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KR-102960688-B1 - ADDITIVE AND CROSSLINKER, NONAQUEOUS LIQUID ELECTROLYTE AND GELL-TYPE OR SOLID POLYMER ELECTROLYTE USING THE SAME

KR102960688B1KR 102960688 B1KR102960688 B1KR 102960688B1KR-102960688-B1

Abstract

The present invention relates to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, and more specifically, to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, which improves the electrochemical stability, thermal stability, flame retardancy, and lifespan of an alkali metal battery using an electrolyte to which the same is added, and is composed of a siloxane compound comprising an amine group substituted with an electron-withdrawing functional group, or an isocyanate group, a boronate pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, or a diethyl phosphate group.

Inventors

  • 이주영
  • 이주현

Assignees

  • 자인에너지 주식회사

Dates

Publication Date
20260507
Application Date
20241128

Claims (11)

  1. Compounds represented by any one of the following chemical formulas 1 to 3: [Chemical Formula 1] In the above chemical formula 1, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethylphosphate group, and an oxypyrrolidin-2,5-dione group; R₂ and R₃ are hydrogen atoms or -COCF₃ , where either R₂ or R₃ is a hydrogen atom, and R 4 is a methyl group; n is an integer from 1 to 1000, o is 0, and the sum of n and o is not 0, and the compound of the above chemical formula 1 can act as an additive in an electrolyte. [Chemical Formula 2] In the above chemical formula 2, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethylphosphate group, and an oxypyrrolidin-2,5-dione group; R₂ and R₃ are hydrogen atoms or -COCF₃ , where either R₂ or R₃ is a hydrogen atom, and R 4 is a methyl group; n is an integer from 1 to 1000, o is 0, and the sum of n and o is not 0, and the compound of Chemical Formula 2 above can act as an additive in an electrolyte. [Chemical Formula 3] In the above chemical formula 3, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a boronic acid pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethyl phosphate group, and an oxypyrrolidin-2,5-dione group; R₂ and R₃ are each independently a hydrogen atom or an electron-withdrawing functional group selected from -SO₂CF₃ , -SO₂CH₂F , -SO₂CH₃CH₂F , -SO₂CHF₂ , -CN , -F, -Cl, -COCF₃ , BF₃K , and -SO₂CN , and R₂ and R₃ do not simultaneously become hydrogen atoms, and R 4 is a hydrogen atom or a methyl group; n and o are integers from 0 to 1000, respectively, and the sum of n and o is not 0; R 5 is -CH 2 -, or And; p is an integer from 0 to 100; R6 is a hydrogen atom or a methyl group, and the compound of Chemical Formula 3 can act as an additive or crosslinking agent in the electrolyte.
  2. In Article 1, The compound represented by the above chemical formula 1 is any one selected from C4-4NCO; C4-4TB; C4-4TH; C4-4THP; C4-4CH; C4-4OPDO; and C4-4PS; The compound represented by the above chemical formula 2 is any one selected from L4-4NCO; L4-4TB; L4-4TH; L4-4THP; L4-4CH; L4-4OPDO; L4-4PS; A compound represented by the above chemical formula 3 is characterized by being selected from Ta-4NCO; Ta-4TMDOB; Ta-4TB; Ta-4TH; Ta-4THP; Ta-4CH; Ta-4OPDO; Ta-4PS; Ta-4TFAc; and Ta-4(di-TFAc).
  3. An electrolyte comprising a compound represented by any one of chemical formulas 1 to 3 of claim 1.
  4. In Paragraph 3, The above electrolyte is characterized by being selected from the group consisting of non-aqueous liquid electrolytes, gel-type polymer electrolytes, and solid polymer electrolytes.
  5. (i) as an additive, a compound represented by any one of the chemical formulas 1 to 3 of claim 1; (ii) non-aqueous solvents; and (iii) A non-aqueous liquid electrolyte characterized by containing an alkali metal ion-containing substance.
  6. (i) as an additive, a compound represented by any one of the chemical formulas 1 to 3 of claim 1; (ii) polymer support; (iii) non-aqueous solvents; and (iv) A gel-type polymer electrolyte characterized by containing an alkali metal ion-containing substance.
  7. (i) a compound represented by any one of the chemical formulas 1 to 3 of claim 1 as an additive; or the compound of claim 1 as an additive comprising one or more compounds selected from polyalkylene glycol dialkyl ether and non-aqueous solvents; (ii) a polymer compound selected from network, comb-shaped, and branched polymer compounds or a crosslinkable polymer compound; (iii) A solid polymer electrolyte characterized by containing an alkali metal ion-containing substance.
  8. An electrochemical cell comprising a cathode, an anode, and an electrolyte of claim 3.
  9. Electrochemical cell manufactured using the non-aqueous liquid electrolyte of claim 5.
  10. A gel-type polymer battery manufactured using the gel-type polymer electrolyte of claim 6.
  11. A solid polymer battery manufactured using the solid polymer electrolyte of claim 7.

