Novel anion acceptor compound and electrolyte comprising same

Abstract

The present invention relates to a novel anion receptor and an electrolyte comprising the same, and more particularly, to a novel anion receptor, and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte comprising the same, the novel anion receptor comprises: a compound comprising a structure in which silicon and nitrogen atoms are bonded, such as a novel silazane in which an amine group substituted with an electron-withdrawing functional group is introduced into a silicon atom or an electron-withdrawing functional group is introduced into a nitrogen atom; or a mixture of a compound comprising a structure in which silicon and nitrogen atoms are bonded, such as these novel silazanes, and a linear hydrocarbon, a cyclic hydrocarbon, a polyalkylene oxide, and a siloxane compound in which an amine group substituted with an electron-withdrawing functional group is introduced or an electron-withdrawing functional group is introduced into a nitrogen atom in the ring; therefore, the ionic conductivity and the cation transport rate of the electrolyte to which the novel anion receptor is added can be improved, and the electrochemical stability of an alkali metal battery using the electrolyte can be improved.

Description

Technical Field

[0001] The present invention relates to a novel anion receptor compound and an electrolyte containing the compound, and more particularly to a novel silazane anion receptor compound and an electrolyte containing the compound. Background Art

[0002] Anion receptors improve anion stability through the interaction of Lewis acid salts. Such anion receptors, as compounds with electron-deficient atoms (N, B), coordinate electron-rich anions to the periphery, thereby preventing anions and lithium cations from combining into ion pairs and allowing lithium cations to move smoothly. The first compound known as anion receptor is an azaether (Aza-Ether) composed of cyclic or linear amides (J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9), which makes the nitrogen atom of the amine group substituted by a perfluoroalkylsulfonyl substituent in an electron-deficient state, so that it can interact appropriately with electron-rich anions through Coulomb attraction. However, these azaethers show limited solubility relative to polar solvents used as typical non-aqueous electrolytes, and the electrochemical stability window of the electrolyte added with LiCl salts cannot meet the 4.0V required for commercial anode materials. In addition, it was found that azaethers are unstable to LiPF6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). In other words, LiPF6 is chemically and thermally unstable, and even at room temperature, solid LiF and gaseous PF5 are balanced. The generation of the gaseous product PF5 further tilts the balance toward the generation of PF5.

[0003]

[0004] In non-aqueous solvents, PF5 tends to trigger a series of reactions, such as ring-opening polymerization or ether bond cleavage consisting of atoms with non-shared electron pairs such as oxygen or nitrogen. Strong Lewis acid PF5 attacks electron pairs, and azaethers are immediately attacked by PF5 due to their large electron density (J. Power Sources, 104 (2002) 260). Therefore, there are significant restrictions on the commercialization of azaether compounds. Due to these restrictions, McBreen et al. used the same method to synthesize anion receptors that selected boron as electron-deficient atoms substituted with functional groups with electron-withdrawing properties (J. Electrochem. Soc., 145 (1998) 2813, 149 (2002) A1460).

[0005] On the other hand, solid polymer electrolytes do not leak electrolytes and have high vibration and impact resistance. They are not only easy to use, but also have very low magnetic discharge and can be used at high temperatures. They not only meet the trend of lightweight and miniaturization of portable electronic devices, the trend of wireless information communication equipment and home appliances, but also can be widely used in large-capacity lithium polymer secondary batteries such as electric vehicles. Many studies have been conducted to improve their performance. Since Wright (PV Wright) discovered polyalkylene oxide (PAO, polyalkylene oxide) solid polymer electrolytes in 1975 (British Polymer Journal, 7, 319), Armand (M. Armand) named it "ion conductive polymer" in 1978. Typical solid polymer electrolytes are composed of lithium salt complexes and polymers with electron donor atoms such as oxygen, nitrogen, and phosphorus. The most representative solid polymer electrolytes known to date are polyethylene oxide (PEO) and its lithium salt complexes, which have a conductivity of 10 at room temperature. -8 S / cm, so it cannot be used in electrochemical devices operating at room temperature. These PAO-type solid polymer electrolytes are highly crystalline, the movement of the molecular chain is restricted, and the ionic conductivity is very low at room temperature. In order to improve the mobility of the molecular chain, the crystalline area existing in the polymer structure should be minimized and the amorphous area should be increased. For this purpose, there have been studies using molecular chain flexible siloxane (Macromol.Chem.Rapid Commun.7 (1986) 115) or phosphazene (J.Am.Chem.Soc., 106 (1984) 6845) as the main chain or introducing PAO with a shorter molecular length as a side chain (Electrochem, Acta, 34 (1989) 635). In addition, although research is underway to introduce one or more cross-linkable functional groups at the end of PAO to produce a solid polymer electrolyte with a network structure, their ionic conductivity at room temperature is only 10 -5 Up to 10 -4 S / cm, which is not suitable for lithium batteries working at room temperature. Therefore, continuous research is being conducted to improve this point. In order to solve this problem, Abraham et al. introduced low molecular weight polyethylene oxide into vinylidene hexafluoride-hexafluoropropylene copolymer to improve ionic conductivity (Chem. Mater., 9 (1997) 1978). In addition, low molecular weight polyethylene glycol dimethyl ether (PEGDME) was added to the photocurable crosslinking agent with PEO as the side chain and siloxane as the main chain, so that under the conditions of film formation, the ionic conductivity at room temperature can reach 8X10 -4S / cm (J.Power Sources 119-121 (2003) 448). However, the calculated cycle efficiency on the Ni electrode remains at around 53%. This low efficiency is due to the rapid corrosion of the newly deposited lithium surface, which leads to passivation of the electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). In other words, according to Vincent's record, the reaction between lithium salt and lithium metal is as follows (Solid State Chem. 17 (1987) 145), where the CF3 radicals generated strip hydrogen atoms from the PEO polymer chain to form HCF3, thereby cutting off the main chain of the polymer from the =COC- functional group generated thereby. At this time, the CH3 generated by the chain cutting attacks the chain together with the CF3 radical or cuts the -CO- bond, and attaches to the electrode surface of the compound in the form of Li-OR and causes passivation.

[0006] LiSO3CF3+Li(s)→2Li++SO3 2- +CF3

[0007] Therefore, in order to solve the above problems, it is necessary to study new substances by designing compounds with structures in which there are no vulnerable nitrogen atoms in the middle of the azaethers or by replacing PAO plasticizers, thereby eliminating electrochemical instability and instability to lithium salts and improving ionic conductivity. Summary of the invention

[0008] The object of the present invention is to provide a novel silazane anion receptor compound, wherein an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom.

[0009] Another object of the present invention is to provide an electrolyte composition that can provide a liquid, gel-type or solid electrolyte, which can improve the ionic conductivity and cation transport rate in the electrolyte and improve the electrochemical stability of batteries (e.g., primary batteries or secondary batteries) using these electrolytes.

[0010] Another object of the present invention is to provide an electrolyte which significantly improves ionic conductivity and electrochemical stability at room temperature.

[0011] Another object of the present invention is to provide a solidified electrolyte and a battery comprising the same, which hardens rapidly above a certain temperature (for example, about 130° C.) and stops the battery from working, thereby preventing fire caused by thermal runaway of the battery.

[0012] In order to achieve the above object, the present invention provides a silazane anion receptor compound selected from the group consisting of the following Chemical Formulas 1 to 5:

[0013] [Chemical formula 1]

[0014]

[0015] [Chemical formula 2]

[0016]

[0017] [Chemical formula 3]

[0018]

[0019] [Chemical formula 4]

[0020]

[0021] [Chemical formula 5]

[0022]

[0023] In Chemical Formulas 1 to 5,

[0024] (a) X is 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, 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),

[0025]

[0026] (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, R1 is selected from a halogen atom and an electron-withdrawing functional group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, and l is an integer from 0 to 20),

[0027] (b) Y is selected from

[0028] as well as

[0029]

[0030] (R2, R3 and R4 are selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, but R2, R3 and R4 cannot be hydrogen atoms at the same time, and m and m' are integers of 0 to 20 respectively),

[0031] (c) R1, R2 and R3 are selected from halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN,

[0032] (d) n is an integer from 0 to 20.

[0033] In addition, the present invention provides an electrolyte composition comprising at least one of the silazane anion receptor compounds represented by Chemical Formula 1 to Chemical Formula 5.

[0034] According to the present invention, it is characterized in that the electrolyte composition further includes one or more compounds selected from the group consisting of the following Chemical Formula 6 to Chemical Formula 15.

[0035] [Chemical formula 6]

[0036]

[0037] [Chemical formula 7]

[0038]

[0039] [Chemical formula 8]

[0040]

[0041] [Chemical formula 9]

[0042]

[0043] [Chemical formula 10]

[0044]

[0045] [Chemical formula 11]

[0046]

[0047] [Chemical formula 12]

[0048]

[0049] [Chemical formula 12-a]

[0050]

[0051] [Chemical formula 12-b]

[0052]

[0053] [Chemical formula 13]

[0054]

[0055] [Chemical formula 14]

[0056]

[0057] [Chemical formula 15]

[0058]

[0059] In Chemical Formula 6 to Chemical Formula 15,

[0060] (a) X is 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, 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),

[0061]

[0062] (R is selected from a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, R1 is selected from a halogen atom and an electron-withdrawing functional group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, and l is an integer from 0 to 20),

[0063] (b) Y is selected from

[0064] as well as

[0065]

[0066] (R2, R3 and R4 are independently selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, but R2, R3 and R4 cannot be hydrogen atoms at the same time, and m and m' are independently integers of 0 to 20),

[0067] (c) W is 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, a linear or branched alkynyl group having 2 to 20 carbon atoms, (b) Y is selected from

[0068] as well as

[0069]

[0070] (R2, R3 and R4 are independently selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, but R2, R3 and R4 cannot be hydrogen atoms at the same time, and m and m' are independently integers of 0 to 20),

[0071] (d) R1 and R1' are independently selected from a hydrogen atom and an electron-withdrawing functional group selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, and R1 and R1' cannot be hydrogen atoms at the same time in the same molecule,

[0072] (e) n and q are each an integer from 0 to 20,

[0073] (f) z is an integer from 1 to 20.

[0074] In addition, the present invention provides a solidified electrolyte produced from the electrolyte composition.

[0075] In addition, the present invention provides a polymer electrolyte film produced from the electrolyte composition.

[0076] In addition, the present invention provides a battery comprising the solidified electrolyte.

[0077] In addition, the present invention provides a recycled battery including the solidified electrolyte.

[0078] The present invention can provide a novel silazane anion receptor compound and a liquid electrolyte (e.g., non-aqueous liquid electrolyte), gel-type or solid electrolyte (e.g., gel-type polymer electrolyte or solid polymer electrolyte, solid sulfide-polymer electrolyte, solid oxide-polymer electrolyte) comprising the compound. In other words, the present invention provides a novel cyclic silazane compound, in which an amine group substituted with an electron-withdrawing functional group is introduced into a silicon atom or an electron-withdrawing functional group is introduced into a nitrogen atom in the ring, and the novel cyclic silazane compound can provide a widely applicable electrolyte, which can be widely used not only as an electrolyte for small lithium polymer secondary batteries applicable to various electronic devices such as portable information terminals such as mobile phones and notebook computers and portable cameras, but also as an electrolyte (e.g., gel-type or solid polymer electrolyte, solid sulfide-polymer electrolyte, solid oxide-polymer electrolyte) for large-capacity secondary batteries (e.g., lithium polymer secondary batteries, lithium metal secondary batteries) used in power storage devices for power averaging and electric vehicles.

