請求項１２～１４のいずれかに記載のレドックスフロー電池。 [0119] Although specific language has been used to describe certain embodiments of the disclosed subject matter, such description is for illustrative purposes only and modifications and variations can be made without departing from the spirit or scope of the subject matter. It should be understood that the
The description of the scope of claims as filed is shown below.
[Claim 1]
A method of forming a redox flow battery membrane comprising:
A polymeric composition comprising polyphosphoric acid, an aromatic or heteroaromatic tetraamino compound, and an aromatic or heteroaromatic carboxylic acid compound, wherein the aromatic or heteroaromatic carboxylic acid compound is an aromatic or heteroaromatic forming a polymeric composition comprising a polycarboxylic acid or its ester, anhydride, or acid chloride and/or comprising an aromatic or heteroaromatic diaminocarboxylic acid;
polymerizing the aromatic or heteroaromatic tetraamino compound with the aromatic or heteroaromatic carboxylic acid compound to form a polymer solution comprising polybenzimidazole dissolved in the polyphosphoric acid;
shaping the polymer solution to form a membrane precursor comprising the polymer solution;
hydrolyzing at least a portion of the polyphosphoric acid of said film precursor to form phosphoric acid and water, whereby said film precursor forms a gel film comprising said polybenzimidazole, wherein said The gel membrane comprises polybenzimidazole and is a self-supporting membrane capable of containing about 60% by weight or more of liquid content without loss of structure; and allowing the gel membrane to imbibe a redox flow battery supporting electrolyte. thing;
The above method, including
[Claim 2]
2. The method of claim 1, wherein said polymeric composition comprises said aromatic or heteroaromatic tetraamino compound and said aromatic or heteroaromatic carboxylic acid compound at a concentration of no greater than about 10% by weight of said polymeric composition. .
[Claim 3]
The aromatic or heteroaromatic tetraamino compound is 2,3,5,6-tetraaminopyridine; 3,3′,4,4′-tetraaminodiphenylsulfone; 3,3′,4,4′-tetra aminodiphenyl ether; 3,3',4,4'-tetraaminobiphenyl;1,2,4,5-tetraaminobenzene;3,3',4,4'-tetraaminobenzophenone;3,3',4,4'-tetraaminodiphenylmethane; and 3,3',4,4'-tetraaminodiphenyldimethylmethane, or salts thereof, or any combination thereof.
[Claim 4]
The aromatic or heteroaromatic carboxylic acid compound is pyridine-2,5-dicarboxylic acid; pyridine-3,5-dicarboxylic acid; pyridine-2,6-dicarboxylic acid; pyridine-2,4-dicarboxylic acid; Phenyl-2,5-pyridinedicarboxylic acid; 3,5-pyrazoledicarboxylic acid; 2,6-pyrimidinedicarboxylic acid; 2,5-pyrazinedicarboxylic acid; 2,4,6-pyridinetricarboxylic acid; benzimidazole-5,6 5-hydroxyisophthalic acid; 4-hydroxyisophthalic acid; 2-hydroxyterephthalic acid; 5-aminoisophthalic acid; 5-N,N-dimethylaminoisophthalic acid; 2,6-dihydroxyisophthalic acid; 4,6-dihydroxyisophthalic acid; 2,3-dihydroxyphthalic acid; 2,4-dihydroxyphthalic acid; 3,4-dihydroxyphthalic acid; -dihydroxynaphthalene-3,6-dicarboxylic acid; diphenylsulfone-4,4'-dicarboxylic acid; isophthalic acid; terephthalic acid; phthalic acid; 3-fluorophthalic acid; fluorophthalic acid; tetrafluoroisophthalic acid; tetrafluoroterephthalic acid; 3-sulfophthalic acid; 5-sulfoisophthalic acid; 2-sulfoterephthalic acid; tetrasulfophthalic acid; 2,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; diphenic acid; diphenyl ether 4,4'-dicarboxylic acid; benzophenone-4,4'-dicarboxylic acid; 4-trifluoromethylphthalic acid; 2,2-bis(4-carboxyphenyl)hexafluoropropane; 4,4'-stilbenedicarboxylic acid; and 4-carboxycinnamic acid, or The method of any one of claims 1-3, including any combination thereof.
[Claim 5]
The method of any of claims 1-4, wherein the film precursor has a thickness of from 20 µm to about 4,000 µm.
