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KR-20260066930-A - POLYMER ELECTROLYTE, LITHIUM METAL BATTERY INCLUDING THE SAME AND METHOD OF MANUFACTURING THEREOF

KR20260066930AKR 20260066930 AKR20260066930 AKR 20260066930AKR-20260066930-A

Abstract

A polymer electrolyte according to the present invention comprises a lithium salt; an organic solvent; a first additive; and a crosslinked polymer polymerized from a crosslinkable monomer, wherein the crosslinkable monomer is at least one of an acrylate-based monomer and a methacrylate-based monomer, and the first additive comprises a first compound represented by the following chemical formula 1: wherein L1 to L3 are each independently directly bonded or C1 to C10 alkylene groups. [Chemical Formula 1]

Inventors

  • 심민지
  • 우명희
  • 차시영
  • 고애희
  • 임홍진
  • 강인아
  • 정한맘

Assignees

  • 삼성에스디아이 주식회사

Dates

Publication Date
20260512
Application Date
20241105

Claims (20)

  1. Lithium salt; Organic solvent; First additive; and A crosslinked polymer polymerized from a crosslinkable monomer, comprising The above-mentioned crosslinkable monomer comprises at least one of an acrylate-based monomer and a methacrylate-based monomer, and The above first additive is a polymer electrolyte comprising a first compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L1 to L3 are each independently directly bonded or C1 to C10 alkylene groups.
  2. In Article 1, The above-mentioned crosslinkable monomer is a polymer electrolyte comprising a second compound represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R1 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a vinyl group.
  3. In Article 1, The above-mentioned crosslinkable monomer is a polymer electrolyte comprising a third compound represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R2 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a vinyl group.
  4. In Article 1, The above chemical formula 1 is a polymer electrolyte represented by the following chemical formula 1-1. [Chemical Formula 1-1]
  5. In Article 1, A polymer electrolyte in which the content of the first additive is 30 to 50 parts by weight per 100 parts by weight of the polymer electrolyte.
  6. In Article 1, The above-mentioned crosslinked polymer is a polymer electrolyte further comprising a fourth compound represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, R3 is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, and R 4 is a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group.
  7. In Article 1, It further includes a second additive, The second additive above is a polymer electrolyte containing nitrile groups.
  8. In Article 7, The second additive is a polymer electrolyte selected from one or more of acetonitrile, adiponitrile, succinitrile, propionitrile, phenylacetonitrile, valeronitrile, and cyclohexane carbonitrile.
  9. In Article 7, The total content of the first additive and the second additive is 30 to 50 parts by weight per 100 parts by weight of the polymer electrolyte.
  10. In Article 1, The above lithium salt is a polymer electrolyte comprising at least one of lithium hexafluorophosphate ( LiPF6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium trifluoromethanesulfonylimide (LiFSI).
  11. In Article 1, The above-mentioned cross-linked polymer has a matrix structure, and The first additive is a polymer electrolyte provided in phase separation within the matrix structure of the crosslinked polymer.
  12. A positive electrode comprising a positive current collector and a positive active material layer on the positive current collector; A cathode comprising a cathode current collector; and A polymer electrolyte between the anode and the cathode, comprising: The above polymer electrolyte is: Lithium salt; Organic solvent; First additive; and A crosslinked polymer polymerized from a crosslinkable monomer, comprising The above-mentioned crosslinkable monomer is at least one of an acrylate-based monomer and a methacrylate-based monomer, and The above first additive is a lithium metal battery comprising a first compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L1 to L3 are each independently directly bonded or C1 to C10 alkylene groups.
  13. In Article 12, A lithium metal battery in which the content of the first additive is 30 to 50 parts by weight per 100 parts by weight of the polymer electrolyte.
  14. In Article 12, It further includes a second additive, The above second additive is a lithium metal battery containing nitrile groups.
  15. In Article 12, A lithium metal battery comprising at least one selected from the group consisting of the above acrylate-based monomer, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylamide, methacrylamide, bisphenol A dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, acrylohexafluoropropylate, methylhydroxyethyl acrylate, and acrylic acid-2-hydroxyethyl ester.
  16. In Article 12, A lithium metal battery comprising at least one methacrylate monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl hydroxyethyl methacrylate, ethyl hydroxyethyl methacrylate, butyl hydroxyethyl methacrylate, 2-ethylhexyl hydroxyethyl methacrylate, bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, dibutyl methacrylate, triethylene glycol dimethacrylate, methyl acryloyl ethyl methacrylate, methacryl ethylamine, methacryloyl chloride, methacryl ethylene glycol, pentaerythritol tetramethacrylate, 2-ethylhexyl hydroxypropyl methacrylate, trimethylolpropane methacrylate, and methacrylic acid-2-hydroxyethyl ester.
  17. Forming a battery structure by arranging a negative current collector, a separator, and a positive electrode; The above-mentioned battery structure is housed in a battery case, and then an electrolyte composition is injected into the battery case; and The above electrolyte composition is cured to form a polymer electrolyte, comprising: The above electrolyte composition comprises crosslinkable monomers, an initiator, and a first additive, and A method for manufacturing a lithium metal battery comprising the first additive being a first compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L1 to L3 are each independently directly bonded or C1 to C10 alkylene groups.
  18. In Article 17, A method for manufacturing a lithium metal battery comprising at least one of a second compound represented by the following chemical formula 2 and a third compound represented by the following chemical formula 3, wherein the above-mentioned crosslinkable monomers are: [Chemical Formula 2] In the above chemical formula 2, R1 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a vinyl group, and [Chemical Formula 3] In the above chemical formula 3, R2 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a vinyl group.
  19. In Article 17, Curing the above electrolyte composition is, The above-mentioned crosslinkable monomers are polymerized to form a crosslinked polymer, the crosslinked polymer has a matrix structure; and A method for manufacturing a lithium metal battery comprising the above first additive being phase-separated within the matrix structure.
  20. In Article 17, A method for manufacturing a lithium metal battery comprising at least one of the initiator azobis(isobutyronitrile) (AIBN), azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis-(cyclohexane-1-carbonitrile) (ACHN), benzoyl peroxide (BPO), tertbutyl peroxypivalate (BPP), and ditertbutyl peroxide (DTBP).