[0079] The present invention can ensure the safety of the electrolyte by reducing the risk of fire caused by thermal runaway, and can provide a solidified electrolyte that can improve the utilization rate of not only batteries for electric vehicles but also power storage devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 It is a graph showing the performance (comparison of relative discharge capacity and voltage) of the battery of the present invention and the comparative example at room temperature. DETAILED DESCRIPTION

[0081] The following is a detailed description of the embodiments with reference to the accompanying drawings. However, since the embodiments can be modified in many ways, the scope of the patent application is not limited or restricted by these embodiments. Instead, it should be understood that all modifications, equivalents and even substitutes made to the embodiments are included in the scope of the rights.

[0082] The terms used in the embodiments are for illustrative purposes only and should not be interpreted as intended to be limiting. Singular expressions include plural expressions unless the context has a clearly different meaning. In this specification, terms such as "include" or "introduce" should be understood to specify the existence of features, numbers, steps, actions, constituent elements, elements or combinations thereof recorded in the specification, without excluding in advance the existence or additional possibility of one or more other features or numbers, steps, actions, constituent elements, elements or combinations thereof.

[0083] Although the terms "first" or "second" are used to describe various components, the components are not limited by these terms. The purpose of the terms is only to distinguish one component from other components. For example, the first component can be named as the second component without departing from the scope of rights determined by the concept of the embodiment, and similarly, the second component can also be named as the first component.

[0084] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as those generally understood by a person having ordinary knowledge in the technical field to which the embodiments belong. Those terms defined in commonly used dictionaries should be interpreted as having the same meaning as that in the context of the relevant technology, and should not be interpreted as ideal or overly formal unless clearly defined in this application.

[0085] In addition, when describing with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the figure numbers, and their repeated descriptions are omitted. When describing the embodiments, when it is determined that the specific description of the relevant known technology may unnecessarily obscure the gist of the embodiments, its detailed description will be omitted.

[0086] Hereinafter, the novel anion receptor of the present invention, its production method and its use will be specifically described with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

[0087] The present invention relates to a novel anion receptor.

[0088] According to one embodiment of the present invention, the anion receptor is a novel silazane-based compound, and may be a novel silazane-based anion receptor compound in which an amine group substituted with an electron withdrawing group is introduced into a nitrogen atom.

[0089] According to one embodiment of the present invention, the anion receptor compound may be a compound represented by the following Chemical Formula 1 to Chemical Formula 5. The compound functions as an anion receptor in an electrolyte composition (e.g., electrolyte), and when used as an additive to an electrolyte composition (e.g., electrolyte), it may improve ion conductivity and cation transport rate, and may improve the electrochemical stability of a battery using it.

[0090] [Chemical formula 1]

[0091]

[0092] [Chemical formula 2]

[0093]

[0094] [Chemical formula 3]

[0095]

[0096] As an example of the present invention, the compound represented by Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3 may be a novel silazane-based anion receptor compound in which a functional group substituted with an electron withdrawing group in silazane is introduced into a nitrogen atom.

[0097] As an example of the present invention, R1, R2, and R3 in Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3 can be selected from halogen atoms, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, and -CN.

[0098] As an example of the present invention, X in Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3 can be selected from halogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, linear or branched alkynyl groups having 2 to 20 carbon atoms, -COR, -OR, -ROR', -Si(R)3, -O-Si(R3),

[0099]

[0100] In X, R, R' and R1 are independently selected from hydrogen atoms, halogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, preferably R and R' are respectively 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 functional 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 from 0 to 20.

[0101] Preferably, in X,

[0102] R in "-COR" may be selected from a linear or branched alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms.

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

[0104] R and R' in "-ROR'" may be linear or branched alkyl groups having 1 to 20 carbon atoms.

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

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

[0107] I can be an integer from 0 to 10 or from 0 to 5.

[0108] More preferably, in Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3, X may be selected from -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]

[0110] (Here, R is selected from a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably -CH3, and R1 is selected from a halogen atom and selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 The electron-withdrawing functional group of the present invention may be more preferably selected from -F, -Cl, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3. I is an integer from 0 to 10, more preferably from 0 to 3).

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

[0112] As an example of the present invention, the compound represented by Chemical Formula 1 can be selected from the following compounds:

[0113] [Chemical formula 1-1]

[0114]

[0115] [Chemical formula 1-2]

[0116]

[0117] [Chemical formula 1-3]

[0118]

[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, may be -CH3.

[0120] As an example of the present invention, the compound represented by Chemical Formula 2 can be selected from the following compounds:

[0121] [Chemical formula 2-1]

[0122]

[0123] [Chemical formula 2-2]

[0124]

[0125] [Chemical formula 2-3]

[0126]

[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, preferably, selected from -F, -CH3, -CH2CH3, and -CH=CH2, and more preferably, it can be -CH3.

[0128] As an example of the present invention, the compound represented by Chemical Formula 3 can be selected from the following compounds:

[0129] [Chemical formula 3-1]

[0130]

[0131] [Chemical formula 3-2]

[0132]

[0133] [Chemical formula 3-3]

[0134]

[0135] In Chemical Formulae 3-1 to 3-3, X is selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, preferably, selected from -F, -CH3, -CH2CH3, and -CH=CH2, more preferably, -CH3.

[0136] [Chemical formula 4]

[0137]

[0138] [Chemical formula 5]

[0139]

[0140] As an example of the present invention, the compound represented by Chemical Formula 4 and Chemical Formula 5 may be a novel silazane-based anion receptor compound in which an amine group substituted with an electron withdrawing group is introduced into silicon.

[0141] As an example of the present invention, in Chemical Formulae 4 to 5, X may be selected from a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR, -OR, -ROR', -Si(R)3, -O-Si(R3),

[0142]

[0143] In X, R, R' and R1 are independently selected from hydrogen atoms, halogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, preferably R and R' are respectively 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 functional 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 from 0 to 20.

[0144] Preferably, in X,

[0145] R in "-COR" may be selected from a linear or branched alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms.

[0146] R in "-OR" may be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0147] R and R' in "-ROR'" may be linear or branched alkyl groups having 1 to 20 carbon atoms.

[0148] R in "-Si(R)3" may be a linear or branched alkyl group having 1 to 20 carbon atoms.

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

[0150] I can be an integer from 0 to 10 or from 0 to 5.

[0151] More preferably, in Chemical Formula 4 and Chemical Formula 5, X may be selected from -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,

[0152]

[0153] (Here, R is selected from a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably -CH3, and R1 is selected from a halogen atom and selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 The electron-withdrawing functional group of the present invention may be more preferably selected from -F, -Cl, -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3. I is an integer from 0 to 10, more preferably from 0 to 3).

[0154] As an example of the present invention, in Chemical Formula 4 and Chemical Formula 5, n is an integer of 0 to 20, and preferably, n may be an integer of 0 to 10.

[0155] As an example of the present invention, in Chemical Formula 4 and Chemical Formula 5, Y may be selected from:

[0156] as well as

[0157]

[0158] In Y, R2, R3 and R4 can be selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, respectively. However, R2, R3 or R2, R3 and R4 in one molecule or Y cannot be hydrogen atoms at the same time, and at least one of them is an electron-withdrawing functional group.

[0159] In Y, m and m' may be integers of 0 to 20. As another example, m and m' in one molecule or Y cannot be "0" at the same time.

[0160] Preferably, R2, R3 and R4 are respectively selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups 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' may be integers of 0 to 20 respectively.

[0161] As an example of this reaction, in Chemical Formula 4, n is an integer of 0 to 20, and preferably, n may be 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]

[0165] [Chemical formula 4-2]

[0166]

[0167] [Chemical formula 4-3]

[0168]

[0169] [Chemical formula 4-4]

[0170]

[0171] [Chemical formula 4-5]

[0172]

[0173] [Chemical formula 4-6]

[0174]

[0175] [Chemical formula 4-7]

[0176]

[0177] [Chemical formula 4-8]

[0178]

[0179] [Chemical formula 4-9]

[0180]

[0181] In Chemical Formulae 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, selected from -F, -CH3, -CH2CH3, and -CH=CH2, 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]

[0185] [Chemical formula 5-2]

[0186]

[0187] [Chemical formula 5-3]

[0188]

[0189] [Chemical formula 5-4]

[0190]

[0191] [Chemical formula 5-5]

[0192]

[0193] [Chemical formula 5-6]

[0194]

[0195] [Chemical formula 5-7]

[0196]

[0197] [Chemical formula 5-8]

[0198]

[0199] [Chemical formula 5-9]

[0200]

[0201] 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, selected from -F, -CH3, -CH2CH3, and -CH=CH2, more preferably, -CH3.

[0202] As an example of the present reaction, the "halogen atom" may be selected from a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably, a fluorine atom and a chlorine atom, more preferably, a fluorine atom.

[0203] As an example of the present invention, the "alkyl group" is linear or branched, and the number of carbon atoms may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. For example, it may be methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, etc.

[0204] As an example of the present invention, "alkenyl" is linear or branched, and the number of carbon atoms may be 2 to 20, 1 to 15, 2 to 10, 2 to 5, or 2 to 3. For example, it may be ethenyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, etc.

[0205] As an example of the present invention, "alkynyl" is linear or branched, and the number of carbon atoms may be 2 to 20, 1 to 15, 2 to 10, 2 to 5, or 2 to 3. For example, it may be ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc.

[0206] As an example of the present invention, "n" may 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.

[0207] As an example of the present invention, "m" and "m'" may 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.

[0208] As an example of the present invention, "I" 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.

[0209] According to an embodiment of the present invention, the anion receptor can be used as the electrolyte composition or process composition mentioned below and is applicable to an electrochemical cell or its accessories. According to one embodiment of the present invention, the electrolyte composition can be used in the form of a liquid, a gel, a solid, or a molded body (film, a thin film, a porous structure, a sheet, etc.).

[0210] The present invention relates to a method for preparing an anion receptor compound.

[0211] According to one embodiment of the present invention, the method for producing an anion receptor compound is equivalent to the method for producing a silazane compound of the compound represented by Chemical Formula 1 to Chemical Formula 5. As an example of the present invention, the compound represented by Chemical Formula 1 to Chemical Formula 5 can be produced according to the following reaction formula.

[0212] According to one embodiment of the present invention, in order to obtain the final product according to the chemical structure design, the starting material, catalyst, solvent, reaction conditions, reaction mechanism, post-treatment (reactant separation, filtration, crystallization, washing, etc.) process can appropriately utilize or replace the known methods in the technical field of the present invention. For example, in a single solvent or mixed solvent 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 above -40°C, above -10°C, above 0°C, above room temperature, above 40°C, above 50°C, above 80°C, above 100°C or from -40°C to 130°C. For example, the reaction temperature can be appropriately selected according to the reflux conditions of the reaction mixture. In addition, catalysts such as platinum catalysts, alkaline substances (triethylamine, diisopropylethylamine, pyridine, etc.) and the like can be further added.