[Claim 6]
The method of any of claims 1-5, wherein said hydrolysis is carried out at a temperature of about 0°C to about 150°C and a relative humidity of about 20% to 100%.
[Claim 7]
The method of any of claims 1-6, further comprising cross-linking the gel film.
[Claim 8]
A redox flow battery membrane comprising:
a polybenzimidazole gel membrane, which is a self-supporting membrane capable of containing about 60% or more by weight liquid inclusions without loss of structure; and a redox flow battery supporting electrolyte absorbed within said polybenzimidazole gel membrane; include;
The redox flow battery membrane, wherein the redox flow battery membrane exhibits an in-plane ionic conductivity in a 2.6 M sulfuric acid solution of about 100 mS/cm 2 or more.
[Claim 9]
The polybenzimidazole of the gel film has the following repeating units:
Figure 2020056275000007
Figure 2020056275000008
Figure 2020056275000009
 (wherein n and m are each independently 1 or more, about 10 or more, or about 100 or more)
or any combination thereof.
[Claim 10]
the supporting electrolyte is a mineral acid such as hydrochloric acid, nitric acid, fluorosulfonic acid, or sulfuric acid, or mixtures thereof; or comprises a combination of one or more mineral acids and/or one or more organic acids; or the supporting electrolyte is sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium sulfide, potassium sulfide, or 10. The redox flow battery membrane of claim 8 or 9, comprising any combination thereof, or wherein the supporting electrolyte comprises tetraalkylammonium cations.
[Claim 11]
The redox flow battery membrane of any of claims 8-10, wherein the redox flow battery membrane is crosslinked.
[Claim 12]
A redox flow battery comprising a polybenzimidazole gel membrane and a redox flow battery supporting electrolyte absorbed within said polybenzimidazole gel membrane, said polybenzimidazole gel membrane comprising about 60% by weight without loss of structure. a self-supporting membrane capable of containing liquid inclusions as defined above, and wherein said redox flow battery can be operated at a current density of about 100 mA/cm 2 or greater.
[Claim 13]
13. The redox flow battery of claim 12, wherein said redox flow battery is a vanadium flow battery.
[Claim 14]
14. The redox flow battery of claim 12 or 13, wherein the redox flow battery has a coulombic efficiency of about 90% or more and/or an energy efficiency of about 75% or more and/or a voltage efficiency of about 80% or more at a current density of 242 mA/ cm2 . The redox flow battery described in .
[Claim 15]
Claims 12-14, wherein the redox flow battery has a coulombic efficiency of about 90% or more and/or an energy efficiency of about 65% or more and/or a voltage efficiency of about 65% or more at a current density of 483 mA/ cm2 . Redox flow battery according to any one of.

Claims (15)

レドックスフロー電池膜を形成する方法であって、
ポリリン酸、芳香族又はヘテロ芳香族テトラアミノ化合物、及び芳香族又はヘテロ芳香族カルボン酸化合物を含む重合組成物であって、前記芳香族又はヘテロ芳香族カルボン酸化合物は、芳香族又はヘテロ芳香族ポリカルボン酸又はそのエステル、無水物、又は酸塩化物を含み、及び／又は芳香族又はヘテロ芳香族ジアミノカルボン酸を含む重合組成物を形成すること；
