Novel anion receptor compound and electrolyte containing the same

Abstract

The present invention relates to a novel anion receptor and an electrolyte containing the same. More specifically, the present invention relates to a novel silazane in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom, which is composed of a compound having a structure in which a silicon atom and a nitrogen atom are bonded, or a mixture of such a novel silazane and a composition selected from linear hydrocarbons, cyclic hydrocarbons, polyalkylene oxides, and siloxane compounds, in which an amine group substituted with an electron withdrawing group is introduced or an electron withdrawing group is introduced into a nitrogen atom in a ring. The present invention relates to a novel anion receptor that improves the ionic conductivity and cation transference number of an electrolyte added with the above mixture, and a non-aqueous liquid electrolyte and a gel or solid polymer electrolyte containing the same, which enhance the electrochemical stability of an alkali metal battery using these electrolytes.

Description

Technical Field

[0001] The present invention relates to a novel anion receptor compound and an electrolyte containing the same, and more particularly to a novel silicon-based anion receptor compound and an electrolyte containing the same.

Background Art

[0002] Anion receptors improve the stability of anions by Lewis acid - salt interactions. These anion receptors are compounds having atoms (N, B) lacking electrons, and by coordinating electron - rich anions around them, they prevent the binding of anions and lithium cations as an ion pair and facilitate the movement of lithium cations. As a first compound known as an anion receptor, a cyclic or linear amide composed of an aza - ether in which the nitrogen atom of an amine group substituted by a perfluoroalkylsulfonyl substituent is made electron - deficient so that it can appropriately interact with an electron - rich anion by Coulomb attraction (J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9). However, these aza - ethers show limited solubility in polar solvents employed as typical non - aqueous electrolytes, and the electrochemical stability window of the electrolyte with added LiCl salt does not meet the 4.0 V required for commercial anode materials. Also, aza - ethers have been found to be unstable to LiPF6 (J. Electrochem. Solid - State Lett., 5 (2002) A248). That is, since LiPF6 is chemically and thermally unstable, solid LiF and gaseous PF5 are in equilibrium even at room temperature, but the generation of this gaseous product PF5 further shifts the equilibrium towards the formation of PF5.

[0003] JPEG2025522864000002.jpg948

[0004] In non-aqueous solvents, PF5 tends to initiate a series of reactions such as ring-opening polymerization and cleavage of ether bonds composed of atoms with unshared electron pairs such as oxygen or nitrogen. PF5, a strong Lewis acid, attacks electron pairs, but aza-ethers have a high electron density and thus are the cause of immediate attack by PF5 (J. Power Sources, 104 (2002) 260). Here, there are significant restrictions on the commercialization of aza-ether compounds. For such reasons, McBreen et al. synthesized an anion receptor that uses the same means and selects boron as an electron-deficient atom substituted with a functional group having an electron-withdrawing property (J. Electrochem. Soc., 145 (1998) 2813, 149 (2002) A1460).

[0005] On the other hand, solid polymer electrolytes not only have no leakage of the electrolyte solution, are highly resistant to vibration and impact, and are convenient to use, but also have very low self-discharge and can be used even at high temperatures. Therefore, they not only meet the trend of weight reduction and miniaturization of portable electronic devices, as well as the wireless trend of information and communication devices and household appliances, but can also be widely applied to large-capacity lithium polymer secondary batteries such as electric vehicles. For these reasons, many studies have been conducted to improve these performances. Since the discovery of polyalkylene oxide (PAO) - based solid polymer electrolytes by P.V Wright in 1975 (British Polymer Journal, 7, 319), M. Armand named it "ion-conductive polymer" in 1978. A typical solid polymer electrolyte is composed of a polymer having electron-donating atoms such as oxygen, nitrogen, and phosphorus together with a lithium salt complex. The most representative solid polymer electrolytes known so far are polyethylene oxide (PEO) and its lithium salt complex, but these have a conductivity of 10 at room temperature -8Due to their low ionic conductivity on the order of S / cm, they cannot be applied to electrochemical devices operating at room temperature. These PAO-based solid polymer electrolytes have high crystallinity, so the movement of molecular chains is restricted and the ionic conductivity at room temperature is very low. To enhance the mobility of molecular chains, it is necessary to minimize the crystalline regions existing in the polymer structure and increase the amorphous regions. For this purpose, studies have been conducted using siloxane (Macromol. Chem. Rapid Commun., 7 (1986) 115) or phosphazene (J. Am. Chem. Soc., 106 (1984) 6845) with flexible molecular chains as the main chain, or introducing PAO with a relatively short molecular length as the side chain (Electrochem. Acta, 34 (1989) 635). In addition, research is underway to produce a solid polymer electrolyte with a network structure by introducing one or more crosslinkable functional groups at the PAO terminals. However, their ionic conductivity at room temperature is on the order of 10 -5 ~10 -4 S / cm, which is not suitable for use in lithium batteries operating at room temperature, so research continues to improve this. To solve such problems, Abraham et al. introduced low molecular weight polyethylene oxide into a vinylidene hexafluoride-hexafluoropropene copolymer to improve the ionic conductivity (Chem. Mater., 9 (1997) 1978). Also, by adding low molecular weight polyethylene glycol dimethyl ether (PEGDME) to a photocurable crosslinking agent with PEO as the side chain and siloxane as the main chain, a maximum of 8×10 -4has shown an ionic conductivity of S / cm (J. Power Sources 119-121 (2003) 448). However, the calculated cycling efficiency on the Ni electrode stopped at about 53%. Such low efficiency is explained by the fact that rapid corrosion of the newly deposited lithium surface causes passivation on the electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). That is, according to Vincent, the reaction between the lithium salt and lithium metal occurs as follows (Solid State Chem. 17 (1987) 145). Here, the CF3 radicals generated pull hydrogen atoms from the PEO polymer chains to form HCF3, as a result of which the main chain of the polymer is cleaved at the =C-O-C- functional groups thus formed. At this time, it is explained that CH3 generated by the cleavage of the chain attacks the chain together with the CF3 radicals or cleaves the -C-O- bond, causing the Li-O-R form compound to adhere to the electrode surface and cause passivation.

[0006] JPEG2025522864000003.jpg972

[0007] Therefore, in order to solve the above-mentioned problems, it is necessary to conduct research on new substances that can eliminate electrochemical instability and instability with respect to lithium salts and increase ionic conductivity by designing compounds with a structure in which there is no nitrogen atom that is easily attacked in the middle of the conjugate like azaether or by replacing the PAO-based plasticizer.

[0008] Summary of the Invention Problems to be Solved by the Invention

[0009] An object of the present invention is to provide a novel silicon-based anion receptor compound in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom.

[0010] Another object of the present invention is to improve the ionic conductivity and cation transference number in an electrolyte, and to enhance the electrochemical stability of a battery (for example, a primary battery or a secondary battery) using these electrolytes, and to provide an electrolyte composition capable of providing a liquid, gel-like or solid electrolyte.

[0011] Another object of the present invention is to provide an electrolyte with significantly improved ionic conductivity and electrochemical stability at room temperature.

[0012] Another object of the present invention is to provide a solidified electrolyte and a battery containing the same, which can rapidly cure when the temperature reaches a certain temperature (for example, about 130 ° C) or higher to stop the operation of the battery and prevent the occurrence of a fire due to thermal runaway of the battery.

[0013] [Means for Solving the Problems]

[0014] In order to achieve the above object, the present invention provides a silicon-based anion receptor compound selected from the group consisting of the following Chemical Formulas 1 to 6.

[0015] [Chemical Formula 1]

[0016] JPEG2025522864000004.jpg2020

[0017] [Chemical Formula 2]

[0018] JPEG2025522864000005.jpg2120

[0019] [Chemical Formula 3]

[0020] JPEG2025522864000006.jpg2121

[0021] [Chemical Formula 4]

[0022] JPEG2025522864000007.jpg2136

[0023] [Chemical Formula 5]

[0024] JPEG2025522864000008.jpg2150

[0025] [Chemical Formula 6]

[0026] JPEG2025522864000009.jpg2745

[0027] Among the above Chemical Formulas 1 to 6,

[0028] (a) X is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR’ (R and R’ are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), JPEG2025522864000010.jpg1630, JPEG2025522864000011.jpg1540,

[0029] JPEG2025522864000012.jpg1234, TIFF2025522864000013.tif1527, JPEG2025522864000014.jpg1531, JPEG2025522864000015.jpg1634、 JPEG2025522864000016.jpg1632、 JPEG2025522864000017.jpg1533、 TIFF2025522864000018.tif1635、 TIFF2025522864000019.tif1935、 JPEG2025522864000020.jpg1638、 JPEG2025522864000021.jpg1632、 JPEG2025522864000022.jpg1733、および JPEG2025522864000023.jpg1747

[0030] (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, R1 is a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN; and l is an integer from 0 to 20) and is selected from

[0031] (b) Y is JPEG2025522864000024.jpg1830、 JPEG2025522864000025.jpg1839および JPEG2025522864000026.jpg1947(R2, R3, and R4 are each selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R2, R3, and R4 are not simultaneously hydrogen atoms; m and m' are each an integer from 0 to 20.) and are selected from

[0032] (c) R1, R2, and R3 are selected from a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN;

[0033] (d) n is an integer from 0 to 20.

[0034]

[0035] The present invention also provides an electrolyte composition containing at least one of the silicon-based anion receptor compounds represented by Chemical Formulas 1 to 6.

[0036] In the present invention, the electrolyte composition is characterized by further containing one or more compounds selected from the group consisting of the following Chemical Formulas 7 to 16.

[0037] [Chemical Formula 7]

[0038] JPEG2025522864000027.jpg2843

[0039] [Chemical Formula 8]

[0040] JPEG2025522864000028.jpg2735

[0041] [Chemical Formula 9]

[0042] JPEG2025522864000029.jpg2736

[0043] [Chemical Formula 10]

[0044] JPEG2025522864000030.jpg3029

[0045] [Chemical Formula 11]

[0046] JPEG2025522864000031.jpg2655

[0047] [Chemical Formula 12]

[0048] JPEG2025522864000032.jpg3062

[0049] [Chemical Formula 13]

[0050] JPEG2025522864000033.jpg1935

[0051] [Chemical Formula 13-a]

[0052] JPEG2025522864000034.jpg1545

[0053] [Chemical Formula 13-b]

[0054] JPEG2025522864000035.jpg1768

[0055] [Chemical Formula 14]

[0056] JPEG2025522864000036.jpg2152

[0057] [Chemical Formula 15]

[0058] JPEG2025522864000037.jpg2051

[0059] [Chemical Formula 16]

[0060] JPEG2025522864000038.jpg4242

[0061] Among the above Chemical Formulas 7 to 16,

[0062] (a) X is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (where R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (where R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR' (where R and R' are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR3 (where R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR3 (where R is a linear or branched alkyl group having 1 to 20 carbon atoms),

[0063] JPEG2025522864000039.jpg1529, JPEG2025522864000040.jpg1539, JPEG2025522864000041.jpg1233, TIFF2025522864000042.tif1527, JPEG2025522864000043.jpg1533, TIFF2025522864000044.tif1736, JPEG2025522864000045.jpg1734, TIFF2025522864000046.tif1531, JPEG2025522864000047.jpg1430, JPEG2025522864000048.jpg1628、 JPEG2025522864000049.jpg1638、 JPEG2025522864000050.jpg1733、 TIFF2025522864000051.tif1938、and JPEG2025522864000052.jpg1746

[0064] (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, R1 is a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN; l is an integer from 0 to 20) is selected from,

[0065] (b) Y is, JPEG2025522864000053.jpg1527、 JPEG2025522864000054.jpg1435 and JPEG2025522864000055.jpg1642 (R2, R3 and R4 are each a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN; provided that R2, R3 and R4 are not simultaneously hydrogen atoms; m and m' are each an integer from 0 to 20.) is selected from,

[0066] (c) W is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, JPEG2025522864000056.jpg1725, JPEG2025522864000057.jpg1637 and JPEG2025522864000058.jpg1742 (R2, R3, and R4 are each a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R2, R3, and R4 are not simultaneously hydrogen atoms; m and m’ are each an integer from 0 to 20.) is selected from

[0067] (d) R1 and R1’ are each a hydrogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R1 and R1’ are not simultaneously hydrogen atoms in the same molecule,

[0068] (e) n and q are each an integer from 0 to 20,

[0069] (f) z is an integer from 1 to 20.

[0070]

[0071] The present invention also provides a solidified electrolyte produced from the electrolyte composition.

[0072] The present invention also provides a polymer electrolyte thin film produced from the electrolyte composition.

[0073] The present invention also provides a battery including the solidified electrolyte.

[0074] The present invention also provides a rechargeable battery including the solidified electrolyte.

[0075]

Advantages of the Invention

[0076] The present invention can provide a novel silicon-based anion receptor compound and a liquid electrolyte (e.g., non-aqueous liquid electrolyte), a gel-like or solid electrolyte (e.g., gel-like polymer electrolyte or solid polymer electrolyte) containing the same. That is, the present invention provides a novel cyclic silicon compound in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom in the ring, and by utilizing this, not only a small lithium polymer secondary battery applied to portable information terminals such as mobile phones and notebook computers and various electronic devices such as camcorders, but also an electrolyte (e.g., gel-like or solid polymer electrolyte, solid sulfide-polymer-based electrolyte, solid oxide-polymer-based electrolyte) for a large-capacity secondary battery (e.g., lithium polymer secondary battery) used in a power storage device for power leveling and an electric vehicle can be widely provided.

[0077] The present invention can provide a solidified electrolyte that can reduce the risk of fire caused by thermal runaway, ensure the stability of the electrolyte, and improve the applicability not only to electric vehicle batteries but also to power storage devices.

[0078]

Brief Description of the Drawings

[0079]

Figure 1

[0080]

BEST MODE FOR CARRYING OUT THE INVENTION

[0081] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to these embodiments, the scope of the patent application is not limited or restricted by these embodiments. It should be understood that all changes, equivalents, or alternatives to the embodiments are included within the scope of the rights.

[0082] The terms used in the embodiments are for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates a different meaning. In this specification, terms such as "including" or "introducing" are used to specify the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and should not be understood to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0083] Terms such as "first" or "second" can be used to describe various components, but these components should not be limited by these terms. These terms are only for the purpose of distinguishing one component from another. For example, without departing from the scope of the rights according to the concept of the embodiment, the first component can be named the second component, and similarly, the second component can be named the first component.

[0084] Unless otherwise defined, all terms used herein, including technical or scientific terms, shall have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments pertain. Terms defined in commonly used dictionaries shall be interpreted to have a meaning consistent with the meaning in the context of the relevant art, and shall not be interpreted in an ideal or overly formal sense unless clearly defined in this application.

[0085] In addition, when referring to the accompanying drawings for description, regardless of the reference numerals in the drawings, the same reference numerals shall be assigned to the same components, and duplicate descriptions thereof shall be omitted. When explaining the embodiments, if it is determined that a specific description of related known technologies may unnecessarily obscure the gist of the embodiments, the detailed description thereof shall be omitted.

[0086]

[0087] Hereinafter, the novel anion receptor of the present invention, its manufacturing method, and its utilization will be specifically described with reference to embodiments and drawings. However, the present invention is not limited to these embodiments and drawings.

[0088] The present invention relates to a novel anion receptor.

[0089] According to an embodiment of the present invention, the anion receptor may be a novel silicon-based compound, which may be a compound that is a novel silicon-based anion receptor in which an amine group substituted with an electron withdrawing group is introduced into a nitrogen atom.

[0090] According to an embodiment of the present invention, the anion receptor compound may be a compound represented by the following Chemical Formulas 1 to 6. The compound serves as an anion receptor in an electrolyte composition (for example, an electrolyte), and when applied as an additive to an electrolyte composition (for example, an electrolyte), it can improve the ionic conductivity and the cation transference number, and enhance the electrochemical stability of a battery utilizing the same.

