High-strength nitrogen-containing heterocyclic ring composite membrane and application thereof

Abstract

The invention discloses a high-strength nitrogen-containing heterocyclic ring composite membrane and application, the composite membrane is prepared from a compound formed by a nitrogen-containing heterocyclic ring polymer I and fibers, whiskers or particles, or the composite membrane is formed by coating fibers, whiskers or particles on a polymer membrane prepared from a nitrogen-containing heterocyclic ring polymer II; or the composite membrane is formed by coating or dipping the nitrogen-containing heterocyclic ring polymer I on the mesh cloth. By introducing the fibers, whiskers or particles and combining the nitrogen-containing heterocyclic ring polymer, the comprehensive performance of the membrane material can be remarkably improved, and the compounding method not only can enhance the mechanical strength of the composite membrane, but also can enhance the long-term mechanical stability of the composite membrane and prolong the service life of the composite membrane.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer functional materials, and in particular to a high-strength nitrogen-containing heterocyclic composite film and its application. Background Art

[0002] In the field of polymer functional materials technology, membranes are an important material widely used in electrochemical devices, energy storage and conversion systems, such as fuel cells, water electrolysis for hydrogen production, and metal-air batteries. Traditional membranes have limitations in performance and strength, particularly in stability and durability in high-temperature, high-humidity, or strong acid-base environments.

[0003] With the increasing demand for high-performance membrane materials, researchers have begun to explore the application of composite materials to improve the mechanical strength and ionic conductivity of membranes. Composite membranes combine the advantages of different materials to enhance the physical properties of membranes while maintaining good ionic conductivity.

[0004] However, existing composite membrane technology still faces some challenges, such as material selection, membrane preparation process, and long-term membrane stability. Therefore, the development of a new type of high-strength composite membrane can effectively solve these problems and has important theoretical significance and practical application value. Summary of the Invention

[0005] Based on the above-mentioned prior art, the present invention provides a class of high-strength nitrogen-containing heterocyclic composite membranes and applications. The present invention can significantly improve the comprehensive performance of membrane materials by introducing fibers, whiskers or particles and combining them with nitrogen-containing heterocyclic polymers. This composite method can not only enhance the mechanical strength of the composite membrane, but also enhance the long-term mechanical stability of the composite membrane and improve the service life of the composite membrane.

[0006] The technical solution adopted to achieve the above-mentioned purpose of the present invention is:

[0007] A high-strength nitrogen-containing heterocyclic composite membrane, wherein the composite membrane is prepared from a composite formed by a nitrogen-containing heterocyclic polymer I and fibers, whiskers or particles;

[0008] Alternatively, the composite membrane is formed by coating fibers, whiskers or particles on a polymer membrane prepared from nitrogen-containing heterocyclic polymer II;

[0009] Alternatively, the composite membrane is formed by coating or impregnating the nitrogen-containing heterocyclic polymer I on or in a mesh;

[0010] The nitrogen-containing heterocyclic polymer I includes a group shown in the following structural formula:

[0011]

[0012] The nitrogen-containing heterocyclic polymer II includes a group shown in the following structural formula:

[0013]

[0014] Among them, R1 to R 14 independently selected from hydrogen, or selected from alkyl or cycloalkyl groups having 1 to 50 carbon atoms, or selected from alkyl or cycloalkyl groups having 1 to 50 carbon atoms substituted by a deuterium atom, a hydroxyl group, an amino group, an ammonium group, a halogen group, a sulfonic acid group, a carboxylic acid group, a carbonyl group, an ether group, or selected from alkoxy groups having 1 to 50 carbon atoms, or selected from one or more combinations of ether groups having 2 to 50 carbon atoms.

[0015] The materials of the fibers, whiskers and particles are independently selected from at least one of glass, ceramics, carbon nitride, silicon nitride, boron carbide, silicon carbide, magnesium oxide, zirconium oxide, titanium oxide, basalt, aluminum oxide, graphite, mineral wool, polyethylene, polypropylene, polytetrafluoroethylene, nylon, aramid, polyetheretherketone, polyphenylene sulfide and polysulfone.

[0016] The glass is alkali-resistant glass, and the ceramic is alkali-resistant or anion-conducting ceramic.

[0017] The mass ratio of the fibers, whiskers or particles to the nitrogen-containing heterocyclic polymer I is 0.0001-0.5:1.

