Novel anion receptor compounds and electrolytes 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 anion receptor that is composed of a compound having a structure in which a silicon atom is bonded to a nitrogen atom, such as a novel silazanes in which an amine group substituted with an electron-withdrawing group has been introduced to the silicon atom or an electron-withdrawing group has been introduced to the nitrogen atom, or a mixture of a compound having a structure in which a silicon atom is bonded to a nitrogen atom, such as the novel silazanes, 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 has been introduced to the nitrogen atom in the ring, and that improves the ionic conductivity and cation transport number of an electrolyte to which the novel anion receptor is added and enhances the electrochemical stability of an alkali metal battery using such an electrolyte, as well as a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the novel anion receptor.

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 silazane-based anion receptor compound and an electrolyte containing the same. [Background technology]

[0002] Anion receptors improve anion stability through Lewis acid-salt interactions. These anion receptors are compounds containing electron-deficient atoms (N, B) that coordinate electron-rich anions around them, preventing the anion from binding to lithium cations as ion pairs and facilitating lithium cation migration. The first known anion receptors are azaethers composed of cyclic or linear amides substituted with perfluoroalkylsulfonyl groups, rendering the nitrogen atom of the amine group electron-deficient and enabling it to interact with electron-rich anions through Coulombic attraction (J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9). However, these azaethers exhibit limited solubility in polar solvents typically employed in nonaqueous electrolytes, and their electrochemical stability window in the presence of LiCl salt does not meet the 4.0 V required for commercial anode materials. Furthermore, it was found that azaethers are unstable with LiPF6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, because LiPF6 is chemically and thermally unstable, even at room temperature, solid LiF and gaseous PF5 are in equilibrium, but the generation of this gaseous product, PF5, further shifts the equilibrium in favor of the production of PF5.

[0003] JPEG2025525467000002.jpg951

[0004] In non-aqueous solvents, PF5 tends to initiate a series of reactions, including ring-opening polymerization and the cleavage of ether bonds formed by atoms with lone electron pairs, such as oxygen or nitrogen. PF5, a strong Lewis acid, attacks electron pairs, but azaethers, due to their high electron density, are subject to immediate attack by PF5 (J. Power Sources, 104 (2002) 260). This severely limits the commercialization of azaether compounds. Given these limitations, McBreen et al. used the same method to synthesize an anion receptor using boron as the electron-deficient atom, substituted with an electron-attracting functional group (J. Electrochem. Soc., 145 (1998) 2813, 149 (2002) A1460).

[0005] Solid polymer electrolytes, on the other hand, are convenient to use due to their non-leakage electrolyte, high resistance to vibration and impact, and low self-discharge. They can also be used at high temperatures. These advantages are in line with the trend toward lighter and more compact portable electronic devices and wireless communication devices and home appliances. They are also widely applicable to high-capacity lithium polymer secondary batteries for electric vehicles and other applications. Therefore, much research has been conducted to improve their performance. Since P.V. Wright discovered polyalkylene oxide (PAO)-based solid polymer electrolytes in 1975 (British Polymer Journal, 7, 319), M. Armand coined the term "ion-conducting polymer" in 1978. A typical solid polymer electrolyte is composed of a polymer containing electron-donating atoms such as oxygen, nitrogen, or phosphorus, along with a lithium salt complex. The most representative solid polymer electrolyte known to date is polyethylene oxide (PEO) and its lithium salt complex, which exhibits a 100% ionic conductivity at room temperature. -8These PAO-based solid polymer electrolytes have low ionic conductivities (s / cm), making them unsuitable for electrochemical devices operating at room temperature. Because of their high crystallinity, these electrolytes restrict the movement of molecular chains, resulting in very low ionic conductivities at room temperature. To increase the mobility of molecular chains, the crystalline regions within the polymer structure must be minimized and the amorphous regions increased. To achieve this, research has been conducted using flexible siloxanes (Macromol. Chem. Rapid Commun., 7 (1986) 115) or phosphazenes (J. Am. Chem. Soc., 106 (1984) 6845) as the main chain, or introducing relatively short PAOs as side chains (Electrochem. Acta, 34 (1989) 635). Research is also underway to create network-structured solid polymer electrolytes by introducing one or more crosslinkable functional groups to the PAO terminals, but the ionic conductivities of these electrolytes at room temperature are only 10 or less. -5 ~10 -4 S / cm, which is unsuitable for use in lithium batteries operating at room temperature, and research is ongoing to improve this. To solve this problem, Abraham et al. introduced low-molecular-weight polyethylene oxide into vinylidene hexafluoride-hexafluoropropene copolymers to improve ionic conductivity (Chem. Mater., 9 (1997) 1978). In addition, by adding low-molecular-weight polyethylene glycol dimethyl ether (PEGDME) to a photocurable crosslinker with PEO side chains and siloxane main chain, it was possible to achieve a maximum ionic conductivity of 8 × 10 at room temperature under film-forming conditions. -4Ionic conductivities of up to 1000 S / cm have been demonstrated (J. Power Sources 119-121 (2003) 448). However, the calculated cycling efficiency on a Ni electrode was only about 53%. This low efficiency is explained by the rapid corrosion of the freshly deposited lithium surface, which results in passivation of the electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). According to Vincent, the reaction between lithium salts and lithium metal proceeds as follows (Solid State Chem. 17 (1987) 145): the CF3 radicals generated here detach hydrogen atoms from the PEO polymer chains to form HCF3, and the resulting =COC- functional groups cleave the polymer backbone. At this time, the CH3 generated by the chain scission attacks the chain together with the CF3 radical or scisses the -CO- bond, resulting in Li-OR compounds adhering to the surface of the electrode and causing passivation.

[0006] JPEG2025525467000003.jpg1177

[0007] Therefore, to solve the above problems, it is necessary to design a compound with a structure that does not have a nitrogen atom that is easily attacked in the middle of the bond, such as an azaether, or to research a new material that can eliminate electrochemical instability and instability to lithium salts and increase ionic conductivity by replacing PAO-based plasticizers.

[0008] Summary of the Invention [Problem to be solved by the invention]

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

[0010] Another object of the present invention is to provide an electrolyte composition that can improve the ionic conductivity and cation transport number in an electrolyte, thereby enhancing the electrochemical stability of a battery (e.g., a primary battery or a secondary battery) using such an electrolyte, and can provide a liquid, gel, or solid electrolyte.

[0011] Another object of the present invention is to provide an electrolyte having 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 rapidly hardens at a certain temperature (e.g., about 130°C) or higher, thereby stopping the operation of the battery and preventing the occurrence of a fire due to thermal runaway of the battery.

[0013] [Means for solving the problem]

[0014] In order to achieve the above object, the present invention provides a silazane-based anion receptor compound selected from the group consisting of the following chemical formulas 1 to 5.

[0015] [Chemical formula 1]

[0016] JPEG2025525467000004.jpg2061

[0017] [Chemical formula 2]

[0018] JPEG2025525467000005.jpg2151

[0019] [Chemical formula 3]

[0020] JPEG2025525467000006.jpg2154

[0021] [Chemical formula 4]

[0022] JPEG2025525467000007.jpg2154

[0023] [Chemical formula 5]

[0024] JPEG2025525467000008.jpg5553

[0025] In the above Chemical Formulas 1 to 5,

[0026] (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), JPEG2025525467000009.jpg1835, JPEG2025525467000010.jpg1539, JPEG2025525467000011.jpg1235, JPEG2025525467000012.jpg1935, JPEG2025525467000013.jpg2043, JPEG2025525467000014.jpg1941, TIFF2025525467000015.tif1837, JPEG2025525467000016.jpg1633, TIFF2025525467000017.tif1635, TIFF2025525467000018.tif1935, JPEG2025525467000019.jpg1739, JPEG2025525467000020.jpg1732, TIFF2025525467000021.tif1938, and TIFF2025525467000022.tif1951

[0027] (R is selected from linear or branched alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms; R1 is selected from halogen atoms; and electron-withdrawing groups 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),

[0028] (b) Y is JPEG2025525467000023.jpg1926, JPEG2025525467000024.jpg1933 and JPEG2025525467000025.jpg2039 (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; with the proviso that R2, R3, and R4 are not simultaneously hydrogen atoms; and m and m' are each an integer of 0 to 20.)

[0029] (c) R1, R2, and R3 are selected from halogen atoms; and electron-withdrawing groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN;

[0030] (d) n is an integer from 0 to 20.

[0031]

[0032] The present invention also provides an electrolyte composition containing at least one of the silazane-based anion receptor compounds represented by Chemical Formulas 1 to 5.

[0033] In the present invention, the electrolyte composition further comprises one or more compounds selected from the group consisting of the following chemical formulas 6 to 15.

[0034] [Chemical formula 6]

[0035] JPEG2025525467000026.jpg2843

[0036] [Chemical formula 7]

[0037] JPEG2025525467000027.jpg2735

[0038] [Chemical formula 8]

[0039] JPEG2025525467000028.jpg2736

[0040] [Chemical formula 9]

[0041] JPEG2025525467000029.jpg3029

[0042] [Chemical formula 10]

[0043] JPEG2025525467000030.jpg2655

[0044] [Chemical formula 11]

[0045] JPEG2025525467000031.jpg3062

[0046] [Chemical formula 12]

[0047] JPEG2025525467000032.jpg1935

[0048] [Chemical formula 12-a]

[0049] JPEG2025525467000033.jpg1545

[0050] [Chemical formula 12-b]

[0051] JPEG2025525467000034.jpg1768

[0052] [Chemical formula 13]

[0053] JPEG2025525467000035.jpg2152

[0054] [Chemical formula 14]

[0055] JPEG2025525467000036.jpg2051

[0056] [Chemical formula 15]

[0057] JPEG2025525467000037.jpg4242

[0058] In Chemical Formula 6 to Chemical Formula 15,

[0059] (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),

[0060] JPEG2025525467000038.jpg1732, JPEG2025525467000039.jpg1744, JPEG2025525467000040.jpg1132, TIFF2025525467000041.tif1527, TIFF2025525467000042.tif1737, TIFF2025525467000043.tif1736, JPEG2025525467000044.jpg1734, TIFF2025525467000045.tif1531, JPEG2025525467000046.jpg1429, JPEG2025525467000047.jpg1729, TIFF2025525467000048.tif1434, TIFF2025525467000049.tif1530, TIFF2025525467000050.tif1938, and TIFF2025525467000051.tif1951

[0061] (R is selected from linear or branched alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms; R1 is selected from halogen atoms; and electron-withdrawing groups 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),

[0062] (b) Y is JPEG2025525467000052.jpg1927, JPEG2025525467000053.jpg1637 and JPEG2025525467000054.jpg1837 (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; with the proviso that R2, R3, and R4 are not simultaneously hydrogen atoms; and m and m' are each an integer of 0 to 20.)

[0063] (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, or a linear or branched alkynyl group having 2 to 20 carbon atoms; (b) Y is JPEG2025525467000055.jpg1724, JPEG2025525467000056.jpg1638 and JPEG2025525467000057.jpg1641 (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; with the proviso that R2, R3, and R4 are not simultaneously hydrogen atoms; and m and m' are each an integer of 0 to 20.)

[0064] (d) R1 and R1' are each selected from 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; wherein R1 and R1' are not simultaneously hydrogen atoms in the same molecule;

[0065] (e) n and q are each an integer of 0 to 20;

[0066] (f) z is an integer from 1 to 20.

[0067]

[0068] The present invention also provides a solid electrolyte prepared from the electrolyte composition.

[0069] The present invention also provides a polymer electrolyte thin film prepared using the electrolyte composition.

[0070] The present invention also provides a battery containing the solid electrolyte.

[0071] The present invention also provides a reusable battery containing the solid electrolyte.

[0072] [Effects of the Invention]

[0073] The present invention provides novel silazane-based anion receptor compounds and liquid electrolytes (e.g., nonaqueous liquid electrolytes), gel or solid electrolytes (e.g., gel or solid polymer electrolytes, solid sulfide-polymer electrolytes, solid oxide-polymer electrolytes) containing the same. Specifically, the present invention provides novel cyclic silazane compounds in which an amine group substituted with an electron-withdrawing group is introduced to a silicon atom or an electron-withdrawing group is introduced to a nitrogen atom in the ring. By utilizing the novel cyclic silazane compounds, electrolytes that can be widely used as electrolytes (e.g., gel or solid polymer electrolytes, solid sulfide-polymer electrolytes, solid oxide-polymer electrolytes) for large-capacity secondary batteries (e.g., lithium polymer secondary batteries, lithium metal secondary batteries) used in power storage devices for power leveling and electric vehicles, as well as compact lithium polymer secondary batteries used in various electronic devices, such as mobile phones, laptop computers, and camcorders.

[0074] 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 increase its usability not only in electric vehicle batteries but also in power storage devices.

[0075] [Brief explanation of the drawings]

[0076] [Figure 1] 1 is a graph showing the performance (comparison of relative discharge capacity vs. voltage) of batteries of the present invention and comparative examples at room temperature.

[0077] DETAILED DESCRIPTION OF THE INVENTION

[0078] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various modifications may 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 modifications, equivalents, or alternatives to the embodiments are included in the scope of the patent application.

[0079] The terms used in the embodiments are merely used for the purpose of explanation and should not be construed as limiting. A singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, terms such as "comprise" or "incorporate" specify the presence of a feature, number, step, operation, component, part, or combination 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.

[0080] Terms such as "first" or "second" may be used to describe various components, but these components should not be limited by these terms. These terms are used only to distinguish one component from another. For example, a first component can be called a second component, and similarly, a second component can be called a first component, without departing from the scope of the concept of an embodiment.

[0081] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments pertain. Terms as defined in commonly used dictionaries should be interpreted to have a meaning consistent with the meaning they have in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly defined in this application.

[0082] In addition, in the description with reference to the accompanying drawings, the same reference numerals will be assigned to the same components regardless of the reference numerals, and duplicate descriptions thereof will be omitted. In describing the embodiments, if it is determined that a detailed description of related publicly known technology may unnecessarily obscure the gist of the embodiments, the detailed description thereof will be omitted.

[0083]

[0084] The novel anion receptor of the present invention, its manufacturing method, and its application will be specifically described below with reference to the following embodiments and drawings, but the present invention is not limited to these embodiments and drawings.

[0085] The present invention relates to novel anion receptors.

[0086] According to one embodiment of the present invention, the anion receptor may be a novel silazane-based compound, in which an amine group substituted with an electron-withdrawing group is introduced to a nitrogen atom.

[0087] According to one embodiment of the present invention, the anion acceptor compound may be a compound represented by the following Chemical Formulas 1 to 5. The compound acts as an anion acceptor in an electrolyte composition (e.g., an electrolyte), and when used as an additive to an electrolyte composition (e.g., an electrolyte), it can improve the ionic conductivity and cation transport number, thereby enhancing the electrochemical stability of a battery utilizing the same.

[0088] [Chemical formula 1]

[0089] JPEG2025525467000058.jpg2061

[0090] [Chemical formula 2]

[0091] JPEG2025525467000059.jpg2151

[0092] [Chemical formula 3]

[0093] JPEG2025525467000060.jpg2154

[0094] As an example of the present invention, the compounds represented by Formula 1, Formula 2, and Formula 3 may be novel silazane-based anion receptor compounds in which a functional group substituted with an electron withdrawing group is introduced to a nitrogen atom in a silazane.

[0095] As an example of the present invention, in Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, R1, R2, and R3 may be selected from a halogen atom, —SO2CF3, —OSO2CF3, —SO2CHF2, —OSO2CHF2, —SO2CH2F, —OSO2CH2F, —COCF3, —OCOCF3, —COCHF2, —OCOCHF2, —COCH2F, —OCOCH2F, —SO2CN, —OSO2CN, —SO2F, —OSO2F, —CF3, —OCF3, and —CN.

