JPWO2020060857A5

JPWO2020060857A5 -

Info

Publication number: JPWO2020060857A5
Application number: JP2021514415A
Authority: JP
Publication date: 2022-09-12

Description

上記の目的は、１つの実施形態において、ＰＢＩフィルムを製造するための方法を提供することによって、本開示に従って達成される。この方法は、ＰＰＡプロセスを介してゲルＰＢＩ膜を形成すること、ゲルＰＢＩ膜をリンスすること、ゲルＰＢＩ膜を、少なくともＸ－Ｙ面方向に拘束すること、リンスしたゲルＰＢＩ膜を乾燥すること、を含んでよく、方法全体を通して有機溶媒が用いられない。さらに、ゲルＰＢＩ膜は、洗浄液でリンスされてもよい。なおさらに、リンスしたゲルＰＢＩ膜は、少なくとも１つの基材に適用されてもよい。なおさらに、リンスしたゲルＰＢＩ膜は、多孔質基材に適用されてもよい。なおさらに、ＰＢＩ膜の拘束は、ＰＢＩ膜に対して、Ｘ、Ｙ、又はＺ面方向に張力を掛けてよい。なおさらに、ＰＢＩフィルムは、連続形成プロセスを介して形成されてよい。なおさらに、ＰＢＩフィルムのポリベンズイミダゾールは、以下の繰り返し単位：

のうちの１若しくは複数、又はこれらのいずれかの組み合わせを含み、式中、ｎ及びｍは、各々独立して、１以上、約１０以上、又は約１００以上である。なおさらに、この方法
は、フィルムを形成することができる。 The above objectives are achieved in accordance with the present disclosure, in one embodiment, by providing a method for manufacturing a PBI film. The method includes forming a gel PBI film via a PPA process, rinsing the gel PBI film, constraining the gel PBI film in at least the XY plane, and drying the rinsed gel PBI film. , and no organic solvent is used throughout the process. Additionally, the gel-PBI membrane may be rinsed with a wash solution. Still further, the rinsed gel PBI film may be applied to at least one substrate. Still further, the rinsed gel PBI membrane may be applied to the porous substrate. Still further, the constraint of the PBI membrane may apply tension to the PBI membrane in the X, Y, or Z plane directions. Still further, the PBI film may be formed via a continuous forming process. Still further, the polybenzimidazole of the PBI film has the following repeat units:

or any combination thereof, wherein n and m are each independently 1 or greater, about 10 or greater, or about 100 or greater. Still further, the method can form a film.

さらなる実施形態では、ＰＢＩフィルムが形成される。フィルムは、ＰＰＡプロセスを介してゲルＰＢＩ膜を形成すること、ゲルＰＢＩ膜をリンスすること、ゲルＰＢＩ膜を、少なくともＸ－Ｙ面方向に拘束すること、リンスしたゲルＰＢＩ膜を乾燥してＰＢＩフィルムを形成すること、を含んでよく、フィルムを形成するための方法全体を通して有機溶媒が用いられない。なおさらに、フィルムは、コーティングとして用いられてよい。なおさらに、フィルムは、５～１５０μｍの厚さを有していてよい。なおさらに、フィルムは、少なくとも２５ＭＰａの破断応力を有する。なおさらに、ＰＢＩフィルムのポリベンズイミダゾールは、以下の繰り返し単位：