[0213] 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 is reacted with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 1-1.

[0214] [Reaction formula 1-1]

[0215]

[0216] (In Reaction Formula 1-1, X and n are respectively as defined in Chemical Formula 1.)

[0217] 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 and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 1-2.

[0218] [Reaction 1-2]

[0219]

[0220] (In Reaction Formula 1-2, X and n are respectively as defined in Chemical Formula 1.)

[0221] 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 and fluorosulfonic acid [HSO3F] react in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 1-3.

[0222] [Reaction 1-3]

[0223]

[0224] (In reaction formula 1-3, X and n are respectively as defined in chemical formula 1.)

[0225] 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 is reacted with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 2-1.

[0226] [Reaction formula 2-1]

[0227]

[0228] (In Reaction Formula 2-1, X and n are as defined in Chemical Formula 2.)

[0229] 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 and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 2-2.

[0230] [Reaction formula 2-2]

[0231]

[0232] (In Reaction Formula 2-2, X and n are respectively as defined in Chemical Formula 2.)

[0233] 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 and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 2-3.

[0234] [Reaction 2-3]

[0235]

[0236] (In Reaction Formula 2-3, X and n are respectively as defined in Chemical Formula 2.)

[0237] 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 is reacted with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 3-1.

[0238] [Reaction formula 3-1]

[0239]

[0240] (In Reaction Formula 3-1, X and n are as defined in Chemical Formula 3.)

[0241] 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 and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 3-2.

[0242] [Reaction formula 3-2]

[0243]

[0244] (In Reaction Formula 3-2, X and n are respectively as defined in Chemical Formula 3.)

[0245] 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 and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added, thereby synthesizing a compound represented by chemical formula 3-3.

[0246] [Reaction formula 3-3]

[0247]

[0248] According to one embodiment of the present invention, as shown in the following reaction formula 4-1, a silazane compound represented by the following chemical formula 4-a is reacted with trifluoroacetic anhydride [CF3CO]2O and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 4-1-b, and the synthesized compound represented by chemical formula 4-1-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-1.

[0249] [Reaction 4-1]

[0250]

[0251] (In Reaction Formula 4-1, X and n are as defined in Chemical Formula 4.)

[0252] According to one embodiment of the present invention, as shown in the following reaction formula 4-2, a silazane compound represented by the following chemical formula 4-a is reacted with trifluoroacetic anhydride [CF3CO]2O] and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 4-1-b, and the synthesized compound represented by chemical formula 4-1-b and an allyl compound in which the nitrogen atom is substituted with -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-2.

[0253] [Reaction 4-2]

[0254]

[0255] (In Reaction Formula 4-2, X and n are as defined in Chemical Formula 4.)

[0256] According to one embodiment of the present invention, as shown in the following reaction formula 4-3, a silazane compound represented by the following chemical formula 4-a is reacted with trifluoroacetic anhydride [CF3CO]2O] and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 4-1-b, and the synthesized compound represented by chemical formula 4-1-b and an allyl compound in which the nitrogen atom is substituted with -SO3F are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-3.

[0257] [Reaction 4-3]

[0258]

[0259] (In Reaction Formula 4-3, X and n are respectively as defined in Chemical Formula 4.)

[0260] According to one embodiment of the present invention, as shown in the following reaction formula 4-4, a silazane compound represented by the following chemical formula 4-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-2-b, and the synthesized compound represented by chemical formula 4-2-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-4.

[0261] [Reaction formula 4-4]

[0262]

[0263] (In Reaction Formula 4-4, X and n are respectively as defined in Chemical Formula 1.)

[0264] According to one embodiment of the present invention, as shown in the following reaction formula 4-5, a silazane compound represented by the following chemical formula 4-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-2-b, and the synthesized compound represented by chemical formula 4-2-b and an allyl compound in which the nitrogen atom is substituted with -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-5.

[0265] [Reaction 4-5]

[0266]

[0267] (In reaction formula 4-5, X and n are respectively as defined in chemical formula 1.)

[0268] According to one embodiment of the present invention, as shown in the following reaction formula 4-6, a silazane compound represented by the following chemical formula 4-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-2-b, and the synthesized compound represented by chemical formula 4-2-b and an allyl compound in which the nitrogen atom is substituted with -SO2F are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-6.

[0269] [Reaction 4-6]

[0270]

[0271] (In reaction formula 4-6, X and n are respectively as defined in chemical formula 1.)

[0272] According to one embodiment of the present invention, as shown in the following reaction formula 4-7, a silazane compound represented by the following chemical formula 4-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-3-b, and the synthesized compound represented by chemical formula 4-3-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-7.

[0273] [Reaction 4-7]

[0274]

[0275] (In reaction formula 4-7, X and n are respectively as defined in chemical formula 1.)

[0276] According to one embodiment of the present invention, as shown in the following reaction formula 4-8, a silazane compound represented by the following chemical formula 4-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-3-b, and the synthesized compound represented by chemical formula 4-3-b and an allyl compound in which the nitrogen atom is replaced by -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-8.

[0277] [Reaction 4-8]

[0278]

[0279] (In reaction formula 4-8, X and n are respectively as defined in chemical formula 1.)

[0280] According to one embodiment of the present invention, as shown in the following reaction formula 4-9, a silazane compound represented by the following chemical formula 4-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 4-3-b, and the synthesized compound represented by chemical formula 4-3-b and an allyl compound in which the nitrogen atom is replaced by -SO2F are induced to undergo a hydrosilation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 4-9.

[0281] [Reaction 4-9]

[0282]

[0283] (In reaction formula 4-9, X and n are respectively as defined in chemical formula 1.)

[0284] According to one embodiment of the present invention, as shown in the following reaction formula 5-1, a silazane compound represented by the following chemical formula 5-a is reacted with trifluoroacetic anhydride [CF3CO]2O] and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 5-1-b, and the synthesized compound represented by chemical formula 5-1-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-1.

[0285] [Reaction formula 5-1]

[0286]

[0287] (In Reaction Formula 5-1, X and n are as defined in Chemical Formula 1.)

[0288] According to one embodiment of the present invention, as shown in the following reaction formula 5-2, a silazane compound represented by the following chemical formula 5-a is reacted with trifluoroacetic anhydride [CF3CO]2O] and triethylamine in a chloroform solvent to synthesize a compound represented by chemical formula 5-1-b, and the synthesized compound represented by chemical formula 5-1-b and an allyl compound in which the nitrogen atom is substituted with -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-2.

[0289] [Reaction formula 5-2]

[0290]

[0291] (In Reaction Formula 5-2, X and n are respectively as defined in Chemical Formula 1.)

[0292] According to one embodiment of the present invention, as shown in the following reaction formula 5-3, a silazane compound represented by the following chemical formula 5-a is reacted with trifluoroacetic anhydride [CF3CO]2O] and triethylamine in a chloroform solvent to synthesize a compound represented by the chemical formula 5-1-b, and the synthesized compound represented by the chemical formula 5-1-b and an allyl compound in which the nitrogen atom is substituted with -SO3F are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by the chemical formula 5-3.

[0293] [Reaction 5-3]

[0294]

[0295] (In Reaction Formula 5-3, X and n are respectively as defined in Chemical Formula 1.)

[0296] According to one embodiment of the present invention, as shown in the following reaction formula 5-4, a silazane compound represented by the following chemical formula 5-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-2-b, and the synthesized compound represented by chemical formula 5-2-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-4.

[0297] [Reaction 5-4]

[0298]

[0299] (In Reaction Formula 5-4, X and n are respectively as defined in Chemical Formula 1.)

[0300] According to one embodiment of the present invention, as shown in the following reaction formula 5-5, a silazane compound represented by the following chemical formula 5-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-2-b, and the synthesized compound represented by chemical formula 5-2-b and an allyl compound in which the nitrogen atom is substituted with -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-5.

[0301] [Reaction 5-5]

[0302]

[0303] (In Reaction Formula 5-5, X and n are respectively as defined in Chemical Formula 1.)

[0304] According to one embodiment of the present invention, as shown in the following reaction formula 5-6, a silazane compound represented by the following chemical formula 5-a and trifluoromethanesulfonic anhydride [(CF3SO2)O] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-2-b, and the synthesized compound represented by chemical formula 5-2-b and an allyl compound in which the nitrogen atom is substituted with -SO3F are induced to undergo a hydrosilylation reaction in a platinum catalyst and tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-6.

[0305] [Reaction 5-6]

[0306]

[0307] (In reaction formula 5-6, X and n are respectively as defined in chemical formula 1.)

[0308] According to one embodiment of the present invention, as shown in the following reaction formula 5-7, a silazane compound represented by the following chemical formula 5-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-3-b, and the synthesized compound represented by chemical formula 5-3-b and an allyl compound in which the nitrogen atom is substituted with -COCF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-7.

[0309] [Reaction 5-7]

[0310]

[0311] (In reaction formula 5-7, X and n are respectively as defined in chemical formula 1.)

[0312] According to one embodiment of the present invention, as shown in the following reaction formula 5-8, a silazane compound represented by the following chemical formula 5-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-3-b, and the synthesized compound represented by chemical formula 5-3-b and an allyl compound in which the nitrogen atom is substituted with -SO2CF3 are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-8.

[0313] [Reaction 5-8]

[0314]

[0315] (In reaction formulas 5-8, X and n are respectively as defined in chemical formula 1.)

[0316] According to one embodiment of the present invention, as shown in the following reaction formula 5-9, a silazane compound represented by the following chemical formula 5-a and fluorosulfonic acid [HSO3F] are reacted in a chloroform solvent to which triethylamine is added to synthesize a compound represented by chemical formula 5-3-b, and the synthesized compound represented by chemical formula 5-3-b and an allyl compound in which the nitrogen atom is replaced by -SO3F are induced to undergo a hydrosilylation reaction in a platinum catalyst and a tetrahydrofuran solvent, thereby synthesizing a compound represented by chemical formula 5-9.

[0317] [Reaction 5-9]

[0318]

[0319] (In reaction formula 5-9, X and n are respectively as defined in chemical formula 1.)

[0320] The present invention relates to an electrolyte composition comprising the novel anion receptor according to the present invention.

[0321] According to one embodiment of the present invention, the anion receptor may include at least one of the novel silazane compounds represented by Chemical Formula 1 to Chemical Formula 5, wherein an amine group substituted with an electron-withdrawing functional group is introduced into a silicon atom or an electron-withdrawing functional group is introduced into a nitrogen atom in a ring.

[0322] According to one embodiment of the present invention, the electrolyte composition further includes: the novel silazane compound; at least one of the linear hydrocarbon compounds represented by Chemical Formula 6, cyclic hydrocarbon compounds represented by Chemical Formulas 7 to 11, polyalkylene oxide compounds represented by Chemical Formula 12, and siloxane compounds represented by Chemical Formulas 13 to 15, which introduce nitrogen atoms in amine groups substituted with electron-withdrawing functional groups, and which can be mixed with the novel silazane compound and included in the electrolyte composition.