[0096] As an example of the present invention, in the above Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3, 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), -O-Si(R),

[0097] JPEG2025525467000061.jpg1630, JPEG2025525467000062.jpg1436, JPEG2025525467000063.jpg1132, JPEG2025525467000064.jpg1425, JPEG2025525467000065.jpg1533, JPEG2025525467000066.jpg1634, JPEG2025525467000067.jpg1734, JPEG2025525467000068.jpg1328, JPEG2025525467000069.jpg1429, JPEG2025525467000070.jpg1730, TIFF2025525467000071.tif1434, TIFF2025525467000072.tif1530, JPEG2025525467000073.jpg1632, and JPEG2025525467000074.jpg1643

[0098]

[0099] can be selected from:

[0100] In the above X, R, R' and R1 are each 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, and preferably wherein R and R' are selected from linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 20 carbon atoms, R1 is selected from halogen atoms; and electron-withdrawing groups 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 of 0 to 20.

[0101] Preferably, in the X,

[0102] R in "-COR" can be selected from linear or branched alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms.

[0103] R in "-OR" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0104] R and R' in "-ROR'" can each be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0105] R in "-Si(R)3" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0106] R in "-O-Si(R)3" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0107] The l may be an integer of 0 to 10; or an integer of 0 to 5.

[0108] More preferably, in the chemical formula 1, chemical formula 2 and chemical formula 3, 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,

[0109] TIFF2025525467000075.tif1427, TIFF2025525467000076.tif1334, TIFF2025525467000077.tif1027, JPEG2025525467000078.jpg1528, JPEG2025525467000079.jpg1634, JPEG2025525467000080.jpg1531, JPEG2025525467000081.jpg1632, JPEG2025525467000082.jpg1328, JPEG2025525467000083.jpg1429, TIFF2025525467000084.tif1935, TIFF2025525467000085.tif1434, JPEG2025525467000086.jpg1632, JPEG2025525467000087.jpg1531, and JPEG2025525467000088.jpg1745

[0110] (wherein R is selected from linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably -CH3, and 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, and -OCF3; and more preferably, -F, -Cl, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3. 1 is an integer of 0 to 10, and more preferably, 0 to 3.

[0111] As an example of the present invention, in the above Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3, n may be an integer of 0-20, and preferably, n may be an integer of 0-10.

[0112] In one embodiment of the present invention, the compound represented by Formula 1 may be selected from the following compounds:

[0113] [Chemical formula 1-1]

[0114] JPEG2025525467000089.jpg2660

[0115]

[0116] [Chemical formula 1-2] JPEG2025525467000090.jpg2457

[0117] [Chemical formula 1-3]

[0118] JPEG2025525467000091.jpg2959

[0119] In Chemical Formulae 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, and is preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0120] In one embodiment of the present invention, the compound represented by Formula 2 may be selected from the following compounds:

[0121] [Chemical formula 2-1]

[0122] JPEG2025525467000092.jpg3251

[0123] [Chemical formula 2-2]

[0124] JPEG2025525467000093.jpg3450

[0125] [Chemical formula 2-3]

[0126] JPEG2025525467000094.jpg3449

[0127] In Chemical Formulae 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, and is preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0128] In one embodiment of the present invention, the compound represented by Formula 3 may be selected from the following compounds:

[0129] [Chemical formula 3-1]

[0130] JPEG2025525467000095.jpg3052

[0131]

[0132] [Chemical formula 3-2]

[0133] JPEG2025525467000096.jpg3752

[0134] [Chemical formula 3-3]

[0135] JPEG2025525467000097.jpg3752

[0136] 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, and is preferably selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0137] [Chemical formula 4]

[0138] JPEG2025525467000098.jpg2154

[0139] [Chemical formula 5]

[0140] JPEG2025525467000099.jpg5152

[0141] As an example of the present invention, the compounds represented by Formula 4 and Formula 5 may be novel silazane-based anion receptor compounds in which an amine group substituted with an electron withdrawing group is introduced into silicon.

[0142] As an example of the present invention, in the above Chemical Formula 4 and Chemical Formula 5, 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), -O-Si(R),

[0143] JPEG2025525467000100.jpg1630, JPEG2025525467000101.jpg1642, JPEG2025525467000102.jpg1131, TIFF2025525467000103.tif1527, JPEG2025525467000104.jpg1532, JPEG2025525467000105.jpg1533, JPEG2025525467000106.jpg1633, TIFF2025525467000107.tif1531, JPEG2025525467000108.jpg1430, JPEG2025525467000109.jpg1730, TIFF2025525467000110.tif1434, TIFF2025525467000111.tif1530, JPEG2025525467000112.jpg1633, and JPEG2025525467000113.jpg1542

[0144] In the X, R, R' and R1 are each selected from an electron-withdrawing group 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 -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, and preferably R and R' are each selected from an electron-withdrawing group selected from a linear or branched alkyl group having 1 to 20 carbon atoms and R1 is selected from an alkyl group and an alkenyl group having 2 to 20 carbon atoms; 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.

[0145] Preferably, in the X,

[0146] R in "-COR" can be selected from linear or branched alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms.

[0147] R in "-OR" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0148] R and R' in "-ROR'" can each be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0149] R in "-Si(R)3" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0150] R in "-O-Si(R)3" can be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0151] The l may be an integer of 0 to 10; or an integer of 0 to 5.

[0152] More preferably, in the chemical formula 4 and the chemical formula 5, 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,

[0153] JPEG2025525467000114.jpg1733, JPEG2025525467000115.jpg1540, JPEG2025525467000116.jpg1029, TIFF2025525467000117.tif1527, TIFF2025525467000118.tif1737, JPEG2025525467000119.jpg1634, JPEG2025525467000120.jpg1633, TIFF2025525467000121.tif1531, JPEG2025525467000122.jpg1531, JPEG2025525467000123.jpg1832, TIFF2025525467000124.tif1434, TIFF2025525467000125.tif1530, JPEG2025525467000126.jpg1633, and JPEG2025525467000127.jpg1747

[0154] (wherein R is selected from linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably -CH3, and 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, and -OCF3; and more preferably, -F, -Cl, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3. 1 is an integer of 0 to 10, and more preferably, 0 to 3.

[0155] As an example of the present invention, in the above Chemical Formula 4 and Chemical Formula 5, n may be an integer of 0 to 20, and preferably, n may be an integer of 0 to 10.

[0156]

[0157] In one embodiment of the present invention, Y in the above Chemical Formula 4 and Chemical Formula 5 is JPEG2025525467000128.jpg1629, JPEG2025525467000129.jpg1735 and JPEG2025525467000130.jpg1744 can be selected.

[0158] In the Y, R2, R3, and R4 can 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, respectively, provided that within one molecule or the Y, R2; R3; or R2, R3, and R4 are not simultaneously hydrogen atoms, and at least one of them is an electron-withdrawing group.

[0159] In the Y, m and m' may each be an integer of 0 to 20. As another example, in one molecule or in the Y, m and m' do not have to be "0" at the same time.

[0160] Preferably, 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; and m and m' can each be an integer of 0 to 20.

[0161] As an example of this reaction, in the above chemical formula 4, n is an integer of 0 to 20, and preferably n is an integer of 0 to 10.

[0162] As an example of this reaction, the compound represented by Chemical Formula 4 can be selected from the following compounds:

[0163] [Chemical formula 4-1]

[0164] JPEG2025525467000131.jpg4244

[0165] [Chemical Formula 4-2]

[0166] JPEG2025525467000132.jpg6050

[0167] [Chemical Formula 4-3]

[0168] JPEG2025525467000133.jpg5459

[0169] [Chemical Formula 4-4]

[0170] JPEG2025525467000134.jpg6257

[0171] [Chemical Formula 4-5]

[0172] JPEG2025525467000135.jpg5956

[0173] [Chemical formula 4-6]

[0174] JPEG2025525467000136.jpg5959

[0175] [Chemical Formula 4-7]

[0176] JPEG2025525467000137.jpg6155

[0177] [Chemical Formula 4-8]

[0178] JPEG2025525467000138.jpg5857

[0179] [Chemical Formula 4-9]

[0180] JPEG2025525467000139.jpg6156

[0181] In Chemical Formulas 4-1 to 4-9, 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 -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0182] As an example of this reaction, the compound represented by Chemical Formula 5 can be selected from the following compounds:

[0183] [Chemical formula 5-1]

[0184] JPEG2025525467000140.jpg5840

[0185]

[0186] [Chemical formula 5-2]

[0187] JPEG2025525467000141.jpg5939

[0188] [Chemical formula 5-3]

[0189] JPEG2025525467000142.jpg6342

[0190]

[0191] [Chemical formula 5-4]

[0192] JPEG2025525467000143.jpg6943

[0193] [Chemical formula 5-5]

[0194] JPEG2025525467000144.jpg6644

[0195] [Chemical formula 5-6]

[0196] JPEG2025525467000145.jpg6343

[0197] [Chemical formula 5-7]

[0198] JPEG2025525467000146.jpg6444

[0199]

[0200] [Chemical formula 5-8]

[0201] JPEG2025525467000147.jpg6642

[0202] [Chemical formula 5-9]

[0203] JPEG2025525467000148.jpg6042

[0204] In Chemical Formulae 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 -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably -CH3.

[0205]

[0206] In one 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 or a chlorine atom, and more preferably a fluorine atom.

[0207] In one example of the present invention, an "alkyl group" may be linear or branched and may 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. Examples include methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0208] In one example of the present invention, the "alkenyl group" may be linear or branched and may 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. Examples include vinyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl.

[0209] In one example of the present invention, the "alkynyl group" may be linear or branched and may 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. Examples include acetylenyl, propynyl, butynyl, pentynyl, and hexynyl.

[0210] In one 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.

[0211] In one example of the present invention, "m" and "an integer from 0 to 20; m'" 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, an integer from 0 to 10, an integer from 0 to 3, an integer from 1 to 15, an integer from 1 to 10, or an integer from 1 to 5, respectively.

[0212] In one 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, an integer from 0 to 10, an integer from 0 to 3, an integer from 1 to 15, an integer from 1 to 10, or an integer from 1 to 5.

[0213] According to an embodiment of the present invention, the anion receptor can be applied to an electrochemical cell or a component thereof as an electrolyte composition or a process composition, as described below. According to an embodiment of the present invention, the electrolyte composition can be applied in the form of a liquid, gel, solid, or molded body (e.g., film, thin film, porous structure, sheet, etc.).

[0214]

[0215] The present invention relates to a method for preparing anion receptor compounds.

[0216] According to one embodiment of the present invention, the method for producing the anion acceptor compound corresponds to a method for producing a silazane-based compound, which is a compound represented by Chemical Formulas 1 to 5. As an example of the present invention, the compounds represented by Chemical Formulas 1 to 5 can be produced according to the following reaction scheme.

[0217] According to one embodiment of the present invention, to obtain a final product according to a chemical structure design, known methods in the art can be used for the starting materials, catalysts, solvents, reaction conditions, reaction mechanism, and post-treatment steps (reactant separation, filtration, crystallization, washing, etc.). For example, the reaction can be carried out in a single solvent or a mixture of solvents, such as water, methanol, isopropanol, ethanol, methylene chloride, dichloromethane, acetonitrile, tetrahydrofuran, methyl tert-butyl ether, chloroform, DMF, and N,N-dimethylacetamide, 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 between -40°C and 130°C. For example, the reaction temperature can be appropriately selected depending on the reflux conditions of the reaction mixture. Additionally, a catalyst such as a platinum catalyst, a basic substance (e.g., triethylamine, diisopropylethylamine, pyridine), etc., can be added.

[0218] According to one embodiment of the present invention, as shown in the following reaction formula 1-1, a silazane compound represented by the following chemical formula 1-a can be reacted with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 1-1.

[0219] [Reaction Scheme 1-1]

[0220] JPEG2025525467000149.jpg29131

[0221] (In the reaction formula 1-1, X and n are as defined in the chemical formula 1.)

[0222]

[0223] According to one embodiment of the present invention, as shown in the following reaction formula 1-2, a silazane compound represented by the following chemical formula 1-a can be reacted with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 1-2.

[0224] [Reaction Scheme 1-2]

[0225] JPEG2025525467000150.jpg35128

[0226] (In the reaction formula 1-2, X and n are as defined in the chemical formula 1.)

[0227]

[0228] According to one embodiment of the present invention, as shown in the following reaction formula 1-3, a silazane compound represented by the following chemical formula 1-a can be reacted with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 1-3.

[0229] [Reaction Scheme 1-3]

[0230] JPEG2025525467000151.jpg37130

[0231] (In the reaction formulas 1-3, X and n are as defined in the chemical formula 1.)

[0232]

[0233] According to one embodiment of the present invention, as shown in the following reaction formula 2-1, a silazane compound represented by the following chemical formula 2-a can be reacted with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 2-1.

[0234] [Reaction Scheme 2-1]

[0235] JPEG2025525467000152.jpg32129

[0236] (In the reaction formula 2-1, X and n are as defined in the chemical formula 2.)

[0237]

[0238] According to one embodiment of the present invention, as shown in the following reaction formula 2-2, a silazane compound represented by the following chemical formula 2-a can be reacted with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 2-2.

[0239] [Reaction Scheme 2-2]

[0240] JPEG2025525467000153.jpg31126

[0241] (In the reaction formula 2-2, X and n are as defined in the chemical formula 2.)

[0242]

[0243] According to one embodiment of the present invention, as shown in the following reaction formula 2-3, a silazane compound represented by the following chemical formula 2-a can be reacted with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 2-3.

[0244] [Reaction Scheme 2-3]

[0245] JPEG2025525467000154.jpg37120

[0246] (In the reaction formula 2-3, X and n are as defined in the chemical formula 2.)

[0247]

[0248] According to one embodiment of the present invention, as shown in the following reaction formula 3-1, a silazane compound represented by the following chemical formula 3-a can be reacted with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 3-1.

[0249] [Reaction Scheme 3-1]

[0250] JPEG2025525467000155.jpg34123

[0251] (In the reaction formula 3-1, X and n are as defined in the chemical formula 3.)

[0252]

[0253] According to one embodiment of the present invention, as shown in the following reaction formula 3-2, a silazane compound represented by the following chemical formula 3-a can be reacted with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 3-2.

[0254] [Reaction Scheme 3-2]

[0255] JPEG2025525467000156.jpg34120

[0256] (In the reaction formula 3-2, X is as defined in the chemical formula 3.)

[0257]

[0258] According to one embodiment of the present invention, as shown in the following reaction formula 3-3, a silazane compound represented by the following chemical formula 3-a can be reacted with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 3-3.

[0259] [Reaction Scheme 3-3]

[0260] JPEG2025525467000157.jpg35118

[0261]

[0262] According to one embodiment of the present invention, as shown in the following reaction formula 4-1, a compound represented by the following chemical formula 4-1 can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 4-1-b, and an allyl compound in which the nitrogen atom is substituted with -COCF in the presence of a platinum catalyst in a tetrahydrofuran solvent to thereby synthesize a compound represented by the chemical formula 4-1.

[0263] [Reaction Scheme 4-1]

[0264] JPEG2025525467000158.jpg72148

[0265] (In the reaction formula 4-1, X and n are as defined in the chemical formula 4.)

[0266]

[0267] According to one embodiment of the present invention, as shown in the following reaction formula 4-2, a compound represented by the chemical formula 4-1-b can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SOCF in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 4-2.

[0268] [Reaction Scheme 4-2]

[0269] JPEG2025525467000159.jpg75145

[0270] (In the reaction formula 4-2, X and n are as defined in the chemical formula 4.)

[0271]

[0272] According to one embodiment of the present invention, as shown in the following reaction formula 4-3, a compound represented by the following chemical formula 4-1-b can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SOF in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 4-3.

[0273] [Reaction Scheme 4-3]

[0274] JPEG2025525467000160.jpg66128

[0275] (In the reaction formula 4-3, X and n are as defined in the chemical formula 4.)

[0276]

[0277] According to one embodiment of the present invention, as shown in the following reaction formula 4-4, a compound represented by the following chemical formula 4-4 can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with triflic anhydride [(CF3SO2)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 4-2-b, and an allyl compound in which the nitrogen atom is substituted with -COCF3, in a tetrahydrofuran solvent using a platinum catalyst to undergo a hydrosilylation reaction.