[0091] [Chemical Formula 1]

[0092] JPEG2025522864000059.jpg2020

[0093] [Chemical Formula 2]

[0094] JPEG2025522864000060.jpg2120

[0095] [Chemical Formula 3]

[0096] JPEG2025522864000061.jpg2121

[0097] [Chemical Formula 4]

[0098] JPEG2025522864000062.jpg2136

[0099] [Chemical Formula 5]

[0100] JPEG2025522864000063.jpg2150

[0101] [Chemical Formula 6]

[0102] JPEG2025522864000064.jpg2745

[0103] As an example of the present invention, the compounds represented by the above Chemical Formula 1 to Chemical Formula 6 can be compounds as novel silicon-based anion receptors in which a functional group substituted with an electron withdrawing group is introduced into a nitrogen atom in silicon.

[0104]

[0105] As an example of the present invention, in the above Chemical Formulas 1 to 6, X is a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR, -OR, -ROR', -Si(R)3, -O-Si(R)3,

[0106] JPEG2025522864000065.jpg1529、 JPEG2025522864000066.jpg1539、 JPEG2025522864000067.jpg1337、 TIFF2025522864000068.tif1527、 JPEG2025522864000069.jpg1635、 TIFF2025522864000070.tif1736、 TIFF2025522864000071.tif1837、 TIFF2025522864000072.tif1531、 JPEG2025522864000073.jpg1328、 TIFF2025522864000074.tif1935、 JPEG2025522864000075.jpg1637、 TIFF2025522864000076.tif1530、 TIFF2025522864000077.tif1938、and TIFF2025522864000078.tif1951

[0107] can be selected from.

[0108] In X, R, R', and R1 are each independently selected from a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN. Preferably, R and R' are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms, and R1 is selected from a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; and l can be an integer from 0 to 20.

[0109] Preferably, in X,

[0110] R in "-COR" can be selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms.

[0111] R in "-OR" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0112] R and R' in "-ROR'" can each independently be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0113] R in "-Si(R)3" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0114] In "-O-Si(R)3", R can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0115] Said l can be an integer from 0 to 10; or from 0 to 5.

[0116] More preferably, in Chemical Formulas 1 to 6, said X is -F, -CH3, -CH2-CH3, -CH=CH2, -CO-CH=CH2, -OCH3, -CH2OCH3, -OCH2CH3, -CH(CH3)2, -O-CH(CH3)2, -C(CH3)3, -Si(CH3)3, -O-Si(CH3)3,

[0117] JPEG2025522864000079.jpg1630, JPEG2025522864000080.jpg1539, JPEG2025522864000081.jpg1234, TIFF2025522864000082.tif1527, TIFF2025522864000083.tif1737, TIFF2025522864000084.tif1736, JPEG2025522864000085.jpg1733, JPEG2025522864000086.jpg1328, JPEG2025522864000087.jpg1532, JPEG2025522864000088.jpg1833, TIFF2025522864000089.tif1434, TIFF2025522864000090.tif1530, JPEG2025522864000091.jpg1633, and JPEG2025522864000092.jpg1542

[0118] (Here, R is selected from linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably -CH3. R1 is a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3; and is more preferably selected from -F, -Cl, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3. l is an integer from 0 to 10, and more preferably can be from 0 to 3.) can be selected from.

[0119] As an example of the present invention, in the above Chemical Formulas 1 to 6, n is an integer from 0 to 20, and preferably, n can be an integer from 0 to 10.

[0120] As an example of the present invention, in the above Chemical Formulas 1 to 6, Y is JPEG2025522864000093.jpg1731, JPEG2025522864000094.jpg1535 and JPEG2025522864000095.jpg1844 can be selected.

[0121] In the above Y, R2, R3, and R4 can each be selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN. However, within one molecule or within the above Y, R2; R3; or R2, R3, and R4 cannot simultaneously be hydrogen atoms, and at least one of them is an electron-withdrawing group.

[0122] In the above Y, m and m' can each be an integer from 0 to 20. As another example, within one molecule or within the above Y, m and m' do not have to simultaneously be "0".

[0123] Preferably, R2, R3, and R4 can each be selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN, and m and m' can each be an integer from 0 to 20.

[0124] As an example of this reaction, in the above Chemical Formula 4, n is an integer from 0 to 20, and preferably, n can be an integer from 0 to 10.

[0125]

[0126] As an example of the present invention, the compound represented by the above Chemical Formula 1 can be selected from the following compounds.

[0127] [Chemical Formula 1-1]

[0128] JPEG2025522864000096.jpg2655

[0129] [Chemical formula 1-2]

[0130] JPEG2025522864000097.jpg3254

[0131] [Chemical formula 1-3]

[0132] JPEG2025522864000098.jpg3252

[0133] In Chemical formulas 1-1 to 1-3, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably can be -CH3.

[0134] As an example of the present invention, the compound represented by Chemical formula 2 can be selected from the following compounds.

[0135] [Chemical formula 2-1]

[0136] JPEG2025522864000099.jpg2270

[0137] [Chemical formula 2-2]

[0138] JPEG2025522864000100.jpg2570

[0139] [Chemical formula 2-3]

[0140] JPEG2025522864000101.jpg2570

[0141] In Chemical Formulas 2-1 to 2-3, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably can be -CH3.

[0142] As an example of the present invention, the compound represented by Chemical Formula 3 can be selected from the following compounds.

[0143] [Chemical Formula 3-1]

[0144] JPEG2025522864000102.jpg4683

[0145] [Chemical Formula 3-2]

[0146] JPEG2025522864000103.jpg4682

[0147] [Chemical Formula 3-3]

[0148] JPEG2025522864000104.jpg5183

[0149] In Chemical Formulas 3-1 to 3-3, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably is -CH3.

[0150] As an example of the present invention, the compound represented by Chemical Formula 4 can be selected from the following compounds.

[0151] [Chemical Formula 4-1]

[0152] JPEG2025522864000105.jpg2989

[0153] [Chemical Formula 4-2]

[0154] JPEG2025522864000106.jpg3093

[0155] [Chemical formula 4-3]

[0156] JPEG2025522864000107.jpg3599

[0157] In the above Chemical formulas 4-1 to 4-3, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, more preferably -CH3, and n is an integer of 0 to 2.

[0158] As an example of the present invention, the compound represented by the above Chemical formula 5 can be selected from the following compounds.

[0159] [Chemical formula 5-1]

[0160] JPEG2025522864000108.jpg30101

[0161] [Chemical formula 5-2]

[0162] JPEG2025522864000109.jpg32102

[0163] [Chemical formula 5-3]

[0164] JPEG2025522864000110.jpg34101

[0165] [Chemical formula 5-4]

[0166] JPEG2025522864000111.jpg6371

[0167] [Chemical formula 5-5]

[0168] JPEG2025522864000112.jpg6472

[0169] [Chemical Formula 5-6]

[0170] JPEG2025522864000113.jpg6870

[0171] [Chemical Formula 5-7]

[0172] JPEG2025522864000114.jpg6389

[0173] [Chemical Formula 5-8]

[0174] JPEG2025522864000115.jpg6396

[0175] [Chemical Formula 5-9]

[0176] JPEG2025522864000116.jpg6495

[0177] In the above Chemical Formulas 5-1 to 5-9, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0178] As an example of the present invention, the compound represented by the above Chemical Formula 6 can be selected from the following compounds.

[0179] [Chemical Formula 6-1]

[0180] JPEG2025522864000117.jpg7596

[0181] [Chemical Formula 6-2]

[0182] JPEG2025522864000118.jpg7587

[0183] [Chemical Formula 6-3]

[0184] JPEG2025522864000119.jpg7188

[0185]

[0186] As an example of this reaction, the "halogen atom" can be selected from a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom and a chlorine atom, and more preferably a fluorine atom.

[0187] As an example of the present invention, the "alkyl group" is linear or branched and can have 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, etc. can be mentioned.

[0188] As an example of the present invention, the "alkenyl group" is linear or branched and can have 2 to 20 carbon atoms, 1 to 15 carbon atoms, 2 to 10 carbon atoms, 2 to 5 carbon atoms, or 2 to 3 carbon atoms. For example, vinyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, etc. can be mentioned.

[0189] As an example of the present invention, the "alkynyl group" is linear or branched and can have 2 to 20 carbon atoms, 1 to 15 carbon atoms, 2 to 10 carbon atoms, 2 to 5 carbon atoms, or 2 to 3 carbon atoms. For example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc. can be mentioned.

[0190] As an example of the present invention, "n" can be an integer from 0 to 20, an integer from 0 to 15, an integer from 0 to 10, an integer from 0 to 5, an integer from 1 to 20, an integer from 1 to 15, an integer from 1 to 10, or an integer from 1 to 5.

[0191] As an example of the present invention, "m" and "an integer from 0 to 20; "m'" can each be an integer from 0 to 20, an integer from 0 to 15, an integer from 0 to 10, an integer from 1 to 20, 0 to 10, 0 to 3, an integer from 1 to 15, an integer from 1 to 10, or an integer from 1 to 5.

[0192] As an example of the present invention, "l" can be an integer from 0 to 20, an integer from 0 to 15, an integer from 0 to 10, an integer from 1 to 20, from 0 to 10, from 0 to 3, an integer from 1 to 15, an integer from 1 to 10, or an integer from 1 to 5.

[0193] According to an embodiment of the present invention, the anion receptor can be applied to an electrochemical cell or its components as an electrolyte composition or a process composition described later. According to one embodiment of the present invention, the electrolyte composition can be applied in the form of a liquid, gel, solid, molded body (such as a film, thin film, porous structure, sheet, etc.).

[0194]

[0195] The present invention relates to a method for producing an anion receptor compound.

[0196] According to one embodiment of the present invention, the method for producing the anion receptor corresponds to the method for producing the compounds represented by Chemical Formula 1 to Chemical Formula 6. As an example of the present invention, the compounds represented by Chemical Formula 1 to Chemical Formula 6 can be produced according to the following reaction formula. According to one embodiment of the present invention, in order to obtain the final product according to the chemical structure design, the starting materials, catalysts, solvents, reaction conditions, reaction mechanisms, post-treatment (such as separation of reactants, filtration, crystallization, washing, etc.) processes can be appropriately utilized or replaced with known methods in the technical field of the present invention. For example, it can be carried out at a reaction temperature of -40°C or higher, -10°C or higher, 0°C or higher, room temperature or higher, 40°C or higher, 50°C or higher, 80°C or higher, 100°C or higher, or -40°C to 130°C in a single solvent or a mixed solvent such as water, methanol, isopropanol, ethanol, methylene chloride, dichloromethane, acetonitrile, tetrahydrofuran, methyl-tert-butyl ether, chloroform, DMF, and N,N-dimethylacetamide. For example, the reaction temperature can be appropriately selected according to the reflux conditions of the reaction mixture. In addition, catalysts such as a platinum catalyst and basic substances (such as triethylamine, diisopropylethylamine, pyridine, etc.) can be further added.

[0197] According to an embodiment of the present invention, as shown in the following Reaction Formula 1-1, a silicon compound represented by the following 1-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 1-1.

[0198] [Reaction Formula 1-1]

[0199] JPEG2025522864000120.jpg30115

[0200] (In the above Reaction Formula 1-1, X is as defined in Chemical Formula 1 above.)

[0201]

[0202] According to an embodiment of the present invention, as shown in the following Reaction Formula 1-2, a silicon compound represented by the following 1-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 1-2.

[0203] [Reaction Formula 1-2]

[0204] JPEG2025522864000121.jpg34123

[0205] (In the above Reaction Formula 1-2, X is as defined in Chemical Formula 1 above.)

[0206]

[0207] According to an embodiment of the present invention, as shown in the following Reaction Formula 2-1, a silicon compound represented by the following 2-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 1-3.

[0208] [Reaction Formula 1-3]

[0209] JPEG2025522864000122.jpg34128

[0210] (In the above Reaction Formulas 1 to 3, X is as defined in the above Chemical Formula 1, respectively.)

[0211]

[0212] According to one embodiment of the present invention, as shown in the following Reaction Formula 2-1, a silicon compound represented by the following 2-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 2-1.

[0213] [Reaction Formula 2-1]

[0214] JPEG2025522864000123.jpg32130

[0215] (In the above Reaction Formula 2-1, X is as defined in the above Chemical Formula 2, respectively.)

[0216]

[0217] According to one embodiment of the present invention, as shown in the following Reaction Formula 2-2, a silicon compound represented by the following 2-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 2-2.

[0218] [Reaction Formula 2-2]

[0219] JPEG2025522864000124.jpg37129

[0220] (In the above Reaction Formula 2-2, X is as defined in the above Chemical Formula 2, respectively.)

[0221]

[0222] According to one embodiment of the present invention, as shown in the following Reaction Formula 2-3, a silicon compound represented by the following 2-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 2-3.

[0223] [Reaction Formula 2-3]

[0224] JPEG2025522864000125.jpg33124

[0225] (In the above Reaction Formula 2-3, X is as defined in the above Chemical Formula 2, respectively.)

[0226]

[0227] According to one embodiment of the present invention, as shown in the following Reaction Formula 3-1, a silicon compound represented by the following 3-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 3-1.

[0228] [Reaction Formula 3-1]

[0229] JPEG2025522864000126.jpg49112

[0230]

[0231] According to one embodiment of the present invention, as shown in the following Reaction Formula 3-2, a silicon compound represented by the following 3-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 3-2.

[0232] [Reaction Formula 3-2]

[0233] JPEG2025522864000127.jpg47109

[0234] (In the reaction formula 3-2, each X is as defined in the chemical formula 3.)

[0235]

[0236] According to an embodiment of the present invention, as shown in the following reaction formula 3-3, a silicon compound represented by the following 3-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 3-3.

[0237] [Reaction formula 3-3]

[0238] JPEG2025522864000128.jpg47122

[0239] (In the reaction formula 3-3, each X is as defined in the chemical formula 3.)

[0240]

[0241] According to an embodiment of the present invention, as shown in the following reaction formula 4-1, a silicon compound represented by the following 4-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 4-1.

[0242] [Reaction formula 4-1]

[0243] JPEG2025522864000129.jpg39123

[0244] (In the reaction formula 4-1, each X is as defined in the chemical formula 4.)

[0245]

[0246] According to one embodiment of the present invention, as shown in the following Reaction Formula 4-2, a silicon compound represented by the following 4-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 4-2.

[0247] [Reaction Formula 4-2]

[0248] JPEG2025522864000130.jpg37125

[0249] (In the above Reaction Formula 4-2, X is as defined in Chemical Formula 4 above.)

[0250]

[0251] According to one embodiment of the present invention, as shown in the following Reaction Formula 4-3, a silicon compound represented by the following 4-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 4-3.

[0252] [Reaction Formula 4-3]

[0253] JPEG2025522864000131.jpg37125

[0254] (In the above Reaction Formula 4-3, X is as defined in Chemical Formula 4 above.)

[0255]

[0256] According to one embodiment of the present invention, as shown in the following Reaction Formula 5-1, a silicon compound represented by the following 5-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 5-1.

[0257] [Reaction Formula 5-1]

[0258] JPEG2025522864000132.jpg34125

[0259] (In the reaction formula 5-1, each X is as defined in the chemical formula 5.)

[0260]

[0261] According to one embodiment of the present invention, as shown in the following reaction formula 5-2, a silicon compound represented by the following 5-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 5-2.

[0262] [Reaction formula 5-2]

[0263] JPEG2025522864000133.jpg34121

[0264] (In the reaction formula 5-2, each X is as defined in the chemical formula 5.)

[0265]

[0266] According to one embodiment of the present invention, as shown in the following reaction formula 5-3, a silicon compound represented by the following 5-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 5-3.