前記芳香族又はヘテロ芳香族テトラアミノ化合物を前記芳香族又はヘテロ芳香族カルボン酸化合物と重合して、前記ポリリン酸中に溶解したポリベンズイミダゾールを含むポリマー溶液を形成すること；
前記ポリマー溶液を成形して、前記ポリマー溶液を含む膜前駆体を形成すること；
前記膜前駆体のポリリン酸の少なくとも一部を加水分解してリン酸及び水を形成し、それにより、前記膜前駆体が、前記ポリベンズイミダゾールを含むゲル膜を形成すること、ここで、当該ゲル膜が、ポリベンズイミダゾールを含み、構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であり；
前記ゲル膜をすすいでリン酸及び残存するポリリン酸を除去すること；及び
前記すすがれたゲル膜に、レドックスフロー電池支持電解質を吸収させること；
を含む、上記方法。 A method of forming a redox flow battery membrane comprising:
A polymeric composition comprising polyphosphoric acid, an aromatic or heteroaromatic tetraamino compound, and an aromatic or heteroaromatic carboxylic acid compound, wherein the aromatic or heteroaromatic carboxylic acid compound is an aromatic or heteroaromatic forming a polymeric composition comprising a polycarboxylic acid or its ester, anhydride, or acid chloride and/or comprising an aromatic or heteroaromatic diaminocarboxylic acid;
polymerizing the aromatic or heteroaromatic tetraamino compound with the aromatic or heteroaromatic carboxylic acid compound to form a polymer solution comprising polybenzimidazole dissolved in the polyphosphoric acid;
shaping the polymer solution to form a membrane precursor comprising the polymer solution;
hydrolyzing at least a portion of the polyphosphoric acid of said film precursor to form phosphoric acid and water, whereby said film precursor forms a gel film comprising said polybenzimidazole, wherein said the gel membrane comprises polybenzimidazole and is a self- supporting membrane capable of containing about 60% or more by weight liquid content without loss of structure;
rinsing the gel membrane to remove phosphoric acid and residual polyphosphoric acid; and allowing the rinsed gel membrane to absorb a redox flow battery supporting electrolyte;
The above method, including 前記重合組成物が、前記重合組成物の約１０重量％以下の濃度の前記芳香族又はヘテロ芳香族テトラアミノ化合物及び前記芳香族又はヘテロ芳香族カルボン酸化合物を含む、請求項１に記載の方法。 2. The method of claim 1, wherein said polymeric composition comprises said aromatic or heteroaromatic tetraamino compound and said aromatic or heteroaromatic carboxylic acid compound at a concentration of about 10% or less by weight of said polymeric composition. . 前記芳香族又はヘテロ芳香族テトラアミノ化合物が、２，３，５，６－テトラアミノピリジン；３，３’，４，４’－テトラアミノジフェニルスルホン；３，３’，４，４’－テトラアミノジフェニルエーテル；３，３’，４，４’－テトラアミノビフェニル；１，２，４，５－テトラアミノベンゼン；３，３’，４，４’－テトラアミノベンゾフェノン；３，３’，４，４’－テトラアミノジフェニルメタン；及び３，３’，４，４’－テトラアミノジフェニルジメチルメタン、又はそれらの塩、或いはそれらの任意の組合せを含む、請求項１又は２に記載の方法。 The aromatic or heteroaromatic tetraamino compound is 2,3,5,6-tetraaminopyridine; 3,3′,4,4′-tetraaminodiphenylsulfone; 3,3′,4,4′-tetra aminodiphenyl ether; 3,3',4,4'-tetraaminobiphenyl; 1,2,4,5-tetraaminobenzene; 3,3',4,4'-tetraaminobenzophenone; 3,3',4, 4'-tetraaminodiphenylmethane; and 3,3',4,4'-tetraaminodiphenyldimethylmethane, or salts thereof, or any combination thereof. 前記芳香族又はヘテロ芳香族カルボン酸化合物が、ピリジン－２，５－ジカルボン酸；ピリジン－３，５－ジカルボン酸；ピリジン－２，６－ジカルボン酸；ピリジン－２，４－ジカルボン酸；４－フェニル－２，５－ピリジンジカルボン酸；３，５－ピラゾールジカルボン酸；２，６－ピリミジンジカルボン酸；２，５－ピラジンジカルボン酸；２，４，６－ピリジントリカルボン酸；ベンズイミダゾール－５，６－ジカルボン酸；５－ヒドロキシイソフタル酸；４－ヒドロキシイソフタル酸；２－ヒドロキシテレフタル酸；５－アミノイソフタル酸；５－Ｎ，Ｎ－ジメチルアミノイソフタル酸；５－Ｎ，Ｎ－ジエチルアミノイソフタル酸；２，５－ジヒドロキシテレフタル酸；２，６－ジヒドロキシイソフタル酸；４，６－ジヒドロキシイソフタル酸；２，３－ジヒドロキシフタル酸；２，４－ジヒドロキシフタル酸；３，４－ジヒドロキシフタル酸；１，８－ジヒドロキシナフタレン－３，６－ジカルボン酸；ジフェニルスルホン－４，４’－ジカルボン酸；イソフタル酸；テレフタル酸；フタル酸；３－フルオロフタル酸；５－フルオロイソフタル酸；２－フルオロテレフタル酸；テトラフルオロフタル酸；テトラフルオロイソフタル酸；テトラフルオロテレフタル酸；３－スルホフタル酸；５－スルホイソフタル酸；２－スルホテレフタル酸；テトラスルホフタル酸；テトラスルホイソフタル酸；テトラスルホテレフタル酸；１，４－ナフタレンジカルボン酸；１，５－ナフタレンジカルボン酸；２，６－ナフタレンジカルボン酸；２，７－ナフタレンジカルボン酸；ジフェン酸；ジフェニルエーテル ４，４’－ジカルボン酸；ベンゾフェノン－４，４’－ジカルボン酸；ビフェニル－４，４’－ジカルボン酸；４－トリフルオロメチルフタル酸；２，２－ビス（４－カルボ