[0278] [Reaction Scheme 4-4]

[0279] JPEG2025525467000161.jpg71122

[0280] (In the reaction formula 4-4, X and n are each defined as in the chemical formula 1.)

[0281]

[0282] According to one embodiment of the present invention, as shown in the following reaction formula 4-5, a compound represented by the following chemical formula 4-5 can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 4-2-b, and an allyl compound in which the nitrogen atom is substituted with -SOCF in the presence of a platinum catalyst in a tetrahydrofuran solvent.

[0283] [Reaction Scheme 4-5]

[0284] JPEG2025525467000162.jpg68126

[0285] (In the reaction formula 4-5, X and n are each defined as in the chemical formula 1.)

[0286]

[0287] According to one embodiment of the present invention, as shown in the following reaction formula 4-6, a compound represented by the following chemical formula 4-2-b can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SOF in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 4-6.

[0288] [Reaction Scheme 4-6]

[0289] JPEG2025525467000163.jpg66129

[0290] (In the reaction formulas 4-6, X and n are each defined as in the chemical formula 1.)

[0291]

[0292] According to one embodiment of the present invention, as shown in reaction formula 4-7 below, a silazane compound represented by the following chemical formula 4-a is reacted with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 4-3-b. This compound is then subjected to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -COCF3 in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by chemical formula 4-7.

[0293] [Reaction Scheme 4-7]

[0294] JPEG2025525467000164.jpg65120

[0295] (In the reaction formulas 4-7, X and n are as defined in the chemical formula 1.)

[0296]

[0297] According to one embodiment of the present invention, as shown in the following reaction formula 4-8, a compound represented by the following chemical formula 4-3-b can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO2CF3 in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 4-8.

[0298] [Reaction Scheme 4-8]

[0299] JPEG2025525467000165.jpg63117

[0300] (In the reaction formulas 4-8, X and n are each defined as in the chemical formula 1.)

[0301]

[0302] According to one embodiment of the present invention, as shown in the following reaction formula 4-9, a compound represented by the following chemical formula 4-3-b can be synthesized by reacting a silazane compound represented by the following chemical formula 4-a with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO2F in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 4-9.

[0303] [Reaction Scheme 4-9]

[0304] JPEG2025525467000166.jpg65120

[0305] (In the reaction formula 4-9, X and n are each defined as in the chemical formula 1.)

[0306]

[0307] According to one embodiment of the present invention, as shown in the following reaction formula 5-1, a compound represented by the following chemical formula 5-1 can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 5-1-b, and an allyl compound in which the nitrogen atom is substituted with -COCF3, in a tetrahydrofuran solvent using a platinum catalyst to undergo a hydrosilylation reaction.

[0308] [Reaction Scheme 5-1]

[0309] JPEG2025525467000167.jpg91118

[0310] (In the reaction formula 5-1, X and n are as defined in the chemical formula 1.)

[0311]

[0312] According to one embodiment of the present invention, as shown in the following reaction formula 5-2, a compound represented by the chemical formula 5-1-b can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO2CF3 in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 5-2.

[0313] [Reaction Scheme 5-2]

[0314] JPEG2025525467000168.jpg76108

[0315] (In the reaction formula 5-2, X and n are each defined as in the chemical formula 1.)

[0316]

[0317] According to one embodiment of the present invention, as shown in the following reaction formula 5-3, a compound represented by the following chemical formula 5-1-b can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with trifluoroacetic anhydride [CFCO]O and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SOF in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by the chemical formula 5-3.

[0318] [Reaction Scheme 5-3]

[0319] JPEG2025525467000169.jpg91109

[0320] (In the reaction formula 5-3, X and n are each defined as in the chemical formula 1.)

[0321]

[0322] According to one embodiment of the present invention, as shown in reaction formula 5-4 below, a silazane compound represented by the following chemical formula 5-a, triflic anhydride [(CF3SO2)O], and triethylamine are reacted in a chloroform solvent to synthesize a compound represented by chemical formula 5-2-b, and an allyl compound in which the nitrogen atom is substituted with -COCF3 are subjected to a hydrosilylation reaction in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by chemical formula 5-4.

[0323] [Reaction Scheme 5-4]

[0324] JPEG2025525467000170.jpg85106

[0325] (In the reaction formula 5-4, X and n are each defined as in the chemical formula 1.)

[0326]

[0327] According to one embodiment of the present invention, as shown in the following reaction formula 5-5, a compound represented by the following chemical formula 5-2-b can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with triflic anhydride [(CF3SO2)O] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO2CF3 in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 5-5.

[0328] [Reaction Scheme 5-5]

[0329] JPEG2025525467000171.jpg7799

[0330] (In the reaction formula 5-5, X and n are as defined in the chemical formula 1.)

[0331]

[0332] According to one embodiment of the present invention, as shown in the following reaction formula 5-6, a compound represented by the following chemical formula 5-6 can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with triflic anhydride [(CFSO)O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 5-2-b, and an allyl compound in which the nitrogen atom is substituted with -SOF, in a tetrahydrofuran solvent using a platinum catalyst to carry out a hydrosilylation reaction.

[0333] [Reaction Scheme 5-6]

[0334] JPEG2025525467000172.jpg74103

[0335] (In the reaction formula 5-6, X and n are each defined as in the chemical formula 1.)

[0336]

[0337] According to one embodiment of the present invention, as shown in the following reaction formula 5-7, a compound represented by the following chemical formula 5-3-b can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -COCF3 in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 5-7.

[0338] [Reaction Scheme 5-7]

[0339] JPEG2025525467000173.jpg7897

[0340] (In the reaction formulas 5-7, X and n are each defined as in the chemical formula 1.)

[0341]

[0342] According to one embodiment of the present invention, as shown in the following reaction formula 5-8, a compound represented by the following chemical formula 5-3-b can be synthesized by reacting a silazane compound represented by the following chemical formula 5-a with fluorosulfonic acid [HSO3F] and triethylamine in a chloroform solvent, and then subjecting the compound to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO2CF3 in a tetrahydrofuran solvent using a platinum catalyst to synthesize a compound represented by the chemical formula 5-8.

[0343] [Reaction Scheme 5-8]

[0344] JPEG2025525467000174.jpg71101

[0345] (In the reaction formulas 5-8, X and n are each defined as in the chemical formula 1.)

[0346]

[0347] According to one embodiment of the present invention, as shown in reaction formula 5-9 below, a silazane compound represented by chemical formula 5-a below, fluorosulfonic acid [HSO3F], and triethylamine are reacted in a chloroform solvent to synthesize a compound represented by chemical formula 5-3-b. The compound is then subjected to a hydrosilylation reaction with an allyl compound in which the nitrogen atom is substituted with -SO3F in the presence of a platinum catalyst in a tetrahydrofuran solvent to synthesize a compound represented by chemical formula 5-9.

[0348] [Reaction Scheme 5-9]

[0349] JPEG2025525467000175.jpg7999

[0350] (In the reaction formula 5-9, X and n are each defined as in the chemical formula 1.)

[0351]

[0352] The present invention relates to electrolyte compositions containing the novel anion receptors according to the present invention.

[0353] According to one embodiment of the present invention, the anion receptor may include at least one of the novel silazane compounds represented by Formulas 1 to 5, in which an amine group substituted with an electron-withdrawing group is introduced to a silicon atom, or an electron-withdrawing group is introduced to a nitrogen atom in a ring.

[0354] According to one embodiment of the present invention, the electrolyte composition further includes the novel silazane compound; and at least one compound selected from the linear hydrocarbon compound represented by Chemical Formula 6, the cyclic hydrocarbon compounds represented by Chemical Formulas 7 to 11, the polyalkylene oxide compound represented by Chemical Formula 12, and the siloxane compounds represented by Chemical Formulas 13 to 15, each of which has a nitrogen atom in an amine group substituted with an electron-withdrawing group introduced therein. The linear hydrocarbon compound represented by Chemical Formula 6, the cyclic hydrocarbon compounds represented by Chemical Formulas 7 to 11, the polyalkylene oxide compound represented by Chemical Formula 12, and the siloxane compounds represented by Chemical Formulas 13 to 15 may be mixed with the novel silazane compound and included in the electrolyte composition.

[0355] Among the functional groups introduced as side chains, amine groups or nitrogen atoms in the ring substituted with electron-withdrawing groups can enhance the dissociation of alkali metal salts, thereby increasing electronegativity and cation mobility. For example, electron-withdrawing groups such as -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, and -OCF3 make the amine group or nitrogen in the ring electron-deficient, forming electrically neutral complexes with the anionic species of the alkali metal salt and enhancing the dissociation of the alkali metal salt. Furthermore, because the hydrogen atoms of the amine groups are substituted with electron-withdrawing groups and the nitrogen atoms are located only at the ends of the hydrocarbon chains, the electrochemical instability, instability to lithium salts (e.g., LiPF6), and steric hindrance caused by the presence of a vulnerable nitrogen atom in the middle of the bond, as in the azaethers introduced in U.S. Pat. Nos. 5,705,689 and 6,120,941, can be eliminated. Furthermore, the nitrogen center is more exposed, allowing easy access for large anions, which promotes dissociation of the lithium salt and increases cation mobility, resulting in high ionic conductivity.

[0356]

[0357] In one embodiment of the present invention, the compound of Formula 6 can act as an anion receptor in an electrolyte composition (or electrolyte).

[0358] [Chemical formula 6]

[0359] JPEG2025525467000176.jpg2843

[0360] In one example of the present invention, X and n in Chemical Formula 6 are as defined in Chemical Formula 1. In Chemical Formula 6, R1 and R1' are each selected from a hydrogen atom; a halogen atom; and an electron-withdrawing group selected from -SO2CF3, -OSO2CF3, -S02CHF2, -OSO2CHF2, -S02CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN; wherein R1 and R1' are not simultaneously hydrogen atoms in the same molecule, and at least one of R and R1' is an electron-withdrawing group.

[0361] In one example of the present invention, in the above Chemical Formula 6, 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, JPEG2025525467000177.jpg1319, JPEG2025525467000178.jpg1527 and JPEG2025525467000179.jpg1447 (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; with the proviso that R2, R3, and R4 are not simultaneously hydrogen atoms, and m and m' are each an integer of 0 to 20.)

[0362] In one embodiment of the present invention, the compound of Formula 6 can be selected from the following compounds:

[0363] JPEG2025525467000180.jpg125103

[0364]

[0365] [Chemical formula 7]

[0366] JPEG2025525467000181.jpg3238

[0367] In one embodiment of the present invention, the compound represented by Chemical Formula 7 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 7, X, R1, and n are as defined in Chemical Formula 1.

[0368] In one embodiment of the present invention, the compound represented by Formula 7 can be selected from the following compounds:

[0369] JPEG2025525467000182.jpg2798

[0370]

[0371] [Chemical formula 8]

[0372] JPEG2025525467000183.jpg2938

[0373] In one embodiment of the present invention, the compound of Formula 8 may act as an anion receptor in an electrolyte composition (or electrolyte), and in Formula 8, R1, X, and n are as defined in Formula 1.

[0374] In one embodiment of the present invention, the compound represented by Formula 8 can be selected from the following formulas:

[0375] JPEG2025525467000184.jpg30102

[0376]

[0377] [Chemical formula 9]

[0378] JPEG2025525467000185.jpg3029

[0379] In one embodiment of the present invention, the compound represented by Chemical Formula 9 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 9, X, Y, and n are as defined in Chemical Formula 1.

[0380] In one embodiment of the present invention, the compound represented by Formula 9 can be selected from the following compounds:

[0381] JPEG2025525467000186.jpg8385

[0382]

[0383] [Chemical formula 10]

[0384] JPEG2025525467000187.jpg2655

[0385] In one embodiment of the present invention, the compound represented by Chemical Formula 10 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 10, X, Y, and n are as defined in Chemical Formula 1.

[0386] In one embodiment of the present invention, the compound represented by Formula 10 can be selected from the following compounds:

[0387] JPEG2025525467000188.jpg6294

[0388]

[0389] [Chemical formula 11]

[0390] JPEG2025525467000189.jpg3062

[0391] In one embodiment of the present invention, the compound represented by Chemical Formula 11 can act as an anion receptor in an electrolyte, where n is as defined in Chemical Formula 1, and R1 and R1' are as defined in Chemical Formula 6.

[0392] In one embodiment of the present invention, the compound represented by Formula 11 can be selected from the following compounds:

[0393] JPEG2025525467000190.jpg41106

[0394]

[0395] [Chemical formula 12]

[0396] JPEG2025525467000191.jpg1935

[0397] [Chemical formula 12-a]

[0398] JPEG2025525467000192.jpg1545

[0399]

[0400] [Chemical formula 12-b]

[0401] JPEG2025525467000193.jpg1768

[0402] As an example of the present invention, the compounds represented by Chemical Formula 12, Chemical Formula 12-a, and Chemical Formula 12-b can serve as an anion receptor in an electrolyte, wherein X, Y, and n are as defined in Chemical Formula 1, 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, JPEG2025525467000194.jpg917, JPEG2025525467000195.jpg1629 and JPEG2025525467000196.jpg1239 (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; with the proviso that R2, R3, and R4 are not simultaneously hydrogen atoms, and m and m' are each an integer of 0 to 20), z is an integer of 1 to 20, and n and q are each an integer of 0 to 20. Preferably, z is an integer of 1 to 10, and n and q may each be an integer of 0 to 10.

[0403] In one embodiment of the present invention, the compounds represented by Chemical Formula 12, Chemical Formula 12-a, and Chemical Formula 12-b can be selected from the following compounds:

[0404] JPEG2025525467000197.jpg39111

[0405]

[0406] [Chemical formula 13]

[0407] JPEG2025525467000198.jpg2152

[0408] In one embodiment of the present invention, the compound represented by Chemical Formula 13 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 13, X, Y, and n are as defined in Chemical Formula 1.

[0409] In one embodiment of the present invention, the compound represented by Formula 13 can be selected from the following compounds:

[0410] JPEG2025525467000199.jpg25117

[0411]

[0412] [Chemical formula 14]

[0413] JPEG2025525467000200.jpg2051

[0414] In one embodiment of the present invention, the compound represented by Formula 14 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Formula 14, X, Y, and n are as defined in Formula 1.

[0415] In one embodiment of the present invention, the compound represented by Formula 14 can be selected from the following compounds:

[0416] JPEG2025525467000201.jpg6872

[0417]

[0418] [Chemical formula 15]

[0419] JPEG2025525467000202.jpg3237

[0420] In one embodiment of the present invention, the compound represented by Chemical Formula 15 may serve as an anion receptor in an electrolyte composition (or electrolyte), and in Chemical Formula 15, X, Y, and n are as defined in Chemical Formula 1.

[0421] In one embodiment of the present invention, the compound represented by Formula 15 can be selected from the following compounds:

[0422] JPEG2025525467000203.jpg36104

[0423]

[0424] According to one embodiment of the present invention, the total anion receptor contained in the electrolyte composition ("silazane-based anion receptor compounds of Formulas 1 to 5 + anion receptors of Formulas 6 to 15") 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 %, or 1 wt % to 2 wt %, based on the total mass of the electrolyte composition. If the content is less than 0.01 wt %, it is difficult to exhibit the performance of the anion receptor. If the content is more than 40 wt %, it is difficult to obtain the effects of improving ionic conductivity, electrochemical stability, and low-temperature performance.

[0425] According to one embodiment of the present invention, at least one of the compounds represented by Chemical Formulae 6 to 15 is present in an amount of 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 the amount falls within the above ranges, an electrolyte having improved ionic conductivity and electrochemical stability at room temperature can be provided.

[0426] According to one embodiment of the present invention, the mixing ratio of at least one of the silazane-based anion receptor compounds represented by Chemical Formulas 1 to 5 and at least one of the compounds represented by Chemical Formulas 6 to 15 among the anion receptors may be in a range of 99:1 to 50:50 (w / w). When the ratio is within the above range, it is possible to obtain the effect of improving ionic conductivity and electrochemical stability at room temperature.