のうちの１若しくは複数、又はこれらのいずれかの組み合わせを含んでよく、式中、ｎ及びｍは、各々独立して、１以上、約１０以上、又は約１００以上である。なおさらに、フ
ィルムは、有機溶媒に実質的に不溶なＰＢＩポリマーを含んでよい。なおさらに、フィルムは、有機若しくは無機の酸又は塩基を吸収して、イオン伝導性膜を形成してもよい。 In a further embodiment, a PBI film is formed. The film is formed by forming a gel PBI film via a PPA process, rinsing the gel PBI film, constraining the gel PBI film in at least the XY plane, drying the rinsed gel PBI film to form a PBI film. forming a film, wherein no organic solvent is used throughout the process for forming the film. Still further, the film may be used as a coating. Still further, the film may have a thickness of 5-150 μm. Still further, the film has a breaking stress of at least 25 MPa. Still further, the polybenzimidazole of the PBI film has the following repeat units:

or any combination thereof, wherein n and m are each independently 1 or greater, about 10 or greater, or about 100 or greater. Still further, the film may comprise a PBI polymer that is substantially insoluble in organic solvents. Still further, the film may absorb organic or inorganic acids or bases to form an ion-conducting membrane.

ＰＢＩゲル膜の例示的なＰＢＩポリマー繰り返し単位としては、限定されないが：

又はこれらのいずれかの組み合わせを挙げることができ、式中、いくつかの実施形態では、ｎ及びｍは、各々独立して、１以上、約１０以上、又は約１００以上である。 Exemplary PBI polymer repeat units for PBI gel films include, but are not limited to:

or any combination thereof, wherein in some embodiments, n and m are each independently 1 or greater, about 10 or greater, or about 100 or greater.

Claims

A method of making a polybenzimidazole (PBI) film comprising:
at least one aromatic or heteroaromatic tetraamino compound and at least one aromatic or heteroaromatic polycarboxylic acid or its ester, anhydride, or acid chloride, or at least one aromatic or heteroaromatic diaminocarboxylic acid; polymerizing an acid and in the presence of a polyphosphoric acid solvent to form a PBI polymer solution comprising a PBI polymer in a solvent comprising said polyphosphoric acid solvent;
treating the PBI polymer solution to form a membrane precursor;
hydrolyzing at least a portion of polyphosphoric acid to produce phosphoric acid and water, thereby causing a sol-gel transition of said PBI polymer solution and solidification of said PBI polymer to form a PBI gel film;
removing the phosphoric acid from the PBI gel film by rinsing the PBI gel film;
drying the rinsed PBI gel film while confined to the porous substrate to obtain a PBI film;
A manufacturing method, including:

2. The method of claim 1, wherein the PBI gel film is rinsed with a series of washes.

3. The method of claim 1 or 2, wherein the rinsed PBI gel film is dried while constrained between the porous substrate and another substrate.

4. The method of claim 3, wherein said another substrate is porous.

A method according to any one of claims 1 to 4, which is a continuous process.

The method of any one of claims 1-5, further comprising allowing the PBI film to absorb an electrolyte.

7. The method of claim 6, wherein said electrolyte comprises sulfuric acid.

A process according to any one of claims 1 to 7, wherein said polymerisation is carried out at a temperature of 220°C or less.

The method of any one of claims 1-8, wherein the PBI polymer solution formed by the polymerization has an intrinsic viscosity of 0.8 dL/g or more.

A dry PBI film having a breaking stress of 25 MPa or more.

A repeating unit with a PBI of:

wherein n and m are each independently 1 or more.

VOSO _４4 Transmittance is 2.60×10 ^－９-9 cm ^２2 /s ~ 4.89 x 10 ^－７-7 cm ^２2 /s.

A dry PBI film according to any one of claims 10 to 12, which is crosslinked.

A redox flow battery comprising a PBI film in which a supporting electrolyte is absorbed in the dry PBI film of claim 10 .

15. The redox flow battery of claim 14, wherein said supporting electrolyte comprises sulfuric acid.

The redox flow battery according to claim 14 or 15, wherein the supporting electrolyte has a concentration of 0.1M to 25M.

The redox flow battery according to any one of claims 14-16, which is a vanadium redox flow battery.

100 mA/cm ^２2 ~450mA/cm ^２2 18. The redox flow battery according to any one of claims 14 to 17, exhibiting a coulombic efficiency of 98% or more under a battery cycling current density of .