[0018] The mass of the fibers, whiskers or particles is 0.001%-75% of the mass of the polymer film prepared from the nitrogen-containing heterocyclic polymer II.

[0019] The material of the mesh is independently selected from at least one of polyphenylene sulfide, polysulfone, polyetheretherketone 6, polytetrafluoroethylene, polyvinylidene fluoride, polypropylene and polyethylene.

[0020] The composite film and polymer film are formed respectively by casting, casting, slit coating, blade coating, spraying or dipping.

[0021] Application of the high-strength nitrogen-containing heterocyclic composite membrane in fuel cells, water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

[0022] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0023] 1. By introducing fibers, whiskers or particles and combining them with the design of nitrogen-containing heterocyclic polymers, the composite membrane significantly improves the mechanical strength of the composite membrane, enhances the long-term mechanical stability of the composite membrane, ensures its durability in various applications, and increases the service life of the composite membrane.

[0024] 2. Under high temperature, high humidity and strong acid and alkali environment, the composite membrane shows excellent stability and durability, further expanding the application scenarios of the composite membrane and improving the service life of the composite membrane. DETAILED DESCRIPTION

[0025] The present invention is described in detail below with reference to specific embodiments.

[0026] Example 1

[0027] 1. 100 mg of polymer P1a was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. This solution was then coated onto an A4-sized polytetrafluoroethylene mesh by doctor blade coating. The mesh was then dried at 120°C for 10 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F1a with a tensile strength of 36 MPa. After immersion in a 20 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 2%, demonstrating that composite membrane F1a possesses excellent long-term mechanical stability and high acid resistance.

[0028]

[0029] 2. 100 mg of polymer P1b was dissolved in 10 mL of dimethyl sulfoxide to obtain a polymer solution. This solution was then coated onto an A4-sized PPS mesh, which was then dried at 120°C for 10 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F1b with a tensile strength of 56 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength loss was less than 1%, demonstrating that composite membrane F1b possesses excellent mechanical stability and high alkali resistance.

[0030] Example 2

[0031] 1. 500 g of polymer P1a and 50 g of glass fiber were uniformly mixed to form a composite. The composite was then dispersed in 2.5 L of dimethyl sulfoxide to obtain a composite solution. The composite solution was cast onto a PET substrate and dried at 100°C for 10 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F2a. F2a exhibited a tensile strength of 53 MPa. After immersion in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 2%, demonstrating that composite membrane F2a exhibits excellent long-term mechanical stability and high acid resistance.

[0032] 2. 100 mg of polymer P1b and 10 mg of alkali-resistant glass fiber were mixed to form a composite. The composite was then dispersed in 20 mL of N,N-dimethylformamide to obtain a composite solution. The composite solution was applied to a glass plate by doctor blade coating and dried at 100°C for 10 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F2b with a tensile strength of 57 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength of F2b decreased by less than 1%, demonstrating that composite membrane F2b possesses excellent mechanical stability and high alkali resistance.

[0033] Example 3

[0034] 1. 100 mg of polymer P2a was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The solution was then applied by knife coating onto a polysulfone (PSU) mesh. The PSU mesh was then dried at 100°C for 12 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F3a with a tensile strength of 72 MPa. After immersion in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 1.5%, demonstrating that composite membrane F3a possesses excellent long-term mechanical stability and high acid resistance.

[0035]

[0036] 2. 100 mg of polymer P2b was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. This solution was then coated onto a PSU mesh by dipping. The PSU mesh was then dried at 100°C for 12 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F3b with a tensile strength of 65 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength of F3b decreased by less than 1%, demonstrating that composite membrane F3b possesses excellent mechanical stability and high alkali resistance.

[0037] Example 4

[0038] 1. 100 mg of polymer P2a and 10 mg of polypropylene fiber were uniformly mixed to form a composite. The composite was then dispersed in 20 mL of dimethyl sulfoxide to obtain a composite solution. The composite solution was coated on a glass plate by doctor blade and dried at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F4a. F4a exhibited a tensile strength of 47 MPa. After immersion in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 3%, demonstrating that composite membrane F4a exhibits excellent long-term mechanical stability and high acid resistance.