[0267] [Reaction formula 5-3]

[0268] JPEG2025522864000134.jpg33118

[0269] (In the reaction formula 5-3, each X is as defined in the chemical formula 5.)

[0270]

[0271] According to one embodiment of the present invention, as shown in the following Reaction Formula 5-4, a silicon compound represented by the following 5-b and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 5-4.

[0272] [Reaction Formula 5-4]

[0273] JPEG2025522864000135.jpg46112

[0274] (In the above Reaction Formula 5-4, X is as defined in the above Chemical Formula 5, respectively.)

[0275]

[0276] According to one embodiment of the present invention, as shown in the following Reaction Formula 5-5, a silicon compound represented by the following 5-b and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 5-5.

[0277] [Reaction Formula 5-5]

[0278] JPEG2025522864000136.jpg57107

[0279] (In the above Reaction Formula 5-5, X is as defined in the above Chemical Formula 5, respectively.)

[0280]

[0281] According to one embodiment of the present invention, as shown in the following Reaction Formula 5-6, a silicon compound represented by the following 5-b and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction with a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 5-6.

[0282] [Reaction Formula 5-6]

[0283] JPEG2025522864000137.jpg4899

[0284] (In the above reaction formula 5-6, each X is as defined in the above chemical formula 5.)

[0285]

[0286] According to one embodiment of the present invention, as shown in the following reaction formula 5-7, a silicon compound represented by the following 5-c and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 5-7.

[0287] [Reaction formula 5-7]

[0288] JPEG2025522864000138.jpg47132

[0289] (In the above reaction formula 5-7, each X is as defined in the above chemical formula 5.)

[0290]

[0291] According to one embodiment of the present invention, as shown in the following reaction formula 5-8, a silicon compound represented by the following 5-c and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 5-8.

[0292] [Reaction formula 5-8]

[0293] JPEG2025522864000139.jpg53121

[0294] (In the above reaction formula 5-8, each X is as defined in the above chemical formula 5.)

[0295]

[0296] According to one embodiment of the present invention, as shown in the following Reaction Formula 5-9, a silicon compound represented by the following 5-c and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 5-9.

[0297] [Reaction Formula 5-9]

[0298] JPEG2025522864000140.jpg47115

[0299] (In the above Reaction Formula 5-9, X is as defined in the above Chemical Formula 5, respectively.)

[0300]

[0301] According to one embodiment of the present invention, as shown in the following Reaction Formula 6-1, a silicon compound represented by the following 6-a and an allyl compound in which a nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 6-1.

[0302] [Reaction Formula 6-1]

[0303] JPEG2025522864000141.jpg60107

[0304] According to one embodiment of the present invention, as shown in the following Reaction Formula 6-2, a silicon compound represented by the following 6-a and an allyl compound in which a nitrogen atom is substituted with -SO2CF3 are subjected to a hydrosilylation reaction using a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 6-2.

[0305] [Reaction Formula 6-2]

[0306] JPEG2025522864000142.jpg50104

[0307]

[0308] According to an embodiment of the present invention, as shown in the following Reaction Formula 6-3, a silicon compound represented by the following 6-a and an allyl compound in which a nitrogen atom is substituted with -SO2F are subjected to a hydrosilylation reaction in the presence of a platinum catalyst and a tetrahydrofuran solvent to synthesize a compound represented by Chemical Formula 6-3.

[0309] [Reaction Formula 6-3]

[0310] JPEG2025522864000143.jpg53103

[0311]

[0312] The present invention relates to an electrolyte composition containing a novel anion receptor according to the present invention.

[0313] According to an embodiment of the present invention, the anion receptor may include at least one of the novel silicon compounds represented by Chemical Formulas 1 to 6, in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom in the ring.

[0314] According to an embodiment of the present invention, the electrolyte composition further includes the novel silicon compound and at least one compound selected from a linear hydrocarbon represented by the following Chemical Formula 7 in which a nitrogen atom in an amine group substituted with an electron withdrawing group is introduced, cyclic hydrocarbons represented by the following Chemical Formulas 8 to 12, a polyalkylene oxide represented by the following Chemical Formula 13, and siloxane compounds represented by Chemical Formulas 14 to 16, which can be mixed with the novel silicon compound and included in the electrolyte composition.

[0315] That is, among the functional groups introduced as side chains, the amine group substituted with an electron-withdrawing group or the nitrogen atom in the ring can increase the electronegativity and cation mobility by promoting the dissociation of the alkali metal salt. For example, by electron-withdrawing groups such as -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, etc., the amine group or the nitrogen in the ring becomes electron-deficient, forming an electrically neutral complex with the anion species of the alkali metal salt and promoting the dissociation of the alkali metal salt. Further, since the hydrogen atom of the amine group has a nitrogen atom substituted with an electron-withdrawing group located only at the end of the hydrocarbon chain, electrochemical instability, instability with respect to lithium salts (e.g., LiPF6), and steric hindrance caused by the presence of a nitrogen atom vulnerable to attack in the middle of the conjugate, as in the azaethers introduced in U.S. Patent Nos. 5,705,689 and 6,120,941, can be eliminated. Since the central part of nitrogen is further exposed and large anions can easily approach, dissociation of the lithium salt is promoted and cation mobility is increased, enabling high ionic conductivity to be obtained.

[0316]

[0317] As an example of the present invention, the compound of the following Chemical Formula 7 can serve as an anion receptor in an electrolyte composition (or electrolyte).

[0318] [Chemical Formula 7]

[0319] JPEG2025522864000144.jpg2843

[0320] As an example of the present invention, in Chemical Formula 7, X and n are as defined in Chemical Formula 1. In Chemical Formula 7, each of R1 and R1' is selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R1 and R1' do not simultaneously become hydrogen atoms within the same molecule, and at least one of R and R1' is an electron-withdrawing group.

[0321] As an example of the present invention, in Chemical Formula 7, W is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, JPEG2025522864000145.jpg1924, JPEG2025522864000146.jpg1835 and JPEG2025522864000147.jpg1649 (R2, R3, and R4 are each selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R2, R3, and R4 do not simultaneously become hydrogen atoms, and m and m' are each an integer from 0 to 20.)

[0322] As an example of the present invention, the compound of Chemical Formula 7 can be selected from the following compounds:

[0323] JPEG2025522864000148.jpg10378

[0324] JPEG2025522864000149.jpg9985

[0325]

[0326] [Chemical formula 8]

[0327] JPEG2025522864000150.jpg3238

[0328] As an example of the present invention, the compound represented by the chemical formula 8 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 8, X, R1, and n are as defined in the chemical formula 1.

[0329] As an example of the present invention, the compound represented by the chemical formula 8 can be selected from the following compounds.

[0330] JPEG2025522864000151.jpg3388

[0331]

[0332] [Chemical formula 9]

[0333] JPEG2025522864000152.jpg2938

[0334] As an example of the present invention, the compound represented by the chemical formula 9 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 9, R1, X, and n are as defined in the chemical formula 1.

[0335] As an example of the present invention, the compound represented by the chemical formula 9 can be selected from the following chemical formulas.

[0336] JPEG2025522864000153.jpg3492

[0337] [Chemical formula 10]

[0338] JPEG2025522864000154.jpg3029

[0339] As an example of the present invention, the compound represented by the chemical formula 10 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 10, X, Y, and n are as defined in the chemical formula 1.

[0340] As an example of the present invention, the compound represented by the chemical formula 10 can be selected from the following compounds.

[0341] JPEG2025522864000155.jpg72107

[0342]

[0343] [Chemical formula 11]

[0344] JPEG2025522864000156.jpg2146

[0345] As an example of the present invention, the compound represented by the chemical formula 11 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 11, X, Y, and n are as defined in the chemical formula 1.

[0346] As an example of the present invention, the compound represented by the chemical formula 11 can be selected from the following compounds.

[0347] JPEG2025522864000157.jpg66113

[0348] [Chemical formula 12]

[0349] JPEG2025522864000158.jpg2960

[0350] As an example of the present invention, the compound represented by the chemical formula 12 can serve as an anion receptor in an electrolyte, n is as defined in the chemical formula 1, and R1 and R1' are as defined in the chemical formula 7.

[0351] As an example of the present invention, the compound represented by the chemical formula 12 can be selected from the following compounds.

[0352] JPEG2025522864000159.jpg38111

[0353] [Chemical formula 13]

[0354] JPEG2025522864000160.jpg1833

[0355] [Chemical formula 13-a]

[0356] JPEG2025522864000161.jpg1443

[0357] [Chemical formula 13-b]

[0358] JPEG2025522864000162.jpg1664

[0359] As an example of the present invention, the compounds represented by the chemical formula 13, chemical formula 13-a, and chemical formula 13-b can serve as anion receptors in an electrolyte, X, Y, and n are as defined in the chemical formula 1, and W is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms. JPEG2025522864000163.jpg1529, JPEG2025522864000164.jpg1832 and JPEG2025522864000165.jpg1749(R2, R3, and R4 are each a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; provided that R2, R3, and R4 are not simultaneously hydrogen atoms, and m and m’ are each an integer from 0 to 20.) are selected from, z is an integer from 1 to 20, and n and q are each an integer from 0 to 20. Preferably, z is an integer from 1 to 10, and n and q can each be an integer from 0 to 10.

[0360] As an example of the present invention, the compounds represented by Chemical Formula 13, Chemical Formula 13-a, and Chemical Formula 13-b can each be selected from the following compounds.

[0361] JPEG2025522864000166.jpg112100

[0362] JPEG2025522864000167.jpg3399

[0363]

[0364] [Chemical Formula 14]

[0365] JPEG2025522864000168.jpg2152

[0366] As an example of the present invention, the compound represented by Chemical Formula 14 can serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 14, X, Y, and n are as defined in Chemical Formula 1.

[0367] As an example of the present invention, the compound represented by Chemical Formula 14 can be selected from the following compounds.

[0368] JPEG2025522864000169.jpg69109

[0369] [Chemical formula 15]

[0370] JPEG2025522864000170.jpg1951

[0371] As an example of the present invention, the compound represented by the chemical formula 15 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 15, X, Y, and n are as defined in the chemical formula 1.

[0372] As an example of the present invention, the compound represented by the chemical formula 15 can be selected from the following compounds.

[0373] JPEG2025522864000171.jpg92103

[0374] [Chemical formula 16]

[0375] JPEG2025522864000172.jpg4138

[0376] As an example of the present invention, the compound represented by the chemical formula 16 can serve as an anion receptor in an electrolyte composition (or electrolyte). In the chemical formula 16, X, Y, and n are as defined in the chemical formula 1.

[0377] As an example of the present invention, the compound represented by the chemical formula 16 can be selected from the following compounds.

[0378] JPEG2025522864000173.jpg6297

[0379] JPEG2025522864000174.jpg9199

[0380]

[0381] According to one embodiment of the present invention, the total anion receptor (the "anion receptor compounds of Chemical Formulas 1 to 6 + the anion receptors of Chemical Formulas 7 to 16") contained in the electrolyte composition is 0.01 wt% to 40 wt%; 0.01 wt% to 35 wt%; 0.01 wt% to 30 wt%; 0.01 wt% to 20 wt%; 0.01 wt% to 10 wt%; 0.1 wt% to 10 wt%; 0.5 wt% to 5 wt%; 1 wt% to 2 wt% based on the total mass of the electrolyte composition. When the content is less than 0.01 wt%, it is difficult to exhibit the performance of the anion receptor. When the content exceeds 40 wt%, it is difficult to obtain the effect of improving ionic conductivity, electrochemical stability, and low-temperature performance.

[0382] According to one embodiment of the present invention, at least one of the compounds represented by Chemical Formulas 7 to 16 is 0.01 wt% to 50 wt% (or less than 50 wt%); 0.1 wt% to 50 wt%; 1 wt% to 50 wt%; 2 wt% to 40 wt%; or 10 wt% to 30 wt% based on the mass of the total anion receptor. When included within the range of the content, an electrolyte with improved ionic conductivity and electrochemical stability at room temperature can be provided.

[0383] According to one embodiment of the present invention, the mixing ratio of at least one of the silicon-based anion receptor compounds represented by Chemical Formulas 1 to 6 and at least one of the compounds represented by Chemical Formulas 7 to 16 among the anion receptors can be included in a ratio of 99:1 to 50:50 (w / w). When included within the above ratio range, the effect of improving ionic conductivity and electrochemical stability at room temperature can be obtained.

[0384] According to an embodiment of the present invention, the electrolyte composition may include an alkali metal ion-containing substance and a non-aqueous solvent. As an example of the present invention, the non-aqueous solvent can be applied without limitation as long as it is a non-aqueous solvent applicable to a battery. For example, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate, dimethylsulfamoyl fluoride, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrate, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxyethane, dimethoxymethane, γ-butyrolactone, methyl formate, sulfolane, acetonitrile, 3-methyl-2-oxazolidinone, and N-methyl-2-pyrrolidinone, and includes at least one selected from the group consisting of, but is not limited to.

[0385] As an example of the present invention, the non-aqueous solvent may be included in an amount of 1% by weight or more; 15% by weight or more; 30% by weight or more; 60% by weight or more; or 80% to 99% by weight based on the remaining amount or the total mass of the electrolyte composition.

[0386] As an example of the present invention, the alkali metal ion-containing substance is an alkali metal ion-containing electrolyte salt. For example, Li as a cation +It can be a lithium salt containing the same. As an example of the present invention, the lithium salt can be applied without limitation as long as it is applicable to the electrolyte of the battery. For example, it can include, but is not limited to, at least one selected from the group consisting of LiSO3CF3, LiCOOC2F5, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, and LiCl.

[0387] As an example of the present invention, the alkali metal ion-containing substance can be 3 wt% - 60 wt%; 3 wt% - 50 wt%; 10 wt% - 50 wt%; 20 wt% - 50 wt%; 3 wt% - 10 wt%; or 3 wt% - 5 wt% based on the total mass of the electrolyte composition in the electrolyte composition, and can supply appropriate alkali ions to provide and maintain stable performance of the battery.

[0388] According to an embodiment of the present invention, the electrolyte composition can form a non-aqueous liquid electrolyte, a gel polymer electrolyte and / or a solid polymer electrolyte, a solid sulfide-polymer-based electrolyte, a solid oxide-polymer-based electrolyte, a solid oxide-polymer-based electrolyte, and can further selectively include additional components according to the type of such electrolyte. For example, a polymer compound, a polymer support, additives (such as a curing initiator, a polymerization inhibitor), a nano metal oxide, etc. can be mentioned.

[0389] According to an embodiment of the present invention, the electrolyte composition can form a non-aqueous liquid electrolyte. For example, the electrolyte composition for the non-aqueous liquid electrolyte is:

[0390] (a) A novel silicon-based anion receptor compound represented by the above Chemical Formula 1 to Chemical Formula 6, in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom in the ring.

[0391] Or, a novel silicon-based anion receptor compound represented by the above Chemical Formula 1 to Chemical Formula 6, and a linear hydrocarbon compound represented by the above Chemical Formula 7 in which an amine group substituted with an electron-withdrawing group is introduced, or an electron-withdrawing group is introduced into a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by the following Chemical Formula 8 to Chemical Formula 12, a polyalkylene oxide compound represented by the above Chemical Formula 13, and an anion receptor which is a mixture with at least one selected from the siloxane compounds represented by the above Chemical Formula 14 to Chemical Formula 16;

[0392] (b) A non-aqueous solvent; and

[0393] (c) An alkali metal ion-containing substance

[0394] may be included.

