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CN-121983608-A - Composite porous substrate film and preparation method thereof

CN121983608ACN 121983608 ACN121983608 ACN 121983608ACN-121983608-A

Abstract

The invention discloses a composite porous substrate film and a preparation method thereof, the composite porous substrate membrane comprises a porous sulfonated resin substrate membrane and a hydrogen bond donor layer at least partially filled in pores of the porous sulfonated resin substrate membrane. The composite porous substrate film and the functional resin material provided by the invention have better interface compatibility and interface binding force, reduce layering risk and provide an application foundation for long-time operation.

Inventors

  • YANG ZEZHOU
  • WANG YANJIE
  • SUN HUA
  • LIN XIAOYIN
  • GAO LONGHUI

Assignees

  • 深圳市科新创界新材料有限公司

Dates

Publication Date
20260505
Application Date
20260114

Claims (10)

  1. 1. A composite porous base membrane comprising a porous sulfonated resin base membrane and a hydrogen bond donor layer at least partially filled within pores of the porous sulfonated resin base membrane.
  2. 2. The composite porous substrate film according to claim 1, wherein the hydrogen bond donor layer has a thickness of 100 nm a or less; preferably, the thickness of the hydrogen bond donor layer is equal to or greater than 20 nm.
  3. 3. The composite porous base film according to claim 1 or 2, wherein the mass percentage of the hydrogen bond donor layer is 0.5 to 10%, preferably 1 to 5%, based on 100% of the total mass of the composite porous base film.
  4. 4. The composite porous substrate membrane according to any one of claims 1 to 3, wherein the composition of the hydrogen bond donor layer comprises at least one of a small molecule polyol, a small molecule polyamine, a saccharide and derivative, and a polymer-based hydrogen bond donor material; Preferably, the small molecule polyol comprises glycerol and/or xylitol; preferably, the small molecule polyamine comprises ethylenediamine and/or hexamethylenediamine; preferably, the saccharides and derivatives comprise maltitol; preferably, the polymeric hydrogen bond donor material comprises at least one of polyglycerol, polyvinyl alcohol or polyamide.
  5. 5. The composite porous base film according to any one of claims 1 to 4, wherein the porosity of the porous sulfonated resin base film is 30 to 90%, preferably 40 to 70%; and/or the average pore diameter of the porous sulfonated resin substrate film is 100-1000 nm, preferably 200-500 nm; And/or the thickness of the porous sulfonated resin base film is 5-50 μm, preferably 10-40 μm.
  6. 6. The composite porous base membrane according to any one of claims 1 to 5, wherein the constituent components of the porous sulfonated resin base membrane include a sulfonated resin material and a crosslinking agent; Preferably, the sulfonated resin comprises at least one of sulfonated polysulfone material, sulfonated polyethersulfone material, sulfonated polyarylethersulfone material, sulfonated polyamide material, sulfonated polyimide material, sulfonated polyetherimide material, sulfonated polyetheretherketone material, sulfonated polyaryletherketone material, sulfonated polyphenylene sulfide material, sulfonated polyphenylene ether material, sulfonated polybenzimidazole material, sulfonated polyphosphazene material, perfluorosulfonic acid, sulfonated polytetrafluoroethylene or sulfonated polyvinylidene fluoride; Preferably, the sulfonation degree of the sulfonated resin is 10-30%, preferably 15-30%; Preferably, the cross-linking agent comprises at least one of epoxy, aldehyde, bismaleimide or organosilicon, and more preferably the cross-linking agent comprises any one or a combination of at least two of polyethylene glycol diglycidyl ether, glutaraldehyde, bismaleimide or 3-aminopropyl triethoxysilane; preferably, the mass ratio of the sulfonated resin material to the crosslinking agent is 100 (0.5-5), and more preferably 100 (1-3).
  7. 7. A method for preparing the composite porous substrate film according to any one of claims 1 to 6, comprising: and setting a solution containing a hydrogen bond donor material on the porous sulfonated resin substrate film, and drying to obtain the composite porous substrate film.
  8. 8. The preparation method according to claim 7, wherein the concentration of the solution containing the hydrogen bond donor material is 1-20 wt%, preferably 3-15 wt%; Preferably, the method of setting comprises dipping or coating; preferably, the impregnation is performed under vacuum conditions, and more preferably, the temperature of the impregnation is 30-50 ℃ and the time is 0.5-2 hours.
  9. 9. The production method according to claim 7 or 8, characterized in that the production method of the porous sulfonated resin base film comprises: the sulfonated resin slurry containing the pore-forming agent is coated, dried and the pore-forming agent is removed to obtain a porous membrane; and (3) soaking the porous membrane in a cross-linking agent solution and performing a cross-linking reaction to obtain the porous sulfonated resin substrate membrane.
  10. 10. An ion exchange membrane comprising the composite porous base membrane of any one of claims 1 to 6 and a functional resin material layer provided on a surface of at least one side of the hydrogen bond donor layer.