[0039] 2. 100 mg of polymer P2b and 10 mg of polypropylene fiber were mixed to form a composite. The composite was then dispersed in 20 mL of N,N-dimethylformamide to obtain a composite solution. The composite solution was then applied to a glass plate and dried at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F4b with a tensile strength of 45 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength of F4b decreased by less than 2%, demonstrating that composite membrane F4b possesses excellent mechanical stability and high alkali resistance.

[0040] Example 5

[0041] 1. Mix 100 mg of polymer P2a and 10 mg of silicon nitride particles to form a composite. Disperse the composite in 20 mL of dimethyl sulfoxide to obtain a composite solution. Apply the composite solution to a glass plate and bake at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F5a. F5a exhibits a tensile strength of 41 MPa. After immersing F5a in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength decay is less than 3%, demonstrating that composite membrane F5a exhibits excellent long-term mechanical stability and high acid resistance.

[0042] 2. Mix 100 mg of polymer P2b and 10 mg of silicon nitride particles to form a composite. Disperse the composite in 20 mL of N,N-dimethylformamide to obtain a composite solution. Apply the composite solution to a glass plate by doctor blade coating and bake at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite film F5b with a tensile strength of 38 MPa. After immersing F5b in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength loss was less than 2%, demonstrating that composite film F5b possesses excellent mechanical stability and high alkali resistance.

[0043] Example 6

[0044] 1. Mix 100 mg of polymer P3a and 10 mg of basalt fiber to form a composite. Disperse the composite in 20 mL of N-methylpyrrolidone to obtain a composite solution. Apply the composite solution to a glass plate by doctor blade coating and bake at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F6a with a tensile strength of 62 MPa. After immersing F6a in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 1.5%, demonstrating that composite membrane F6a exhibits excellent long-term mechanical stability and high acid resistance.

[0045] 2. 100 mg of polymer P3b and 10 mg of mineral wool fiber were mixed to form a composite. The composite was then dispersed in 20 mL of N-methylpyrrolidone to obtain a composite solution. The composite solution was then applied to a glass plate by doctor blade coating and dried at 100°C for 20 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F6b with a tensile strength of 59 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength of F6b decreased by less than 1%, demonstrating excellent mechanical stability and high alkali resistance.

[0046]

[0047] Example 7

[0048] 1. 100 mg of polymer P4a was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. The polymer solution was sprayed onto a nylon mesh, which was then dried at 100°C for 12 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F7a with a tensile strength of 63 MPa. After immersion in a 5 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength of F7a decreased by less than 2%, demonstrating that composite membrane F7a possesses excellent long-term mechanical stability and high acid resistance.

[0049]

[0050] 2. 100g of polymer P4b was dissolved in 1L of dimethyl sulfoxide to obtain a polymer solution. This solution was then applied to a polyetheretherketone (PEEK) mesh by slot coating. The PEEK mesh was then dried at 120°C for 10 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F7b with a tensile strength of 57 MPa. After immersion in a 30wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength of F7b decreased by less than 3%, demonstrating that composite membrane F7b possesses excellent mechanical stability and high alkali resistance.

[0051] Example 8

[0052] 1. 100 mg of polymer P4a was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. This solution was then dip-coated onto a polytetrafluoroethylene mesh. The mesh was then dried at 100°C for 12 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F8a. F8a exhibited a tensile strength of 39 MPa. After immersion in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 3%, demonstrating that composite membrane F8a exhibits excellent long-term mechanical stability and high acid resistance.

[0053] 2. 100 mg of polymer P4b was dissolved in 20 mL of dimethyl sulfoxide to obtain a polymer solution. This solution was then applied by knife coating onto a PSU mesh. The PSS mesh was then dried at 120°C for 10 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F8b with a tensile strength of 54 MPa. After immersing F5b in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength decayed by less than 2%, demonstrating that composite membrane F8b possesses excellent mechanical stability and high alkali resistance.

[0054] Example 9

[0055] 1. 100 mg of polymer P1a and 10 mg of aramid fiber were uniformly mixed to form a composite. The composite was then dispersed in 20 mL of N-methylpyrrolidone to obtain a composite solution. The composite solution was coated on a glass plate and dried at 100°C for 20 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F9a. F9a exhibited a tensile strength of 61 MPa. After immersion in a 10 wt% aqueous sulfuric acid solution at 80°C for 2000 hours, the tensile strength loss was less than 1.5%, demonstrating that composite membrane F6a possesses excellent long-term mechanical stability and high acid resistance.