[0395] As an example of the present invention, in the electrolyte composition for the non-aqueous liquid electrolyte, the (a) anion receptor, the (b) non-aqueous solvent, and the (c) alkali metal ion-containing substance are as described in the electrolyte composition. Preferably, among the electrolyte compositions for the non-aqueous liquid electrolyte, based on the total mass of the electrolyte composition, the anion receptor is 0.01% by weight to 5% by weight, the non-aqueous solvent is 80% by weight or more; or 95 to 99% by weight, and the alkali metal ion-containing substance may be 10% by weight to 30% by weight; 12% by weight to 20% by weight; or 12% by weight to 15% by weight.

[0396] According to one embodiment of the present invention, the electrolyte composition can form a gel polymer electrolyte. For example, the electrolyte composition for the gel polymer electrolyte is:

[0397] (a) A novel silicon-based anion receptor compound represented by the above Chemical Formula 1 to Chemical Formula 6, in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom within the ring; or a mixture of the novel silicon-based anion receptor compound represented by the above Chemical Formula 1 to Chemical Formula 6 and at least one selected from a linear hydrocarbon compound represented by the above Chemical Formula 7 in which an amine group substituted with an electron withdrawing group is introduced, a cyclic hydrocarbon compound represented by Chemical Formula 8 to Chemical Formula 12, a polyalkylene oxide compound represented by Chemical Formula 13, and a siloxane compound represented by Chemical Formula 14 to Chemical Formula 16; which is an anion receptor,

[0398] (b) A polymer compound selected from linear, network, comb-shaped and branched polymer compounds, a crosslinkable polymer compound, or both of them,

[0399] (c) A polymer support,

[0400] (d) A non-aqueous solvent, and

[0401] (e) can contain an alkali metal ion-containing substance.

[0402] As an example of the present invention, in the electrolyte composition for the gel polymer electrolyte, the (a) anion receptor, the (d) non-aqueous solvent and the (e) alkali metal ion-containing substance are as described in the electrolyte composition. Preferably, in the electrolyte composition for the gel polymer electrolyte, based on the total mass of the electrolyte composition, the (a) anion receptor is 0.01% by weight to 30% by weight, the (d) non-aqueous solvent is 20% by weight to 80% by weight, and the (e) alkali metal ion-containing substance can be 10% by weight to 30% by weight.

[0403] As an example of the present invention, in the electrolyte composition for the gel polymer electrolyte, the polymer compound selected from among the (b) linear, network, comb-shaped, and branched polymer compounds can be applied without limitation as long as it is applicable to a battery (for example, an electrolyte). For example, it can include a flexible inorganic polymer, a linear polyether, or both of these.

[0404] As an example of the present invention, the flexible inorganic polymer is selected from among polysiloxane, polyphosphazene, or a copolymer thereof, and the linear polyether can be a polyalkylene oxide.

[0405] As an example of the present invention, the crosslinkable polymer compound can be applied without limitation as long as it is applicable to a battery (for example, an electrolyte). For example, the crosslinkable polymer compound can include at least one selected from the group consisting of a flexible inorganic polymer or a polymer compound having a linear polyether main chain as a basic skeleton and functional groups such as acrylic, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinylmonomethyl introduced at the terminals, but is not limited thereto. For example, the crosslinkable polymer compound can be bisphenol A ethoxylate dimethacrylate (Bis-15m) represented by the following Chemical Formula 17, polyethylene glycol dimethacrylate (PEGDMA) represented by the following Chemical Formula 18, vinylene carbonate (VC) represented by the following Chemical Formula 19, or vinyl ethylene carbonate (VEC) represented by the following Chemical Formula 20, but is not limited thereto.

[0406]

[0407] [Chemical Formula 17]

[0408] JPEG2025522864000175.jpg1976

[0409] [Chemical Formula 18]

[0410] JPEG2025522864000176.jpg2448

[0411] [Chemical Formula 19]

[0412] JPEG2025522864000177.jpg1825

[0413] [Chemical Formula 20]

[0414] JPEG2025522864000178.jpg2227

[0415]

[0416] As an example of the present invention, among the linear, network, comb-shaped, and branched polymer compounds in (b) above, the polymer compound, the crosslinkable polymer compound, or both of them may be 0.01% by weight to 30% by weight based on the total mass of the electrolyte composition for the gel polymer electrolyte. When included within the above ratio range, a composition with improved mechanical properties and processability can be provided. For example, when it exceeds 80% by weight, the viscosity may be high and the processability may decrease, and when it is less than 20% by weight, the mechanical properties may decrease.

[0417] As an example of the present invention, the (c) polymer support can be applied without limitation as long as it is a polymer support applicable to a battery (for example, an electrolyte). As an example of the present invention, it can include at least one selected from the group consisting of polyalkylene glycol-based polymers, polysiloxane-based polymers, polyacrylonitrile (PAN)-based polymers, and polyvinylidene fluoride (PVDF)-hexafluoropropylene-based polymers, but is not limited thereto.

[0418] As an example of the present invention, the polymer support may be 1% by weight to 40% by weight; or 5% by weight to 40% by weight based on the total mass of the electrolyte composition for the gel polymer electrolyte. When included within the above range, the polymer support can solve the liquid leakage problem that may occur in the gel polymer electrolyte and provide an electrolyte with improved stability and electrical performance.

[0419] According to one embodiment of the present invention, when the electrolyte composition for the gel polymer electrolyte contains the crosslinkable polymer compound, it can further contain a curing initiator. As an example of the present invention, the curing initiator can include a photo-curing initiator, a thermo-curing initiator, or both of them. For example, the photo-curing initiator can include at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methylbenzoin ethyl ether, benzoin phenyl ether, α-acyl oxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, and Michler's ketone, etc., but is not limited thereto. For example, the thermo-curing initiator can include an azoisobutyronitrile-based compound, a peroxide-based compound, or both of them. More specifically, it can include at least one selected from the group consisting of 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tetramethylbutyl peroxy neodecanoate, bis(4-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, butyl peroxy neodecanoate, dipropyl peroxydicarbonate, etc., but is not limited thereto.

[0420] As an example of the present invention, the curing initiator is, in the electrolyte composition for the gel polymer electrolyte, based on the total mass of the electrolyte composition, 1×10 -4It can be 0% by weight to 0.1% by weight. When included within the above range, an electrolyte with improved stability and electrical performance can be provided.

[0421] According to one embodiment of the present invention, the electrolyte composition for the gel polymer electrolyte may further include a polymerization inhibitor together with the curing initiator in order to prevent cross-linking of a specific polymer compound below an appropriate temperature, or when including a polymer compound that should not be cross-linked below an appropriate temperature. That is, by adding the polymerization inhibitor, a solidified electrolyte having a solidifying agent function can be provided.

[0422] As an example of the present invention, the polymerization inhibitor can be applied without limitation as long as it is a polymerization inhibitor applicable to a battery (for example, an electrolyte), and can be applied without limitation as long as it has a polymerization inhibiting function or a polymerization suppressing function. For example, at least one selected from the group consisting of p-benzoquinone, 4-methoxyphenol, 4-t-butylcatechol, phenothiazine, hydroquinone, naphthoquinone, phenanthroquinone, toluquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acryloyloxy-p-benzoquinone, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,5-di-t-amylhydroquinone, etc., but is not limited thereto.

[0423] As an example of the present invention, the polymerization inhibitor is included in an amount of 0.01% by weight to 3% by weight based on the total mass of the electrolyte in the gel polymer electrolyte. When included within the above range, cross-linking of a specific polymer compound can be suppressed, curing during storage and transportation of the product can be prevented, and an electrolyte can be provided that can induce cross-linking at a specific temperature to prevent a decrease in the function of the electrolyte and a decrease in the performance of the battery due to high temperature or thermal runaway.

[0424] According to one embodiment of the present invention, the electrolyte composition can form a solid polymer electrolyte. For example, the electrolyte composition for the solid polymer electrolyte is:

[0425] (a) A silicon-based anion receptor compound represented by the above Chemical Formulas 1 to 6, in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom in the ring;

[0426] Or, a mixture of the silicon-based anion receptor compound represented by the above Chemical Formulas 1 to 6 and at least one selected from a linear hydrocarbon compound represented by the above Chemical Formula 8, in which an amine group substituted with an electron withdrawing group is introduced, or an electron withdrawing group is introduced into a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by the following Chemical Formulas 8 to 12, a polyalkylene oxide compound represented by the following Chemical Formula 13, and a siloxane compound represented by the above Chemical Formulas 14 to 16; an anion receptor;

[0427] (b) A polymer compound selected from linear, network, comb-shaped, and branched polymer compounds, or a crosslinkable polymer compound;

[0428] (c) A polymer support;

[0429] (d) A non-aqueous solvent; and

[0430] (e) It can contain an alkali metal ion-containing substance.

[0431]

[0432] In addition, the electrolyte composition for the solid polymer electrolyte can further contain (f) a polyalkylene glycol dialkyl ether and a single or two or more compounds selected from the non-aqueous solvent.

[0433] As an example of the present invention, in the electrolyte composition for the solid polymer electrolyte, the (a) anion receptor, the (d) non-aqueous solvent, and the (e) alkali metal ion-containing substance are as described in the electrolyte composition. Preferably, among the electrolyte compositions for the solid polymer electrolyte, the (a) anion receptor is 0.01% by weight to 30% by weight, the (d) non-aqueous solvent is 0% by weight to 10% by weight, and the (e) alkali metal ion-containing substance can be 10% by weight to 70% by weight.

[0434] As an example of the present invention, in the electrolyte composition for the solid polymer electrolyte, the polymer compound selected from among the linear, network, comb-shaped, and branched polymer compounds can be applied without limitation as long as it is applicable to a battery (for example, an electrolyte), and examples thereof include flexible inorganic polymers, linear polyethers, or both of these.

[0435] As an example of the present invention, the flexible inorganic polymer is polysiloxane, polyphosphazene, or a copolymer thereof, and the linear polyether can be polyalkylene oxide.

[0436] As an example of the present invention, the crosslinkable polymer compound can be applied without limitation as long as it is applicable to a battery (for example, an electrolyte), and as described above, compounds of Chemical Formulas 17 to 20 can be exemplified, but are not limited thereto.

[0437]

[0438] As an example of the present invention, the polymer compound selected from among the linear, network, comb-shaped, and branched molecular compounds, the crosslinkable polymer compound, or both of these can be 20% by weight to 90% by weight in the electrolyte composition for the solid polymer electrolyte. When included within the above ratio range, the mechanical properties are improved, and stable battery performance can be provided.

[0439] As an example of the present invention, the polymer support can be applied without limitation as long as it is a polymer support applicable to a battery (for example, an electrolyte). As an example of the present invention, it can include, but is not limited to, at least one selected from the group consisting of polyalkylene glycol-based polymers, polysiloxane-based polymers, polyacrylonitrile (PAN)-based polymers, and polyvinylidene fluoride (PVDF)-hexafluoropropylene-based polymers.

[0440] As an example of the present invention, the polymer support can be 1% to 30% by weight based on the total mass of the electrolyte composition among the electrolyte compositions for the solid polymer electrolyte. When included within the above range, an electrolyte with improved stability and electrical performance can be provided.

[0441] According to an embodiment of the present invention, when the electrolyte composition for the solid polymer electrolyte contains the crosslinkable polymer compound, it can further contain a curing initiator. As an example of the present invention, the curing initiator can include a photo-curing initiator, a thermo-curing initiator, or both of them. For example, the photo-curing initiator can include at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methylbenzoin ethyl ether, benzoin phenyl ether, α-acyl oxime ester, α,α-ditoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler’s ketone, etc., but is not limited thereto. For example, the thermo-curing initiator can include an azoisobutyronitrile-based compound, a peroxide-based compound, or both of them. More specifically, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tetramethylbutylperoxy neodecanoate, bis(4-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, butylperoxy neodecanoate, dipropyl peroxydicarbonate, etc. can be mentioned, but is not limited thereto.

[0442] As an example of the present invention, the curing initiator can be 1×10 based on the total mass of the electrolyte composition among the electrolyte compositions for the solid polymer electrolyte. -4 It can be from wt% to 0.1 wt%. When it is included within the above range, the polymer support can provide an electrolyte with improved stability and electrical performance.

[0443] According to an embodiment of the present invention, the electrolyte composition for the solid polymer electrolyte may further include a polymerization inhibitor together with the curing initiator in order to prevent crosslinking of a specific polymer compound below an appropriate temperature or when including a polymer compound that should not be crosslinked. That is, a solidified electrolyte can be produced by adding the polymerization inhibitor.

[0444] As an example of the present invention, the polymerization inhibitor can be applied without limitation as long as it is a polymer support applicable to a battery (for example, an electrolyte), and can be applied without limitation as long as it has a polymerization inhibition function or a polymerization suppression function. For example, at least one selected from the group consisting of p-benzoquinone, 4-methoxyphenol, 4-t-butylcatechol, phenothiazine, hydroquinone, naphthoquinone, phenanthrenequinone, toluquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acryloyloxy-p-benzoquinone, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone can be included, but is not limited thereto.

[0445] As an example of the present invention, the polymerization inhibitor is included in the solid polymer electrolyte in an amount of 0.01% by weight to 3% by weight based on the total mass of the electrolyte. When included within the above range, crosslinking of a specific polymer compound can be suppressed, curing during storage and transportation of the product can be prevented, and an electrolyte can be provided that can induce crosslinking at a specific temperature and prevent a decrease in the function of the electrolyte and a decrease in the performance of the battery due to high temperature or thermal runaway.

[0446] According to an embodiment of the present invention, the polyalkylene glycol dialkyl ether or non-aqueous solvent that may be contained in the solid polymer electrolyte serves as a plasticizer together with the anion receptor of the present invention. For example, examples of the polyalkylene glycol dialkyl ether include polyethylene glycol dimethyl ether (PEGDME), polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl ether, polypropylene glycol / polyethylene glycol copolymer with dibutyl ether terminals, and polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymer with dibutyl ether terminals, etc., and may include at least one selected from the group consisting of these, but is not limited thereto.

[0447] As an example of the present invention, the polyalkylene glycol dialkyl ether or non-aqueous solvent may be 1 wt% to 30 wt% in the electrolyte composition for the solid polymer electrolyte.

[0448] According to an embodiment of the present invention, the electrolyte composition can form a solidified electrolyte. For example, the electrolyte composition for the solidified electrolyte is:

[0449] (a) The silicon-based anion receptor compound represented by Chemical Formula 1 to Chemical Formula 6 in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom, or an electron withdrawing group is introduced into a nitrogen atom in the ring.

[0450] Alternatively, an anion receptor which is a mixture of a silicon-based anion receptor compound represented by the chemical formula 1 to chemical formula 6 and at least one selected from a linear hydrocarbon compound represented by the chemical formula 7 in which an amine group substituted with an electron-withdrawing group is introduced or an electron-withdrawing group is introduced into a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by the following chemical formula 8 to chemical formula 12, a polyalkylene oxide compound represented by the chemical formula 13, and a siloxane compound represented by the chemical formula 14 to chemical formula 16;

[0451] (b) A polymer compound selected from linear, network, comb-shaped and branched polymer compounds or a crosslinkable polymer compound;

[0452] (c) A polymer support;

[0453] (d) A non-aqueous solvent;

[0454] (e) An alkali metal ion-containing substance; and

[0455] (f) May contain a polymerization inhibitor.

[0456]

[0457] Optionally, (g) the electrolyte composition for the solid polymer electrolyte may further contain a single or two or more compounds selected from polyalkylene glycol dialkyl ethers and the non-aqueous solvent.

[0458] As an example of the present invention, the components (a) to (g) are as described in the electrolyte composition for the gel polymer electrolyte or the solid polymer electrolyte. Preferably, the total content of the polymer compound, the crosslinkable polymer compound, and the anion receptor is 12% by weight or more; or 13% by weight or more in the electrolyte composition for the solidified electrolyte. When included above such a minimum content range, a solidifying function capable of a rapid curing reaction can be provided at a temperature where there is a possibility of fire in the electrolyte or the battery, for example, about 130°C or higher. Further, the non-aqueous solvent (d) can be 20% by weight to 80% by weight in the electrolyte composition for the solidified electrolyte.