[0427] According to one embodiment of the present invention, the electrolyte composition may include an alkali metal ion-containing material and a non-aqueous solvent. In one embodiment of the present invention, the non-aqueous solvent may be any non-aqueous solvent applicable to batteries, and examples of the non-aqueous solvent include ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, dimethyl sulfamoyl fluoride, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and the like. The organic solvent may include, but is not limited to, at least one selected from the group consisting of ethylene carbonate, vinylene carbonate, ethers, organic carbonates, lactones, formates, esters, sulfonates, nitrates, 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.

[0428] In one embodiment of the present invention, the non-aqueous solvent may be included in an amount of 1 wt % or more, 15 wt % or more, 30 wt % or more, 60 wt % or more, or 80 wt % to 99 wt % based on the remaining amount of the electrolyte composition or the total mass of the electrolyte composition.

[0429] In one embodiment of the present invention, the alkali metal ion-containing substance is an alkali metal ion-containing electrolyte salt, for example, Li as a cation. +In one embodiment of the present invention, the lithium salt may be any lithium salt that is applicable to a battery electrolyte, and may 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.

[0430] In one embodiment of the present invention, the alkali metal ion-containing material may be present in the electrolyte composition in an amount of 3 wt % to 60 wt %, 3 wt % to 50 wt %, 10 wt % to 50 wt %, 20 wt % to 50 wt %, 3 wt % to 10 wt %, or 3 wt % to 5 wt %, based on the total weight of the electrolyte composition, and may supply an appropriate amount of alkali ions to provide and maintain stable battery performance.

[0431] According to one embodiment of the present invention, the electrolyte composition may form a non-aqueous liquid electrolyte, a gel polymer electrolyte and / or a solid polymer electrolyte, a solid sulfide-polymer electrolyte, a solid oxide-polymer electrolyte, or a solid oxide-polymer electrolyte, and may further include additional components selectively depending on the type of electrolyte, such as a polymer compound, a polymer support, an additive (e.g., a curing initiator, a polymerization inhibitor), a sulfide, an oxide, or a nanometal oxide.

[0432] According to one 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 can be:

[0433] (a) Novel silazane-based anion receptor compounds represented by the above chemical formulas 1 to 3, in which an amine group substituted with an electron-withdrawing group is introduced to a silicon atom, or an electron-withdrawing group is introduced to a nitrogen atom in a ring;

[0434] Alternatively, an anion receptor which is a mixture of the novel silazane-based anion receptor compound represented by any one of Chemical Formulas 1 to 5 and at least one selected from the group consisting of a linear hydrocarbon compound represented by Chemical Formula 6 having an amine group substituted with an electron-withdrawing group introduced therein or an electron-withdrawing group introduced to a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by Chemical Formulas 7 to 11 below, a polyalkylene oxide compound represented by Chemical Formula 12 above, and a siloxane compound represented by Chemical Formulas 13 to 15 above.

[0435] (b) a non-aqueous solvent, and

[0436] (c) It may contain an alkali metal ion-containing substance.

[0437] In one example of the present invention, the (a) anion receptor, the (b) non-aqueous solvent, and the (c) alkali metal ion-containing substance in the electrolyte composition for a non-aqueous liquid electrolyte are as described above. Preferably, in the electrolyte composition for a non-aqueous liquid electrolyte, the anion receptor is 0.01 wt % to 5 wt %, the non-aqueous solvent is 80 wt % or more, or 95 to 99 wt %, and the alkali metal ion-containing substance is 10 wt % to 30 wt %, 12 wt % to 20 wt %, or 12 wt % to 15 wt %, based on the total mass of the electrolyte composition.

[0438] According to one embodiment of the present invention, the electrolyte composition can form a gel polymer electrolyte, and for example, the electrolyte composition for the gel polymer electrolyte is:

[0439] (a) An anion receptor which is a novel silazane-based anion receptor compound represented by any one of Chemical Formulas 1 to 5, in which an amine group substituted with an electron-withdrawing group has been introduced to a silicon atom, or an electron-withdrawing group has been introduced to a nitrogen atom in the ring; or a mixture of a novel silazane-based anion receptor compound represented by any one of Chemical Formulas 1 to 5, and at least one selected from a linear hydrocarbon compound represented by Chemical Formula 6, in which an amine group substituted with an electron-withdrawing group has been introduced to a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by Chemical Formulas 7 to 11 below, a polyalkylene oxide compound represented by Chemical Formula 12, and a siloxane compound represented by Chemical Formulas 13 to 15:

[0440] (b) a polymeric compound selected from linear, network, comb, and branched polymeric compounds, a crosslinkable polymeric compound, or both;

[0441] (c) polymeric support;

[0442] (d) a non-aqueous solvent, and

[0443] (e) It may contain an alkali metal ion-containing substance.

[0444] In one 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 above for the electrolyte composition. Preferably, in the electrolyte composition for the gel polymer electrolyte, the (a) anion receptor is 0.01 wt % to 30 wt %, the (d) non-aqueous solvent is 20 wt % to 80 wt %, and the (e) alkali metal ion-containing substance is 10 wt % to 30 wt %, based on the total mass of the electrolyte composition.

[0445] In one example of the present invention, in the electrolyte composition for the gel polymer electrolyte, the (b) polymer compound selected from linear, network, comb, and branched polymer compounds may be used without limitation as long as it is applicable to a battery (e.g., an electrolyte), and may include, for example, a flexible inorganic polymer, a linear polyether, or both.

[0446] In one embodiment of the present invention, the flexible inorganic polymer may be selected from polysiloxane, polyphosphazene, or a copolymer thereof, and the linear polyether may be polyalkylene oxide.

[0447] In one embodiment of the present invention, the crosslinkable polymer compound can be used without limitation as long as it is applicable to batteries (e.g., electrolytes). For example, the crosslinkable polymer compound can include, but is not limited to, at least one selected from the group consisting of flexible inorganic polymers or polymer compounds having a linear polyether main chain as a basic skeleton and terminal functional groups such as acrylic, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinylmonomethyl. For example, the crosslinkable polymer compound can be, but is not limited to, bisphenol A ethoxylate dimethacrylate (Bis-15m) represented by the following Formula 16, polyethylene glycol dimethacrylate (PEGDMA) represented by the following Formula 17, vinylene carbonate (VC) represented by the following Formula 18, or vinylethylene carbonate (VEC) represented by the following Formula 19.

[0448]

[0449] [Chemical formula 16]

[0450] JPEG2025525467000204.jpg1877

[0451] [Chemical formula 17]

[0452] JPEG2025525467000205.jpg2857

[0453] [Chemical formula 18]

[0454] JPEG2025525467000206.jpg2332

[0455] [Chemical formula 19]

[0456] JPEG2025525467000207.jpg2836

[0457] In one embodiment of the present invention, the (b) polymer compound selected from linear, network, comb, and branched polymer compounds, the crosslinkable polymer compound, or both of them may be present in an electrolyte composition for the gel polymer electrolyte in an amount of 0.01 wt % to 30 wt % based on the total weight of the electrolyte composition. When included within the above ratio range, a composition with improved mechanical properties and processability can be provided. For example, if the ratio exceeds 80 wt %, the viscosity may be high and processability may be reduced, and if it is less than 20 wt %, the mechanical properties may be reduced.

[0458] As an example of the present invention, the (c) polymer support may be any polymer support applicable to a battery (e.g., an electrolyte) without any limitations, and may 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.

[0459] In one embodiment of the present invention, the polymer support may be present in an amount of 1 wt % to 40 wt % or 5 wt % to 40 wt % of the electrolyte composition for the gel polymer electrolyte, based on the total weight of the electrolyte composition. When the amount falls within the above range, the polymer support can solve the problem of liquid leakage that can occur in gel polymer electrolytes, and can provide an electrolyte with improved stability and electrical performance.

[0460] According to an embodiment of the present invention, when the electrolyte composition for the gel polymer electrolyte includes the crosslinkable polymer compound, it may further include a curable initiator. In one example of the present invention, the curable initiator may include a photocurable initiator, a thermally curable initiator, or both. For example, the photocurable initiator may include, but is not limited to, at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), t-butyl peroxypivalate, 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. For example, the thermosetting initiator may include an azoisobutyronitrile-based compound, a peroxide-based compound, or both. More specifically, the thermosetting initiator may include, but is not limited to, 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), tetramethylbutylperoxyneodecanoate, bis(4-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxycarbonate, butylperoxyneodecanoate, dipropylperoxydicarbonate, and the like.

[0461] In one embodiment of the present invention, the curing initiator is present in an amount of 1×10 based on the total mass of the electrolyte composition for the gel polymer electrolyte. -4The content may be 0.1% by weight to 0.5% by weight. When the content is within the above range, an electrolyte having improved stability and electrical performance can be provided.

[0462] 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 to prevent crosslinking of a specific polymer compound below an appropriate temperature, or when the electrolyte composition includes a polymer compound that must not be crosslinked below an appropriate temperature. That is, by adding the polymerization inhibitor, a solidified electrolyte having a solidification function can be provided.

[0463] In one embodiment of the present invention, the polymerization inhibitor may be any polymerization inhibitor that is applicable to batteries (e.g., electrolytes) and has a polymerization inhibiting or suppressing function, including, but not limited to, 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-acyloxy-p-benzoquinone, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone.

[0464] In one example of the present invention, the polymerization inhibitor is included in the gel polymer electrolyte in an amount of 0.01 wt % to 3 wt % based on the total mass of the electrolyte. When the polymerization inhibitor is included within this range, it is possible to provide an electrolyte that can suppress crosslinking of a specific polymer compound, prevent hardening of the product during storage and transportation, and induce crosslinking at a specific temperature, thereby preventing deterioration of electrolyte function and battery performance due to high temperature or thermal runaway.

[0465] 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:

[0466] (a) Anion receptors containing silazane-based anion receptor compounds represented by Chemical Formulas 1 to 5, in which an amine group substituted with an electron-withdrawing group is introduced to a silicon atom, or an electron-withdrawing group is introduced to a nitrogen atom in a ring;

[0467] Alternatively, an anion receptor comprising a silazane-based anion receptor compound represented by any one of Chemical Formulas 1 to 5, and at least one selected from a linear hydrocarbon compound represented by Chemical Formula 6 below, into which an amine group substituted with an electron-withdrawing group has been introduced or into which an electron-withdrawing group has been introduced to a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by Chemical Formulas 7 to 11 below, a polyalkylene oxide compound represented by Chemical Formula 12 below, and a siloxane compound represented by Chemical Formulas 13 to 15 below;

[0468] (b) a polymeric compound or a crosslinkable polymeric compound selected from linear, network, comb, and branched polymeric compounds;

[0469] (c) polymeric support;

[0470] (d) a non-aqueous solvent; and

[0471] (e) It may contain an alkali metal ion-containing substance.

[0472] The electrolyte composition for the solid polymer electrolyte may further include one or more compounds selected from (f) polyalkylene glycol dialkyl ethers and the non-aqueous solvents.

[0473] In one 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 above for the electrolyte composition. Preferably, in the electrolyte composition for the solid polymer electrolyte, the (a) anion receptor is 0.01 wt % to 30 wt %, the (d) non-aqueous solvent is 0 wt % to 10 wt %, and the (e) alkali metal ion-containing substance is 10 wt % to 70 wt %.

[0474] In one example of the present invention, in the electrolyte composition for the solid polymer electrolyte, the polymer compound selected from the linear, network, comb, and branched polymer compounds may be used without limitation as long as it is applicable to a battery (e.g., an electrolyte), and may include, for example, a flexible inorganic polymer, a linear polyether, or both.

[0475] In one embodiment of the present invention, the flexible inorganic polymer may be polysiloxane, polyphosphazene, or a copolymer thereof, and the linear polyether may be polyalkylene oxide.

[0476] As an example of the present invention, the crosslinkable polymer compound can be used without limitation as long as it is applicable to batteries (e.g., electrolytes), and for example, the crosslinkable polymer compound can include, but is not limited to, at least one selected from the group consisting of flexible inorganic polymers or polymer compounds having a linear polyether main chain as a basic skeleton and terminally introduced functional groups such as acrylic, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinylmonomethyl. For example, the crosslinkable polymer compound can include, but is not limited to, bisphenol A ethoxylate dimethacrylate (Bis-15m) represented by Chemical Formula 16 above and polyethylene glycol dimethacrylate (PEGDMA) represented by Chemical Formula 17 above.

[0477]

[0478] In one embodiment of the present invention, the polymer compound, the crosslinkable polymer compound, or both selected from the linear, network, comb, and branched molecular compounds may be present in an amount of 20 to 90 wt % in the electrolyte composition for the solid polymer electrolyte. When included within the above ratio range, the mechanical properties can be improved, providing stable battery performance.

[0479] As an example of the present invention, the polymer support may be any polymer support applicable to a battery (e.g., an electrolyte) without limitation, and may 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.

[0480] In one embodiment of the present invention, the polymer support may be present in an amount of 1 wt % to 30 wt % of the electrolyte composition for the solid polymer electrolyte, based on the total weight of the electrolyte composition. When the amount falls within the above range, an electrolyte with improved stability and electrical performance can be provided.

[0481] According to an embodiment of the present invention, when the electrolyte composition for the solid polymer electrolyte includes the crosslinkable polymer compound, it may further include a curable initiator. In one example of the present invention, the curable initiator may include a photocurable initiator, a thermally curable initiator, or both. For example, the photocurable initiator may include, but is not limited to, at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), t-butyl peroxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methylbenzoin ethyl ether, benzoin phenyl ether, α-acyl oxime ester, α,α-dithoxyacetophenone, 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. For example, the thermosetting initiator may include an azoisobutyronitrile-based compound, a peroxide-based compound, or both. More specific examples include, but are not limited to, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tetramethylbutylperoxyneodecanoate, bis(4-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxycarbonate, butylperoxyneodecanoate, and dipropylperoxydicarbonate.

[0482] In one embodiment of the present invention, the curing initiator is present in an amount of 1×10 based on the total mass of the electrolyte composition for the solid polymer electrolyte. -4 The content of the polymer support may be 0.1% by weight to 0.5% by weight. When the content falls within the above range, the polymer support can provide an electrolyte with improved stability and electrical performance.

[0483] According to one embodiment of the present invention, the electrolyte composition for the solid polymer electrolyte may further include a polymerization inhibitor together with the curing initiator to prevent crosslinking of a specific polymer compound below an appropriate temperature, or when the electrolyte composition includes a polymer compound that should not be crosslinked. That is, a solidified electrolyte may be prepared by adding the polymerization inhibitor.

[0484] In one embodiment of the present invention, the polymerization inhibitor may be used without limitation as long as it is a polymer support applicable to batteries (e.g., electrolytes) and has a polymerization inhibiting or suppressing function, for example, p-benzoquinone, 4-methoxyphenol, 4-t-butylcatechol, phenothiazine, hydroquinone, naphthoquinone, phenanthroquinone, toluquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone, but is not limited to at least one selected from the group consisting of these.

[0485] In one example of the present invention, the polymerization inhibitor is included in the solid polymer electrolyte in an amount of 0.01 wt % to 3 wt % based on the total mass of the electrolyte. When the polymerization inhibitor is included within this range, it is possible to provide an electrolyte that can suppress crosslinking of a specific polymer compound, prevent hardening of the product during storage and transportation, and induce crosslinking at a specific temperature, thereby preventing deterioration of electrolyte function and battery performance due to high temperature or thermal runaway.

[0486] According to one 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 may include, but are not limited to, at least one selected from the group consisting of 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, dibutyl ether-terminated polypropylene glycol / polyethylene glycol copolymer, and dibutyl ether-terminated polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymer.

[0487] In one example of the present invention, the polyalkylene glycol dialkyl ether or the non-aqueous solvent may be 1 wt % to 30 wt % in the electrolyte composition for the solid polymer electrolyte.