[0323] In other words, among the functional groups introduced into the side chains, the amine groups or nitrogen atoms in the ring substituted with electron-withdrawing functional groups can improve electronegativity and cationic mobility by promoting the dissociation of alkali metal salts. For example, through electron-withdrawing functional groups such as -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3, etc., the nitrogen in the amine groups or rings is in an electron-deficient state, thereby forming an electrically neutral complex with the anionic species of the alkali metal salt to promote the dissociation of the alkali metal salt. In addition, due to the hydrogen atom of the amine group, the nitrogen atom replaced by the electron-withdrawing functional group is only located at the end of the hydrocarbon chain. Therefore, the electrochemical instability, instability to lithium salts (for example, LiPF6) and steric hindrance caused by the presence of vulnerable nitrogen atoms in the middle of the azaether and other combinations disclosed in U.S. Patents 5,705,689 and 6,120,941 can be eliminated, and the central part of the nitrogen is further exposed, and the large anions can be easily approached, thereby promoting the dissociation of the lithium salt and increasing the mobility of the cations, so that high ionic conductivity can be obtained.

[0324] As an example of the present invention, the compound of Chemical Formula 6 may function as an anion receptor in an electrolyte composition (or electrolyte).

[0325] [Chemical formula 6]

[0326]

[0327] As an example of the present invention, in Chemical Formula 6, X and n are the same as defined in Chemical Formula 1. In Chemical Formula 6, R1 and R1' are respectively selected from hydrogen atoms, halogen atoms and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, R1 and R1' cannot be hydrogen atoms at the same time in the same molecule, and at least one of R1 and R1' is an electron-withdrawing functional group.

[0328] As an example of the present invention, in Chemical Formula 6, W may be 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, a linear or branched alkynyl group having 2 to 20 carbon atoms,

[0329] as well as

[0330]

[0331] (R2, R3 and R4 are respectively selected from hydrogen atoms; halogen atoms; and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, but R2, R3 and R4 cannot be hydrogen atoms at the same time, and m and m' are respectively integers from 0 to 20).

[0332] As an example of the present invention, the compound of Chemical Formula 6 can be selected from:

[0333]

[0334] [Chemical formula 7]

[0335]

[0336] As an example of the present invention, the compound represented by Chemical Formula 7 may function 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.

[0337] As an example of the present invention, the compound represented by Chemical Formula 7 can be selected from the following compounds:

[0338]

[0339] [Chemical formula 8]

[0340]

[0341] As an example of the present invention, the compound of Chemical Formula 8, wherein R1, X and n are as defined in Chemical Formula 1, can function as an anion receptor in an electrolyte composition (or electrolyte).

[0342] As an example of the present invention, the compound represented by Chemical Formula 8 can be selected from the following chemical formulas:

[0343]

[0344] [Chemical formula 9]

[0345]

[0346] As an example of the present invention, a compound represented by Chemical Formula 9, wherein X, Y and n are as defined in Chemical Formula 1, may function as an anion receptor in an electrolyte composition (or electrolyte).

[0347] As an example of the present invention, the compound represented by Chemical Formula 9 can be selected from the following compounds:

[0348]

[0349] [Chemical formula 10]

[0350]

[0351] As an example of the present invention, a compound represented by Chemical Formula 10, wherein X, Y and n are as defined in Chemical Formula 1, may function as an anion receptor in an electrolyte composition (or electrolyte).

[0352] As an example of the present invention, the compound represented by Chemical Formula 10 can be selected from the following compounds:

[0353]

[0354] [Chemical formula 11]

[0355]

[0356] As an example of the present invention, the compound represented by Chemical Formula 11 may function as an anion receptor in an electrolyte, n is as defined in Chemical Formula 1, and R1 and R1′ are as defined in Chemical Formula 6.

[0357] As an example of the present invention, the compound represented by Chemical Formula 11 can be selected from the following compounds:

[0358]

[0359] [Chemical formula 12]

[0360]

[0361] [Chemical formula 12-a]

[0362]

[0363] [Chemical formula 12-b]

[0364]

[0365] As an example of the present invention, the compounds represented by Chemical Formula 12, Chemical Formula 12-a and Chemical Formula 12-b can function as an anion receptor in an electrolyte, X, Y and n are as defined in Chemical Formula 1, W is 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, a linear or branched alkynyl group having 2 to 20 carbon atoms,

[0366] as well as

[0367]

[0368] (R2, R3 and R4 are selected from hydrogen atoms; halogen atoms; and electron-withdrawing functional groups selected from -SO2CF3, -OSO2CF3, -SO2CHF2, -OSO2CHF2, -SO2CH2F, -OSO2CH2F, -COCF3, -OCOCF3, -COCHF2, -OCOCHF2, -COCH2F, -OCOCH2F, -SO2CN, -OSO2CN, -SO2F, -OSO2F, -CF3, -OCF3 and -CN, but R2, R3 and R4 cannot be hydrogen atoms at the same time, and m and m' are integers of 0 to 20, respectively), z is an integer of 1 to 20, and n and q are integers of 0 to 20, respectively. Preferably, z is an integer of 1 to 10, and n and q may be integers of 0 to 10, respectively.

[0369] As an example 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:

[0370]

[0371] [Chemical formula 13]

[0372]

[0373] As an example of the present invention, a compound represented by Chemical Formula 13, wherein X, Y and n are as defined in Chemical Formula 1, may function as an anion receptor in an electrolyte composition (or electrolyte).

[0374] As an example of the present invention, the compound represented by Chemical Formula 13 can be selected from the following compounds:

[0375]

[0376] [Chemical formula 14]

[0377]

[0378] As an example of the present invention, a compound represented by Chemical Formula 14, wherein X, Y and n are as defined in Chemical Formula 1, may function as an anion receptor in an electrolyte composition (or electrolyte).

[0379] As an example of the present invention, the compound represented by Chemical Formula 14 can be selected from the following compounds:

[0380]

[0381] [Chemical formula 15]

[0382]

[0383] As an example of the present invention, a compound represented by Chemical Formula 15, wherein X, Y and n are as defined in Chemical Formula 1, may function as an anion receptor in an electrolyte composition (or electrolyte).

[0384] As an example of the present invention, the compound represented by Chemical Formula 15 can be selected from the following compounds:

[0385]

[0386] According to one embodiment of the present invention, all anion receptors contained in the electrolyte composition ("silazane anion receptor compounds of Chemical Formulas 1 to 5 + anion receptors of Chemical Formulas 6 to 15") account for 0.01 wt% to 40 wt%, 0.01 wt% to 35 wt%, 0.01 wt% to 30 wt%, 0.01 wt% to 20 wt%, 0.01 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.5 wt% to 5 wt%, 1 wt% to 2 wt%, based on the total mass of the electrolyte composition, and when the content is lower than 0.01 wt%, it is difficult to exhibit the performance of the anion receptor, and when it exceeds 40 wt%, it may be difficult to obtain the effects of improving ionic conductivity, electrochemical stability and low-temperature performance.

[0387] According to one embodiment of the present invention, at least one of the compounds represented by Chemical Formula 6 to Chemical Formula 15 accounts for 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 total mass of the anion receptor, and if included within the above content range, an electrolyte having improved ionic conductivity and electrochemical stability at room temperature can be provided.

[0388] According to one embodiment of the present invention, in the anion receptor, the mixing ratio of at least one of the silazane anion receptor compounds represented by Chemical Formula 1 to Chemical Formula 5 and at least one of the compounds represented by Chemical Formula 6 to Chemical Formula 15 may be included in a ratio of 99:1 to 50:50 (w / w), and if it is included in the above ratio range, the effect of improving ionic conductivity and electrochemical stability at room temperature can be obtained.

[0389] According to one embodiment of the present invention, the electrolyte composition may include a substance containing alkali metal ions and a non-aqueous solvent. As an example of the present invention, the non-aqueous solvent can be used without restriction as long as it is applicable to the battery, and may include at least one selected from the group consisting of the following substances, such as: ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate, dimethyl sulfamoyl fluoride, 1,2-butylene carbonate, 2,3-butylene carbonate, carbonate 1,2-pentenyl carbonate, 2,3-pentenyl carbonate, vinylene carbonate, ethyl ether, organic carbonate, lactone, formates, esters, sulfonates, nitrites, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxyethane, dimethoxymethane, y-butyrolactone, methyl formate, cyclopentane, acetonitrile, 3-methyl-2-oxazolidinone and N-methyl-2-pyrrolidone, but are not limited thereto.

[0390] As an example of the present invention, the non-aqueous solvent in the electrolyte composition may include: 1 weight % or more, 15 weight % or more, 30 weight % or more, 60 weight % or more, or 80 weight % to 99 weight % based on the remaining amount or the total mass of the electrolyte composition.

[0391] As an example of the present invention, the substance containing alkali metal ions is an electrolyte salt containing alkali metal ions, for example, it can be a lithium salt containing Li+ as a cation. As an example of the present invention, the lithium salt can be used without limitation as long as it is applicable to the electrolyte of the battery, for example, it can include 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, but is not limited thereto.

[0392] As an example of the present invention, the substance containing alkali metal ions in the electrolyte composition can be 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 mass of the electrolyte composition, and can supply appropriate alkaline ions to provide and maintain stable performance of the battery.

[0393] According to one embodiment of the present invention, the electrolyte composition may form a non-aqueous liquid electrolyte, a gel-type polymer electrolyte and / or a solid polymer electrolyte, a solid sulfide-polymer electrolyte, a solid oxide-polymer electrolyte, and may selectively further include additional components according to the types of these electrolytes. For example, it may be a polymer compound, a polymer support, an additive (e.g., a hardening initiator, a polymerization inhibitor), a sulfide, an oxide, a nano-metal oxide, etc.

[0394] According to one embodiment of the present invention, the electrolyte composition may form a non-aqueous liquid electrolyte. For example, the electrolyte composition for the non-aqueous liquid electrolyte may include:

[0395] (a) a novel silazane anion receptor compound represented by the above Chemical Formulae 1 to 5, wherein an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom in a ring;

[0396] Alternatively, a novel silazane anion receptor compound represented by Chemical Formulas 1 to 5 and at least one anion receptor selected from the following compounds: a linear hydrocarbon compound represented by Chemical Formula 6, in which an amine group substituted with an electron-withdrawing functional group is introduced or an electron-withdrawing functional group is introduced into a nitrogen atom in a ring, a cyclic hydrocarbon compound represented by the following Chemical Formulas 7 to 11, a polyalkylene oxide compound represented by Chemical Formula 12, and a siloxane compound represented by Chemical Formulas 13 to 15;

[0397] (b) a non-aqueous solvent; and

[0398] (c) Substances containing alkali metal ions.

[0399] As an example of the present invention, in an electrolyte composition for a non-aqueous liquid electrolyte, (a) anion receptor, (b) non-aqueous solvent and (c) substance containing alkali metal ions are as mentioned in the above-mentioned electrolyte composition. Preferably, in the electrolyte composition for a non-aqueous liquid electrolyte, based on the total mass of the electrolyte composition, 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 substance containing alkali metal ions can be 10 wt% to 30 wt%, 12 wt% to 20 wt% or 12 wt% to 15 wt%.