[0459] The present invention relates to an electrolyte containing a novel silicon-based anion receptor according to the present invention.

[0460] According to an embodiment of the present invention, the electrolyte is produced from the electrolyte composition according to the present invention. For example, the electrolyte can be a liquid, gel, or solid electrolyte. For example, the electrolyte can be a non-aqueous liquid electrolyte, a gel polymer electrolyte, a solid polymer electrolyte, a polymer electrolyte thin film, and / or a solidified electrolyte.

[0461] According to an embodiment of the present invention, the solidified electrolyte can be produced from the electrolyte composition for the gel polymer electrolyte and / or the electrolyte composition for the solid polymer electrolyte, or can be an electrolyte composition in which the curing reaction has not progressed. Further, it has a viscosity and / or fluidity close to or like that of a liquid. When applied to a battery, curing proceeds rapidly and quickly at a certain temperature, for example, 120°C or higher; or 130°C or higher, interrupting the operation of the battery, ensuring the thermal runaway and stability of the battery at high temperature, and preventing risks such as fire.

[0462] According to an embodiment of the present invention, the polymer electrolyte thin film can be produced, for example, by a curing process using the electrolyte composition for the gel polymer electrolyte and / or the electrolyte composition for the solid polymer electrolyte.

[0463] According to an embodiment of the present invention, the polymer electrolyte thin film can be manufactured by the following steps. As an example of the present invention, the manufacturing method can include a step of mixing constituent components to manufacture an electrolyte composition, and a step of coating the composition on a substrate and forming a thin film through drying and curing.

[0464] As an example of the present invention, when forming the gel polymer electrolyte thin film, the step of manufacturing the electrolyte composition is to manufacture a gel polymer electrolyte composition, put a non-aqueous solvent, an anion receptor, an alkali metal ion-containing substance, etc. into a container at an appropriate mixing ratio, stir the mixture with a stirrer to manufacture a solution, and then add a polymer support and mix them with each other. At this time, when mixing the polymer support, if necessary, a predetermined heat can be applied to melt it to manufacture a mixed solution of the gel polymer electrolyte composition for manufacturing the gel polymer electrolyte thin film of the present invention.

[0465] For example, the step of forming the thin film is to coat the mixed solution of the manufactured composition on a support substrate made of glass or polyethylene with an appropriate thickness, or a commercial Mylar film, and then dry the coated substrate, or expose it to electron beams, ultraviolet rays or gamma rays, or heat it to cause a curing reaction to form a thin film. As another example, the step of forming the thin film is to apply the composition mixed solution on the support substrate, fix thickness-adjusting spacers at both ends of the support substrate, cover it with another support substrate, and then use the curing irradiator or heat source to cause a curing reaction to manufacture a gel polymer electrolyte thin film.

[0466] As an example of the present invention, when forming the solid polymer electrolyte thin film, for example, the step of manufacturing the electrolyte composition is to manufacture a solid polymer electrolyte composition. An anion receptor or a polyalkylene glycol dialkyl ether or a non-aqueous solvent and an alkali metal ion-containing substance are placed in a container at an appropriate mixing ratio, and the mixture is stirred with a stirrer to produce a solution. Then, a network, branched or comb-shaped polymer compound or a crosslinkable polymer compound can be added and mixed with each other. Next, when mixing the network, branched or comb-shaped polymer compound, predetermined heat can be applied and dissolved as needed. At this time, in the case of a crosslinkable polymer compound in the mixed solution, a curing initiator and a polymerization inhibitor can be added and stirred to produce a mixed solution of the solid polymer electrolyte composition for manufacturing the solid polymer electrolyte thin film of the present invention.

[0467] For example, in the step of forming the thin film, the mixed solution of the manufactured composition is coated on a support substrate made of glass or polyethylene with an appropriate thickness, or a commercial Mylar film, and then the coated substrate is dried, or exposed to electron beams, ultraviolet rays or gamma rays, or heated to cause a curing reaction to form a thin film. As another example, in the step of forming the thin film, the composition mixed solution is applied on the support substrate, thickness adjustment spacers are fixed at both ends of the support substrate, and another support substrate is covered thereon, and then a solid polymer electrolyte thin film can be manufactured by causing a curing reaction using the curing irradiator or heat source.

[0468] The present invention relates to parts or components of an electrochemical cell, including a novel silicon-based anion receptor compound according to the present invention.

[0469] According to an embodiment of the present invention, it can be a cathode, an anode, a current collector thereof and / or a separator coated or impregnated with the silicon-based anion receptor compound, an electrolyte containing the silicon-based anion receptor compound, a battery film, etc.

[0470] For example, the silicon-based anion receptor compound can be applied to an electrolyte composition, a composition for a process, and the like.

[0471] For example, the cathode and the anode can be charged with the silicon-based anion receptor compound during the production of an electrode slurry containing an active material.

[0472] For example, it can be a separator impregnated or coated with the silicon-based anion receptor compound.

[0473] For example, it can be a battery film (e.g., a polymer electrolyte thin film), a film, and / or a sheet containing the silicon-based anion receptor compound or produced (e.g., cured, molded, etc.) with the electrolyte composition.

[0474] For example, the electrolyte can be a liquid, gel, or solid electrolyte using the electrolyte composition according to the present invention. The gel and solid electrolytes can be a gel polymer electrolyte thin film or a solid polymer electrolyte thin film, respectively.

[0475] The present invention relates to an electrochemical cell containing a silicon-based anion receptor compound according to the present invention.

[0476] According to an embodiment of the present invention, the electrochemical cell is a secondary or rechargeable battery and can include a liquid, gel, and / or solid electrolyte (e.g., a gel polymer electrolyte and a solid polymer electrolyte) produced with the electrolyte composition according to the present invention.

[0477] According to an embodiment of the present invention, a battery using the liquid or gel polymer electrolyte of the present invention includes a cathode, an anode, and a separator, and a battery using the solid polymer electrolyte of the present invention can include a cathode and an anode. In addition to the above-described battery configuration, for driving or operating the battery, a configuration known in the technical field of the present invention can be further included, but it is not specifically mentioned herein.

[0478] According to an embodiment of the present invention, the cathode and anode used in the battery can be those manufactured according to the cathodes, anodes and their manufacturing methods known in the technical field of the present invention, and the battery assembly can also be manufactured by the method of assembling ordinary cathodes, anodes and electrolytes.

[0479] As an example of the present invention, the cathode can include lithium; lithium alloys such as Li-Al, Li-Si, Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; Li x Intercalation compounds of lithium metal oxides such as WO2 or LiMoO2; intercalation compounds of lithium metal sulfides such as LiTiS2; mixtures thereof, or mixtures of these with alkali metals, but are not limited thereto.

[0480] As an example of the present invention, the anode can include transition metal oxides, transition metal chalcogenides, poly(carbon disulfide) polymers, organic-disulfide redox polymers, polyaniline, organic-disulfide / polyaniline composites, or mixtures containing these with oxychloride, but are not limited thereto.

[0481] According to an embodiment of the present invention, a primary battery composed of a non-aqueous liquid electrolyte containing the silicon-based anion receptor compound of the present invention is:

[0482] (a) A cathode containing lithium, a lithium alloy, a lithium-carbon intercalation compound, a lithium-graphite intercalation compound, a lithium metal oxide intercalation compound, a mixture containing these, or an alkali metal;

[0483] (b) An anode containing a transition metal oxide, a transition metal chalcogenide, a poly(carbon disulfide) polymer, an organic-disulfide redox polymer, polyaniline, an organic-disulfide / polyaniline composite, and an oxychloride, such as SO2, CuO, CuS, Ag2CrO4, I2, PbI2, PbS, SOCl2, V2O5, MoO3, MnO2, or polycarbon monofluoride (CF) n An anode containing;

[0484] (c) The non-aqueous liquid electrolyte of the present invention described above; and

[0485] (d) A separator is included, and the anode and cathode can be manufactured and the battery assembled by known methods.

[0486] According to one embodiment of the present invention, a secondary battery comprising a non-aqueous liquid electrolyte containing an anion receptor of the present invention is:

[0487] (a) A cathode containing lithium, a lithium alloy such as Li-Al, Li-Si, Li-Cd, a lithium-carbon intercalation compound, a lithium-graphite intercalation compound, a lithium metal oxide intercalation compound such as Li x WO2 or LiMoO2, or a substance in which lithium metal can act reversibly, such as a lithium metal sulfide intercalation compound such as LiTiS2;

[0488] (b) Li 2.5 V6O 13 、Li 1.2 V2O5、LiCoO2、LiNiO2、LiNi 1-x M x O2 (where M is Co, Mg, Al or Ti), a transition metal oxide capable of intercalating lithium such as LiMn2O4 or LiMnO2; a transition metal halide; or a chalcogenide such as LiNbSe3, LiTiS2 or LiMoS2; etc. An anode containing;

[0489] (c) The non-aqueous liquid electrolyte of the present invention described above; and

[0490] (d) It includes a separator, and the anode, cathode can be manufactured and the battery can be assembled by known methods.

[0491] According to an embodiment of the present invention, a secondary battery composed of a gel polymer electrolyte containing the silicon-based anion receptor compound of the present invention can include the gel polymer electrolyte of the present invention together with the cathode, anode, and separator used in the secondary battery composed of the non-aqueous liquid electrolyte.

[0492] According to an embodiment of the present invention, a secondary battery composed of a solid polymer electrolyte containing the silicon-based anion receptor compound can include the solid polymer electrolyte of the present invention together with the cathode and anode used in the secondary battery composed of the non-aqueous liquid electrolyte.

[0493] According to an embodiment of the present invention, the battery is a battery that uses an electrolyte containing a non-aqueous solvent, and can be, for example, a lithium-ion battery, a lithium-ion polymer battery, an alkali metal battery, etc., but is not limited thereto.

[0494] According to an embodiment of the present invention, the battery can be reused by replacing the used waste electrolyte.

[0495] The present invention relates to a reused battery manufactured using the anion receptor according to the present invention.

[0496] According to an embodiment of the present invention, the reused battery can be a reusable battery in which the waste electrolyte in a used waste battery (for example, a battery for an electric vehicle) is replaced and filled with an electrolyte containing the silicon-based anion receptor compound. That is, the reused battery can be composed of the components of the used waste battery and an electrolyte containing the silicon-based anion receptor compound according to the present invention.

[0497] According to an embodiment of the present invention, the rechargeable battery is for manufacturing a rechargeable battery by an electrolyte replacement and filling method including the silicon-based anion receptor compound of the present invention, and the method for manufacturing the rechargeable battery includes:

[0498] (a) preparing a waste battery;

[0499] (b) removing the waste electrolyte and other impurities in the waste battery; and

[0500] (c) injecting the electrolyte according to the present invention into the waste battery to regenerate it. It can include these steps.

[0501] As an example of the present invention, the steps of preparing a waste battery and removing the waste electrolyte and other impurities in the waste battery can be performed in a dry room or an inert atmosphere.

[0502] As an example of the present invention, the step of removing the waste electrolyte and other impurities in the waste battery can be performed under vacuum conditions.

[0503] As an example of the present invention, for the step of injecting the electrolyte according to the present invention into the waste battery to regenerate it, after introducing a new electrolyte into the waste battery, a method of applying vibration at a certain temperature can be used. For example, the temperature can be 20°C to 50°C.

[0504] According to an embodiment of the present invention, the rechargeable battery and its manufacturing method are made by replacing and filling the waste electrolyte in a used electric vehicle battery (waste battery) with an electrolyte containing the silicon-based anion receptor compound according to the present invention to make it reusable. For example, in the case of a waste battery used for an electric vehicle, since there is a high risk of explosion and fire when it is in a charged state, after completely discharging the charged current, it may be necessary to separate the battery pack and then separate it into each cell. Each discharged cell can be evaluated for its charge capacity and discharge capacity using a charger and classified by grade according to the capacity.

[0505] For example, the cells are classified into cells with a capacity of 80% or more, 68% - 80%, and 68% or less. The regeneration process is performed on the cells with a capacity of 68% or less where the capacity has significantly decreased. For the cells with a decreased capacity, after bringing them to a fully discharged state, holes are made in each cell in a dry room or an inert atmosphere environment, and the existing electrolyte, generated gas, and impurities can be removed by vacuum. Then, an electrolyte containing an additive capable of restoring the performance is injected into the cell to plug the holes, and the electrolyte is uniformly distributed through a process of shaking the cell for a certain period of time under conditions of a certain temperature (25°C - 50°C) to activate the anode / cathode active materials and increase the activity of Li ions, thereby restoring the capacity of the battery.

[0506] [Embodiment for Carrying Out the Invention]

[0507] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples are merely for illustrating the present invention, and the content of the present invention is not limited to the following Examples.

[0508]

[0509] [Example 1]

[0510] [Reaction Formula 1-1] Synthesis of 2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-N-(3-trimethylsilyl-propyl)-acetamide (Compound 1-1)

[0511] JPEG2025522864000179.jpg2993

[0512] Trimethylsilane (7.42 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (24.91 g, 0.1 mol) were dissolved in 50 ml of tetrahydrofuran and added dropwise. Under a nitrogen atmosphere, the mixture was refluxed at 65 °C for 8 hours, cooled to room temperature, activated carbon was added and stirred, filtered, and then toluene was evaporated under reduced pressure to obtain the product 2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-N-(3-trimethylsilyl-propyl)-acetamide (Compound 1-1).

[0513] 1 H NMR (300 MHz, CDCl3): ppm 0.00 (m, 9H), 0.62 (m, 2H), 1.6 (m, 2H), 3.48 (m, 2H); 13 C NMR (300 MHz, CDCl3): ppm 0.3, 13.3, 23.7, 44.0, 122.6, 168.9; 19 F NMR (CDCl3): ppm -77.2 (s)

[0514]

[0515] [Reaction Scheme 1-2] Synthesis of 1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)-N-(3-(trimethylsilyl)propyl)methanesulfonamide (Compound 1-2)

[0516] JPEG2025522864000180.jpg3697

[0517] Trimethyl-silane (7.42 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoro-methanesulfonyl)sulfonyl)-methanesulfonamide (32.12 g, 0.1 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above, to obtain the product 1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)-N-(3-(trimethylsilyl)propyl)methanesulfonamide (Compound 1-2).

[0518] 1 H NMR (300 MHz, CDCl3): ppm 0.00 (m, 9H), 0.62 (m, 2H), 1.6 (m, 2H), 2.65 (m, 2H); 13 C NMR (300 MHz, CDCl3): ppm 0.3, 13.3, 21.9, 40.0, 145.8; 19 F NMR (CDCl3): ppm -74.5 (s)

[0519]

[0520] [Reaction Scheme 1-3] Synthesis of (fluorosulfonyl)(3-(trimethylsilyl)propyl)sulfamoyl fluoride (Compound 1-3)

[0521] JPEG2025522864000181.jpg3398

[0522] Trimethylsilane (7.42 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (22.12 g, 0.1 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above, to obtain the product (fluorosulfonyl)(3-(trimethylsilyl)propyl)sulfamoyl fluoride (Compound 1-3).

[0523] 11H NMR (300 MHz, CDCl3): δ 0.06 (m, 9H), 0.62 (m, 2H), 1.6 (m, 2H), 2.65 (m, 2H); 13 13C NMR (300 MHz, CDCl3): δ 2.1, 20.1, 30.4, 33.9; 19 19F NMR (CDCl3): δ -74.5 (s)

[0524]

[0525] [Example 2]

[0526] [Reaction Formula 2-1] Synthesis of N-[3-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silan-yl)-propyl]-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 2-1)

[0527] JPEG2025522864000182.jpg30102

[0528] Dimethyl-silane (6.02 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (49.82 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product N-[3-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silan-yl)-propyl]-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 2-1).

