Cross-Linked Perfluorinated Polymer Electrolyte for Fuel Cells

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Solution Overview

Problem

Current proton exchange membrane (PEM) fuel cells face challenges in operating at high temperatures and low relative humidity conditions due to the limitations of existing perfluorinated sulfonic acid (PFSA) polymers, which become water-soluble when attempting to decrease their equivalent weight (EW) below a certain threshold, compromising their suitability for PEM applications.

Innovation Solution

A method is developed to fabricate water-insoluble, low EW perfluorinated polymer electrolyte materials by converting sulfonyl fluoride groups to sulfonamide and then to sulfonimide groups, creating a 3-dimensional cross-linked structure that maintains proton conductivity while preventing water solubility, using a process involving free radical polymerization, amidification with ammonia, and gelation with sulfonyl fluoride-containing agents.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If TFE content is decreased to increase proton conductivity, then conductivity is improved, but the polymer becomes water soluble

Engineering Contradiction:
Improveproton conductivityVSAvoidwater solubility
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent creates a composite structure by cross-linking linear PFSA polymer chains through sulfonimide groups. This forms a three-dimensional network that combines the high proton conductivity of low-EW PFSA polymers with the water insolubility provided by the cross-linked gel structure, effectively resolving the contradiction between conductivity and water stability

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention transitions from a linear one-dimensional polymer structure to a three-dimensional cross-linked network structure. This dimensional change allows the polymer to maintain low equivalent weight for high conductivity while the spatial network prevents water solubility by creating a gel structure that traps the polymer chains

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

2Reliability

If TFE content is decreased to achieve lower EW, then proton conductivity increases, but mechanical properties deteriorate

Engineering Contradiction:
Improveproton conductivityVSAvoidmechanical properties
Core Design Contradiction:
ReliabilityVSStrength

Solution Approach 1:

The cross-linked gel structure acts as a reinforcing network within the polymer matrix, providing mechanical strength to compensate for the reduced TFE content. This composite approach allows the material to simultaneously achieve high proton conductivity and adequate mechanical properties

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

By forming a three-dimensional cross-linked network, the patent creates additional structural support in multiple dimensions. This spatial network provides mechanical integrity to the low-EW polymer that would otherwise be too flexible or weak due to reduced TFE content

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

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 polymer electrolyte materials exhibit high proton conductivity at high temperatures and low relative humidity conditions while maintaining mechanical and chemical stability, making them suitable for PEM fuel cells without becoming water-soluble.

Implementation Method 1

The perfluorinated polymer resin is exposed to ammonia gas to convert the sulfonyl fluoride groups to sulfonamide groups

Methodology Applied
Scientific EffectChemical reaction (amidification): Chemical Bonding

Implementation Method 2

The perfluorinated polymer in sulfonamide form is contacted with chemical agent(s) to convert sulfonamide to sulfonimide in a 3- dimensional cross-linked structure

Methodology Applied
Scientific EffectChemical reaction (gelation): Chemical Bonding

Implementation Method 3

PFSA polymer is usually prepared by free radical copolymerization of tetrafluoroethylene (TFE) and per-fluorinated (per-F) vinyl ether monomer

Methodology Applied
Scientific EffectFree radical polymerization: Chemical Bonding

Implementation Method 4

Each side chain terminates in a sulfonic acid group that works as a proton exchange site to transfer or conduct protons between the anode and cathode electrodes

Methodology Applied
Scientific EffectProton conduction: Conduction (electrical)

Data Source

PatentEP2946426B1Method of fabricating an electrolyte material
Publication Date: 2020.04.22 AUDI AG
  • EP2946426B1 patent drawingFigure 1
  • EP2946426B1 patent drawing

AI summary

A method of fabricating low EW, water insoluble electrolyte materials includes providing a perfluorinated polymer resin that includes perfluorinated carbon-carbon backbone chain and sulfonyl fluoride ended perfluorinated side chains, extending from the perfluorinated backbone chains via an ether linkage, exposing the perfluorinated polymer resin to ammonia gas to convert the sulfonyl fluoride groups to sulfonamide groups, -SO2-NH2, which reacts with sulfonyl fluoride containing chemical agent(s) to form sulfonimide groups, and at the same time, generates low EW, 3-dimensional cross-linked, water-insoluble perfluorinated polymer electrolyte materials.