[0400] According to one embodiment of the present invention, the electrolyte composition may form a gel-type polymer electrolyte. For example, the electrolyte composition for the gel-type polymer electrolyte may include:

[0401] (a) a novel silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5, in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom in a ring; or an anion receptor mixed with the novel silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5 and at least one selected from the following compounds: a linear hydrocarbon compound represented by Chemical Formula 6, in which an amine group substituted with an electron withdrawing group is introduced into a nitrogen atom in a ring or an electron withdrawing group is introduced into a nitrogen atom in a ring, a cyclic hydrocarbon compound represented by the following Chemical Formulas 7 to 11, a polyalkylene oxide compound represented by Chemical Formula 12, and a siloxane compound represented by Chemical Formula 13 to Chemical Formula 15;

[0402] (b) a polymer compound selected from linear, network, comb-shaped and branched polymer compounds, a cross-linkable polymer compound or both;

[0403] (c) a polymer support;

[0404] (d) a non-aqueous solvent; and

[0405] (e) Substances containing alkali metal ions.

[0406] As an example of the present invention, in the electrolyte composition for gel-type polymer electrolyte, (a) anion receptor, (d) non-aqueous solvent and (e) substance containing alkali metal ions are as mentioned in the electrolyte composition. Preferably, in the electrolyte composition for gel-type polymer electrolyte, based on the total weight of the electrolyte composition, (a) anion receptor is 0.01 wt% to 30 wt%, (d) non-aqueous solvent is 20 wt% to 80 wt%, and (e) substance containing alkali metal ions can be 10 wt% to 30 wt%.

[0407] As an example of the present invention, in the electrolyte composition for gel-type polymer electrolyte, (b) a polymer compound selected from linear, network, comb-tooth and branched polymer compounds can be used without restriction as long as it is suitable for batteries (e.g., electrolytes), for example, it can include flexible inorganic polymers, linear polyethers or both.

[0408] As an example of the present invention, the flexible inorganic polymer is selected from polysiloxane, polyphosphazene or copolymers thereof, and the linear polyether can be polyalkylene oxide.

[0409] As an example of the present invention, a cross-linkable polymer compound can be used without limitation as long as it is applicable to a battery (e.g., an electrolyte). For example, a cross-linkable polymer compound has a flexible inorganic polymer or a linear polyether main chain as a basic skeleton, and may include at least one selected from the group consisting of polymer compounds having functional groups such as acrylic acid, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinylmonomethyl introduced into the terminal. For example, the cross-linkable polymer compound may be ethoxylated bisphenol A dimethacrylate (Bis-15m) of the following chemical formula 16, polyethylene glycol dimethacrylate (PEGDMA) represented by the following chemical formula 17, vinylene carbonate (VC) represented by the following chemical formula 18, and vinylethylene carbonate (VEC) represented by the following chemical formula 19, but is not limited thereto.

[0410] [Chemical formula 16]

[0411]

[0412] [Chemical formula 17]

[0413]

[0414] [Chemical formula 18]

[0415]

[0416] [Chemical formula 19]

[0417]

[0418] As an example of the present invention, (b) a polymer compound selected from linear, network, comb-shaped and branched polymer compounds, a cross-linkable polymer compound or both in the electrolyte composition for gel polymer electrolyte can be 0.01 wt % to 30 wt % based on the total mass of the electrolyte composition. If included in the above ratio range, a composition with improved mechanical properties and processability can be provided. For example, when it exceeds 80 wt %, the viscosity is high and the processability is reduced, and when it is less than 20 wt %, the mechanical properties are reduced.

[0419] As an example of the present invention, (c) the polymer support can be used without restriction as long as it is suitable for batteries (for example: electrolyte). As an example of the present invention, it can include at least one selected from the group consisting of polyalkylene glycol polymers, polysiloxane polymers, polyacrylonitrile (PAN) polymers and polyvinylidene fluoride (PVDF)-hexafluoropropylene polymers, but is not limited to this.

[0420] As an example of the present invention, the polymer support may be 1 wt % to 40 wt % or 5 wt % to 40 wt % in the electrolyte composition for the gel-type polymer electrolyte, based on the total mass of the electrolyte composition. If included in the above range, the polymer support can solve the leakage problem that may occur in the gel-type polymer electrolyte and provide an electrolyte with improved stability and electrical properties.

[0421] According to one embodiment of the present invention, when the electrolyte composition for the gel-type polymer electrolyte includes a cross-linkable polymer compound, a hardening initiator may also be included. As an example of the present invention, although the hardening initiator may include a photohardening initiator, a heat-hardening initiator, or both, for example, the photohardening initiator may include at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), tert-butyl peroxy pivalate, ethyl anisole, isopropyl anisole, α-methylbenzoic acid ethyl ether, benzoic acid phenyl ether, α-acyl oxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoylbenzoic acid, and Michler's ketone, but is not limited thereto. For example, the thermosetting initiator may include an azoisobutyronitrile compound, a peroxide compound or both, and more specifically, may include at least one selected from the group consisting of 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tetramethylbutyl peroxyneodecanoate, bis(4-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, etc., but is not limited thereto.

[0422] As an example of the present invention, the curing initiator may be present in the electrolyte composition for the gel-type polymer electrolyte in an amount of 1×10 -4 % to 0.1% by weight. If included within the above range, an electrolyte having improved stability and electrical properties can be provided.

[0423] According to one embodiment of the present invention, in order to prevent a specific polymer compound from being cross-linked below a suitable temperature or including a polymer compound that cannot be cross-linked below a suitable temperature, the electrolyte composition for the gel-type polymer electrolyte may further include a polymerization inhibitor in addition to the hardening initiator. In other words, a solidified electrolyte having a curing agent function may be provided by adding the polymerization inhibitor.

[0424] As an example of the present invention, the polymerization inhibitor can be used without limitation as long as it is applicable to batteries (e.g., electrolytes), and can be used without limitation as long as it has a polymerization inhibiting function or a polymerization inhibiting function. For example, it can include at least one selected from the group consisting of p-benzoquinone, 4-methoxyphenol, 4-tert-butylcatechol, phenothiazine, hydroquinone, naphthoquinone, phenanthrenequinone, toluenequinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicarboxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, 2,5-di-tert-butylhydroxybenzoquinone, p-tert-butylcatechol, mono-tert-butylhydroxybenzoquinone, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-amylhydroquinone, etc., but is not limited thereto.

[0425] As an example of the present invention, the polymerization inhibitor is contained in a gel-type polymer electrolyte in an amount of 0.01 wt % to 3 wt % based on the total mass of the electrolyte. If it is contained within the above range, it is possible to provide an electrolyte that can inhibit the cross-linking of specific polymer compounds, prevent hardening during product storage and transportation, induce cross-linking at a specific temperature, and prevent degradation of electrolyte function and battery performance due to high temperature or thermal runaway.

[0426] According to one embodiment of the present invention, the electrolyte composition may form a solid polymer electrolyte. For example, the electrolyte composition for the solid polymer electrolyte may include:

[0427] (a) an anion receptor, comprising a silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5 in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom in a ring;

[0428] Alternatively, an anion receptor, comprising: a silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5; and at least one selected from the following compounds: a linear hydrocarbon compound represented by Chemical Formula 6, a cyclic hydrocarbon compound represented by the following Chemical Formulas 7 to 11, a polyalkylene oxide compound represented by Chemical Formula 12, and a siloxane compound represented by Chemical Formulas 13 to 15, wherein an amine group substituted with an electron-withdrawing functional group is introduced or an electron-withdrawing functional group is introduced into a nitrogen atom in a ring;

[0429] (b) a polymer compound selected from linear, network, comb-shaped and branched polymer compounds or a cross-linkable polymer compound;

[0430] (c) a polymer support;

[0431] (d) a non-aqueous solvent; and

[0432] (e) Substances containing alkali metal ions.

[0433] In addition, the electrolyte composition for the solid polymer electrolyte may further include: (f) a single compound or two or more compounds selected from the group consisting of polyalkylene glycol dialkyl ethers and non-aqueous solvents.

[0434] As an example of the present invention, in the electrolyte composition for solid polymer electrolyte, (a) anion receptor, (d) non-aqueous solvent and (e) substance containing alkali metal ions are as mentioned in the above electrolyte composition. Preferably, in the electrolyte composition for solid polymer electrolyte, (a) anion receptor is 0.01 wt% to 30 wt%, (d) non-aqueous solvent is 0 wt% to 10 wt%, and (e) substance containing alkali metal ions can be 10 wt% to 70 wt%.

[0435] As an example of the present invention, in the electrolyte composition for solid polymer electrolytes, polymer compounds selected from linear, network, comb-tooth and branched polymer compounds can be used without restriction as long as they are suitable for batteries (e.g., electrolytes), for example, they can include flexible inorganic polymers, linear polyethers or both.

[0436] As an example of the present invention, the flexible inorganic polymer is polysiloxane, polyphosphazene or a copolymer thereof, and the linear polyether may be polyalkylene oxide.

[0437] As an example of the present invention, a cross-linkable polymer compound can be used without limitation as long as it is applicable to a battery (e.g., an electrolyte). For example, the cross-linkable polymer compound has a flexible inorganic polymer or a linear polyether main chain as a basic skeleton, and may include at least one selected from the group consisting of polymer compounds having functional groups such as acrylic acid, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinylmonomethyl introduced to the terminal, but is not limited thereto. For example, the cross-linkable polymer compound may be ethoxylated bisphenol A dimethacrylate (Bis-15m) represented by the following chemical formula 16 and polyethylene glycol dimethacrylate (PEGDMA) represented by the following chemical formula 17, but is not limited thereto.

[0438] As an example of the present invention, a polymer compound selected from linear, network, comb-shaped and branched polymer compounds, a cross-linkable polymer compound or both can be 20 wt % to 90 wt % in the electrolyte composition for solid polymer electrolyte. If included in the above ratio range, mechanical properties can be improved and stable performance of the battery can be provided.

[0439] As an example of the present invention, the polymer support can be used without restriction as long as it is a polymer support suitable for batteries (e.g., electrolytes). As an example of the present invention, it can include at least one selected from the group consisting of polyalkylene glycol polymers, polysiloxane polymers, polyacrylonitrile (PAN) polymers and polyvinylidene fluoride (PVDF)-hexafluoropropylene polymers, but is not limited to this.

[0440] As an example of the present invention, the polymer support may be 1 wt % to 30 wt % in the electrolyte composition for solid polymer electrolytes based on the total mass of the electrolyte composition. If included in the above range, an electrolyte with improved stability and electrical properties can be provided.