[0529] 1 1H NMR (300 MHz, CDCl3): δ 0.00 (m, 6H), 0.62 (m, 4H), 1.6 (m, 4H), 3.48 (m, 4H); 1313C NMR (300 MHz, CDCl3): ppm -1.9, 11.1, 24.0, 44.0, 122.6, 168.9; 19 19F NMR (CDCl3): ppm -77.3 (s)

[0530]

[0531] [Reaction Scheme 2-2] Synthesis of N,N'-((dimethylsilanediyl)bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 2-2)

[0532] JPEG2025522864000183.jpg32100

[0533] Dimethyl-silane (6.02 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoro-methanesulfonyl)sulfonyl)-methanesulfonamide (64.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N'-((dimethylsilanediyl)bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 2-2).

[0534] 1 1H NMR (300 MHz, CDCl3): ppm 0.00 (m, 6H), 0.62 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H); 13 13C NMR (300 MHz, CDCl3): ppm -1.9, 11.1, 22.2, 40.0, 145.8; 19 19F NMR (CDCl3): ppm -74.3 (s)

[0535]

[0536] Synthesis of ((Dimethylsilanediyl)bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 2-3) [Reaction Formula 2-3]

[0537] JPEG2025522864000184.jpg3298

[0538] Dimethyl-silane (6.02 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (44.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product ((dimethylsilanediyl)bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 2-3).

[0539] 1 H NMR (300 MHz, CDCl3): ppm 0.21 (m, 6H), 0.62 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 0.7, 17.9, 30.7, 33.9; 19 F NMR (CDCl3): ppm -74.3 (s)

[0540]

[0541] [Example 3]

[0542] [Reaction Formula 3-1] Synthesis of N-[3-(Bis-{3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-methyl-silanilyl)-propyl]-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 3-1)

[0543] JPEG2025522864000185.jpg4993

[0544] Methyl-silane (4.61 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (74.73 g, 0.3 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above, to obtain the product N-[3-(bis-{3-[bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-methyl-silanilyl)-propyl]-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 3-1).

[0545] 1 H NMR (300 MHz, CDCl3): ppm 0.00 (m, 3H), 0.62 (m, 6H), 1.6 (m, 6H), 3.48 (m, 6H); 13 C NMR (300 MHz, CDCl3): ppm -4.1, 8.9, 24.3, 44.0, 122.6, 168.9; 19 F NMR (CDCl3): ppm -77.2 (s)

[0546]

[0547] [Reaction Formula 3-2] Synthesis of N,N’,N’’-((methylsilanetriyl)tris(propane-3,1-diyl))tris(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 3-2)

[0548] JPEG2025522864000186.jpg4691

[0549] Methyl-silane (4.61 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoromethanesulfonyl)sulfonyl)-methanesulfonamide (96.36 g, 0.3 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N’,N’’-((methylsilanetriyl)tris(propane-3,1-diyl))tris(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 3-2).

[0550] 1 H NMR (300 MHz, CDCl3): ppm 0.00 (m, 3H), 0.62 (m, 6H), 1.6 (m, 6H), 2.65 (m, 6H); 13 C NMR (300 MHz, CDCl3): ppm -4.1, 8.9, 22.5, 40.0, 145.8; 19 F NMR (CDCl3): ppm -65.2 (s)

[0551]

[0552] [Reaction Scheme 3-3] Synthesis of ((methylsilanetriyl)tris(propane-3,1-diyl)tris((fluorosulfonyl)sulfamoyl fluoride) (Compound 3-3)

[0553] JPEG2025522864000187.jpg44103

[0554] Methyl-silane (4.61 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (66.36 g, 0.3 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((methylsilanetriyl)tris(propane-3,1-diyl)tris((fluorosulfonyl)sulfamoyl fluoride) (Compound 3-3).

[0555] 1 H NMR (300 MHz, CDCl3): ppm 0.21 (m, 3H), 0.62 (m, 6H), 1.6 (m, 6H), 2.65 (m, 6H); 13 C NMR (300 MHz, CDCl3): ppm -0.4, 15.7, 33.9; 19 F NMR (CDCl3): ppm -65.2 (s)

[0556]

[0557] [Example 4]

[0558] [Reaction Formula 4-1] Synthesis of N-(3-{[2-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanyl)-ethyl]-dimethyl-silanyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 4-1)

[0559] JPEG2025522864000188.jpg30121

[0560] 1,2-Bis-dimethylsilanyl-ethane (14.64 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (49.82 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product N-(3-{[2-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanyl)-ethyl]-dimethyl-silanyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 4-1).

[0561] 11H NMR (300 MHz, CDCl3): δ 0 (m, 12H), 0.62 (m, 4H), 0.7 (m, 4H), 1.6 (m, 4H), 3.48 (m, 4H); 13 13C NMR (300 MHz, CDCl3): δ -2.2, 9.0, 10.8, 24.0, 44.0, 122.6, 168.9; 19 19F NMR (CDCl3): δ -79.4 (s)

[0562]

[0563] [Reaction Scheme 4-2] Synthesis of N,N'-((ethane-1,2-diylbis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 4-2)

[0564] JPEG2025522864000189.jpg30112

[0565] 1,2-Bis-dimethylsilyl-ethane (14.64 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoromethanesulfonyl)sulfonyl)methanesulfonamide (64.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N'-((ethane-1,2-diylbis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 4-2).

[0566] 1 1H NMR (300 MHz, CDCl3): δ 0 (m, 12H), 0.62 (m, 4H), 0.7 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H), 7.54 (m, 2H); 1313C NMR (300 MHz, CDCl3): ppm -2.2, 9.0, 10.8, 22.2, 40.0, 145.8; 19 19F NMR (CDCl3): ppm -79.2 (s)

[0567]

[0568] [Reaction Scheme 4-3] Synthesis of ((ethane-1,2-diylbis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 4-3)

[0569] JPEG2025522864000190.jpg27120

[0570] 1,2-Bis-dimethylsilyl-ethane (14.64 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (44.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((ethane-1,2-diylbis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 4-3).

[0571] 1 1H NMR (300 MHz, CDCl3): ppm 0.21 (m, 12H), 0.62 (m, 4H), 0.7 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H); 13 13C NMR (300 MHz, CDCl3): ppm 0.4, 15.0, 17.6, 30.7, 33.9; 19 19F NMR (CDCl3): ppm -79.2 (s)

[0572]

[0573] [Example 5]

[0574] [Reaction Formula 5-1] Synthesis of N-(3-{[2-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanilyl)-phenyl]-dimethyl-silanilyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-1)

[0575] JPEG2025522864000191.jpg27113

[0576] 1,4-Bis-dimethylsilanilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (49.82 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product N-(3-{[2-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanilyl)-phenyl]-dimethyl-silanilyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-1).

[0577] 1 H NMR (300 MHz, CDCl3): ppm 0.66(m, 12H), 1.45(m, 4H), 1.60(m, 4H), 348(m, 4H), 7.46(m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 23.6, 44.0, 122.6, 132.7, 168.9; 19 F NMR (CDCl3): ppm -78.5 (s)

[0578]

[0579] [Reaction Formula 5-2] Synthesis of N,N'-((1,4-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-2)

[0580] JPEG2025522864000192.jpg28113

[0581] 1,4-Bis-dimethylsilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoro-methanesulfonyl)sulfonyl)-methanesulfonamide (64.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product N,N'-((1,4-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-2).

[0582] 1 H NMR (300 MHz, CDCl3): ppm 0.66 (m, 12H), 1.45 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H), 7.46 (m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 21.8, 40.0, 132.7, 145.8; 19 F NMR (CDCl3): ppm -79.4 (s)

[0583]

[0584] [Reaction Formula 5-3] Synthesis of ((1,4-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-3)

[0585] JPEG2025522864000193.jpg25120

[0586] 1,4-Bis-dimethylsilanil - benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (44.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((1,4-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-3).

[0587] 1 H NMR (300 MHz, CDCl3): ppm 0.25(m, 12H), 1.45(m, 4H), 1.6(m, 4H), 2.65(m, 4H), 7.23(m, 2H), 7.38(m, 2H); 13 C NMR (300 MHz, CDCl3): ppm -2.6, 12.5, 30.3, 31.4, 129.4, 136.2; 19 F NMR (CDCl3): ppm -79.3 (s)

[0588]

[0589] [Reaction Scheme 5-4] Synthesis of N-(3-{[2-({3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanil)-phenyl]-dimethyl-silanil}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-4)

[0590] JPEG2025522864000194.jpg41107

[0591] 1,2-Bis-dimethylsilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (49.82 g, 0.2 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above, to obtain the product N-(3-{[2-({3-[bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silyl)-phenyl]-dimethyl-silyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-4).

[0592] 1 H NMR (300 MHz, CDCl3): ppm 0.66(m, 12H), 1.45(m, 4H), 1.60(m, 4H), 3.48(m, 4H), 7.22(m, 2H), 7.46(m, 2H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 23.6, 44.0, 122.6, 128.2, 132.7, 145.0, 168.9; 19 F NMR (CDCl3): ppm -78.5 (s)

[0593]

[0594] [Reaction Formula 5-5] Synthesis of N,N’-((1,2-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-5)

[0595] JPEG2025522864000195.jpg38100

[0596] 1,2-Bis-dimethylsilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoromethanesulfonyl)sulfonyl)-methanesulfonamide (64.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N'-((1,2-phenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-5).

[0597] 1 H NMR (300 MHz, CDCl3): ppm 0.66 (m, 12H), 1.45 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H), 7.22 (m, 2H), 7.46 (m, 2H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 21.8, 40.0, 128.2, 132.7, 145.0, 145.8; 19 F NMR (CDCl3): ppm -79.3 (s)

[0598]

[0599] [Reaction Scheme 5-6] Synthesis of ((1,2-diphenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-6)

[0600] JPEG2025522864000196.jpg39101

[0601] 1,2-Bis-dimethylsilanilyl-benzene (19.44 g, 0.1 mol), a Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (44.24 g, 0.2 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((1,2-diphenylenebis(dimethylsilanediyl))bis(propane-3,1-diyl))bis((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-6).

[0602] 1 H NMR (300 MHz, CDCl3): ppm 0.25 (m, 12H), 1.45 (m, 4H), 1.6 (m, 4H), 2.65 (m, 4H), 7.23 (m, 2H), 7.38 (m, 2H); 13 C NMR (300 MHz, CDCl3): ppm -2.6, 12.5, 30.3, 31.4, 129.4, 136.2; 19 F NMR (CDCl3): ppm -79.3 (s)

[0603]

[0604] [Reaction Scheme 5-7] Synthesis of N-(3-{[2-({3-[acetyl-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanilyl)-4-({3-[bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanilyl)-phenyl]-dimethyl-silanilyl}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-7)

[0605] JPEG2025522864000197.jpg41108

[0606] 1,2,4-Tris-dimethylsilanil-benzene (25.26 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (74.73 g, 0.3 mol) were reacted under the same conditions as in Reaction Formula 1-1 of Example 1 above to obtain the product N-(3-{[2-({3-[acetyl-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanil)-4-({3-[bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-dimethyl-silanil)-phenyl]-dimethyl-silanil}-propyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (Compound 5-7).

[0607] 1 H NMR (300 MHz, CDCl3): ppm 0.66 (m, 12H), 1.45 (m, 6H), 1.60 (m, 6H), 3.48 (m, 6H), 7.44 (m, 2H), 7.68 (m, 1H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 23.6, 23.6, 44.0, 122.6, 132.0, 133.4, 137.6, 144.3, 145.4, 168.9; 19 F NMR (CDCl3): ppm -78.5 (s)

[0608]

[0609] [Reaction Formula 5-8] Synthesis of N,N’,N’’-((benzene-1,2,4-triyltris(dimethylsilanediyl))tris(propane-3,1-diyl))tris(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-8)

[0610] JPEG2025522864000198.jpg40107

[0611] 1,2-Bis-dimethylsilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoromethanesulfonyl)sulfonyl)-methanesulfonamide (96.72 g, 0.3 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N’,N’’-((benzene-1,2,4-triyltris(dimethylsilanediyl))tris(propane-3,1-diyl))tris(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide) (Compound 5-8).

[0612] 1 H NMR (300 MHz, CDCl3): ppm 0.66 (m, 18H), 1.45 (m, 6H), 1.60 (m, 6H), 2.65 (m, 6H), 7.44 (m, 2H), 7.68 (m, 1H); 13 C NMR (300 MHz, CDCl3): ppm 0.2, 13.2, 23.6, 40.0, 132.0, 133.0, 133.4, 137.6, 144.3, 145.4, 145.8; 19 F NMR (CDCl3): ppm -78.7 (s)

[0613]

[0614] [Reaction Scheme 5-9] Synthesis of ((benzene-1,2,4-triyltris(dimethylsilanediyl))tris(propane-3,1-diyl))tris((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-9)

[0615] JPEG2025522864000199.jpg40110

[0616] 1,2-bis-dimethylsilanilyl-benzene (19.44 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (66.36 g, 0.3 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((benzene-1,2,4-triyltris(dimethylsilanediyl))tris(propane-3,1-diyl))tris((fluorosulfonyl)sulfamoyl fluoride) (Compound 5-9).

[0617] 1 H NMR (300 MHz, CDCl3): ppm 0.25 (m, 18H), 1.45 (m, 6H), 1.60 (m, 6H), 2.65 (m, 6H), 7.36 (m, 3H), 7.68 (m, 1H); 13 C NMR (300 MHz, CDCl3): ppm -2.6, 12.5, 30.3, 31.4, 122.4, 128.7, 134.0, 139.8, 140.8; 19 F NMR (CDCl3): ppm -78.7 (s)

[0618]

[0619] [Example 6]

[0620] [Reaction Scheme 6-1] Synthesis of N-{3-[bis-[3-(bis-(2,2,2-trifluoro-acetyl)-amino)-propyl]-(4-{tris-[3-(bis-(2,2,2-trifluoro-acetyl)-amino)-propyl]-silanilyl}-phenyl)-silanilyl]-propyl}-2,2,2-trifluoro-acetamide (Compound 6-1)

[0621] JPEG2025522864000200.jpg45103

[0622] 1,4-Bis-silanilyl-benzene (13.83 g, 0.1 mol), a Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (149.46 g, 0.6 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N-{3-[bis-[3-(bis-(2,2,2-trifluoro-acetyl)-amino)-propyl]-(4-{tris-[3-(bis-(2,2,2-trifluoro-acetyl)-amino)-propyl]-silanilyl}-phenyl)-silanilyl]-propyl}-2,2,2-trifluoroacetamide (Compound 6-1).

[0623] 1 H NMR (300 MHz, CDCl3): ppm 1.45 (m, 12H), 1.60 (m, 12H), 3.48 (m, 12H), 7.46 (m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 8.8, 24.2, 44.0, 122.6, 132.7, 140.5, 168.9; 19 F NMR (CDCl3): ppm -78.3 (s)

[0624]

[0625] [Reaction Scheme 6-2] Synthesis of N,N’,N’’,N’’’,N’’’’,N’’’’’-((1,4-phenylenebis(silanetetrayl))hexakis(propane-3,1-diyl))hexakis(1,1,1,1-tetrafluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (Compound 6-2)

[0626] JPEG2025522864000201.jpg51111

[0627] 1,4-Bis-silanilyl-benzene (13.83 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and N-allyl-1,1,1-trifluoro-N-((trifluoromethanesulfonyl)sulfonyl)-methanesulfonamide (193.44 g, 0.3 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product N,N’,N’’,N’’’,N’’’’,N’’’’’-((1,4-phenylenebis(silane tetrayl))hexakis(propane-3,1-diyl))hexakis(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (Compound 6-2).