キシフェニル）ヘキサフルオロプロパン；４，４’－スチルベンジカルボン酸；及び４－カルボキシ桂皮酸、又はそれらの任意の組み合わせを含む、請求項１～３のいずれかに記載の方法。 The aromatic or heteroaromatic carboxylic acid compound is pyridine-2,5-dicarboxylic acid; pyridine-3,5-dicarboxylic acid; pyridine-2,6-dicarboxylic acid; pyridine-2,4-dicarboxylic acid; Phenyl-2,5-pyridinedicarboxylic acid; 3,5-pyrazoledicarboxylic acid; 2,6-pyrimidinedicarboxylic acid; 2,5-pyrazinedicarboxylic acid; 2,4,6-pyridinetricarboxylic acid; benzimidazole-5,6 5-hydroxyisophthalic acid; 4-hydroxyisophthalic acid; 2-hydroxyterephthalic acid; 5-aminoisophthalic acid; 5-N,N-dimethylaminoisophthalic acid; 2,6-dihydroxyisophthalic acid; 4,6-dihydroxyisophthalic acid; 2,3-dihydroxyphthalic acid; 2,4-dihydroxyphthalic acid; 3,4-dihydroxyphthalic acid; -dihydroxynaphthalene-3,6-dicarboxylic acid; diphenylsulfone-4,4'-dicarboxylic acid; isophthalic acid; terephthalic acid; phthalic acid; 3-fluorophthalic acid; fluorophthalic acid; tetrafluoroisophthalic acid; tetrafluoroterephthalic acid; 3-sulfophthalic acid; 5-sulfoisophthalic acid; 2-sulfoterephthalic acid; tetrasulfophthalic acid; 2,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; diphenic acid; diphenyl ether 4,4'-dicarboxylic acid; benzophenone-4,4'-dicarboxylic acid; 4-trifluoromethylphthalic acid; 2,2-bis(4-carboxyphenyl)hexafluoropropane; 4,4'-stilbenedicarboxylic acid; and 4-carboxycinnamic acid, or The method of any one of claims 1-3, including any combination thereof. 前記膜前駆体が２０μｍ～約４，０００μｍの厚さを有する、請求項１～４のいずれかに記載の方法。 The method of any of claims 1-4, wherein the film precursor has a thickness of from 20 µm to about 4,000 µm. 前記加水分解を、約０℃～約１５０℃の温度及び約２０％～１００％の相対湿度において行う、請求項１～５のいずれかに記載の方法。 The method of any of claims 1-5, wherein said hydrolysis is performed at a temperature of about 0°C to about 150°C and a relative humidity of about 20% to 100%. 前記ゲル膜を架橋することを更に含む、請求項１～６のいずれかに記載の方法。 The method of any of claims 1-6, further comprising cross-linking the gel film. レドックスフロー電池膜であって、
構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であるポリベンズイミダゾールゲル膜；及び
前記ポリベンズイミダゾールゲル膜内に吸収されたレドックスフロー電池支持電解質；を含み；
前記レドックスフロー電池膜は、約１００ｍＳ／ｃｍ２以上の２．６Ｍ硫酸溶液中における面内イオン伝導率を示す、上記レドックスフロー電池膜。 A redox flow battery membrane comprising:
a polybenzimidazole gel membrane, which is a self-supporting membrane capable of containing about 60% or more by weight liquid inclusions without loss of structure; and a redox flow battery supporting electrolyte absorbed within said polybenzimidazole gel membrane; include;
The redox flow battery membrane, wherein the redox flow battery membrane exhibits an in-plane ionic conductivity in a 2.6 M sulfuric acid solution of about 100 mS/cm 2 or more. 前記ゲル膜の前記ポリベンズイミダゾールが、次の繰り返し単位：
