Surface-modified nanofibers, electrolyte membrane, method for producing electrolyte membrane, membrane electrode assembly and solid polymer fuel cell

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Solution Overview

Problem

Existing polymer electrolyte membranes for solid polymer fuel cells face challenges in achieving a balance between satisfactory ion conductivity and gas barrier properties, particularly in thin membranes with thicknesses of 20 µm or less, which are prone to poor proton conductivity and increased gas permeation.

Innovation Solution

The development of surface-modified nanofibers by alternately layering acidic and basic molecules on polymer nanofibers, followed by filling voids in a non-woven fabric with a matrix polymer, to create a composite electrolyte membrane that enhances ion conductivity and mechanical strength while maintaining gas barrier properties.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If the membrane thickness is reduced to lower membrane resistance, then ion conductivity is improved, but gas permeation increases and oxidation stability deteriorates

Engineering Contradiction:
Improveion conductivityVSAvoidgas permeation
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent employs a composite membrane structure combining PBI base polymer with sulfonated polyimide (SPI) and phosphoric acid. This composite approach creates a multi-functional membrane where the PBI provides mechanical strength and thermal stability, SPI contributes sulfonic acid groups for proton conduction, and phosphoric acid enhances ion conductivity. The synergistic combination allows the thin membrane to maintain low gas permeation while achieving high ion conductivity, resolving the contradiction between reduced thickness and gas barrier properties.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent introduces sulfonic acid groups locally into specific regions of the PBI matrix through SPI incorporation. This local modification creates proton-conducting pathways in specific zones without compromising the overall structural integrity and gas barrier properties of the membrane. The localized functional groups enable high ion conductivity in the conduction pathways while the bulk PBI structure maintains low gas permeation, allowing thin membrane design without sacrificing gas barrier performance.

Inventive Principle:
Principle #3Local quality

2Reliability

If the number of sulfonic acid groups is increased to improve ion conductivity, then proton conduction is enhanced, but mechanical strength decreases and membrane deformation increases

Engineering Contradiction:
Improveion conductivityVSAvoidmechanical strength
Core Design Contradiction:
ReliabilityVSStrength

Solution Approach 1:

The patent localizes sulfonic acid groups within SPI domains dispersed in the PBI matrix, rather than uniformly distributing them throughout the entire membrane. This localized concentration of ion-conducting groups creates efficient proton pathways while the surrounding PBI structure maintains mechanical strength. The spatial separation of ion conduction function (in SPI regions) and structural support function (in PBI regions) resolves the contradiction between high ion conductivity and mechanical strength.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The composite structure of PBI/SPI/phosphoric acid allows functional differentiation where SPI provides sulfonic acid groups for ion conductivity and PBI provides mechanical strength. The phosphoric acid doping further enhances ion conductivity without compromising the structural framework. This composite approach enables the membrane to achieve high proton conduction while maintaining excellent mechanical properties through the reinforcing PBI matrix.

Inventive Principle:
Principle #40Composite materials

3Reliability

If fluorine-based electrolyte materials are used to improve membrane performance, then ion conductivity is enhanced, but costs increase and long-term stability deteriorates

Engineering Contradiction:
Improveion conductivityVSAvoidlong-term stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent changes the chemical composition parameters from fluorine-based materials to hydrocarbon-based PBI/SPI composite. By adjusting the sulfonic acid group concentration through SPI content and phosphoric acid doping level, the membrane achieves high ion conductivity comparable to fluorine-based materials. The hydrocarbon-based composition inherently provides better chemical stability and resistance to degradation, resolving the contradiction between ion conductivity and long-term stability while reducing costs.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The resulting electrolyte membrane exhibits superior ion conductivity, gas barrier properties, and mechanical strength even at thicknesses of 20 µm or less, effectively addressing the limitations of previous membranes by providing a thin, stable, and efficient proton conduction pathway.

Implementation Method 1

exhibiting high ion conductivity across a broad temperature range from a low temperature of approximately -20°C to a high temperature of approximately 120°C

Methodology Applied
Scientific EffectProton conduction: Conduction (electrical)

Implementation Method 2

a matrix polymer is introduced into a nanofiber non-woven fabric

Methodology Applied
Scientific EffectPhysical filling: Physical Containment

Implementation Method 3

surface-modified nanofibers by alternately layering acidic and basic molecules on polymer nanofibers

Methodology Applied
Scientific EffectIon conduction through layered structure: Conduction (electrical)

Data Source

PatentEP3505677B1Surface-modified nanofibers, electrolyte membrane, method for producing electrolyte membrane, membrane electrode assembly and solid polymer fuel cell
Publication Date: 2024.12.18 TOKYO METROPOLITAN PUBLIC UNIVERSITY CORPORATION
  • EP3505677B1 patent drawingFigure 1~2
  • EP3505677B1 patent drawingFigure 3A~4
  • EP3505677B1 patent drawingFigure 5~6

AI summary

To develop novel nanofibers that constitute a composite electrolyte membrane and provide an electrolyte membrane which has sufficient ion conductivity (proton conductivity) and gas barrier properties even if formed into a thin membrane of 30 µm or less. [Solution] Surface-modified nanofibers which are obtained by modifying the surfaces of polymer nanofibers with an acidic substance and a basic substance, and which are characterized in that the acidic substance has proton conductivity and the basic substance increases the modification amount of the acidic substance; an electrolyte membrane which contains these nanofibers; and a method for producing a composite membrane, which comprises a step for forming a nonwoven fabric formed of polymer nanofibers, a step for subjecting the nonwoven fabric to a surface modification treatment, a step for integrating the surface-modified nanofibers and a matrix polymer by filling the pores of the nonwoven fabric with the matrix polymer, and a step for subjecting an electrolyte membrane containing the surface-modified nanofibers to a post-treatment.