[0056] 2. 100 mg of polymer P1b and 10 mg of zirconia fiber were uniformly mixed to obtain a composite. The composite was then dispersed in 20 mL of N-methylpyrrolidone to obtain a composite solution. The composite solution was applied to a glass plate by doctor blade coating and dried at 100°C for 20 hours to obtain a high-strength nitrogen-containing heterocyclic composite membrane F9b with a tensile strength of 65 MPa. After immersion of F9b in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength loss was less than 1%, demonstrating that the composite membrane F9b possesses excellent mechanical stability and high alkali resistance.

[0057] Example 10

[0058] 1. 100 mg of polymer P3b, 10 mg of zirconium oxide particles, and 20 mg of polyetheretherketone fiber were uniformly mixed to form a composite. The composite was then dispersed in 20 mL of dimethyl sulfoxide to obtain a composite solution. The composite solution was then applied as a doctor blade onto a glass plate and dried at 100°C for 20 hours to produce a high-strength nitrogen-containing heterocyclic composite membrane F10a. F10a exhibited a tensile strength of 61 MPa. After immersion in a 30 wt% KOH aqueous solution at 80°C for 2000 hours, the tensile strength loss was less than 2%. This demonstrates that composite membrane F10a exhibits excellent mechanical stability and high alkali resistance.

Claims

1. A high-strength nitrogen-containing heterocyclic composite membrane, characterized by: The composite membrane is prepared from a composite formed by a nitrogen-containing heterocyclic polymer I and fibers, whiskers or particles; Alternatively, the composite membrane is formed by coating fibers, whiskers or particles on a polymer membrane prepared from nitrogen-containing heterocyclic polymer II; Alternatively, the composite membrane is formed by coating or impregnating the nitrogen-containing heterocyclic polymer I on or in a mesh; The nitrogen-containing heterocyclic polymer I includes a group shown in the following structural formula: The nitrogen-containing heterocyclic polymer II includes a group shown in the following structural formula: Among them, R1 to R 14 independently selected from hydrogen, or selected from alkyl or cycloalkyl groups having 1 to 50 carbon atoms, or selected from alkyl or cycloalkyl groups having 1 to 50 carbon atoms substituted by a deuterium atom, a hydroxyl group, an amino group, an ammonium group, a halogen group, a sulfonic acid group, a carboxylic acid group, a carbonyl group, an ether group, or selected from alkoxy groups having 1 to 50 carbon atoms, or selected from one or more combinations of ether groups having 2 to 50 carbon atoms.

2. The high-strength nitrogen-containing heterocyclic composite film according to claim 1, characterized in that: The materials of the fibers, whiskers and particles are independently selected from at least one of glass, ceramics, carbon nitride, silicon nitride, boron carbide, silicon carbide, magnesium oxide, zirconium oxide, titanium oxide, basalt, aluminum oxide, graphite, mineral wool, polyethylene, polypropylene, polytetrafluoroethylene, nylon, aramid, polyetheretherketone, polyphenylene sulfide and polysulfone.

3. The high-strength nitrogen-containing heterocyclic composite film according to claim 2, characterized in that: The glass is alkali-resistant glass, and the ceramic is alkali-resistant or anion-conducting ceramic.

4. The high-strength nitrogen-containing heterocyclic composite film according to claim 1, characterized in that: The mass ratio of the fibers, whiskers or particles to the nitrogen-containing heterocyclic polymer I is 0.0001-0.5:

1.

5. The high-strength nitrogen-containing heterocyclic composite film according to claim 1, characterized in that: The mass of the fibers, whiskers or particles is 0.001%-75% of the mass of the polymer film prepared from the nitrogen-containing heterocyclic polymer II.

6. The high-strength nitrogen-containing heterocyclic composite film according to claim 1, characterized in that: The material of the mesh is independently selected from at least one of polyphenylene sulfide, polysulfone, polyetheretherketone, polytetrafluoroethylene, polyvinylidene fluoride, aramid, polypropylene and polyethylene.

7. The high-strength nitrogen-containing heterocyclic composite film according to claim 1, characterized in that: The composite film and polymer film are formed respectively by casting, casting, slit coating, blade coating, spraying or dipping.

8. Use of the high-strength nitrogen-containing heterocyclic composite membrane according to claim 1 in fuel cells, water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

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