Electrically conducting poly(pyrazoles)
Inventors
Martin, Brett D. • Giles, Ian D. • Naciri, Jawad • Charles, Paul T. • Trammell, Scott A. • Deschamps, Jeffrey R. • DePriest, Jeffrey C.
Assignees
Publication Number
US-12291639-B2
Publication Date
2025-05-06
Expiration Date
2038-12-12
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Abstract
This disclosure concerns electrically conducting poly(pyrazoles). The concept of oligomerizing and polymerizing substituted aminopyrazole derivatives combined with a monomer activation procedure involving base-mediated conversion of the protonated pyrazole ring nitrogen to amine salt was developed. This disclosure concerns the specific chemistries needed for the synthesis of a pyrazole monomer used in the polymer synthesis. The procedure used for blending the novel polypyrazoles with other compounds needed for construction of solar cells for testing was developed. This disclosure concerns the concept of using these types of heteroatom-rich, electron-deficient oligomers or polymers as n-dopable or p-dopable electron acceptors in photovoltaic cells. This disclosure concerns synthesizing the starting monomer compounds and polypyrazoles.
Core Innovation
This disclosure concerns electrically conducting poly(pyrazoles), specifically the development of the chemical methods for oligomerizing and polymerizing substituted aminopyrazole derivatives. A key aspect of the innovation is the monomer activation procedure involving base-mediated conversion of the protonated pyrazole ring nitrogen to an amine salt, enabling the formation of the poly(pyrazoles).
The invention also includes the specific chemistry required to synthesize pyrazole monomers used in these polymer syntheses and the procedures for blending the novel polypyrazoles with other components necessary to construct solar cells for testing. Furthermore, these heteroatom-rich, electron-deficient oligomers or polymers are utilized as n-dopable or p-dopable electron acceptors in photovoltaic cells.
The problem being addressed is the need for renewable energy sources which are cost-effective and efficient. Conventional silicon-based solar cells are efficient but costly to manufacture, while existing polymer-based solar cells tend to be expensive to synthesize and often have low efficiencies. This invention aims to create polypyrazoles that can be produced simply and inexpensively from low-cost starting materials, while delivering higher electron transport rates, versatile redox behavior, and improved photovoltaic efficiency at a lower cost than commercially available polymers.
Claims Coverage
The patent includes one independent claim which focuses on a method of synthesizing a specific electrically conducting poly(pyrazole) and its key synthesis parameters.
Method of making poly(3-aminopyrazole-4-carbonitrile)
A stepwise procedure comprising adding water and potassium hydroxide to a flask, dissolving potassium hydroxide, adding 3-aminopyrazole-4-carbonitrile and heating to dissolve it, followed by adding sodium or potassium persulfate to form an electrically conducting poly(pyrazole) specifically polymer length up to a 15-mer.
Temperature and complex formation during synthesis
The dissolving of 3-aminopyrazole-4-carbonitrile occurs at approximately 70°C, enabling formation of a 1:1 molar complex between potassium ions and the deprotonated nitrogen atom of the pyrazole ring.
Molar ratio of oxidant to monomer
Use of sodium or potassium persulfate added gradually to achieve a final molar ratio of 1.2 moles persulfate to 1.0 moles 3-aminopyrazole-4-carbonitrile during the polymerization step.
The claim covers a controlled chemical synthesis method for poly(3-aminopyrazole-4-carbonitrile) involving specific reaction conditions—temperature, complex formation between potassium and pyrazole nitrogen, and oxidant ratio—resulting in an electrically conducting polymer with defined chain length.
Stated Advantages
The invention enables increases in solar cell efficiency compared to commercially available polymers.
It costs significantly less to synthesize than virtually all commercially available solar cell polymers, with starting materials at approximately $2.00 per gram in bulk.
High electron transport rates and versatile redox behavior of the polypyrazoles facilitate easy and rapid production and investigation of derivatives.
Solar cells constructed using these polymers generate photocurrents up to 5.1 times higher than similar cells made using commercially available polymers.
The responsivity of solar cells using these polymers is 2.9 to 70-fold higher than cells using other known polymers.
Polypyrazoles exhibit higher conductivity than related oligomers, enhancing their effectiveness as electron donors or acceptors.
Documented Applications
Use of electrically conducting poly(pyrazoles) as electron acceptors or donors in organic photovoltaic solar cells.
Blending of polypyrazoles with other compounds to construct solar cells for testing and performance evaluation.
Employment of polypyrazole-based polymers in solar cells to achieve higher photocurrent generation than conventional polymer combinations.
Use of heteroatom-rich, electron-deficient polymers as n-dopable or p-dopable electron acceptors in photovoltaic devices.
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