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KR-102962417-B1 - Ionic Sulfur Polymer Composite Comprising a Network Formed by Covalent Bonding Between an Ionic Crosslinking Linker and Sulfur, and Manufacturing Method thereof

KR102962417B1KR 102962417 B1KR102962417 B1KR 102962417B1KR-102962417-B1

Abstract

The present invention relates to an ionic crosslinking linker and an ionic sulfur polymer composite in which sulfur is covalently bonded to the ionic crosslinking linker. The ionic sulfur polymer composite according to the present invention is characterized by containing a large amount of sulfur.

Inventors

  • 이민재
  • 신종찬
  • 이용제
  • 채정원

Assignees

  • 국립군산대학교산학협력단

Dates

Publication Date
20260507
Application Date
20250429

Claims (12)

  1. Characterized by being prepared by the reaction of sulfur and one or more ionic crosslinkers selected from the following Chemical Formulas 1 and 2, An ionic sulfur polymer composite characterized by a sulfur content of 80 weight% or more. [Chemical Formula 1] [Chemical Formula 2] (In Chemical Formula 1 or Chemical Formula 2, R 1 is -(CH 2 ) a -, -(CH 2 CH 2 O) b - and It includes one or more connectors selected from, wherein a, b, and c are each integers from 0 or 1 to 24, and a+b+c is an integer from 1 to 60, and R₂ is hydrogen or -CH₃ , and m and n are 1, and X⁻ is Tf 2 N⁻ .
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  5. In Article 1, The above ionic sulfur polymer composite is characterized by being prepared by the reaction of sulfur with a terminal acrylic or methacrylic group contained in one or more ionic crosslinkers selected from Chemical Formula 1 and Chemical Formula 2.
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  10. By the method for manufacturing an ionic sulfur polymer composite of claim 1, The method comprises the step of mixing one or more ionic crosslinking linkers selected from Formula 1 and Formula 2, an initiator, and sulfur, and reacting at 140 to 180 ℃, and A method for manufacturing an ionic sulfur polymer composite characterized by satisfying a mixing ratio of sulfur to ionic crosslinker of 60:40 to 75:25.
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  12. In Article 10, A method for manufacturing an ionic sulfur polymer composite characterized in that the above-mentioned initiator is a disulfide-based initiator.

Description

Ionic Sulfur Polymer Composite Comprising a Network Formed by Covalent Bonding Between an Ionic Crosslinking Linker and Sulfur, and Manufacturing Method thereof The present invention relates to an ionic sulfur polymer composite comprising an ionic crosslinking linker, a network in which sulfur is covalently bonded to the ionic crosslinking linker, and a method for manufacturing the same. Sulfur is one of the abundant resources on Earth and has been utilized as a key active material in lithium-sulfur batteries due to its very high theoretical electric capacity of 1672 mAh/g. However, lithium-sulfur batteries have several limitations in commercialization. In lithium-sulfur batteries, polysulfides are generated during the discharge process. These generated polysulfides readily dissolve in the liquid electrolyte, migrate to the negative electrode, and are subsequently oxidized, which can trigger a polysulfide shuttle effect circulating within the cell. This polysulfide shuttle effect can lead to various problems, such as reduced charge/discharge efficiency, capacity loss, and shortened lifespan. To prevent these issues, attempts have been made to immobilize polysulfides by mixing ionic liquids into the positive electrode; however, problems regarding reduced long-term reliability due to phase separation and leakage of the ionic liquids have been reported. Meanwhile, conventional sulfur-polymer composites have the problem that sulfur is easily leached from the polymer material because it is physically mixed or fixed through non-covalent bond-based interactions, and long-term instability may occur if sulfur is lost due to such leaching. Accordingly, there is a need to develop a material that overcomes conventional problems to efficiently immobilize polysulfides while ensuring long-term reliability by preventing sulfur leaching through covalent bonding with sulfur. Figure 1 briefly illustrates the process of manufacturing an ionic sulfur polymer according to one embodiment of the present invention. Figures 2 and 3 show the 1H NMR analysis results of an ionic crosslinking linker according to one embodiment of the present invention. Figure 4 shows the results of analyzing an ionic sulfur polymer prepared according to one embodiment of the present invention using FT-IR (Fourier Transform Infrared Spectroscopy). Figure 5 shows the thermogravimetric analysis results of an ionic sulfur polymer prepared according to an embodiment of the present invention. Figure 6 shows the results of differential scanning calorimetry (DSC) analysis of an ionic sulfur polymer prepared according to an embodiment of the present invention. The advantages and features of the embodiments of the present invention, and the methods for achieving them, will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but may be implemented in various different forms. These embodiments are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. Throughout the specification, the same reference numerals refer to the same components. In describing the embodiments of the present invention, specific descriptions of known functions or configurations will be omitted if it is determined that such detailed descriptions could unnecessarily obscure the essence of the invention. Furthermore, the terms described below are defined in consideration of their functions in the embodiments of the present invention, and these definitions may vary depending on the intentions or practices of the user or operator. Therefore, such definitions should be based on the content throughout this specification. The ionic crosslinker according to the present invention is characterized by satisfying the following chemical formula 1 or the following chemical formula 2. [Chemical Formula 1] [Chemical Formula 2] In Chemical Formula 1 or Chemical Formula 2, R 1 is -(CH 2 ) a -, -(CH 2 CH 2 O) b - and It comprises one or more linkers selected from, wherein a, b and c are each integers from 0 or 1 to 24, a+b+c are integers from 2 to 36, R2 is hydrogen or -CH3 , m and n are each 1, 2 or 3 , X- is any one selected from Cl- , Br- , I- , NO3- , CF3CO2- , BF4- , PF6- , BPh4- , Tf2N- , SbF6- , AsF6- , ClO4- , CF3SO3- , ( FSO2 ) 2N- and ( CF3SO2 ) 2N- , and in BPh4- , Ph is a phenyl group . The ionic crosslinker according to the present invention satisfies Chemical Formula 1 or Chemical Formula 2, and has the characteristic that the polymer composite produced when crosslinked with sulfur can secure a high sulfur content. Preferably , in the above chemical formula 1 , X- may be one or more selected from CF₃SO₃- , ( FSO₂ ) ₂N- , and ( CF₃SO₂ ) ₂N- , and by using such X- , thermal stability can be