Description

Composite porous substrate film and preparation method thereof Technical Field The invention belongs to the technical field of ion exchange membranes, and particularly relates to a composite porous substrate membrane and a preparation method thereof. Background The following statements are merely to provide background information related to the present disclosure and may not necessarily constitute prior art. The ion exchange membrane is one of important components in fuel cells, flow batteries and the like, needs to have the dual functions of physical isolation and ion conduction, is one of key technologies for restricting the development and the application of the batteries although not participating in electrochemical reaction, has direct relation with the ion exchange membrane in the application performance, the operation stability and the like of the fuel cells and the flow batteries, and plays an important role in improving the comprehensive performance of the batteries by improving the performance of the ion exchange membrane. Currently, in order to improve the hydrophilicity of an ion exchange membrane, general practices include introducing a hydrophilic layer on the surface, but the hydrophilic layer is easy to fall off during long-time application, resulting in reduced battery performance and safety risks. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a composite porous substrate film and a preparation method thereof. In order to achieve the aim of the invention, the invention adopts the following technical scheme: in a first aspect, the present invention provides a composite porous base membrane comprising a porous sulfonated resin base membrane and a hydrogen bond donor layer at least partially filled within the pores of the porous sulfonated resin base membrane. In a second aspect, the present invention provides a method for preparing a composite porous substrate membrane according to the first aspect, the method comprising: and setting a solution containing a hydrogen bond donor material on the porous sulfonated resin substrate film, and drying to obtain the composite porous substrate film. In a third aspect, an ion exchange membrane comprises the composite porous base membrane of the first aspect and a functional resin material layer disposed on a surface of at least one side of the hydrogen bond donor layer. According to the invention, the sulfonated resin base film is introduced, the sulfonic acid group carried by the sulfonated resin can increase the hydrophilicity of the base film, so that the solution infiltration of the functional resin material is facilitated, the compatibility between the base film and the functional resin material is improved, and meanwhile, the sulfonic acid group can form a hydrogen bond effect with the functional resin material, so that the binding force between the two is improved; On the basis of the invention, a hydrogen bond donor layer is introduced, and the hydrogen bond donor layer contains a plurality of hydrogen bond donor groups (such as hydroxyl groups and/or amino groups) which can form hydrogen bond action between the sulfonated resin base film and the functional resin material layer, so as to play a role of acting as an adhesive between the base film and the functional resin material layer, and remarkably improve the interfacial binding force between the base film and the functional resin material layer; Therefore, the composite porous substrate membrane provided by the invention has better hydrophilicity, and meanwhile, the interface binding force between the composite porous substrate membrane and the functional resin material layer is higher, so that the risk of layering is reduced, and an application foundation is provided for long-time operation. Detailed Description The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention. The terms "first," "second," and the like, as used herein, are used for distinguishing between different objects and not for describing a particular sequential or sub-relationship, unless otherwise indicated. Unless otherwise indicated, terms used in the present application have well-known meanings commonly understood by those skilled in the art. Unless otherwise indicated, the values of the parameters mentioned in the present application may be determined by various test methods commonly used in the art, for example, may be determined acc