[0628] 1 H NMR (300 MHz, CDCl3): ppm 1.45 (m, 12H), 1.60 (m, 12H), 2.65 (m, 12H), 7.46 (m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 8.8, 22.4, 40.0, 132.7, 145.8; 19 F NMR (CDCl3): ppm -78.6 (s)

[0629]

[0630] [Reaction Scheme 6-3] Synthesis of ((1,4-phenylenebis(silane tetrayl))hexakis(propane-3,1-diyl))hexakis((fluorosulfonyl)sulfamoyl fluoride) (Compound 6-3)

[0631] JPEG2025522864000202.jpg46110

[0632] 1,4-Bis-silanilyl-benzene (13.83 g, 0.1 mol), a Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst, and allyl(trifluoromethylsulfonyl)sulfamoyl fluoride (132.7 g, 0.6 mol) were reacted under the same conditions as in Reaction Scheme 1-1 of Example 1 above to obtain the product ((1,4-phenylenebis(silanetetrayl))hexakis(propane-3,1-diyl))hexakis((fluorosulfonyl)sulfamoyl fluoride) (Compound 6-3).

[0633] 1 H NMR (300 MHz, CDCl3): ppm 1.45 (m, 12H), 1.60 (m, 12H), 2.65 (m, 12H), 7.38 (m, 4H); 13 C NMR (300 MHz, CDCl3): ppm 8.1, 30.9, 31.4, 133.6, 140.5; 19 F NMR (CDCl3): ppm -78.6 (s)

[0634]

[0635] Example 7. Manufacture of Ion-Conductive Thin Film (1)

[0636] The anion receptor compound 1-1 (0.25 g) produced in Example 1-1 was mixed with a crosslinking agent, bisphenol A ethoxylate dimethacrylate (manufactured by Aldrich, Mw = 1,700, "BIS-15m", 0.25 g), poly(ethylene glycol) dimethyl ether (Mw = 350, "PEGDME 300", 0.5 g), and lithium trifluoromethanesulfonimide (Li(CF3SO2)2N, 0.7809 g). Dimethylphenylacetophenone (DMPA, 0.0075 g) was added to this mixture, and the mixture solution was applied to a conductive glass substrate and then exposed to ultraviolet light with a wavelength of 350 nm for 30 minutes under a nitrogen atmosphere. A solid polymer thin film was produced by this light irradiation.

[0637]

[0638] Example 8. Manufacture of Ion-Conductive Thin Film (2)

[0639] To the anionic receptor compound 1-2 (0.25 g) and lithium trifluoromethanesulfonate (0.7234 g) produced in Example 1-2, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0640]

[0641] Example 9. Manufacture of Ion-Conductive Thin Film (3)

[0642] To the anionic receptor compound 1-3 (0.25 g) and lithium trifluoromethanesulfonate (0.7499 g) produced in Examples 1 to 3, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0643]

[0644] Example 10. Manufacture of Ion-Conductive Thin Film (4)

[0645] To the anionic receptor compound 2-1 (0.25 g) and lithium trifluoromethanesulfonate (0.6597 g) produced in Example 2-1, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0646]

[0647] Example 11. Manufacture of Ion-Conductive Thin Film (5)

[0648] To 0.25 g of the anion receptor compound 2-2 produced in Example 2-2 and 0.6237 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7 above. A solid polymer thin film was produced in the same manner as in Example 7 above.

[0649]

[0650] Example 12. Manufacture of Ion-Conductive Thin Film (6)

[0651] To 0.25 g of the anion receptor compound 2-3 produced in Example 2-3 and 0.6109 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7 above, and a solid polymer thin film was produced in the same manner as in Example 7 above.

[0652]

[0653] Example 13. Manufacture of Ion-Conductive Thin Film (7)

[0654] To 0.25 g of the anion receptor compound 3-1 produced in Example 3-1 and 0.4846 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7 above, and a solid polymer thin film was produced in the same manner as in Example 7 above.

[0655]

[0656] Example 14. Manufacture of Ion-Conductive Thin Film (8)

[0657] To 0.25 g of the anion receptor compound 3-2 produced in Example 3-2 and 0.4530 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0658]

[0659] Example 15. Manufacture of Ion-Conductive Thin Film (9)

[0660] To 0.25 g of the anion receptor compound 3-3 produced in Example 3-3 and 0.4877 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0661]

[0662] Example 16. Manufacture of Ion-Conductive Thin Film (10)

[0663] To 0.25 g of the anion receptor compound 4-1 produced in Example 4-1 and 0.4846 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0664]

[0665] Example 17. Manufacture of Ion-Conductive Thin Film (11)

[0666] To the anion receptor compound 4-2 (0.25 g) produced in Example 4-2 and lithium trifluoromethanesulfonate imide (0.4530 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0667]

[0668] Example 18. Manufacture of Ion-Conductive Thin Film (12)

[0669] To the anion receptor compound 4-3 (0.25 g) produced in Example 4-3 and lithium trifluoromethanesulfonate imide (0.4877 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0670]

[0671] Example 19. Manufacture of Ion-Conductive Thin Film (13)

[0672] To the anion receptor compound 5-1 (0.25 g) produced in Example 5-1 and lithium trifluoromethanesulfonate imide (0.4846 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0673]

[0674] Example 20. Manufacture of Ion-Conductive Thin Film (14)

[0675] To the anion receptor compound 5-2 (0.25 g) produced in Example 5-2 and lithium trifluoromethanesulfonate imide (0.4530 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0676]

[0677] Example 21. Manufacture of Ion-Conductive Thin Film (15)

[0678] To the anion receptor compound 5-3 (0.25 g) produced in Example 5-3 and lithium trifluoromethanesulfonate imide (0.4877 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0679]

[0680] Example 22. Manufacture of Ion-Conductive Thin Film (16)

[0681] To the anion receptor compound 5-4 (0.25 g) produced in Example 5-4 and lithium trifluoromethanesulfonate imide (0.4846 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0682]

[0683] Example 23. Manufacture of Ion-Conductive Thin Film (17)

[0684] To 0.25 g of the anion receptor compound 5-5 produced in Example 5-5 and 0.4530 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0685]

[0686] Example 24. Manufacture of Ion-Conductive Thin Film (18)

[0687] To 0.25 g of the anion receptor compound 5-3 produced in Example 5-6 and 0.4877 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0688]

[0689] Example 25. Manufacture of Ion-Conductive Thin Film (19)

[0690] To 0.25 g of the anion receptor compound 5-7 produced in Example 5-7 and 0.4846 g of lithium trifluoromethanesulfonateimide, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0691]

[0692] Example 26. Manufacture of Ion-Conductive Thin Film (20)

[0693] To the anion receptor compound 5-8 (0.25 g) and lithium trifluoromethanesulfonate imide (0.4530 g) produced in Examples 5-8, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0694]

[0695] Example 27. Manufacture of Ion-Conductive Thin Film (21)

[0696] To the anion receptor compound 5-9 (0.25 g) and lithium trifluoromethanesulfonate imide (0.4877 g) produced in Example 5-9, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0697]

[0698] Example 28. Manufacture of Ion-Conductive Thin Film (22)

[0699] To the anion receptor compound 6-1 (0.25 g) and lithium trifluoromethanesulfonate imide (0.4846 g) produced in Example 6-1, bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0700]

[0701] Example 29. Manufacture of Ion-Conductive Thin Film (23)

[0702] To the anion receptor compound 6-2 (0.25 g) produced in Example 6-2 and lithium trifluoromethanesulfonate (0.4530 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0703]

[0704] Example 30. Manufacture of Ion-Conductive Thin Film (24)

[0705] To the anion receptor compound 6-3 (0.25 g) produced in Example 6-3 and lithium trifluoromethanesulfonate (0.4877 g), bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone, which are crosslinking agents, were mixed and added in the same amounts as in Example 7, and a solid polymer thin film was produced in the same manner as in Example 7.

[0706]

[0707] [Table 1]

[0708] JPEG2025522864000203.jpg9591

[0709] Comparative Example 1. Manufacture of Thin Film Without Anion Receptor

[0710] Using the composition of the compounds as shown in Table 1 above, a solid polymer thin film was produced in the same manner as in Example 7. As shown in Table 1, the polymer electrolyte of the comparative example does not contain an anion receptor.

[0711]

[0712] Experimental Examples 1 - 25. Ion Conductivity Experiments

[0713] The ionic conductivities of the solid polymer electrolyte thin films produced in Examples 7 to 30 and Comparative Example 1 were measured. The ionic conductivity was measured by the following method.

[0714] After applying the solid polymer electrolyte composition onto a band-shaped conductive glass substrate or a lithium-copper foil, it was photocured, thoroughly dried, and then the AC impedance between band-shaped or sandwich-shaped electrodes was measured under a nitrogen atmosphere. The measured values were analyzed with a frequency response analyzer to determine the complex impedance.

[0715] The band-shaped electrodes were manufactured and used by attaching a masking tape with a width of 0.5 - 2 mm to the center of conductive glass (ITO) at intervals of about 0.5 - 2 mm, placing it in an etching solution for etching, and then washing and drying. The results of measuring the ionic conductivity at 30 °C for the manufactured solid polymer electrolyte thin films are shown in Table 2 below.

[0716] [Table 2] JPEG2025522864000204.jpg9863

[0717] From the above results, it can be seen that the solid polymer electrolyte containing an anion receptor exhibits higher ionic conductivity than the solid polymer electrolyte without an anion receptor.

[0718]

[0719] Example 31. Manufacture of Battery Using Liquid Electrolyte Containing Anion Receptor

[0720] The anion receptor compound 1-1 (AR-7 in Figure 1, 0.015 g) manufactured in Example 1-1, the in-ion receptor compound 2-1 (AR-8B in Figure 1, 0.015 g) manufactured in Example 2-1, and the anion receptor compound 1-3 (AR-8C, 0.015 g) manufactured in Example 3-1 were mixed with an organic solvent EC / DMC / EMC (1:1:1, 1M LiPF6) (1.0 g). In a dry room (humidity: within 3%), a battery was assembled by sandwiching a polypropylene separator impregnated with the above mixture solution between an NMC ternary anode and a graphite carbon cathode and vacuum-sealing them.

[0721]

[0722] Comparative Example 2. Manufacture of Battery Using Liquid Electrolyte Without Anion Receptor

[0723] A separator impregnated with 1.0 g of an organic solvent EC / DMC / DEC (1:1:1, 1 M LiPF6), an NMC ternary anode, and a graphite carbon cathode were assembled in the same manner as in Example 31 to fabricate a battery.

[0724]

[0725] Experimental Example 26. Lithium Cycling Performance Experiment

[0726] The lithium cycling performance and efficiency of the batteries fabricated in Example 31 and Comparative Example 2 of the present invention were measured at room temperature using a charge-discharge experimental apparatus (Maccor 4000). Charging and discharging were performed at 1C. The battery was charged and discharged between 3.0 V and 4.2 V at a constant current density of 0.6 mA / cm 2 (charging) and 1.5 mA / cm 2 (discharging).

[0727] FIG. 1 shows a comparison of the capacity retention rate at high temperature (60 °C) over time for batteries fabricated using an electrolyte containing the anion receptor compound 1-1 (AR7 in FIG. 1), the anion receptor compound (AR-8B in FIG. 1), and the anion receptor compound (AR-8C in FIG. 1) of the present invention, and an electrolyte not containing the anion receptor compound 1-1 of the present invention. The battery using the electrolyte containing the anion receptor compound 1-1 (AR-7 in FIG. 1), the anion receptor compound (AR-8B in FIG. 1), and the anion receptor compound (AR-8C in FIG. 1) showed a significantly higher capacity retention rate than the battery using the electrolyte without the anion receptor compound (Ref).

[0728] Therefore, the above results suggest that using an anion receptor results in a high capacity retention rate at high temperature and a low internal resistance increase rate, indicating an extended battery life and high temperature stability.

[0729] Further, the present invention provides a battery that reuses a spent electrolyte in a used electric vehicle battery (waste battery) by replacing and filling it with an electrolyte added with the anion receptor.

[0730] Hereinafter, a method for manufacturing a reusable battery by replacing and filling a novel electrolyte containing the anion receptor of the present invention will be described.

[0731] The method for manufacturing a reusable battery of the present invention includes a step of preparing a waste battery, a step of removing the waste electrolyte and other impurities in the waste battery, and a step of injecting and regenerating the novel electrolyte of the present invention into the waste battery.

[0732] The step of removing the waste electrolyte and other impurities in the waste battery can be performed in a dry room or an inert atmosphere.

[0733] Alternatively, the step of removing the waste electrolyte and other impurities in the waste battery can be performed under vacuum conditions.

[0734] In the step of injecting and regenerating the novel electrolyte into the waste battery, after injecting the novel electrolyte into the waste battery, a method of applying vibration at a certain temperature can be used, and the certain temperature can be 20 to 50°C.

[0735] To explain the method of regenerating the waste battery in more detail, in the case of a used electric vehicle waste battery, since there is a high risk of explosion and fire when it is in a charged state, after completely discharging the charged current, it is necessary to separate the battery pack and separate it into each cell. Each discharged cell is evaluated for its charge capacity and discharge capacity using a charger and classified into grades according to the capacity.

[0736] For example, the cells are classified into cells with a capacity of 80% or more, 68 to 80%, and 68% or less, and the regeneration process is performed on the cells with a capacity of 68% or less with a significantly reduced capacity.

[0737] After completely discharging the cells with reduced capacity, holes are drilled in each cell in a dry room or an inert atmosphere environment, and the existing electrolyte, generated gas, and impurities are removed by vacuum. Then, an electrolyte containing an additive capable of restoring performance is injected into the cells, and the holes are sealed. Thereafter, the electrolyte is uniformly distributed through a process of shaking the cells for a certain period of time under conditions of a constant temperature (25 to 50 °C) to activate the anode / cathode active materials and increase the activity of Li ions, thereby restoring the capacity of the battery.

[0738] Hereinafter, a method for manufacturing a reusable battery using an electrolyte according to the present invention will be described in detail.

[0739]

[0740] Example 32. Manufacture of Reusable Battery

[0741] (1) Preparation of Waste Batteries

[0742] In this example, after disassembling the modules from the battery pack operating in an electric bus and separating them into unit cells, the cells classified as having a discharge capacity of less than 12 Ah (less than 68% of the initial capacity ratio) based on the discharge capacity were discharged to 2.5 V at 0.5 C discharge, and then, in an inert atmosphere in a dry room or a glove box, holes were drilled in the cells using a syringe, and suction was performed under vacuum to remove the existing waste electrolyte, generated gas, and impurities and used.

[0743]

[0744] (2) Cell reassembly and cell activation

[0745] Using a syringe, a new electrolyte of the present invention was injected, the holes were sealed, and then, while maintaining the temperature at 25 to 30 °C, vibration was applied to the left and right to shake and age. Thereafter, a current of 0.1 C rate (2.1 A) was applied and constant current charging was performed up to 4.2 V, and then constant voltage charging at 4.2 V was performed so that the current value was 0.01 C (0.21 A).

[0746]

[0747] Comparative Example 3. Manufacture of Reusable Battery

[0748] It was produced in the same manner as in Example 32, except that a non-aqueous electrolyte containing 1 M of LiPF6 in a mixed solvent having a volume ratio of 3:3:4 of EC:EMC:DMC was used without any additional additives.

[0749]

[0750] Experimental Example 27. Evaluation of Reusable Battery

[0751] When the battery produced in Example 32 was evaluated for the constant current discharge capacity at a current value of 0.1 C (2.1 A) in the range of 3.0 to 4.2 V using a charger, the discharge capacity recovered from a capacity of 6.2 Ah to a capacity of 14.8 Ah.

