Polyelectrolyte Single Crystal Proton Conductivity via Supramolecular Assembly
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Solution Overview
Problem
The synthesis of ionic polymeric or polyelectrolyte single crystals (PSCs) is challenging due to strong Coulombic repulsive interactions during the self-assembly of cationic or anionic appendages from ionic monomers, making topochemical synthesis elusive in all-solid-state batteries and fuel cells.
Innovation Solution
A supramolecular composition comprising an ordered arrangement of organic ions with polymerizable arms and counterions, where the arms react through noncovalent interactions to form polyelectrolyte polymers and crystals via topochemical photopolymerization, allowing for the formation of macroscopically sized single-crystalline polymers with high crystallinity.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Manufacturing precision
If ionic monomers undergo self-assembly to form polyelectrolyte single crystals, then the desired ordered crystalline structure is achieved, but strong Coulombic repulsive interactions prevent successful topochemical synthesis
Solution Approach 1:
The patent applies preliminary action by first forming a supramolecular complex between the ionic monomer and neutral host molecules in a controlled manner before initiating polymerization. This pre-organization of monomers into ordered supramolecular assemblies precedes the topochemical reaction, allowing the crystalline structure to be established before the polymerization process begins, thereby overcoming the Coulombic repulsion that would otherwise prevent ordered assembly.
Solution Approach 2:
The patent employs an intermediary approach by introducing neutral host molecules (such as crown ethers or cycloextrins) that act as mediators between the ionic monomers. These host molecules form supramolecular complexes with the ionic monomers, shielding the charged groups and reducing Coulombic repulsion. This intermediary structure enables the ionic monomers to self-assemble into ordered crystalline arrays that can subsequently undergo topochemical polymerization.
2Volume of moving object
If topochemical photopolymerization is applied to supramolecular compositions, then macroscopically sized single-crystalline polymers are formed, but precise control over composition and structure is required
Solution Approach 1:
The patent applies local quality by designing the supramolecular composition with specific local interactions between host and guest molecules. The neutral host molecules are selected to have complementary binding sites that locally interact with specific functional groups on the ionic monomers. This local recognition and binding ensures precise control over the orientation and positioning of monomers within the supramolecular assembly, which in turn controls the composition and structure of the resulting polymer crystal while allowing macroscopic size.
3Stability of the object's composition
If self-assembly of cationic or anionic appendages occurs, then polyelectrolyte structure forms, but strong Coulombic repulsive interactions hinder the process
Solution Approach 1:
The patent employs neutral host molecules as intermediaries that form supramolecular complexes with the charged appendages. These host molecules physically shield the ionic groups, reducing the strength of Coulombic repulsive interactions. This mediation allows the cationic or anionic appendages to self-assemble into stable polyelectrolyte structures without being prevented by excessive electrostatic repulsion.
Solution Approach 2:
The patent creates a composite supramolecular system combining neutral host molecules with ionic monomers. This composite structure leverages the properties of both components: the neutral host provides structural organization and shields electrostatic interactions, while the ionic monomer provides the desired polyelectrolyte functionality. The resulting composite supramolecular composition enables stable structure formation despite Coulombic repulsion.
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
This approach enables the quantitative synthesis of polyelectrolyte single crystals with precise control over composition and structure, resulting in materials with high proton conductivity and mechanical stability, suitable for applications in proton-conducting materials.
Implementation Method 1
the arms react through noncovalent interactions to form polyelectrolyte polymers and crystals
Implementation Method 2
form polyelectrolyte polymers and crystals via topochemical photopolymerization
Implementation Method 3
Polyelectrolyte Single Crystal for Proton Conductivity
Data Source
AI summary
Disclosed herein are supramolecular compositions, polyelectrolyte polymers, and polyelectrolyte crystals for proton conductivity prepared from organic ions, the organic ion comprising a molecular hub and arms extending therefrom, wherein the arms comprise a polymerizable moiety. Also disclosed herein are method of making and using the compositions, polymers, and crystals described herein.