[0488] According to one embodiment of the present invention, the electrolyte composition can form a solidified electrolyte, for example, the electrolyte composition for the solidified electrolyte is:

[0489] (a) Anion receptors containing silazane-based anion receptor compounds represented by Chemical Formulas 1 to 5, in which an amine group substituted with an electron-withdrawing group is introduced to a silicon atom, or an electron-withdrawing group is introduced to a nitrogen atom in a ring;

[0490] Alternatively, an anion receptor comprising a silazane-based anion receptor compound represented by any one of Chemical Formulas 1 to 5, and at least one selected from a linear hydrocarbon compound represented by Chemical Formula 6 below, into which an amine group substituted with an electron-withdrawing group has been introduced or an electron-withdrawing group has been introduced to a nitrogen atom in the ring, a cyclic hydrocarbon compound represented by Chemical Formulas 7 to 11 below, a polyalkylene oxide compound represented by Chemical Formula 12 below, and a siloxane compound represented by Chemical Formulas 13 to 15 below;

[0491] (b) a polymeric compound or a crosslinkable polymeric compound selected from linear, network, comb, and branched polymeric compounds;

[0492] (c) polymeric support;

[0493] (d) non-aqueous solvents;

[0494] (e) alkali metal ion-containing materials; and

[0495] (f) A polymerization inhibitor may be included.

[0496] Optionally, (vii) the electrolyte composition for the solid polymer electrolyte may further include one or more compounds selected from polyalkylene glycol dialkyl ethers and the non-aqueous solvents.

[0497] In one embodiment of the present invention, the components (a) to (vii) 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 in the electrolyte composition for the solidified electrolyte is 12 wt % or more, or 13 wt % or more. When included in an amount equal to or greater than this minimum content range, the electrolyte or battery can be solidified to provide a rapid curing reaction at temperatures above a fire risk, such as about 130°C or higher. Furthermore, the nonaqueous solvent (d) can be present in an amount of 20 wt % to 80 wt % of the electrolyte composition for the solidified electrolyte.

[0498] The present invention relates to electrolytes containing the novel anion receptors according to the present invention.

[0499] According to one embodiment of the present invention, the electrolyte is prepared using the electrolyte composition according to the present invention, and the electrolyte may be a liquid, gel, or solid electrolyte, for example, a non-aqueous liquid electrolyte, a gel polymer electrolyte, a solid polymer electrolyte, a thin polymer electrolyte film, and / or a solidified electrolyte.

[0500] According to one embodiment of the present invention, the solidified electrolyte may be prepared from the electrolyte composition for the gel polymer electrolyte and / or the electrolyte composition for the solid polymer electrolyte, or may be an electrolyte composition in which a curing reaction has not progressed. Furthermore, the solidified electrolyte has a viscosity and / or fluidity similar to or similar to that of a liquid. When applied to a battery, the solidified electrolyte rapidly cures at a certain temperature, for example, at a high temperature of 120°C or higher, or at a high temperature of 130°C or higher, thereby interrupting the operation of the battery and preventing thermal runaway and fire risks by ensuring battery stability at high temperatures.

[0501] According to one embodiment of the present invention, the polymer electrolyte thin film may be prepared by, for example, a curing process using an electrolyte composition for the gel polymer electrolyte and / or an electrolyte composition for the solid polymer electrolyte.

[0502] According to one embodiment of the present invention, the polymer electrolyte thin film may be manufactured by the following process: In one example of the present invention, the manufacturing method may include mixing components to prepare an electrolyte composition, and coating the electrolyte composition on a substrate, drying, and curing the coating to form a thin film.

[0503] In one example of the present invention, when the gel polymer electrolyte thin film is formed,

[0504] The step of preparing the electrolyte composition may involve preparing a gel polymer electrolyte composition, placing a non-aqueous solvent, an anion receptor, an alkali metal ion-containing material, etc. in a container in an appropriate mixing ratio, stirring the mixture with a stirrer to prepare a solution, and then adding and mixing the polymer support. During mixing, the polymer support may be melted by applying a predetermined amount of heat as needed to prepare a gel polymer electrolyte composition mixture for preparing the gel polymer electrolyte thin film of the present invention.

[0505] For example, the thin film forming step can be performed by coating the prepared composition mixture to an appropriate thickness on a support substrate made of glass or polyethylene, or a commercially available Mylar film, and then drying the coated substrate, or exposing it to electron beams, ultraviolet rays, or gamma rays, or heating it to cause a curing reaction to form a thin film. As another example, the thin film forming step can be performed by applying the composition mixture to the support substrate, fixing spacers for adjusting the thickness on both ends of the support substrate, covering it with another support substrate, and then causing a curing reaction using the curing irradiator or heat source to form a gel-type polymer electrolyte thin film.

[0506] In one example of the present invention, when forming the solid polymer electrolyte thin film,

[0507] For example, the step of preparing the electrolyte composition may involve preparing a solid polymer electrolyte composition. The anion receptor, polyalkylene glycol dialkyl ether, or non-aqueous solvent and alkali metal ion-containing material may be placed in a container in an appropriate mixing ratio, the mixture may be stirred with a stirrer to prepare a solution, and then a network, branched, or comb-like polymer compound or a crosslinkable polymer compound may be added and mixed. The network, branched, or comb-like polymer compound may then be dissolved by applying a predetermined amount of heat, if necessary, during mixing. In the case of a crosslinkable polymer compound, a curing initiator and a polymerization inhibitor may be added to the mixture and stirred to prepare a solid polymer electrolyte composition mixture for preparing a solid polymer electrolyte thin film of the present invention.

[0508] For example, the thin film forming step can be performed by coating the prepared composition mixture to an appropriate thickness on a support substrate made of glass or polyethylene, or a commercially available Mylar film, and then drying the coated substrate, or exposing it to electron beams, ultraviolet rays, or gamma rays, or heating it to cause a curing reaction. As another example, the thin film forming step can be performed by applying the composition mixture to the support substrate, fixing spacers for adjusting the thickness on both ends of the support substrate, covering it with another support substrate, and then causing a curing reaction using the curing irradiator or heat source to produce a solid polymer electrolyte thin film.

[0509] The present invention relates to electrochemical cell parts or components which contain the novel silazane-based anion receptor compounds according to the present invention.

[0510] According to one embodiment of the present invention, the silazane-based anion receptor compound may be coated or impregnated in a cathode, an anode, a current collector and / or a separator thereof, an electrolyte containing the silazane-based anion receptor compound, or a membrane for a battery.

[0511] For example, the silazane-based anion receptor compound can be used in electrolyte compositions, process compositions, and the like.

[0512] For example, the silazane-based anion receptor compound can be added to the cathode and the anode during the preparation of electrode slurry containing the active material.

[0513] For example, the separator may be impregnated or coated with the silazane-based anion receptor compound.

[0514] For example, the electrolyte composition may be a membrane (e.g., a thin polymer electrolyte film), film, and / or sheet for a battery that includes the silazane-based anion receptor compound or is manufactured (e.g., cured, molded, etc.) from the electrolyte composition.

[0515] For example, the electrolyte may be a liquid, gel, or solid electrolyte using the electrolyte composition according to the present invention. The gel and solid electrolytes may be a gel polymer electrolyte thin film or a solid polymer electrolyte thin film, respectively.

[0516] The present invention relates to electrochemical cells containing silazane-based anion receptor compounds according to the present invention.

[0517] According to one embodiment of the present invention, the electrochemical cell may be a secondary or rechargeable battery and may include a liquid, gel, and / or solid electrolyte (e.g., a gel polymer electrolyte and a solid polymer electrolyte) prepared from the electrolyte composition according to the present invention.

[0518] According to one embodiment of the present invention, a battery using the liquid or gel polymer electrolyte of the present invention may include a cathode, an anode, and a separator, and a battery using the solid polymer electrolyte of the present invention may include a cathode and an anode. In addition to the above-mentioned battery components, the battery may further include components known in the technical field of the present invention for driving or operating the battery, but these will not be specifically mentioned herein.

[0519] According to one embodiment of the present invention, the cathode and anode used in the battery may be manufactured according to a cathode and anode used in a battery and a method for manufacturing the same known in the technical field of the present invention, and the battery may be assembled by a conventional method for assembling a cathode, an anode, and an electrolyte.

[0520] In one embodiment of the present invention, the cathode may be made of lithium; lithium alloys such as Li-Al, Li-Si, Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; Li x These may include, but are not limited to, lithium metal oxide intercalation compounds such as WO2 or LiMoO2; lithium metal sulfide intercalation compounds such as LiTiS2; mixtures thereof, or mixtures thereof with alkali metals.

[0521] In one embodiment of the present invention, the anode may include, but is not limited to, a transition metal oxide, a transition metal chalcogenide, a poly(carbon disulfide) polymer, an organic-disulfide redox polymer, a polyaniline, an organic-disulfide / polyaniline composite, or a mixture thereof containing an oxychloride.

[0522] According to one embodiment of the present invention, a primary battery comprising a non-aqueous liquid electrolyte containing a silazane-based anion receptor compound of the present invention comprises:

[0523] (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 any of these, or an alkali metal;

[0524] (b) Anodes containing transition metal oxides, transition metal chalcogenides, poly(carbon disulfide) polymers, organic-disulfide redox polymers, polyaniline, organic-disulfide / polyaniline composites, and oxychlorides, such as SO2, CuO, CuS, Ag2CrO4, I2, PbI2, PbS, SOCl2, V2O5, MoO3, MnO2, or polycarbon monofluoride (CF). n an anode containing;

[0525] (c) the non-aqueous liquid electrolyte of the present invention as described above; and

[0526] (d) The separator, anode, cathode, and battery assembly can be carried out by known methods.

[0527] According to one embodiment of the present invention, a secondary battery comprising a non-aqueous liquid electrolyte containing the silazane-based anion receptor compound of the present invention comprises:

[0528] (a) Lithium, lithium alloys such as Li-Al, Li-Si, and Li-Cd, lithium-carbon intercalation compounds, lithium-graphite intercalation compounds, Li x a cathode containing lithium metal or a material capable of reversibly reacting with lithium metal, such as a lithium metal oxide intercalation compound, such as WO2 or LiMoO2, or a lithium metal sulfide intercalation compound, such as LiTiS2;

[0529] (b) Li 2.5 V6O 13 , Li 1.2 V2O5, LiCoO2, LiNiO2, LiNi 1-x M x anodes containing transition metal oxides capable of intercalating lithium, such as LiMnO (where M is Co, Mg, Al, or Ti), LiMnO, or LiMnO; transition metal halides; or chalcogenides, such as LiNbSe, LiTiS, or LiMoS;

[0530] (c) the non-aqueous liquid electrolyte of the present invention as described above; and

[0531] (d) The separator, anode, cathode, and battery assembly can be carried out by known methods.

[0532] According to one embodiment of the present invention, a secondary battery comprising a gel polymer electrolyte containing the silazane-based anion receptor compound of the present invention can include the gel polymer electrolyte of the present invention together with a cathode, an anode, and a separator used in a secondary battery comprising the nonaqueous liquid electrolyte.

[0533] According to one embodiment of the present invention, a secondary battery comprising a solid polymer electrolyte containing the silazane-based anion receptor compound may include the solid polymer electrolyte of the present invention together with the cathode and anode used in the secondary battery comprising the non-aqueous liquid electrolyte.

[0534] According to one embodiment of the present invention, the battery is a battery that uses an electrolyte containing a non-aqueous solvent, and may be, for example, a lithium ion battery, a lithium ion polymer battery, an alkali metal battery, or the like, but is not limited to these.

[0535] According to one embodiment of the present invention, the battery can be reused by replacing the spent waste electrolyte.

[0536] The present invention relates to reusable batteries made with an anion receptor according to the present invention.

[0537] According to one embodiment of the present invention, the reused battery can be a reusable battery obtained by replacing the waste electrolyte in a used waste battery (e.g., an electric vehicle battery) with an electrolyte containing the silazane-based anion receptor compound. That is, the reused battery can be composed of components of a used waste battery and an electrolyte containing the silazane-based anion receptor compound according to the present invention.

[0538] According to one embodiment of the present invention, the reusable battery is manufactured by replacing and filling an electrolyte containing the silazane-based anion receptor compound of the present invention, and the manufacturing method of the reusable battery is as follows:

[0539] (a) preparing waste batteries;

[0540] (b) removing waste electrolyte and other impurities from the waste batteries; and

[0541] (c) injecting the electrolyte according to the present invention into the waste battery to regenerate it;

[0542] In one embodiment of the present invention, the steps of preparing waste batteries and removing waste electrolyte and other impurities from the waste batteries may be performed in a dry room or in an inert atmosphere.

[0543] In one embodiment of the present invention, the step of removing the waste electrolyte and other impurities from the waste batteries may be performed under vacuum conditions.

[0544] As an example of the present invention, the step of injecting the electrolyte according to the present invention into the waste battery to regenerate it may be performed by adding a new electrolyte to the waste battery and then vibrating the waste battery at a certain temperature, for example, the temperature may be 20°C to 50°C.

[0545] According to one embodiment of the present invention, the reused battery and its manufacturing method are manufactured by replacing and filling the waste electrolyte in a used electric vehicle battery (waste battery) with an electrolyte containing a silazane-based anion acceptor compound according to the present invention to make the battery reusable. For example, in the case of a waste battery used for an electric vehicle, there is a high risk of explosion and fire when it is charged, so a process of completely discharging the charged current and then separating the battery pack into individual cells may be necessary. Each discharged cell can be evaluated for its charge capacity and discharge capacity using a charger / discharger, and classified according to its capacity.

[0546] For example, cells are divided into those with capacities over 80%, 68% to 80%, and below 68%, and the regeneration process is performed on cells with a significant drop in capacity below 68%. Cells with a drop in capacity are fully discharged, and then holes are drilled in each cell in a dry room or inert atmosphere, and the existing electrolyte, generated gas, and impurities are removed under vacuum. An electrolyte containing an additive that can restore performance is then injected into the cell to seal the holes, and the cell is then rocked for a certain period of time under a constant temperature (25°C to 50°C) to evenly distribute the electrolyte, activate the anode and cathode active materials, and increase the activity of Li-ions, restoring the battery's capacity.

[0547] MODE FOR CARRYING OUT THE INVENTION

[0548] The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples are merely for the purpose of illustrating the present invention, and the content of the present invention is not limited to the following examples.

[0549]

[0550] Manufacturing Example 1

[0551] Synthesis of N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide JPEG2025525467000208.jpg1678

[0552] Allylamine (0.119 g, 2.08 mmol) was reacted with trifluoroacetic anhydride (0.49 mL, 3.2 mmol) and 2,6-di-tert-butyl-4-methyl-pyridine (0.637 g, 3.11 mmol) dissolved in 3 mL of carbon tetrachloride for 4 hours, and the pyridinium triflate was removed by filtration to give the product, N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide.

[0553] 1H NMR (300MHz, CDCl3): ppm 4.37 (m, 2H), 5.07-5.26 (m, 2H), 5.80 (m, 1H); 13 C NMR (CDCl3): ppm 43.0, 116.9, 122.9, 132.3, 167.2; 19 F NMR (CDCl3): ppm -79.2 (s)

[0554]

[0555] Manufacturing Example 2

[0556] Synthesis of N-allyl-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide JPEG2025525467000209.jpg2378

[0557] To a mixture of allylamine (0.5 g, 8.76 mmol) and triethylamine (2.0 g, 20 mmol) in 40 mL of chloroform at -40°C, 5.0 g of triflic anhydride (18 mmol) was added dropwise under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and the volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 mL of 4 M NaOH and washed three times with 25 mL of chloroform. The aqueous component was neutralized with HCl and then washed three times with 30 mL of chloroform. The organic extract was then dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield the product, N-allyl-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide.