[0441] According to one embodiment of the present invention, when a cross-linkable polymer compound is included, the electrolyte composition for a solid polymer electrolyte may further include a hardening initiator. As an example of the present invention, the hardening initiator may include a photohardening initiator, a heat-hardening initiator, or both. For example, the photohardening initiator may include at least one selected from the group consisting of dimethylphenylacetophenone (DMPA), tert-butyl peroxy pivalate, ethyl anisole, isopropyl anisole, α-methylbenzoic acid ethyl ether, benzoic acid phenyl ether, α-acyl oxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoylbenzoic acid, and Michler's ketone, but is not limited thereto. For example, the thermal curing initiator may include an azoisobutyronitrile compound, a peroxide compound or both, and more specifically, it may be 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tetramethylbutyl peroxyneodecanoate, bis(4-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, etc., but are not limited thereto.

[0442] As an example of the present invention, the curing initiator may be present in the electrolyte composition for the solid polymer electrolyte in an amount of 1×10 -4 wt % to 0.1 wt %. If included within the above range, the polymer support can provide an electrolyte having improved stability and electrical properties.

[0443] According to one embodiment of the present invention, in order to prevent a specific polymer compound from being cross-linked below an appropriate temperature or including a polymer compound that cannot be cross-linked, the electrolyte composition for a solid polymer electrolyte may further include a polymerization inhibitor in addition to a hardening initiator. In other words, a solidified electrolyte may be manufactured by adding a polymerization inhibitor.

[0444] As an example of the present invention, the polymerization inhibitor can be used without limitation as long as it is applicable to batteries (e.g., electrolytes), and can be used without limitation as long as it has a polymerization inhibiting function or a polymerization inhibiting function. For example, it can include at least one selected from the group consisting of p-benzoquinone, 4-methoxyphenol, 4-tert-butylcatechol, phenothiazine, hydroquinone, naphthoquinone, phenanthrenequinone, toluenequinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicarboxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, 2,5-di-tert-butylhydroxybenzoquinone, p-tert-butylcatechol, mono-tert-butylhydroxybenzoquinone, 2,5-di-tert-amylhydroquinone, and 2,5-di-tert-amylhydroquinone, but is not limited thereto.

[0445] As an example of the present invention, the polymerization inhibitor is contained in a solid polymer electrolyte in an amount of 0.01 wt % to 3 wt % based on the total mass of the electrolyte. If it is contained within the above range, it is possible to provide an electrolyte that can inhibit the cross-linking of specific polymer compounds, prevent hardening during product storage and transportation, induce cross-linking at a specific temperature, and prevent a decrease in electrolyte function and battery performance due to high temperature or thermal runaway.

[0446] According to one embodiment of the present invention, the polyalkylene glycol dialkyl ether or non-aqueous solvent that may be included in the solid polymer electrolyte acts as a plasticizer, just like the anion receptor of the present invention. For example, examples of polyalkylene glycol dialkyl ethers may include 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, but are not limited thereto.

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

[0448] According to one embodiment of the present invention, the electrolyte composition may form a solidified electrolyte. For example, the electrolyte composition for the solidified electrolyte may include:

[0449] (a) an anion receptor, comprising a silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5 in which an amine group substituted with an electron withdrawing group is introduced into a silicon atom or an electron withdrawing group is introduced into a nitrogen atom in a ring;

[0450] Alternatively, an anion receptor, comprising: a silazane anion receptor compound represented by Chemical Formula 1 to Chemical Formula 5; and at least one selected from the following compounds: a linear hydrocarbon compound represented by the following Chemical Formula 6, a cyclic hydrocarbon compound represented by the following Chemical Formulas 7 to 11, a polyalkylene oxide compound represented by Chemical Formula 12, and a siloxane compound represented by Chemical Formulas 13 to 15, wherein an amine group substituted with an electron-withdrawing functional group is introduced or an electron-withdrawing functional group is introduced into a nitrogen atom in a ring;

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

[0452] (c) a polymer support;

[0453] (d) non-aqueous solvents;

[0454] (e) substances containing alkali metal ions; and

[0455] (f) Polymerization inhibitors.

[0456] In addition, (vii) the electrolyte composition for solid polymer electrolyte may also selectively include: a single compound or two or more compounds selected from polyalkylene glycol dialkyl ethers and non-aqueous solvents.

[0457] As an example of the present invention, the above-mentioned (a) to (vii) components are the same as those mentioned in the electrolyte composition for gel-type polymer electrolyte or solid polymer electrolyte. Preferably, the total content of the polymer compound, the cross-linkable polymer compound and the anion receptor in the electrolyte composition for solidifying the electrolyte is 12% by weight or more or 13% by weight or more, and if it contains more than the minimum content range, it can provide a curing function of a rapid hardening reaction at a temperature at which a fire may occur in the electrolyte or battery, for example, at a temperature of about 130° C. or more. In addition, (d) the non-aqueous solvent can be 20% by weight to 80% by weight in the electrolyte composition for solidifying the electrolyte.

[0458] The present invention relates to an electrolyte comprising the novel anion receptor according to the invention.

[0459] According to one embodiment of the present invention, the electrolyte is made of the electrolyte composition according to the present invention, for example, the electrolyte can be a liquid, gel-type or solid electrolyte. For example, the electrolyte can be a non-aqueous liquid electrolyte, a gel-type polymer electrolyte, a solid polymer electrolyte, a polymer electrolyte film and / or a solid electrolyte.

[0460] According to one embodiment of the present invention, the solidified electrolyte may be made of an electrolyte composition for a gel-type polymer electrolyte and / or an electrolyte composition for a solid polymer electrolyte, or may be an electrolyte composition that does not undergo a hardening reaction. In addition, it has a viscosity or fluidity close to or the same as that of a liquid, and when applied to a battery, it can be quickly hardened at a certain temperature, such as a high temperature above 120°C or above 130°C, thereby interrupting the operation of the battery, and ensuring the stability of the battery under thermal runaway and high temperature, thereby preventing risks such as fire.

[0461] According to one embodiment of the present invention, the polymer electrolyte film can be manufactured using an electrolyte composition for a gel-type polymer electrolyte and / or an electrolyte composition for a solid polymer electrolyte, for example, through a curing process.

[0462] According to one embodiment of the present invention, a polymer electrolyte film can be manufactured by the following process. As an example of the present invention, the manufacturing method may include the following steps: manufacturing an electrolyte composition by mixing components; and coating on a substrate, and forming a film through drying and hardening.

[0463] As an example of the present invention, when a gel-type polymer electrolyte film is formed,

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

[0465] For example, in the step of forming a thin film, the prepared mixed solution of the composition is coated on a supporting substrate made of glass or polyethylene or a commercial polyester film (Mylar film) with an appropriate thickness, and then the coated substrate can be dried or exposed to electron rays, ultraviolet rays or gamma rays, or heated to cause a curing reaction, thereby forming a thin film. As another example, in the step of forming a thin film, the mixed solution of the composition is coated on a supporting substrate, and a spacer for thickness adjustment is fixed to both ends of the supporting substrate, and then after covering another supporting substrate thereon, a curing reaction is performed using a curing irradiator or a heat source, thereby manufacturing a gel-type polymer electrolyte film.

[0466] As an example of the present invention, when a solid polymer electrolyte film is formed,

[0467] For example, the step of manufacturing the electrolyte composition is to manufacture a solid polymer electrolyte composition, put an anion receptor or polyalkylene glycol dialkyl ether or non-aqueous solvent and a substance containing alkali metal ions in a container at an appropriate mixing ratio, and stir the mixture with a stirrer, add a network type, branched or comb-shaped polymer compound or a cross-linked polymer compound after preparing the solution, and mix them with each other. Then, when mixing the network type, branched or comb-shaped polymer compound, a certain amount of heat can be applied to melt it if necessary. At this time, if the mixed solution is a cross-linked polymer compound, a mixed solution of a solid polymer electrolyte composition for manufacturing a solid polymer electrolyte film of the present invention can be prepared by adding a hardening initiator and a polymerization inhibitor and stirring.

[0468] For example, in the step of forming a thin film, the prepared mixed solution of the composition is coated on a supporting substrate made of glass or polyethylene or a commercial polyester film at an appropriate thickness, and then the coated substrate can be dried or exposed to electron rays, ultraviolet rays or gamma rays, or heated to produce a curing reaction, thereby forming a thin film. As another example, in the step of forming a thin film, the mixed solution of the composition is coated on a supporting substrate, and a spacer for thickness adjustment is fixed to both ends of the supporting substrate, and then after covering another supporting substrate thereon, a curing reaction is performed using a curing irradiator or a heat source, thereby manufacturing a solid polymer electrolyte film.

[0469] The present invention relates to an accessory or a constituent element of an electrochemical cell comprising the novel silazane anion receptor compound according to the present invention.

[0470] According to one embodiment of the present invention, the negative electrode, positive electrode, current collector and / or separator thereof, electrolyte including the above-mentioned silazane anion receptor compound, battery membrane, etc. may be coated or impregnated with the above-mentioned silazane anion receptor compound.

[0471] For example, the silazane-based anion receptor compound can be used as an electrolyte composition, a process composition, and the like.

[0472] For example, when preparing an electrode slurry including an active material, the negative electrode and the positive electrode may be charged with a silazane-based anion receptor compound.

[0473] For example, it may be a membrane impregnated or coated with a silazane-based anion receptor compound.

[0474] For example, it may include a silazane anion receptor compound or may be manufactured (eg, cured, molded, etc.) from an electrolyte composition to form a battery membrane (eg, a polymer electrolyte membrane), a film and / or a sheet.

[0475] For example, the electrolyte may be a liquid, gel-type or solid electrolyte using the electrolyte composition according to the present invention. The gel-type and solid electrolytes may be a gel-type polymer electrolyte film or a solid polymer electrolyte film, respectively.

[0476] The present invention relates to an electrochemical cell comprising the silazane-type anion receptor compound according to the present invention.

[0477] According to one embodiment of the present invention, the electrochemical cell may be a primary or secondary battery and may include a liquid, gel-type and / or solid electrolyte (eg, gel-type polymer electrolyte and solid polymer electrolyte) made from the electrolyte composition according to the present invention.

[0478] According to one embodiment of the present invention, a battery using the liquid or gel polymer electrolyte of the present invention includes a negative electrode, a positive electrode and a separator, and a battery using the solid polymer electrolyte of the present invention may include a negative electrode and a positive electrode. In addition to the above-mentioned battery constitutions, for the driving or operation of the battery, it may also include constitutions known in the technical field of the present invention, but not specifically mentioned herein.

[0479] According to one embodiment of the present invention, the negative electrode and the positive electrode used in the battery can use the negative electrode, the positive electrode used in the battery known in the technical field of the present invention and the negative electrode and the positive electrode made according to their manufacturing methods, and the assembly of the battery can also be manufactured by the usual method of assembling the negative electrode, the positive electrode and the electrolyte.

[0480] As an example of the present invention, the negative electrode may include: lithium; lithium alloys such as Li-Al, Li-Si, Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; Li x Intercalation compounds of lithium metal oxides such as WO2 or LiMoO2; intercalation compounds of lithium metal sulfides such as LiTiS2; mixtures thereof or mixtures thereof with alkali metals, but not limited thereto.

[0481] As an example of the present invention, the positive electrode may include transition metal oxides, transition metal chalcogenides, poly(carbon disulfide) polymers, organic disulfide redox polymers, polyaniline, organic disulfide / polyaniline complexes, or mixtures thereof and oxychloride, but are not limited thereto.