Description

Additives and crosslinkers and non-aqueous liquid electrolytes and gel-type or solid polymer electrolytes containing the same The present invention relates to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, and more specifically, to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, which improves the electrochemical stability, thermal stability, flame retardancy, and lifespan of an alkali metal battery using an electrolyte to which the same is added, and is composed of a siloxane compound comprising an amine group substituted with an electron-withdrawing functional group, or an isocyanate group, a boronate pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, or a diethyl phosphate group. To meet the demand for high-capacity, high-output, and long-life power storage devices as power sources for advanced industries such as robots and UAM (Urban Air Mobility) and to expand the use of eco-friendly electric vehicles in response to global warming and the depletion of fossil fuels, there is a need for such devices. Various studies are being conducted focusing on cathode, anode, separator, and electrolyte materials to improve lithium-ion batteries as power sources for these products. Among the component materials that determine the performance of these power sources, the electrolyte significantly affects not only itself but also the performance of the electrode. If the electrolytes used in conventional lithium-ion batteries are used as is, there is a problem where electrochemical stability rapidly deteriorates due to reactions and degradation between the electrode and the electrolyte during long-term charging and discharging. Furthermore, in the case of electric vehicles or ESS (Energy Storage Systems) equipped with multiple battery packs, the risk of fire caused by ignition resulting from battery damage due to physical damage, overcharging, or over-discharging is emerging as a major social issue. As part of efforts to overcome the problems associated with these electrolytes, research on anion acceptors is underway, and anion acceptors enhance anion stability through Lewis acid-salt interactions. Anion acceptors are compounds containing electron-deficient atoms (nitrogen or boron) that facilitate the movement of anions and lithium cations by coordinating electron-rich anions around them. The first known compounds as anion acceptors are aza-ethers composed of cyclic or linear amides, in which the nitrogen atom of an amine group substituted by a perfluoroalkylsulfonyl substituent is made electron-deficient, allowing it to interact appropriately with electron-rich anions through Coulomb attraction. (J. Electrochem. Soc., 143(1996)3825, 146(2000)9). However, these aza-ethers exhibit limited solubility in polar solvents adopted as typical non-aqueous electrolytes, and it has been found that the electrochemical stability window of the electrolyte with added LiCl salts does not meet the 4.0 V required for commercially available cathode materials, and is unstable in LiPF6 (J. Electrochem. Solid-State Lett., 5(2002) A248). That is, LiPF6 is chemically and thermally unstable and is in equilibrium with solid LiF and gaseous PF5 even at room temperature, and the generation of this gaseous product, PF5 , further tilts the equilibrium toward the formation of PF5 . In non-aqueous solvents, PF5 tends to initiate a series of reactions, such as ring-opening polymerization or the breaking of ether bonds composed of atoms with non-covalent electron pairs, such as oxygen or nitrogen. As a strong Lewis acid, PF5 attacks electron pairs, and the high electron density of aza-ether causes it to be subjected to immediate attack by PF5 . (J. Power Sources, 104(2002)260). Figure 1 is a graph showing the cycling performance of a liquid electrolyte using the additive of the present invention (Experimental Example 2). The present invention will be explained in more detail below through the following examples. The following examples are intended to illustrate the present invention and do not limit the scope of the invention.