[0558] 1 H NMR (300MHz, CDCl3): ppm 3.32 (m, 2H), 5.15 (m, 2H), 5.83 (m, 1H); 13 C NMR (300MHz, CDCl3): 40, 114.9, 134.3, 145.9; 19 F NMR (CDCl3): ppm -79.8 (s)

[0559]

[0560] Manufacturing Example 3

[0561] Synthesis of allyl(fluorosulfonyl)sulfamoyl fluoride JPEG2025525467000210.jpg2374

[0562] To a mixture of allylamine (0.5 g, 8.76 mmol) and triethylamine (2.0 g, 20 mmol) in 40 mL of chloroform at -40°C, 3.6 g of fluorosulfonic acid (18 mmol) was added dropwise under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and the volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 mL of 4 M NaOH and washed three times with 25 mL of chloroform. The aqueous component was neutralized with HCl and then washed three times with 30 mL of chloroform. The organic extract was then dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield the product, allyl(fluorosulfonyl)sulfamoyl fluoride.

[0563] 1 H NMR (300MHz, CDCl3): ppm 3.32 (m, 2H), 5.19 (m, 1H), 5.22 (m, 1H), 5.87 (m, 1H); 13 C NMR (300MHz, CDCl3): 31.4, 117.4, 134.2; 19 F NMR (CDCl3): ppm -79.7 (s)

[0564]

[0565] [Example 1-1]: Synthesis of N,N-bis(dimethyl(vinyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-1)

[0566] [Reaction Scheme 1-1]

[0567] JPEG2025525467000211.jpg33108

[0568] To a mixture of 1,1,3,3-tetramethyl-1,3-divinyldisilazane (3.15 g, 17.5 mmol) in 40 mL of chloroform at 0 °C, triethylamine (2.0 g, 2.0 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were added dropwise under a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, and the volatiles were removed under reduced pressure. Removal of the chloroform under vacuum afforded the product, N,N-bis(dimethyl(vinyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-1).

[0569] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 12H), 5.1(m, 2H), 5.3(m, 2H), 5.4(m, 2H); 13 C NMR (300MHz, CDCl3): 1.3, 120.6, 123.0, 138.0 19 F NMR (CDCl3): ppm -77.3 (s)

[0570]

[0571] [Example 1-2]: Synthesis of N,N-bis(dimethyl(vinyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-2)

[0572] [Reaction Scheme 1-2]

[0573] JPEG2025525467000212.jpg30104

[0574] Triflic anhydride (5.0 g, 18 mmol) was added dropwise to a mixture of 1,1,3,3-tetramethyl-1,3-divinyldisilazane (3.24 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) in 40 mL of chloroform at -40 °C under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and the volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 mL of 4 M NaOH and washed three times with 25 mL of chloroform. The aqueous component was neutralized with HCl and then washed three times with 30 mL of chloroform. The organic extract was then dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield the product, N,N-bis(dimethyl(vinyl)silyl)-1,1,1-trifluoromethanesulfonamide (compound 1-2).

[0575] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 12H), 5.1(m, 2H), 5.2(m, 2H), 5.4(m, 2H), ; 13 C NMR (300MHz, CDCl3): -2.3, 0.0, 1.1, 119.1; 19 F NMR (CDCl3): ppm -76.1 (s)

[0576]

[0577] [Example 1-3]: Synthesis of bis(dimethyl(vinyl)silyl)sulfamoyl fluoride (Compound 1-3)

[0578] [Reaction Scheme 1-3]

[0579] JPEG2025525467000213.jpg33108

[0580] To a mixture of 1,1,3,3-tetramethyl-1,3-divinyldisilazane (3.24 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) in 40 mL of chloroform at -40°C, 3.6 g of fluorosulfonic acid (18 mmol) was added dropwise under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and the volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 mL of 4 M NaOH and washed three times with 25 mL of chloroform. The aqueous component was neutralized with HCl and then washed three times with 30 mL of chloroform. The organic extract was then dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield the product, bis(dimethyl(vinyl)silyl)sulfamoyl fluoride (compound 1-3).

[0581] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 12H), 5.1(m, 2H), 5.3(m, 3H), 5.4(m, 2H); 13 C NMR (300MHz, CDCl3): 0.1, 123.0, 138.0; 19 F NMR (CDCl3): ppm -78.1 (s)

[0582]

[0583] [Example 1-4]: Synthesis of 2,2,2-trifluoro-N,N-bis(trimethylsilyl)acetamide (Compound 1-4)

[0584] [Reaction Scheme 1-4]

[0585] JPEG2025525467000214.jpg36108

[0586] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product 2,2,2-trifluoro-N,N-bis(trimethylsilyl)acetamide (Compound 1-4).

[0587] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H); 13 C NMR (300MHz, CDCl3): 2.2, 120.4, 173.0; 19 F NMR (CDCl3): ppm -77.2 (s)

[0588]

[0589] [Example 1-5]: Synthesis of 1,1,1-trifluoro-N,N-bis(trimethylsilyl)methanesulfonamide (Compound 1-5)

[0590] [Reaction Scheme 1-5]

[0591] JPEG2025525467000215.jpg3298

[0592] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and triflic anhydride (5 g, 18 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product 1,1,1-trifluoro-N,N-bis(trimethylsilyl)methanesulfonamide (Compound 1-5).

[0593] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H); 13 C NMR (300MHz, CDCl3): 1.3, 153.6; 19 F NMR (CDCl3): ppm -76.7 (s)

[0594]

[0595] [Example 1-6]: Synthesis of bis(trimethylsilyl)sulfamoyl fluoride (Compound 1-6)

[0596] [Reaction Scheme 1-6]

[0597] JPEG2025525467000216.jpg34108

[0598] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and fluorosulfonic acid (3.6 g, 18 mmol) were reacted in a manner similar to that of Reaction Scheme 1-3 to obtain the product bis(trimethylsilyl)sulfamoyl fluoride (Compound 1-6).

[0599] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H); 13 C NMR (300 MHz, CDCl3): 1.0; 19 F NMR (CDCl3): ppm -76.7 (s)

[0600]

[0601] [Example 1-7]: Synthesis of N,N-bis(octyldimethylsilyl)-2,2,2-trifluoroacetamide (Compound 1-7)

[0602] [Reaction Scheme 1-7]

[0603] JPEG2025525467000217.jpg32106

[0604] 1,1,3,3-Tetramethyl-1,3-dioctyl-disilazane (6.26 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product N,N-bis(octyldimethylsilyl)-2,2,2-trifluoroacetamide (Compound 1-7).

[0605] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 12H), 0.90(m, 6H), 1.4(m, 28H), 1.3(m, 8H), 1.33(m, 4H); 13 C NMR (300MHz, CDCl3): -0.3, 4.2, 9.2, 120.4, 173.0; 19 F NMR (CDCl3): ppm -77.4 (s)

[0606]

[0607] [Example 1-8]: Synthesis of N,N-bis(octyldimethylsilyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-8)

[0608] [Reaction Scheme 1-8]

[0609] JPEG2025525467000218.jpg30104

[0610] 1,1,1,3,3,3-Hexamethyl-dioctyl-disilazane (6.26 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and triflic anhydride (5 g, 18 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product N,N-bis(octyldimethylsilyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-8).

[0611] 1H NMR (300MHz, CDCl3): ppm 0.08 (m, 12H), 0.9(m, 6H), 1.4(m, 28); 13 C NMR (300MHz, CDCl3): -1.2, 4.2, 8.3, 153.6; 19 F NMR (CDCl3): ppm -76.7 (s)

[0612]

[0613] [Example 1-9]: Synthesis of bis(octyldimethylsilyl)sulfamoyl fluoride (Compound 1-9)

[0614] [Reaction Scheme 1-9]

[0615] JPEG2025525467000219.jpg29102

[0616] 1,1,1,3,3,3-Hexamethyl-dioctyl-disilazane (6.26 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and fluorosulfonic acid (3.6 g, 18 mmol) were reacted in a manner similar to that described in Reaction Scheme 1-3 to obtain the product bis(octyldimethylsilyl)sulfamoyl fluoride (Compound 1-9).

[0617] 1 H NMR (300MHz, CDCl3): ppm 0.08 (m, 12H), 0.9 (m, 6H), 1.4(m, 28H); 13 C NMR (300MHz, CDCl3): -1.5, 4.2, 8.0; 19 F NMR (CDCl3): ppm -76.7 (s)

[0618]

[0619] [Example 1-10]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-10)

[0620] [Reaction Scheme 1-10]

[0621] JPEG2025525467000220.jpg3099

[0622] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-10).

[0623] 1 H NMR (300MHz, CDCl3): ppm 0.66(m, 12H), 7.18(m, 4H), 7.27(m, 4H), 7.45(m, 4H); 13 C NMR (300MHz, CDCl3): 5.8, 120.4, 129.5, 130.0, 133.9, 139.6, 173.0; 19 F NMR (CDCl3): ppm -77.5 (s)

[0624]

[0625] [Example 1-11]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-11)

[0626] [Reaction Scheme 1-11]

[0627] JPEG2025525467000221.jpg32108

[0628] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and triflic anhydride (5 g, 18 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-11).

[0629] 1 H NMR (300MHz, CDCl3): ppm 0.66(m, 12H), 7.18(m, 4H), 7.27(m, 4H), 7.45(m, 2H), ; 13 C NMR (300MHz, CDCl3): 4.9, 129.5, 130.0, 133.9, 139.6, 153.6; 19 F NMR (CDCl3): ppm -76.8 (s)

[0630]

[0631] [Example 1-12]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluorosulfonamide (Compound 1-12)

[0632] [Reaction Scheme 1-12]

[0633] JPEG2025525467000222.jpg3399

[0634] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and fluorosulfonic acid (3.6 g, 18 mmol) were reacted in the same manner as in Reaction Scheme 1-3 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluorosulfonamide (Compound 1-12).

[0635] 1H NMR (300MHz, CDCl3): ppm 0.66(m, 12H), 7.18(m, 4H), 7.27(m, 4H), 7.45(m, 2H), ; 13 C NMR (300MHz, CDCl3): 4.9, 129.5, 130.0, 133.9, 139.6, 153.6; 19 F NMR (CDCl3): ppm -76.9 (s)

[0636]

[0637] [Example 1-13]: Synthesis of 2,2,2-trifluoro-N,N-bis(methyldiphenylsilyl)acetamide (Compound 1-13)

[0638] [Reaction Scheme 1-13]

[0639] JPEG2025525467000223.jpg3394

[0640] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product 2,2,2-trifluoro-N,N-bis(methyldiphenylsilyl)acetamide (Compound 1-13).

[0641] 1 H NMR (300MHz, CDCl3): ppm 0.66(m, 6H), 7.37(m, 8H), 7.46(m, 8H), 7.55(m, 4H); 13 C NMR (300MHz, CDCl3): 2.5, 120.4, 127.4, 129.5, 130.0, 135.8, 173.0; 19 F NMR (CDCl3): ppm -77.8 (s)

[0642]

[0643] [Example 1-14]: Synthesis of 1,1,1-trifluoro-N,N-bis(methyldiphenylsilyl)methanesulfonamide (Compound 1-14)

[0644] [Reaction Scheme 1-14]

[0645] JPEG2025525467000224.jpg36106

[0646] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and triflic anhydride (5 g, 18 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product 1,1,1-trifluoro-N,N-bis(methyldiphenylsilyl)methanesulfonamide (Compound 1-14).

[0647] 1 H NMR (300MHz, CDCl3): ppm 0.66(m, 6H), 7.37(m, 8H), 7.46(m, 8H), 7.55(m, 4H); 13 C NMR (300MHz, CDCl3): 1.6, 127.4, 129.5, 130.0, 135.8, 153.6; 19 F NMR (CDCl3): ppm -76.6 (s)

[0648]

[0649] [Example 1-15]: Synthesis of bis(methyldiphenylsilyl)sulfamoyl fluoride (Compound 1-15)

[0650] [Reaction Scheme 1-15]

[0651] JPEG2025525467000225.jpg3696

[0652] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol), triethylamine (2.0 g, 20 mmol), and fluorosulfonic acid (3.6 g, 18 mmol) were reacted in a manner similar to that of Reaction Scheme 1-3 to obtain the product bis(methyldiphenylsilyl)sulfamoyl fluoride (Compound 1-15).

[0653] 1 H NMR (300MHz, CDCl3): ppm 0.66(m, 6H), 7.37(m, 8H), 7.46(m, 8H), 7.55(m, 4H); 13 C NMR (300MHz, CDCl3): 1.3, 127.4, 129.5, 130.0, 135.8; 19 F NMR (CDCl3): ppm -76.6 (s)

[0654]

[0655] [Example 2-1]: Synthesis of N-(bis(2,2,2-trifluoroacetyl)carbamoyl)-2,2,2-trifluoro-N-(triethoxysilyl)acetamide (Compound 2-1)

[0656] [Reaction Scheme 2-1]

[0657] JPEG2025525467000226.jpg35106

[0658] N-(triethoxysilyl)-urea (3.89 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product N-(bis(2,2,2-trifluoroacetyl)carbamoyl)-2,2,2-trifluoro-N-(triethoxysilyl)acetamide (Compound 2-1).

[0659] 1H NMR (300MHz, CDCl3): ppm 1.22(m, 9H), 3.83(m, 6H); 13 C NMR (300MHz, CDCl3): 17.6, 47.9, 121.6, 125.3, 168.7, 170.7; 19 F NMR (CDCl3): ppm -78.2 (s)

[0660]

[0661] [Example 2-2]: Synthesis of N-(bis((trifluoromethyl)sulfonyl)carbamoyl)-1,1,1-trifluoro-N-(triethoxysilyl)methanesulfonamide (Compound 2-2)

[0662] [Reaction Scheme 2-2]

[0663] JPEG2025525467000227.jpg33100

[0664] N-(triethoxysilyl)-urea (3.89 g, 17.5 mmol), triethylamine (6.0 g, 60 mmol), and triflic anhydride (15 g, 54 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product N-(bis((trifluoromethyl)sulfonyl)carbamoyl)-1,1,1-trifluoro-N-(triethoxysilyl)methanesulfonamide (Compound 2-2).

[0665] 1 H NMR (300MHz, CDCl3): ppm 1.22(m, 9H), 3.83(m, 6H); 13 C NMR (300MHz, CDCl3): 17.6, 47.9, 144.8, 149.4, 161.0; 19 F NMR (CDCl3): ppm -76.1 (s)

[0666]

[0667] [Example 2-3]: Synthesis of (bis(fluorosulfonyl)carbamoyl)(triethoxysilyl)sulfamoyl fluoride (Compound 2-3)

[0668] [Reaction Scheme 2-3]

[0669] JPEG2025525467000228.jpg32102

[0670] N-(triethoxylyl)-urea (3.89 g, 17.5 mmol), triethylamine (6.0 g, 60 mmol), and fluorosulfonic acid (10.8 g, 54 mmol) were reacted in the same manner as in Reaction Scheme 1-3 to obtain the product (bis(fluorosulfonyl)carbamoyl)(triethoxysilyl)sulfamoyl fluoride (Compound 2-3).

[0671] 1 H NMR (300MHz, CDCl3): ppm 1.21(m, 9H), 3.83(m, 6H); 13 C NMR (300MHz, CDCl3): 18.1, 55.1, 161.0; 19 F NMR (CDCl3): ppm -76.1 (s)

[0672]

[0673] [Example 3-1]: Synthesis of N,N'-carbonylbis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 3-1)

[0674] [Reaction Scheme 3-1]

[0675] JPEG2025525467000229.jpg32104

[0676] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 to obtain the product N,N'-carbonylbis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide (Compound 3-1).

[0677] 1 H NMR (300MHz, CDCl3): ppm 0.08(s, 18H); 13 C NMR (300MHz, CDCl3): -2.0, 116.2, 157.0, 170.7; 19 F NMR (CDCl3): ppm -78.4 (s)

[0678]

[0679] [Example 3-2]: Synthesis of N,N'-carbonylbis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide (Compound 3-2)

[0680] [Reaction Scheme 3-2]

[0681] JPEG2025525467000230.jpg33104

[0682] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol), triethylamine (4.0 g, 40 mmol), and triflic anhydride (10 g, 36 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain the product N,N'-carbonylbis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide) (Compound 3-2).