Description

Polymer electrolyte, lithium metal battery including the same, and method of manufacturing the same The invention relates to a polymer electrolyte, a lithium metal battery containing the same, and a method for manufacturing the same. Currently commercially available lithium secondary batteries mainly use carbon-based negative electrode active materials such as graphite. Carbon-based negative electrode active materials do not change in volume during charging and discharging, so the stability of lithium secondary batteries is high. The theoretical electric capacity of graphite is small, about 372 mAh/g. Lithium metal can be used as a negative electrode active material. The theoretical electric capacity of lithium metal is approximately 3,860 mAh/g, which is larger than that of graphite. During charging and discharging, dendrites may form on the surface of lithium metal due to side reactions with the electrolyte, and the growth of these dendrites can cause a short circuit between the positive and negative electrodes. Consequently, the lifespan characteristics of lithium metal batteries containing lithium metal may be degraded. To solve the aforementioned problems, methods have been proposed in which a protective film is introduced to minimize contact between lithium and the electrolyte to reduce side reactions, or in which a gel polymer electrolyte is used to minimize the exposure of the electrolyte on the electrode surface and create a uniform flow of lithium ions throughout the electrode to suppress lithium dendrite growth by introducing the liquid electrolyte into the network of the cross-linked polymer. FIG. 1 is a conceptual diagram briefly illustrating a lithium metal battery according to embodiments of the present invention. FIG. 2 is a conceptual diagram briefly illustrating a lithium metal battery according to embodiments of the present invention. FIGS. 3 to 5 are schematic diagrams illustrating a lithium battery according to one embodiment. Figure 6 is an enlarged cross-sectional view of the M region of Figure 1. In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention are described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and various modifications can be made. The description of these embodiments is 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. In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the components are exaggerated for the effective description of the technical content. Throughout the specification, parts indicated by the same reference numeral represent the same components. Unless otherwise specified in this specification, the singular form may also include the plural. Additionally, unless otherwise specified, "A or B" may mean "comprising A, comprising B, or comprising A and B." As used herein, "comprises" and/or "comprising" do not exclude the presence or addition of one or more other components to the mentioned components. In this specification, "combination of these" may mean a mixture of components, a laminate, a composite, a copolymer, an alloy, a blend, and a reaction product, etc. In this specification, "metal" may include both metals and metalloids such as silicon and germanium in an elemental or ionic state. In this specification, "alloy" may mean a mixture of two or more metals. In this specification, "anode active material" may refer to an anode material capable of undergoing lithiation and delithiation. In this specification, "anode active material" may refer to an anode material capable of undergoing lithiation and delithiation. In this specification, "lithiation" and "to lithiate" may refer to the process of adding lithium to a positive electrode active material or a negative electrode active material. In this specification, "delithiation" and "to delithiate" may refer to the process of removing lithium from a positive electrode active material or a negative electrode active material. In this specification, "charge" and "to charge" may refer to the process of providing electrochemical energy to a battery. In this specification, "discharge" and "discharge" may refer to the process of removing electrochemical energy from a battery. In this specification, "anode" may refer to an electrode where electrochemical reduction and lithiation occur during the discharge process. In this specification, "cathode" may refer to an electrode where electrochemical oxidation and delithiation occur during the discharge process. Unless otherwise defined in this specification, the particle size