Figure 2020056275000001
Figure 2020056275000002
Figure 2020056275000003
 （式中、ｎ及びｍは、それぞれ独立して、１以上、約１０以上、又は約１００以上である）
の１以上又はそれらの任意の組み合わせを含む、請求項８に記載のレドックスフロー電池膜。 The polybenzimidazole of the gel film has the following repeating units:
Figure 2020056275000001
Figure 2020056275000002
Figure 2020056275000003
 (wherein n and m are each independently 1 or more, about 10 or more, or about 100 or more)
or any combination thereof. 前記支持電解質が、塩酸、硝酸、フルオロスルホン酸、又は硫酸、或いはそれらの混合物のような鉱酸；酢酸、ギ酸、ｐ－トルエンスルホン酸、又はトリフルオロメタンスルホン酸、或いはそれらの混合物のような強有機酸；或いは１以上の鉱酸及び／又は１以上の有機酸の組合せを含むか；或いは前記支持電解質が、塩化ナトリウム、塩化カリウム、水酸化ナトリウム、水酸化カリウム、硫化ナトリウム、硫化カリウム、又はそれらの任意の組合せを含むか、或いは前記支持電解質が、テトラアルキルアンモニウムカチオンを含む、請求項８又は９に記載のレドックスフロー電池膜。 the supporting electrolyte is a mineral acid such as hydrochloric acid, nitric acid, fluorosulfonic acid, or sulfuric acid, or mixtures thereof; or comprises a combination of one or more mineral acids and/or one or more organic acids; or the supporting electrolyte is sodium chloride, potassium chloride, sodium hydroxide, potassium hydroxide, sodium sulfide, potassium sulfide, or 10. The redox flow battery membrane of claim 8 or 9, comprising any combination thereof, or wherein the supporting electrolyte comprises tetraalkylammonium cations. 前記レドックスフロー電池膜が架橋されている、請求項８～１０のいずれかに記載のレドックスフロー電池膜。 The redox flow battery membrane of any of claims 8-10, wherein the redox flow battery membrane is crosslinked. ポリベンズイミダゾールゲル膜、及び前記ポリベンズイミダゾールゲル膜内に吸収されているレドックスフロー電池支持電解質を含むレドックスフロー電池であって、前記ポリベンズイミダゾールゲル膜は、構造を失うことなく約６０重量％以上の液体含有物を含ませることができる自己支持膜であり、前記レドックスフロー電池は、約１００ｍＡ／ｃｍ２以上の電流密度で作動させることができる、上記レドックスフロー電池。 A redox flow battery comprising a polybenzimidazole gel membrane and a redox flow battery supporting electrolyte absorbed within said polybenzimidazole gel membrane, said polybenzimidazole gel membrane comprising about 60% by weight without loss of structure. a self-supporting membrane capable of containing liquid inclusions as defined above, and wherein said redox flow battery can be operated at a current density of about 100 mA/cm 2 or greater. 前記レドックスフロー電池がバナジウムフロー電池である、請求項１２に記載のレドックスフロー電池。 13. The redox flow battery of claim 12, wherein said redox flow battery is a vanadium flow battery. 前記レドックスフロー電池が、２４２ｍＡ／ｃｍ２の電流密度において、約９０％以上のクーロン効率及び／又は約７５％以上のエネルギー効率及び／又は約８０％以上の電圧効率を有する、請求項１２又は１３に記載のレドックスフロー電池。 14. The redox flow battery of claim 12 or 13, wherein the redox flow battery has a coulombic efficiency of about 90% or more and/or an energy efficiency of about 75% or more and/or a voltage efficiency of about 80% or more at a current density of 242 mA/ cm2 . The redox flow battery described in . 前記レドックスフロー電池が、４８３ｍＡ／ｃｍ２の電流密度において、約９０％以上のクーロン効率及び／又は約６５％以上のエネルギー効率及び／又は約６５％以上の電圧効率を有する、請求項１２～１４のいずれかに記載のレドックスフロー電池。 Claims 12-14, wherein the redox flow battery has a coulombic efficiency of about 90% or more and/or an energy efficiency of about 65% or more and/or a voltage efficiency of about 65% or more at a current density of 483 mA/ cm2 . Redox flow battery according to any one of.
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