[0683] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H); 13 C NMR (300MHz, CDCl3): -2.9, 149.4, 161.0; 19F NMR (CDCl3): ppm -76.8 (s)

[0684]

[0685] [Example 3-3]: Synthesis of carbonylbis((trimethylsilyl)sulfamoyl fluoride) (compound 3-3)

[0686] [Reaction Scheme 3-3]

[0687] JPEG2025525467000231.jpg3097

[0688] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol), triethylamine (4.0 g, 40 mmol), and fluorosulfonic acid (7.2 g, 36 mmol) were reacted in the same manner as in Reaction Scheme 1-3 to obtain the product carbonylbis((trimethylsilyl)sulfamoyl fluoride) (Compound 3-3).

[0689] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H); 13 C NMR (300MHz, CDCl3): -3.2, 161.0; 19 F NMR (CDCl3): ppm -76.7 (s)

[0690]

[0691] [Example 4-1]: Synthesis of N,N'-(methyl(3-(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamido)propyl)silanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 4-1)

[0692] [Reaction Scheme 4-1]

[0693] JPEG2025525467000232.jpg54107

[0694] N,N'-(methylsilanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide), a product obtained by reacting 1-methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) in the same manner as in Reaction Scheme 1-1.

[0695] Dimethylsilane (41.26 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-trifluoroacetyl)-acetamide (49.82 g, 0.2 mol) dissolved in 50 mL of tetrahydrofuran were added dropwise. The mixture was refluxed at 65 °C for 8 hours under a nitrogen atmosphere, cooled to room temperature, and then activated carbon was added and stirred. After filtration, the toluene was evaporated under reduced pressure to give the product N,N'-(methyl(3-(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamido)propyl)silanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 4-1).

[0696] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H), 0.14(m, 3H), 1.02(m, 2H), 1.6(m, 2H), 4.40(m, 2H); 13 C NMR (300MHz, CDCl3): 1.2, 5.3, 19.7, 27.6, 44.3, 115.7, 120.1, 156.1, 171.0; 19 F NMR (CDCl3): ppm -78.7 (s)

[0697]

[0698] [Example 4-2]: Synthesis of N,N'-(methyl(3-(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methylsulfonamido)propyl)silanediyl)bis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide) (Compound 4-2)

[0699] [Reaction Scheme 4-2]

[0700] JPEG2025525467000233.jpg69107

[0701] To a mixture of 1-methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) at -40°C, triflic anhydride (10.0 g, 36 mmol) was added in the same manner as in Reaction Scheme 1-2, to which N,N'-(methylsilanediyl)bis(1,1,1-trifluoro-N-trimethylsilyl)methanesulfonamide (64.2 g, 0.1 mol), the product obtained, and a Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex compound (Pt(O)) catalyst and N-allyl-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (49.82 g, 0.2 mol) dissolved in 50 ml of tetrahydrofuran, were added dropwise. The mixture was refluxed at 65°C for 8 hours under a nitrogen atmosphere, cooled to room temperature, and then activated carbon was added and stirred. After filtration, the toluene was evaporated under reduced pressure to obtain the product N,N'-(methyl(3-(1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methylsulfonamido)propyl)silanediyl)bis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide) (compound 4-2).

[0702] 1 H NMR (300MHz, CDCl3): ppm 0.08(m, 18H), 0.14(m, 3H), 1.02(m, 2H), 1.6(m, 2H), 2.65(m, 2H); 13C NMR (300MHz, CDCl3): -0.6, 4.4, 17.9, 25.8, 41.9, 158.3, 165.8,; 19 F NMR (CDCl3): ppm -78.9 (s)

[0703]

[0704] [Example 4-3]: Synthesis of ((3-(3-(bis(fluorosulfonyl)amino)propyl)(methyl)silanediyl)bis((trimethylsilyl)sulfamoyl fluoride) (Compound 4-3)

[0705] [Reaction Scheme 4-3]

[0706] JPEG2025525467000234.jpg58107

[0707] A mixture of 1-methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) was mixed at -40°C, and fluorosulfonic acid (7.2 g, 36 mmol) was added to the mixture in the same manner as in Reaction Scheme 1-3 to obtain the product (methylsilanediyl)bis((trimethylsilyl)sulfamoyl fluoride) (38.5 g, 0.1 mol) and Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex compound. A Pt(O) catalyst and allyl(fluorosulfonyl)sulfamoyl fluoride (44.2 g, 0.2 mol) were dissolved in 50 mL of tetrahydrofuran and added dropwise. The mixture was refluxed at 65°C for 8 hours under a nitrogen atmosphere and cooled to room temperature. Activated carbon was added, the mixture was stirred, and filtered. The toluene was evaporated under reduced pressure to give the product ((3-(bis(fluorosulfonyl)amino)propyl)(methyl)silanediyl)bis((trimethylsilyl)sulfamoyl fluoride) (compound 4-3).

[0708] 1H NMR (300MHz, CDCl3): ppm 0.08(m, 18H), 0.14(m, 3H), 1.02(m, 2H), 1.6(m, 2H), 2.65(m, 2H); 13 C NMR (300MHz, CDCl3): -1.2, 4.1, 17.3, 25.2, 33.3; 19 F NMR (CDCl3): ppm -78.8 (s)

[0709]

[0710] [Example 5-1]: Synthesis of 2,2,2-trifluoro-1-[2,2,4,4,6,6-hexamethyl-3,5-bis-(2,2,2-trifluoro-acetyl)-[1,3,5,2,4,6]triazasilinan-1-yl]-ethanone (compound 5-1)

[0711] [Reaction Scheme 5-1]

[0712] JPEG2025525467000235.jpg31102

[0713] 2,2,4,4,6,6-Hexamethyl-[1,3,5,2,4,6]triazatrisilane (3.84 g, 17.5 mmol), triethylamine (2.0 g, 2.0 mmol), and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were reacted in the same manner as in Reaction Scheme 1-1 above to obtain the product, 2,2,2-trifluoro-1-[2,2,4,4,6,6-hexamethyl-3,5-bis-(2,2,2-trifluoroacetyl)-[1,3,5,2,4,6]triazasilinan-1-yl]-ethanone (Compound 5-1).

[0714] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 18H); 13 C NMR (300MHz, CDCl3): -0.6, 119.8, 173.0; 19 F NMR (CDCl3): ppm -78.5 (s)

[0715]

[0716] [Example 5-2]: Synthesis of 2,2,4,4,6,6-hexamethyl-1,3,5-tris-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilinane (Compound 5-2)

[0717] [Reaction Scheme 5-2]

[0718] JPEG2025525467000236.jpg31104

[0719] 2,2,4,4,6,6-Hexamethyl-[1,3,5,2,4,6]triazatrisilane (3.84 g, 17.5 mmol), triethylamine (6.0 g, 60 mmol), and triflic anhydride (15 g, 54 mmol) were reacted in the same manner as in Reaction Scheme 1-2 to obtain 2,2,4,4,6,6-hexamethyl-1,3,5-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilinane (compound 5-2).

[0720] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 18H); 13 C NMR (300MHz, CDCl3): -2.4, 153.0; 19 F NMR (CDCl3): ppm -76.3 (s)

[0721]

[0722] [Example 5-3]: Synthesis of 2,2,4,4,6,6-hexamethyl-1,3,5-tris-fluoromethanesulfonyl-[1,3,5,2,4,6]triazasilinane (Compound 5-3)

[0723] [Reaction Scheme 5-3]

[0724] JPEG2025525467000237.jpg3296

[0725] 2,2,4,4,6,6-Hexamethyl-[1,3,5,2,4,6]triazatrisilane (3.84 g, 17.5 mmol), triethylamine (6.0 g, 60 mmol), and fluorosulfonic acid (10.8 g, 54 mmol) were reacted in a manner similar to that of Reaction Scheme 1-2 to obtain 2,2,4,4,6,6-hexamethyl-1,3,5-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilinane (compound 5-2).

[0726] 1 H NMR (300MHz, CDCl3): ppm 0.14(m, 18H); 13 C NMR (300MHz, CDCl3): -3.0; 19 F NMR (CDCl3): ppm -76.3 (s)

[0727]

[0728] Example 6. Preparation of ion-conductive thin film (1)

[0729] Anion receptor compound 1-1 (0.25 g) prepared in Example 1-1 was mixed with bisphenol A ethoxylate dimethacrylate (Aldrich, Mw = 1,700, "BIS-15m," 0.25 g) of formula 16 (a crosslinker), poly(ethylene glycol) dimethyl ether (Mw = 350, "PEGDME 300," 0.5 g), and lithium trifluoromethanesulfonimide (Li(CFSO)N, 0.7809 g). Dimethylphenylacetophenone (DMPA, 0.0075 g) was added to the mixture, and the resulting solution was applied to a conductive glass substrate and exposed to ultraviolet light at 350 nm for 30 minutes under a nitrogen atmosphere. A solid polymer thin film was fabricated by this light irradiation.

[0730]

[0731] Example 7. Preparation of ion-conductive thin film (2)

[0732] The anion receptor compound 1-2 (0.25 g) prepared in Example 1-2 and lithium trifluoromethanesulfonimide (0.7234 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0733]

[0734] Example 8. Preparation of ion-conductive thin film (3)

[0735] The anion receptor compound 1-3 (0.25 g) prepared in Examples 1 to 3 and lithium trifluoromethanesulfonimide (0.7499 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Chemical Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0736]

[0737] Example 9. Preparation of ion-conductive thin film (4)

[0738] The anion receptor compound 1-4 (0.25 g) prepared in Example 1-4 and lithium trifluoromethanesulfonimide (0.6597 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0739]

[0740] Example 10. Preparation of ion-conductive thin film (5)

[0741] Anion receptor compound 1-5 (0.25 g) prepared in Example 1-5 and lithium trifluoromethanesulfonimide (0.6237 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6. A solid polymer thin film was prepared in the same manner as in Example 6.

[0742]

[0743] Example 11. Preparation of ion-conductive thin film (6)

[0744] The anion receptor compound 1-6 (0.25 g) prepared in Example 1-6 and lithium trifluoromethanesulfonimide (0.6109 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0745]

[0746] Example 12. Preparation of ion-conductive thin film (7)

[0747] The anion receptor compound 1-7 (0.25 g) prepared in Example 1-7 and lithium trifluoromethanesulfonimide (0.6128 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0748]

[0749] Example 13. Preparation of ion-conductive thin film (8)

[0750] The anion receptor compound 1-8 (0.25 g) prepared in Example 8 and lithium trifluoromethanesulfonimide (0.6134 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0751]

[0752] Example 14. Preparation of ion-conductive thin film (9)

[0753] The anion receptor compound 1-9 (0.25 g) prepared in Example 1-9 and lithium trifluoromethanesulfonimide (0.6159 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0754]

[0755] Example 15. Preparation of ion-conductive thin film (10)

[0756] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-10 and lithium trifluoromethanesulfonimide (0.6143 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0757]

[0758] Example 16. Preparation of ion-conductive thin film (11)

[0759] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-11 and lithium trifluoromethanesulfonimide (0.6142 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0760]

[0761] Example 17. Preparation of ion-conductive thin film (12)

[0762] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-12 and lithium trifluoromethanesulfonimide (0.6138 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0763]

[0764] Example 18. Preparation of ion-conductive thin film (13)

[0765] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-13 and lithium trifluoromethanesulfonimide (0.6145 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0766]

[0767] Example 19. Preparation of ion-conductive thin film (14)

[0768] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-14 and lithium trifluoromethanesulfonimide (0.6189 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0769]

[0770] Example 20. Preparation of ion-conductive thin film (15)

[0771] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-15 and lithium trifluoromethanesulfonimide (0.6195 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0772]

[0773] Example 21. Preparation of ion-conductive thin film (16)

[0774] The anion receptor compound 2-1 (0.25 g) prepared in Example 2-1 and lithium trifluoromethanesulfonimide (0.4548 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0775]

[0776] Example 22. Preparation of ion-conductive thin film (17)

[0777] The anion receptor compound 2-2 (0.25 g) prepared in Example 2-2 and lithium trifluoromethanesulfonimide (0.4846 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0778]

[0779] Example 23. Preparation of ion-conductive thin film (18)

[0780] The anion receptor compound 2-2 (0.25 g) prepared in Example 2-3 and lithium trifluoromethanesulfonimide (0.4837 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0781]

[0782] Example 24. Preparation of ion-conductive thin film (19)

[0783] The anion receptor compound 3-1 (0.25 g) prepared in Example 3-1 and lithium trifluoromethanesulfonimide (0.4530 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0784]

[0785] Example 25. Preparation of ion-conductive thin film (20)

[0786] The anion receptor compound 3-2 (0.25 g) prepared in Example 3-2 and lithium trifluoromethanesulfonimide (0.4877 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0787]

[0788] Example 26. Preparation of ion-conductive thin film (21)

[0789] The anion receptor compound 3-3 (0.25 g) prepared in Example 3-3 and lithium trifluoromethanesulfonimide (0.4867 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0790]

[0791] Example 27. Preparation of ion-conductive thin film (22)

[0792] The anion receptor compound 4-1 (0.25 g) prepared in Example 4-1 and lithium trifluoromethanesulfonimide (0.4877 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0793]

[0794] Example 28. Preparation of ion-conductive thin film (23)

[0795] The anion receptor compound 4-2 (0.25 g) prepared in Example 4-2 and lithium trifluoromethanesulfonimide (0.4879 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0796]

[0797] Example 29. Preparation of ion-conductive thin film (24)

[0798] The anion receptor compound 4-3 (0.25 g) prepared in Example 4-3 and lithium trifluoromethanesulfonimide (0.4897 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0799]

[0800] Example 30. Preparation of ion-conductive thin film (25)

[0801] The anion receptor compound 5-1 (0.25 g) prepared in Example 5-1 and lithium trifluoromethanesulfonimide (0.4894 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0802]

[0803] Example 31. Preparation of ion-conductive thin film (26)

[0804] The anion receptor compound 5-2 (0.25 g) prepared in Example 5-2 and lithium trifluoromethanesulfonimide (0.4889 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0805]

[0806] Example 32. Preparation of ion-conductive thin film (27)

[0807] The anion receptor compound 5-3 (0.25 g) prepared in Example 5-3 and lithium trifluoromethanesulfonimide (0.4884 g) were mixed with the crosslinking agent bisphenol A ethoxylate dimethacrylate of Formula 16, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone in the same amounts as in Example 6, and a solid polymer thin film was prepared in the same manner as in Example 6.

[0808]

[0809] [Table 1] JPEG2025525467000238.jpg8277

[0810]

[0811] Comparative Example 1. Preparation of a thin film containing no anion receptor

[0812] A solid polymer thin film was produced in the same manner as in Example 6, using the composition of the compounds used as shown in Table 1. As shown in Table 1, the polymer electrolyte of the comparative example did not contain an anion receptor.

[0813]

[0814] Experimental Examples 1-28. Ion Conductivity Experiments

[0815] The ionic conductivity was measured for the solid polymer electrolyte thin films produced in Examples 6 to 32 and Comparative Example 1. The ionic conductivity was measured by the following method.

[0816] The solid polymer electrolyte composition was applied to a band-type conductive glass substrate or a lithium-copper foil, photo-cured, and thoroughly dried. The AC impedance between the band-type or sandwich-type electrodes was measured under a nitrogen atmosphere, and the measured value was analyzed using a frequency response analyzer to obtain the complex impedance.

[0817] The band-type electrodes were fabricated by attaching 0.5-2 mm wide masking tape to the center of conductive glass (ITO) at intervals of about 0.5-2 mm, etching it in an etching solution, and then washing and drying. The ionic conductivity of the fabricated solid polymer electrolyte thin film was measured at a temperature of 30°C, and the results are shown in Table 2 below.

[0818]

[0819] [Table 2] JPEG2025525467000239.jpg7548

[0820] The above results show that the solid polymer electrolyte containing an anion receptor exhibits higher ionic conductivity than the solid polymer electrolyte not containing an anion receptor.