[0752] On the other hand, as a result of evaluating the battery produced in Comparative Example 3, although there was an increase in capacity from a capacity of 6.2 Ah to a capacity of 10.5 Ah, sufficient capacity was not recovered.

[0753]

[0754] Further, in the present invention, after operating as a normal lithium ion battery until a certain temperature (preferably 70 °C) is reached using the electrolyte of the present invention, in order to prevent the risk of fire due to a rapid increase in the temperature of the battery caused by thermal runaway of the battery, when the temperature reaches a certain temperature (preferably 130 °C) or higher, a solidifying electrolyte is provided that can rapidly (within 5 to 10 minutes) harden to stop the operation of the battery.

[0755] Hereinafter, a method for producing a solidifying electrolyte containing an anion receptor of the present invention will be described.

[0756] In the case of a solidifying electrolyte, first, an anion receptor, a crosslinking agent, a curing type initiator, and a polymerization inhibitor are added to an electrolytic solution, and the mixture is stirred to produce a composition mixture liquid for producing the solidifying electrolyte of the present invention as shown in Table 3 below.

[0757] Hereinafter, the manufacturing example of the solidified electrolyte composition mixture and the curing experiment results will be described in detail.

[0758]

[0759] Comparative Example 4. Manufacture of Solidified Electrolyte

[0760] The anion receptor compound 1-1 (0.24 g) produced in Example 1 and 6.15 g of triethylene glycol dimethacrylate (manufactured by Aldrich, "TEGDA"), which is a cross-linking agent, were mixed into 60 g of an electrolyte solution (EC:EMC:DMC = 3:3:4, LiPF6 1 mol / L). To this mixture, 0.01 g of Luperox TBEC (manufactured by Aldrich), which is an initiator, was added to produce a solidified electrolyte.

[0761]

[0762] Comparative Example 5. Manufacture of Solidified Electrolyte

[0763] 6.06 g of the cross-linking agent (TEGDA), the anion receptor compound 1-1, the electrolyte solution, and the initiator were mixed in the same amounts as in Comparative Example 3 to produce a solidified electrolyte.

[0764]

[0765] Comparative Example 6. Manufacture of Solidified Electrolyte

[0766] 6.04 g of the cross-linking agent (TEGDA), the anion receptor compound 1-1, the electrolyte solution, and the initiator were mixed in the same amounts as in Comparative Example 3 to produce a solidified electrolyte.

[0767]

[0768] Comparative Example 7. Manufacture of Solidified Electrolyte

[0769] 6.00 g of the cross-linking agent (TEGDA), the anion receptor compound 1-1, the electrolyte solution, and the initiator were mixed in the same amounts as in Comparative Example 3 to produce a solidified electrolyte.

[0770]

[0771] Comparative Example 8. Manufacture of Solidified Electrolyte

[0772] 5.40 g of crosslinking agent (TEGDA), the anion receptor compound 1-1, the electrolyte, and the initiator were mixed in the same amounts as in Comparative Example 3 to produce a solidified electrolyte.

[0773]

[0774] Comparative Example 9. Manufacture of Solidified Electrolyte

[0775] 4.50 g of crosslinking agent (TEGDA), the anion receptor compound 1-1, the electrolyte, and the initiator were mixed in the same amounts as in Comparative Example 3 to produce a solidified electrolyte.

[0776]

[0777] Comparative Example 10. Manufacture of Solidified Electrolyte

[0778] 0.30 g of the anion receptor compound 1-1 produced in Example 1 and 8.40 g of the crosslinking agent triethylene glycol dimethacrylate (manufactured by Aldrich, "TEGDA") were mixed with 60 g of an electrolyte (EC:EMC:DMC = 3:3:4, LiPF6 1 mol / L). To this mixture, 0.01 g of Luperox TBEC (manufactured by Aldrich) as an initiator and 1.2 mg of 4-methoxyphenol as a polymerization inhibitor were added to produce a solidified electrolyte.

[0779]

[0780] Example 33. Manufacture of Solidified Electrolyte

[0781] The anionic receptor compound 1-1 (0.33 g) produced in Example 1 and 9.23 g of triethylene glycol dimethacrylate (manufactured by Aldrich, "TEGDA"), which is a cross-linking agent, were mixed into 60 g of an electrolytic solution (EC:EMC:DMC = 3:3:4, 1 mol / L LiPF6). To this mixture, 0.01 g of Luperox TBEC (manufactured by Aldrich), which is an initiator, and 1.2 mg of 4-methoxyphenol (manufactured by Aldrich), which is a polymerization inhibitor, were added to produce a solidified electrolyte.

[0782]

[0783] [Table 3] JPEG2025522864000205.jpg49105

[0784] *Additive = Cross-linking agent + Anionic receptor

[0785]

[0786] Experimental Example 27. Curing Experiment of Solidified Electrolyte (1)

[0787] The solidified electrolyte solutions produced in Comparative Examples 4 to 9 were placed in a 50 ml round flask, and the curing times were measured by visual observation at 50°C, 70°C, 90°C, 110°C, and 130°C under a nitrogen atmosphere.

[0788] The measurement results of Comparative Examples 4 to 9 are shown in Table 4 below.

[0789] [Table 4] JPEG2025522864000206.jpg3090

[0790] (In the above table, X indicates uncured, and O indicates cured)

[0791] From Table 4 above, it can be seen that in the case of Comparative Examples 4 to 6, all of them cured at temperatures from 50°C to 130°C and cannot be used as solidifying agents. Also, in the case of Comparative Examples 7 to 9, none of them cured at temperatures from 50°C to 130°C, and it can also be seen that they cannot be used as solidifying agents.

[0792] From Table 4 above, it can be seen that in order to cure, the total content of the additives must be at least 12.33%.

[0793]

[0794] Experimental Example 28. Curing Experiment of Solidified Electrolyte (2)

[0795] The solidified electrolyte solutions produced in Comparative Example 10 and Example 33 were each cured, and the curing time was measured in the same manner as in Experimental Example 27 above.

[0796] The measurement results of Comparative Example 10 and Example 33 are shown in Table 5 below.

[0797] [Table 5] JPEG2025522864000207.jpg1497

[0798] (In the above table, X indicates uncured, and O indicates cured)

[0799] From Table 5 above, it can be seen that in the case of Example 33, it does not cure at temperatures below 70°C, but cures rapidly in only 5 minutes at a high temperature of 130°C and can be used as a solidifying agent. However, in the case of Comparative Example 10, it can be seen that it cures even at temperatures below 70°C and cannot be used as a solidifying agent.

[0800] From Table 3 above, it can be seen that when 1.2 mg of a polymerization inhibitor is added to both Example 33 and Comparative Example 10, only when the total content of the additives is at least 13.74% as in Example 33, it can be used as a solidifying agent without curing at temperatures below 70°C.

[0801] As described above, the liquid electrolyte using the novel anion receptor according to the embodiment as an additive can provide an electrolyte with improved lithium cycling performance and efficiency, and thus can be used as an electrolyte additive for a high-capacity lithium-ion battery. Further, the polymer electrolyte containing the novel anion receptor of the present invention can provide an electrolyte with significantly improved ionic conductivity and electrochemical stability at room temperature. Therefore, it is widely applicable not only to small lithium polymer secondary batteries applied to portable information terminals such as mobile phones and notebook computers and various electronic devices such as camcorders, but also to polymer electrolytes of large-capacity lithium polymer secondary batteries used in power storage devices for load leveling and electric vehicles. Further, when the temperature rises above a certain temperature (130 ° C), it can be rapidly cured within 5 minutes to reduce the operation of the battery, and thus a solid electrolyte can be provided that can prevent the risk of fire due to a rapid increase in temperature caused by thermal runaway of the battery. Such solid electrolytes are expected to have a large increase in demand not only for electric vehicle batteries where fire accidents frequently occur and ensuring safety in use is the most urgent task, but also for power storage devices.

[0802]

[0803] As described above, the embodiments have been described with reference to the limited drawings, but those having ordinary knowledge in the relevant technical field can apply various technical modifications and variations based on the above. For example, even if the described technology is performed in an order different from the described method, and / or the components of the described system, structure, device, circuit, etc. are combined or assembled in a form different from the described method, or are replaced or substituted by other components or equivalents, appropriate results can be achieved.

[0804] Therefore, other embodiments, other examples, and those equivalent to the claims also fall within the scope of the claims described below.

Industrial Applicability

[0805] According to one embodiment of the present invention, the present invention provides a battery with significantly improved ionic conductivity and electrochemical stability by using a compound which is a novel silicon-based ion receptor and a liquid electrolyte (e.g., non-aqueous liquid electrolyte), a gel or solid electrolyte (e.g., gel or solid polymer electrolyte, solid sulfide-polymer based electrolyte, solid oxide-polymer based electrolyte). Moreover, a method capable of recycling a spent battery by an electrolyte exchange method and a reused battery can be provided.

Claims

1. A silicon-based anion receptor compound selected from the group consisting of the following chemical formulas 1 to 6: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] [Chemical formula 6] In the above chemical formulas 1 to 6, (a) X is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR' (R and R' are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR ３ (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR ３ (R is a linear or branched alkyl group having 1 to 20 carbon atoms), 、 、 、 、 、 、 、 、 、 、 、 、 , and (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and R １ is a halogen atom; and -SO ２ CF ３ , -OSO ２ CF ３ , -SO ２ CHF ２ , -OSO ２ CHF ２ , -SO ２ CH ２ F, -OSO ２ CH ２ F, -COCF ３ , -OCOCF ３ , -COCHF ２ , -OCOCHF ２ , -COCH ２ F, -OCOCH ２ F, -SO ２ CN, -OSO ２ CN, -SO ２ F, -OSO ２ F, -CF ３ , -OCF ３ and is selected from electron-withdrawing groups selected from -CN; l is an integer from 0 to 20), and is selected from (b) Y is 、 , and (R ２ , R ３ and R ４ are each a hydrogen atom; a halogen atom; and -SO ２ CF ３ , -OSO ２ CF ３ , -SO ２ CHF ２ , -OSO ２ CHF ２ , -SO ２ CH ２ F, -OSO ２ CH ２ F, -COCF ３ , -OCOCF ３ , -COCHF ２ , -OCOCHF ２ , -COCH ２ F, -OCOCH ２ F, -SO ２ CN, -OSO ２ CN, -SO ２ F, -OSO ２ F, -CF ３ , -OCF ３ and -CN; and are selected from, provided that R ２ , R ３ and R ４ do not simultaneously become hydrogen atoms; m and m' are each an integer from 0 to 20.) and are selected from, (c) R １ , R ２ and R ３ are each a halogen atom; and -SO ２ CF ３ , -OSO ２ CF ３ , -SO ２ CHF ２ , -OSO ２ CHF ２ , -SO ２ CH ２ F, -OSO ２ CH ２ F, -COCF ３ , -OCOCF ３ , -COCHF ２ , -OCOCHF ２ , -COCH ２ F, -OCOCH ２ F, -SO ２ CN, -OSO ２ CN, -SO ２ F, -OSO ２ F, -CF ３ , -OCF ３ and are each selected from electron-withdrawing groups selected from -CN; (d) n is an integer from 0 to 20.

2. The above chemical formula 1 is selected from the group consisting of ; The above chemical formula 2 is selected from the group consisting of ; The above chemical formula 3 is selected from the group consisting of ; The above chemical formula 4 is selected from the group consisting of ; The above chemical formula 5 is selected from the group consisting of ; The above chemical formula 6 is selected from the group consisting of , The silicon-based anion receptor compound according to claim 1.

3. An electrolyte composition containing at least one of the silicon-based anion receptor compounds represented by chemical formulas 1 to 6 according to claim 1.

4. The electrolyte composition according to claim 3, further comprising one or more compounds selected from the group consisting of the following chemical formulas 7 to 16: [Chemical formula 7] A. [Chemical formula 8] [Chemical formula 9] [Chemical formula 10] [Chemical formula 11] [Chemical formula 12] [Chemical formula 13] [Chemical formula 13-a] [Chemical formula 13-b] [Chemical formula 14] [Chemical formula 15] [Chemical formula 16] In the above chemical formulas 7 to 16, (a) X is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR' (R and R' are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR ３ (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR ３ (R is a linear or branched alkyl group having 1 to 20 carbon atoms), 、 、 、 、 、 、 、 、 、 、 、 、 , and (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and R １ is a halogen atom; and -SO ２ CF ３ , -OSO ２ CF ３ , -SO ２ CHF ２ , -OSO ２ CHF ２ , -SO ２ CH ２ F, -OSO ２ CH ２ F, -COCF ３ , -OCOCF ３ , -COCHF ２ , -OCOCHF ２ , -COCH ２ F, -OCOCH ２ F, -SO ２ CN, -OSO ２ CN, -SO ２ F, -OSO ２ F, -CF ３ , -OCF ３ and an electron-withdrawing group selected from -CN; and l is an integer from 0 to 20), and is selected from (b) Y is 、 , and (R ２ , R ３ and R ４ are each a hydrogen atom; a halogen atom; and -SO ２ CF ３ 、-OSO ２ CF ３ 、-SO ２ CHF ２ 、-OSO ２ CHF ２ 、-SO ２ CH ２ F、-OSO ２ CH ２ F、-COCF ３ 、-OCOCF ３ 、-COCHF ２ 、-OCOCHF ２ 、-COCH ２ F、-OCOCH ２ F、-SO ２ CN、-OSO ２ CN、-SO ２ F、-OSO ２ F、-CF ３ 、-OCF ３ and an electron-withdrawing group selected from -CN; provided that R ２ 、R ３ and R ４ are not simultaneously hydrogen atoms; m and m' are each an integer from 0 to 20.) and is selected from (c) W is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, 、 , and (R ２ , R ３ and R ４ are each a hydrogen atom; a halogen atom; and -SO ２ CF ３ 、-OSO ２ CF ３ 、-SO ２ CHF ２ 、-OSO ２ CHF ２ 、-SO ２ CH ２ F、-OSO ２ CH ２ F、-COCF ３ 、-OCOCF ３ 、-COCHF ２ 、-OCOCHF ２ 、-COCH ２ F、-OCOCH ２ F、-SO ２ CN、-OSO ２ CN、-SO ２ F、-OSO ２ F、-CF ３ 、-OCF ３ and an electron-withdrawing group selected from -CN; provided that R ２ 、R ３ and R ４ are not simultaneously hydrogen atoms; m and m' are each an integer from 0 to 20.) and are selected from (d) R １ and R １ ’are each a hydrogen atom; and -SO ２ CF ３ ,-OSO ２ CF ３ ,-SO ２ CHF ２ ,-OSO ２ CHF ２ ,-SO ２ CH ２ F,-OSO ２ CH ２ F,-COCF ３ ,-OCOCF ３ ,-COCHF ２ ,-OCOCHF ２ ,-COCH ２ F,-OCOCH ２ F,-SO ２ CN,-OSO ２ CN,-SO ２ F,-OSO ２ F,-CF ３ ,-OCF ３ and an electron-withdrawing group selected from -CN; wherein the R １ and R １ ’do not simultaneously become hydrogen atoms within the same molecule, (e) n and q are each an integer from 0 to 20, (f) z is an integer from 1 to 20.

5. The electrolyte composition according to claim 4, comprising 0.01 to 40% by weight of one or more silicon-based anion receptor compounds selected from the group consisting of chemical formulas 1 to 6 and one or more compounds selected from the group consisting of chemical formulas 7 to 16.

6. The electrolyte composition according to claim 3, wherein the electrolyte composition forms a liquid, gel or solid electrolyte.

7. A solidified electrolyte produced from the electrolyte composition according to claim 3 or 4.

8. A polymer electrolyte thin film produced from the electrolyte composition according to claim 3 or 4.

9. A battery containing the solidified electrolyte according to claim 7.

10. A rechargeable battery containing the solidified electrolyte according to claim 7.

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