[0482] According to one embodiment of the present invention, a primary battery composed of a non-aqueous liquid electrolyte including the silazane anion receptor compound of the present invention comprises:

[0483] (a) a negative electrode comprising lithium, a lithium alloy, a lithium-carbon intercalation compound, a lithium-graphite intercalation compound, a lithium metal oxide intercalation compound, a mixture thereof or an alkali metal;

[0484] (b) A positive electrode comprising a transition metal oxide, a transition metal chalcogenide, a poly(carbon disulfide) polymer, an organic disulfide redox polymer, polyaniline, an organic disulfide / polyaniline complex, and an oxychloride, for example, SO2, CuO, CuS, Ag2CrO4, I2, PbI2, PbS, SOCl2, V2O5, MoO3, MnO2, or a polycarbon monofluoride (CF) n ;

[0485] (c) the aforementioned non-aqueous liquid electrolyte of the present invention; and

[0486] (d) a diaphragm,

[0487] The positive electrode and the negative electrode can be manufactured and the battery can be assembled by known methods.

[0488] According to one embodiment of the present invention, a secondary battery composed of a non-aqueous liquid electrolyte containing the silazane anion receptor compound of the present invention comprises:

[0489] (a) Anode, which contains lithium; lithium alloys such as Li-Al, Li-Si, Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; Li x Lithium metal or a substance that causes a reversible effect on lithium metal, such as lithium metal oxide intercalation compounds such as WO2 or LiMoO2; or lithium metal sulfide intercalation compounds such as LiTiS2;

[0490] (b) The positive electrode contains a Li intercalation layer. 2.5 V6O 13 , Li 1.2 V2O5, LiCoO2, LiNiO2, LiNi 1-x M xO2 (where M is Co, Mg, Al or Ti), lithium transition metal oxides such as LiMn2O4 or LiMnO2; transition metal halides; or chalcogenides such as LiNbSe3, LiTiS2 or LiMoS2;

[0491] (c) the aforementioned non-aqueous liquid electrolyte of the present invention; and

[0492] (d) a diaphragm,

[0493] The positive electrode and the negative electrode can be manufactured and the battery can be assembled by known methods.

[0494] According to one embodiment of the present invention, a secondary battery composed of a gel-type polymer electrolyte including the silazane anion receptor compound of the present invention may include a negative electrode, a positive electrode, a separator used in a secondary battery composed of a non-aqueous liquid electrolyte, and the gel-type polymer electrolyte of the present invention.

[0495] According to one embodiment of the present invention, a secondary battery composed of a solid polymer electrolyte including a silazane-based anion receptor compound may include a negative electrode used in a secondary battery composed of a non-aqueous liquid electrolyte, a positive electrode, and the solid polymer electrolyte of the present invention.

[0496] According to one embodiment of the present invention, the battery may be a battery using an electrolyte including a non-aqueous solvent, for example, a lithium ion battery, a lithium ion polymer battery, an alkali metal battery, etc., but is not limited thereto.

[0497] According to one embodiment of the present invention, the battery can be reused by replacing the spent electrolyte after use.

[0498] The present invention relates to a recycling battery made using the anion receptor according to the present invention.

[0499] According to one embodiment of the present invention, the recycled battery can be a reusable battery in which the waste electrolyte in the used waste battery (e.g., battery for electric vehicle) is replaced with an electrolyte containing a silazane anion receptor compound. In other words, the recycled battery can be composed of the components of the used waste battery and the electrolyte containing the silazane anion receptor compound of the present invention.

[0500] According to one embodiment of the present invention, a reused battery is a reusable battery manufactured by a replacement filling method of an electrolyte including the silazane anion receptor compound of the present invention, and the manufacturing method of the reused battery may include the following steps:

[0501] (a) Prepare waste batteries;

[0502] (b) removing spent electrolyte and other impurities from spent batteries; and

[0503] (c) injecting the electrolyte according to the present invention into the spent battery for regeneration.

[0504] As an example of the present invention, the steps of preparing waste batteries and removing waste electrolyte and other impurities in the waste batteries may be performed in a drying room or in an inert atmosphere.

[0505] As an example of the present invention, the step of removing spent electrolyte and other impurities in spent batteries may be performed under vacuum conditions.

[0506] As an example of the present invention, in the step of injecting the electrolyte according to the present invention into the waste battery for regeneration, a method of injecting new electrolyte into the waste battery and then vibrating it at a constant temperature can be used, for example, the temperature can be 20°C to 50°C.

[0507] According to one embodiment of the present invention, a reused battery and a manufacturing method thereof are to replace the waste electrolyte in the used electric vehicle battery (waste battery) with an electrolyte containing the silazane anion receptor compound according to the present invention so that it can be reused. For example, the waste battery for electric vehicles has a high risk of explosion and fire in a charged state. Therefore, after the charged current is completely discharged, it may be necessary to separate the battery pack and separate it into individual battery cells. Each discharged battery cell can be evaluated for charging capacity and discharging capacity using a charger and discharger, and graded according to capacity.

[0508] For example, the battery cells are divided into those with a capacity of more than 80%, 68% to 80%, and less than 68%. The battery cells with a capacity of less than 68% that has dropped significantly are subjected to the regeneration process. After the battery cells with dropped capacity are completely discharged, holes are opened in each battery cell in a dry room or inert atmosphere, and the existing electrolyte and the generated gas and impurities are removed by vacuum. Thereafter, an electrolyte containing an additive that can restore performance is injected into the battery cell and the hole is blocked. The battery cell is shaken for a period of time at a certain temperature (25°C to 50°C) to evenly distribute the electrolyte, activate the positive / negative active materials, and increase the activity of Li ions, thereby restoring the battery capacity.

[0509] Hereinafter, the present invention will be described in more detail according to the examples and comparative examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[0510] [Production Example 1]: Synthesis of N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide

[0511]

[0512] 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 pyridinium triflate was removed by filtration to obtain the product N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide.

[0513] 1 H 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).

[0514] [Production Example 2]: Synthesis of N-allyl-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide

[0515]

[0516] Allylamine (0.5g, 8.76mmol) and triethylamine (2.0g, 20mmol) are mixed in 40ml chloroform at -40 ℃, and in the mixed mixture, 5.0g trifluoromethanesulfonic anhydride (18mmol) is added dropwise under nitrogen atmosphere. The solution is stirred at room temperature for 4 hours, and volatile substances are removed under reduced pressure. The remaining viscous liquid is dissolved in 30ml of 4MNaOH, and washed three times with 25ml chloroform, and the water-soluble component is neutralized with HCI, and then washed 3 times with 30ml chloroform. Then, the organic extract is dried and filtered with anhydrous MgSO4. Chloroform is removed under vacuum to obtain the resultant N-allyl-1,1,1-trifluoro-N-((trifluoromethyl) sulfonyl) methanesulfonamide.

[0517] 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).

[0518] [Production Example 3]: Synthesis of allyl (fluorosulfonyl)sulfamoyl fluoride

[0519]

[0520] Allylamine (0.5g, 8.76mmol) and triethylamine (2.0g, 20mmol) are mixed in 40ml chloroform at-40 ℃, in the mixed mixture, 3.6g of fluorosulfonic acid (18mmol) is added dropwise under nitrogen atmosphere. The solution is stirred at room temperature for 4 hours, and volatile substances are removed under reduced pressure. The remaining viscous liquid is dissolved in 30ml of 4M NaOH, and washed three times with 25ml chloroform, and water-soluble components are neutralized with HCI, and then washed 3 times with 30ml chloroform. Then, organic extract is dried and filtered with anhydrous MgSO4. Chloroform is removed under vacuum, and resultant allyl (fluorosulfonyl) sulfamoyl fluoride is obtained.

[0521] 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).

[0522] [Example 1-1]: Synthesis of N,N-bis(dimethyl(vinyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-1)

[0523] [Reaction formula 1-1]

[0524]

[0525] 1,1,3,3-Tetramethyl-1,3-divinyl-disilazane (3.15 g, 17.5 mmol) was mixed in 40 ml of chloroform at 0°C, and triethylamine (2.0 g, 2.0 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) were added dropwise to the mixed mixture under a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, and the volatile substances were removed under reduced pressure. The chloroform was removed under vacuum to obtain the product N,N-bis(dimethyl(vinyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-1).

[0526] 1 H NMR (300MHz, CDCl3): ppm 0.14 (m, 12H), 5.1 (m, 2H), 5.3 (m, 2H), 5.4 (m, 2H); 13CNMR (300MHz, CDCl3): 1.3, 120.6, 123.0, 138.0; 19 F NMR (CDCl3): ppm-77.3 (s).

[0527] [Example 1-2]: Synthesis of N,N-bis(dimethyl(vinyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-2)

[0528] [Reaction 1-2]

[0529]

[0530] 1,1,3,3-tetramethyl-1,3-divinyl-disilazane (3.24 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) were mixed in 40 ml of chloroform at -40 ° C, and trifluoromethanesulfonic anhydride (5.0 g, 18 mmol) was added dropwise to the mixed mixture under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and the volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 ml of 4M NaOH and washed three times with 25 ml of chloroform, the water-soluble components were neutralized with HCI, and then washed three times with 30 ml of chloroform. Then, the organic extract was dried with anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to obtain the resultant N, N-bis (dimethyl (vinyl) silyl) -1,1,1-trifluoromethanesulfonamide (Compound 1-2).

[0531] 1 H NMR (300MHz, CDCl3): ppm 0.14 (m, 12H), 5.1 (m, 2H), 5.2 (m, 2H), 5.4 (m, 2H); 13 CNMR (300MHz, CDCl3): -2.3,0.0,1.1,119.1; 19 F NMR (CDCl3): ppm-76.1 (s).

[0532] [Example 1-3]: Synthesis of bis(dimethyl(vinyl)silyl)sulfamoyl fluoride (Compound 1-3)

[0533] [Reaction 1-3]

[0534]

[0535] 1,1,3,3-tetramethyl-1,3-divinyl-disilazane (3.24 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) were mixed in 40 ml of chloroform at -40 ° C, and 3.6 g of fluorosulfonic acid (18 mmol) was added dropwise to the mixed mixture under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 ml of 4M NaOH, washed three times with 25 ml of chloroform, the water-soluble components were neutralized with HCI, and then washed three times with 30 ml of chloroform. Then, the organic extract was dried with anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to obtain the resultant bis(dimethyl(vinyl)silyl)sulfamoyl fluoride (compound 1-3).

[0536] 1 H NMR (300MHz, CDCl3): ppm 0.14 (m, 12H), 5.1 (m, 2H), 5.3 (m, 3H), 5.4 (m, 2H); 13 CNMR (300MHz, CDCl3): 0.1, 123.0, 138.0; 19 F NMR (CDCl3): ppm-78.1 (s).

[0537] [Example 1-4]: Synthesis of 2,2,2-trifluoro-N,N-bis(trimethylsilyl)acetamide (Compound 1-4)

[0538] [Reaction 1-4]

[0539]

[0540] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product 2,2,2-trifluoro-N,N-bis(trimethylsilyl)acetamide (compound 1-4).

[0541] 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).