[0821]

[0822] Example 33. Fabrication of a battery using a liquid electrolyte containing an anion receptor

[0823] Anion receptor compound 1-1 (AR-8B, 0.015 g) prepared in Example 1-1 and anion receptor compound 3-1 (AR-7, 0.015 g) prepared in Example 3-1 were mixed with organic solvent EC / DMC / EMC (1:1:1, 1M LiPF6) (1.0 g). A battery was assembled in a dry room (humidity: 3% or less) by sandwiching a polypropylene separator impregnated with the above mixture solution between an NMC ternary anode and a graphite carbon cathode, and vacuum sealing the mixture.

[0824]

[0825] Comparative Example 2. Preparation of a battery using a liquid electrolyte containing no anion receptor

[0826] A separator impregnated with 1.0 g of organic solvent EC / DMC / DEC (1:1:1, 1M LiPF6), an NMC ternary anode, and a graphite carbon cathode were assembled in the same manner as in Example 33 to prepare a battery.

[0827]

[0828] Experimental Example 29. Lithium cycling performance experiment

[0829] The lithium cycling performance and efficiency of the batteries prepared in Example 33 and Comparative Example 2 were measured at room temperature using a charge-discharge tester (Maccor 4000). Charge and discharge were performed at 1 C. The batteries were charged and discharged at 0.6 mA / cm against an NMC counter electrode. 2 (Charging), 1.5mA / cm 2 The battery was charged and discharged between 3.0 V and 4.2 V at a constant current density (discharge).

[0830] A comparison of the capacity retention rate at high temperature (60°C) over time between batteries manufactured using an electrolyte containing anion receptor compound 1-1 of the present invention and an electrolyte not containing anion receptor compound 1-1 of the present invention is shown in Figure 1. The batteries using electrolytes containing anion receptor compound 1-1 (AR-7 in Figure 1) and anion receptor compound 3-1 (AR-8B in Figure 1) showed significantly higher capacity retention rates than the batteries using an electrolyte not containing anion receptor compound (Ref).

[0831] Therefore, the above results suggest that the use of an anion receptor results in a high capacity retention rate and a low internal resistance increase rate at high temperatures, which indicates an extension of the battery's lifespan and high-temperature stability.

[0832] The present invention also provides a reusable battery in which the waste electrolyte in a used electric vehicle battery (waste battery) is replaced and filled with the electrolyte to which the anion receptor has been added.

[0833] The following describes how to make a reusable battery by replacing and filling the novel electrolyte containing the anion receptor of the present invention.

[0834] The method for manufacturing a reusable battery of the present invention includes the steps of preparing a waste battery, removing waste electrolyte and other impurities from the waste battery, and regenerating the waste battery by injecting the novel electrolyte of the present invention into the waste battery.

[0835] The step of removing the waste electrolyte and other impurities from the waste batteries may be carried out in a dry room or in an inert atmosphere.

[0836] Alternatively, the step of removing the waste electrolyte and other impurities from the waste batteries may be performed under vacuum conditions.

[0837] The step of injecting a new electrolyte into the waste battery to regenerate it may be performed by applying vibration at a constant temperature after injecting the new electrolyte into the waste battery, and the constant temperature may be 20 to 50°C.

[0838] To explain the method of recycling the waste batteries in more detail, in the case of used electric vehicle batteries, there is a high risk of explosion and fire when they are charged, so it is necessary to completely discharge the charged current and then separate the battery pack into individual cells. Each discharged cell is evaluated for its charge capacity and discharge capacity using a charger / discharger, and classified according to its capacity.

[0839] For example, the cells are divided into those with capacities of 80% or more, 68% to 80%, and 68% or less, and the cells with a significantly reduced capacity of 68% or less are subjected to a regeneration process.

[0840] Cells with reduced capacity should be fully discharged and then stored in a dry room or inert atmosphere. A hole is drilled in each cell and a vacuum is used to remove the existing electrolyte, generated gas, and impurities. An electrolyte containing an additive that can restore performance is then injected into the cell and the hole is sealed. The cell is then shaken for a certain period of time at a constant temperature (25-50°C) to distribute the electrolyte evenly, activating the anode and cathode active materials and increasing the activity of the Li-ions, thereby restoring the battery's capacity.

[0841] The method of using the electrolyte of the present invention to make a reusable battery is described in detail below.

[0842]

[0843] Example 34. Fabrication of a reusable battery

[0844] (1) Preparation of waste batteries

[0845] In this example, modules were disassembled from battery packs used in electric buses and separated into unit cells. Cells classified based on discharge capacity as less than 12 Ah (less than 68% of the initial capacity) were then discharged to 2.5 V at 0.5 C. Then, in an inert atmosphere in a dry room or glove box, holes were pierced in the cells using a syringe and vacuum suction was applied to remove the existing waste electrolyte, generated gas, and impurities before use.

[0846]

[0847] (2) Cell reassembly and activation

[0848] The novel electrolyte of the present invention was injected using a syringe, the hole was sealed, and then the battery was aged by shaking it from side to side while maintaining the temperature at 25 to 30°C. After that, a current of 0.1C rate (2.1A) was applied to charge the battery to 4.2V at a constant current, and then a constant voltage charge of 4.2V was performed at a current value of 0.01C (0.21A).

[0849]

[0850] Comparative Example 3. Manufacturing of a reusable battery

[0851] The battery was prepared in the same manner as in Example 34, except that a non-aqueous electrolyte containing 1M LiPF6 in a mixed solvent of EC:EMC:DMC in a volume ratio of 3:3:4 was used without any additives.

[0852]

[0853] Experimental Example 30. Evaluation of reusable batteries

[0854] The battery produced in Example 34 was evaluated for 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 / discharger. As a result, the discharge capacity recovered from 6.2 Ah to 14.8 Ah.

[0855] On the other hand, evaluation of the battery produced in Comparative Example 3 showed that although the discharge capacity increased from 6.2 Ah to 10.5 Ah, a sufficient capacity was not recovered.

[0856]

[0857] The present invention also provides a solidified electrolyte that uses the electrolyte of the present invention to operate as a normal lithium ion battery until it reaches a certain temperature (preferably 70°C), and then rapidly hardens (within 5 to 10 minutes) to stop the operation of the battery when it reaches a certain temperature (preferably 130°C) or higher, in order to prevent the risk of fire caused by a sudden rise in battery temperature due to thermal runaway.

[0858] The method for producing the solid electrolyte containing the anion receptor of the present invention will be described below.

[0859] In the case of a solidified electrolyte, first, an anion receptor, a crosslinking agent, a curing initiator, and a polymerization inhibitor are added to an electrolytic solution, and the mixture is stirred to prepare a composition mixture for producing the solidified electrolyte of the present invention, as shown in Table 3 below.

[0860] A manufacturing example of the solidified electrolyte composition mixed solution and the results of the hardening experiment will be described in detail below.

[0861]

[0862] Comparative Example 4. Production of solid electrolyte

[0863] Anion receptor compound 1-1 (0.24 g) prepared in Example 1 and 6.15 g of triethylene glycol dimethacrylate (TEGDA, manufactured by Aldrich) of Formula 17, which serves as a crosslinker, were mixed with 60 g of an electrolyte solution (EC:EMC:DMC=3:3:4, LiPF 61 mol / L). 0.01 g of an initiator, Luperox TBEC (manufactured by Aldrich), was added to the mixture to prepare a solid electrolyte.

[0864]

[0865] Comparative Example 5. Production of solid electrolyte

[0866] 6.06 g of a crosslinking agent (TEGDA), an anion receptor compound 1-1, an electrolyte solution, and an initiator were mixed in the same amounts as those in Comparative Example 3 to prepare a solid electrolyte.

[0867]

[0868] Comparative Example 6. Production of solid electrolyte

[0869] 6.04 g of a crosslinking agent (TEGDA), anion receptor compound 1-1, an electrolyte solution, and an initiator were mixed in the same amounts as those in Comparative Example 3 to prepare a solid electrolyte.

[0870]

[0871] Comparative Example 7. Production of solid electrolyte

[0872] 6.00 g of a crosslinking agent (TEGDA), anion receptor compound 1-1, an electrolyte solution, and an initiator were mixed in the same amounts as those in Comparative Example 3 to prepare a solid electrolyte.

[0873]

[0874] Comparative Example 8. Production of solid electrolyte

[0875] 5.40 g of a crosslinking agent (TEGDA), anion receptor compound 1-1, an electrolyte, and an initiator were mixed in the same amounts as those in Comparative Example 3 to prepare a solid electrolyte.

[0876]

[0877] Comparative Example 9. Production of solid electrolyte

[0878] 4.50 g of a crosslinking agent (TEGDA), anion receptor compound 1-1, an electrolyte, and an initiator were mixed in the same amounts as those in Comparative Example 3 to prepare a solid electrolyte.

[0879]

[0880] Comparative Example 10. Production of solid electrolyte

[0881] Anion receptor compound 1-1 (0.30 g) prepared in Example 1 and 8.40 g of triethylene glycol dimethacrylate (manufactured by Aldrich, "TEGDA") as a crosslinker were mixed with 60 g of electrolyte (EC:EMC:DMC=3:3:4, LiPF 61 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 prepare a solid electrolyte.

[0882]

[0883] Example 35. Preparation of solid electrolyte

[0884] Anion receptor compound 1-1 (0.33 g) prepared in Example 1 and 9.23 g of triethylene glycol dimethacrylate (manufactured by Aldrich, "TEGDA") as a crosslinker were mixed with 60 g of electrolyte (EC:EMC:DMC=3:3:4, LiPF 61 mol / L). To this mixture, 0.01 g of Luperox TBEC (manufactured by Aldrich) as an initiator and 1.2 mg of 4-methoxyphenol (manufactured by Aldrich) as a polymerization inhibitor were added to prepare a solid electrolyte.

[0885]

[0886] [Table 3] *Additives = Crosslinker + Anion Receptor JPEG2025525467000240.jpg3882

[0887]

[0888] Experimental Example 31. Hardening experiment of solidified electrolyte (1)

[0889] The solidified electrolyte solutions prepared in Comparative Examples 4 to 9 were placed in 50 ml round flasks, 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.

[0890] The measurement results of Comparative Examples 4 to 9 are shown in Table 4 below.

[0891] [Table 4] JPEG2025525467000241.jpg2366

[0892]

[0893] (In the table above, X means uncured and O means cured)

[0894] From Table 4, it can be seen that in the cases of Comparative Examples 4 to 6, all of them hardened at temperatures between 50°C and 130°C and could not be used as a solidifying agent. In addition, in the cases of Comparative Examples 7 to 9, none of them hardened at temperatures between 50°C and 130°C and could not be used as a solidifying agent either.

[0895] From Table 4 above, it can be seen that in order to achieve cure, the total content of additives must be at least 12.33%.

[0896]

[0897] Experimental Example 32. Hardening experiment of solidified electrolyte (2)

[0898] The solidified electrolyte solutions prepared in Comparative Example 10 and Example 35 were measured for their hardening times in the same manner as in Experimental Example 31.

[0899] The measurement results of Comparative Example 10 and Example 35 are shown in Table 5 below.

[0900] [Table 5] JPEG2025525467000242.jpg1177

[0901] (In the table above, X means uncured and O means cured)

[0902] From Table 5, it can be seen that in the case of Example 35, it does not harden at temperatures below 70°C, but hardens rapidly in just 5 minutes at a high temperature of 130°C, making it usable as a solidifying agent. However, in the case of Comparative Example 10, it hardens even at temperatures below 70°C, making it unusable as a solidifying agent.

[0903] From Table 3, it can be seen that in both Example 35 and Comparative Example 10, when 1.2 mg of polymerization inhibitor was added, the total content of additives was at least 13.74% as in Example 35, and the composition could be used as a solidifier without hardening at temperatures below 70°C.

[0904] As described above, liquid electrolytes using the novel anion receptor additives according to the present invention can provide electrolytes with improved lithium cycling performance and efficiency, and thus can be used as electrolyte additives for high-capacity lithium-ion batteries. Furthermore, polymer electrolytes containing the novel anion receptors of the present invention can provide electrolytes with significantly improved ionic conductivity and electrochemical stability at room temperature, and thus can be widely used as polymer electrolytes for compact lithium polymer secondary batteries used in various electronic devices, such as mobile phones, laptops, and camcorders, as well as for large-capacity lithium polymer secondary batteries used in power storage devices for power leveling and electric vehicles. Furthermore, a solid electrolyte is provided that rapidly hardens within five minutes above a certain temperature (130°C), thereby reducing the battery's performance and preventing the risk of fire caused by a sudden rise in temperature due to thermal runaway. Demand for such solid electrolytes is expected to grow not only in electric vehicle batteries, where ensuring safety during use is a top priority due to the recent frequent occurrence of fire accidents, but also in power storage devices.

[0905]

[0906] Although the embodiments have been described above with limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, the described techniques may be performed in a different order than described, and / or the components of the described systems, structures, devices, circuits, etc. may be combined or combined in a different manner than described, or may be replaced or substituted by other components or equivalents, and still achieve suitable results.

[0907] Therefore, other embodiments, examples, and equivalents of the claims are within the scope of the following claims. [Industrial Applicability]

[0908] The present invention provides a battery with significantly improved ionic conductivity and electrochemical stability by using a novel silazane-based anion receptor compound and a liquid electrolyte (e.g., a non-aqueous liquid electrolyte), gel or solid electrolyte (e.g., a gel polymer electrolyte or solid polymer electrolyte, a solid sulfide-polymer electrolyte, or a solid oxide-polymer electrolyte) containing the same, as well as a method for recycling used batteries by electrolyte exchange, and a reusable battery.

Claims

1. A silazane-based anion receptor compound selected from the group consisting of the following formulas 1 to 5: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] In the above Chemical Formulas 1 to 5, (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), or -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; R １ represents 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 l is an integer from 0 to 20; (b) Y is 、 and (R ２ , R ３ and R ４ respectively represent 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; with the proviso that R ２ , R ３ and R ４ are not simultaneously hydrogen atoms; and m and m′ are each an integer of 0 to 20; (c) R １ , R ２ and R ３ represents 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 an electron withdrawing group selected from —CN; (d) n is an integer from 0 to 20.

2. The formula 1 is selected from the group consisting of: The chemical formula 2 is selected from the group consisting of: The chemical formula 3 is selected from the group consisting of: The chemical formula 4 is selected from the group consisting of: The chemical formula 5 is 2. The silazane-based anion receptor compound of claim 1, selected from the group consisting of:

3. 10. An electrolyte composition comprising at least one of the silazane-based anion receptor compounds represented by Chemical Formulas 1 to 5 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 6 to 15: [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] [Chemical formula 10] [Chemical formula 11] [Chemical formula 12] [Chemical formula 12-a] [Chemical formula 12-b] [Chemical formula 13] [Chemical formula 14] [Chemical formula 15] In Chemical Formula 6 to Chemical Formula 15, (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), or -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; R １ represents 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 l is an integer from 0 to 20; (b) Y is 、 and (R ２ , R ３ and R ４ are hydrogen atoms; Halogen atoms; 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; with the proviso that R ２ , R ３ and R ４ are not simultaneously hydrogen atoms; and m and m′ are each an integer of 0 to 20; (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, or a linear or branched alkynyl group having 2 to 20 carbon atoms; (b) Y is 、 and (R ２ , R ３ and R ４ are hydrogen atoms; Halogen atoms; 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; with the proviso that R ２ , R ３ and R ４ are not simultaneously hydrogen atoms; and m and m′ are each an integer of 0 to 20; (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 —CN; １ and R １ ' cannot be a hydrogen atom at the same time in 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. 5. The electrolyte composition according to claim 4, comprising 0.01 to 40 wt % of one or more silazane-based anion receptor compounds selected from the group consisting of Chemical Formulas 1 to 5, and one or more compounds selected from the group consisting of Chemical Formulas 6 to 15.

6. The electrolyte composition according to claim 3 , which 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 comprising the solidified electrolyte of claim 7.

10. A reusable battery comprising the solidified electrolyte of claim 7.

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