[0542] [Example 1-5]: Synthesis of 1,1,1-trifluoro-N,N-bis(trimethylsilyl)methanesulfonamide (Compound 1-5)

[0543] [Reaction 1-5]

[0544]

[0545] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoromethanesulfonic anhydride (5.0 g, 18 mmol) by the same method as reaction formula 1-2 to obtain the product 1,1,1-trifluoro-N,N-bis(trimethylsilyl)methanesulfonamide (compound 1-5).

[0546] 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).

[0547] [Example 1-6]: Synthesis of bis(trimethylsilyl)sulfamoyl fluoride (Compound 1-6)

[0548] [Reaction 1-6]

[0549]

[0550] 1,1,1,3,3,3-Hexamethyl-disilazane (2.82 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and fluorosulfonic acid (3.6 g, 18 mmol) by the same method as reaction formula 1-3 to obtain the product bis(trimethylsilyl)sulfamoyl fluoride (compound 1-6).

[0551] 1 H NMR (300MHz, CDCl3): ppm 0.08 (m, 18H); 13 C NMR (300MHz, CDCl3): 1.0; 19 F NMR (CDCl3): ppm-76.7 (s).

[0552] [Example 1-7]: Synthesis of N,N-bis(octyldimethylsilyl)-2,2,2-trifluoroacetamide (Compound 1-7)

[0553] [Reaction 1-7]

[0554]

[0555] 1,1,3,3-Tetramethyl-1,3-dioctyl-disilazane (6.26 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product N,N-bis(octyldimethylsilyl)-2,2,2-trifluoroacetamide (compound 1-7).

[0556] 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).

[0557] [Example 1-8]: Synthesis of N,N-bis(octyldimethylsilyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-8)

[0558] [Reaction 1-8]

[0559]

[0560] 1,1,1,3,3,3-Hexamethyl-dioctyl-disilazane (6.26 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoromethanesulfonic anhydride (5.0 g, 18 mmol) by the same method as reaction formula 1-2 to obtain the product N,N-bis(octyldimethylsilyl)-1,1,1-trifluoromethanesulfonamide (compound 1-8).

[0561] 1 H NMR (300MHz, CDCl3): ppm 0.08 (m, 12H), 0.9 (m, 6H), 1.4 (m, 28H); 13 C NMR (300MHz, CDCl3): -1.2, 4.2, 8.3, 153.6; 19 F NMR (CDCl3): ppm-76.7 (s).

[0562] [Example 1-9]: Synthesis of bis(octyldimethylsilyl)sulfamoyl fluoride (Compound 1-9)

[0563] [Reaction 1-9]

[0564]

[0565] 1,1,1,3,3,3-Hexamethyl-dioctyl-disilazane (6.26 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and fluorosulfonic acid (3.6 g, 18 mmol) by the same method as reaction formula 1-3 to obtain the product bis(octyldimethylsilyl)sulfamoyl fluoride (compound 1-9).

[0566] 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).

[0567] [Example 1-10]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-2,2,2-trifluoroacetamide (Compound 1-10)

[0568] [Reaction formula 1-10]

[0569]

[0570] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-2,2,2-trifluoroacetamide (compound 1-10).

[0571] 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).

[0572] [Example 1-11]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-11)

[0573] [Reaction 1-11]

[0574]

[0575] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoromethanesulfonic anhydride (5 g, 18 mmol) by the same method as reaction formula 1-2 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluoromethanesulfonamide (Compound 1-11).

[0576] 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).

[0577] [Example 1-12]: Synthesis of N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluorosulfonamide (Compound 1-12)

[0578] [Reaction 1-12]

[0579]

[0580] 1,1,3,3-Tetramethyl-1,3-diphenyl-disilazane (5.00 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and fluorosulfonic acid (3.6 g, 18 mmol) by the same method as reaction formula 1-3 to obtain the product N,N-bis(dimethyl(phenyl)silyl)-1,1,1-trifluorosulfonamide (Compound 1-12).

[0581] 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-76.9 (s).

[0582] [Example 1-13]: Synthesis of 2,2,2-trifluoro-N,N-bis(methyldiphenylsilyl)acetamide (Compound 1-13)

[0583] [Reaction 1-13]

[0584]

[0585] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol) is reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product 2,2,2-trifluoro-N,N-bis(methyldiphenylsilyl)acetamide (compound 1-13).

[0586] 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).

[0587] [Example 1-14]: Synthesis of 1,1,1-trifluoro-N,N-bis(methyldiphenylsilyl)methanesulfonamide (Compound 1-14)

[0588] [Reaction 1-14]

[0589]

[0590] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoromethanesulfonic anhydride (5.0 g, 18 mmol) by the same method as reaction formula 1-2 to obtain the product 1,1,1-trifluoro-N,N-bis(methyldiphenylsilyl)methanesulfonamide (compound 1-14).

[0591] 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).

[0592] [Example 1-15]: Synthesis of bis(methyldiphenylsilyl)sulfamoyl fluoride (Compound 1-15)

[0593] [Reaction 1-15]

[0594]

[0595] 1,3-Dimethyl-1,1,3,3-tetraphenyl-disilazane (7.17 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and fluorosulfonic acid (3.6 g, 18 mmol) by the same method as reaction formula 1-3 to obtain the product bis(methyldiphenylsilyl)sulfamoyl fluoride (compound 1-15).

[0596] 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).

[0597] [Example 2-1]: Synthesis of N-(bis(2,2,2-trifluoroacetyl)carbamoyl)-2,2,2-trifluoro-N-(triethoxysilyl)acetamide (Compound 2-1)

[0598] [Reaction formula 2-1]

[0599]

[0600] N-(Triethoxysilyl)-urea (3.89 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product N-(bis(2,2,2-trifluoroacetyl)carbamoyl)-2,2,2-trifluoro-N-(triethoxysilyl)acetamide (compound 2-1).

[0601] 1 H 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).

[0602] [Example 2-2]: Synthesis of N-(bis((trifluoromethyl)sulfonyl)carbamoyl)-1,1,1-trifluoro-N-(triethoxysilyl)methanesulfonamide (Compound 2-2)

[0603] [Reaction formula 2-2]

[0604]

[0605] N-(Triethoxysilyl)-urea (3.89 g, 17.5 mmol) was reacted with triethylamine (6.0 g, 60 mmol) and trifluoromethanesulfonic anhydride (15 g, 54 mmol) by the same method as reaction formula 1-2 to obtain the product N-(bis((trifluoromethyl)sulfonyl)carbamoyl)-1,1,1-trifluoro-N-(triethoxysilyl)methanesulfonamide (compound 2-2).

[0606] 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).

[0607] [Example 2-3]: Synthesis of (bis(fluorosulfonyl)carbamoyl)(triethoxysilyl)sulfamoyl fluoride (Compound 2-3)

[0608] [Reaction 2-3]

[0609]

[0610] N-(Triethoxysilyl)-urea (3.89 g, 17.5 mmol) was reacted with triethylamine (6.0 g, 60 mmol) and fluorosulfonic acid (10.8 g, 54 mmol) by the same method as reaction formula 1-3 to obtain the product (bis(fluorosulfonyl)carbamoyl)(triethoxysilyl)sulfamoyl fluoride (Compound 2-3).

[0611] 1 H NMR (300MHz, CDCl3): ppm 1.22 (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).

[0612] [Example 3-1]: Synthesis of N,N'-carbonylbis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 3-1)

[0613] [Reaction formula 3-1]

[0614]

[0615] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product N,N'-carbonylbis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 3-1).

[0616] 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).

[0617] [Example 3-2]: Synthesis of N,N'-carbonylbis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide) (Compound 3-2)

[0618] [Reaction formula 3-2]

[0619]

[0620] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol) was reacted with triethylamine (4.0 g, 40 mmol) and trifluoromethanesulfonic anhydride (10 g, 36 mmol) by the same method as reaction formula 1-2 to obtain the product N,N'-carbonylbis(1,1,1-trifluoro-N-(trimethylsilyl)methanesulfonamide) (Compound 3-2).

[0621] 1 H NMR (300MHz, CDCl3): ppm 0.08 (m, 18H); 13 C NMR (300MHz, CDCl3): -2.9,149.4,161.0; 19 F NMR (CDCl3): ppm-76.8 (s).

[0622] [Example 3-3]: Synthesis of Carbonyl Bis((Trimethylsilyl)Sulfamoyl Fluoride) (Compound 3-3)

[0623] [Reaction formula 3-3]

[0624]

[0625] N,N'-bis(trimethylsilyl)-urea (3.58 g, 17.5 mmol) was reacted with triethylamine (4.0 g, 40 mmol) and fluorosulfonic acid (7.2 g, 36 mmol) in the same manner as reaction formula 1-3 to obtain carbonylbis((trimethylsilyl)sulfamoyl fluoride) (Compound 3-3).

[0626] 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).

[0627] [Example 4-1]: Synthesis of N,N'-(methyl(3-(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetylamino)propyl)silanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 4-1)

[0628] [Reaction formula 4-1]

[0629]

[0630] 1-Methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product N,N'-(methylsilanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide)dimethyl-silane.

[0631] The obtained product N,N'-(methylsilanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide)dimethyl-silane (41.26 g, 0.1 mol) and Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (49.82 g, 0.2 mol) were dissolved and dropped into 50 ml of tetrahydrofuran. After reflux at 65°C for 8 hours under a nitrogen atmosphere, the mixture was cooled to room temperature, activated carbon was added, stirred and filtered, and toluene was evaporated under reduced pressure to obtain the product N,N'-(methyl(3-(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetylamino)propyl)silanediyl)bis(2,2,2-trifluoro-N-(trimethylsilyl)acetamide) (Compound 4-1).

[0632] 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).

[0633] [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)

[0634] [Reaction 4-2]

[0635]

[0636] 1-Methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) were mixed at -40°C. In the mixed mixture, trifluoromethanesulfonic anhydride (10 g, 36 mmol) was reacted as in reaction formula 1-2 to obtain a product N,N'-(methylsilanediyl)bis(1,1,1-trifluoro-N-trimethylsilyl)methanesulfonamide. The obtained product N,N '-(Methylsilanediyl)bis(1,1,1-trifluoro-N-trimethylsilyl)methanesulfonamide (64.2 g, 0.1 mol), Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and N-allyl-1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (49.82 g, 0.2 mol) were dissolved and dropped into 50 ml of tetrahydrofuran. The mixture was refluxed at 65°C for 8 hours under a nitrogen atmosphere and then cooled to room temperature. Activated carbon was then added, stirred and filtered, and 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).

[0637] 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); 13 C 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).

[0638] [Example 4-3]: Synthesis of ((3-(bis(fluorosulfonyl)amino)propyl)(methyl)silanediyl)bis((trimethylsilyl)sulfamoyl fluoride) (Compound 4-3)

[0639] [Reaction 4-3]

[0640]

[0641] 1-Methyl-N,N'-bis(trimethylsilyl)silanediamine (3.86 g, 17.5 mmol) and triethylamine (2.0 g, 20 mmol) were mixed at -40°C, and fluorosulfonic acid (7.2 g, 36 mmol) was reacted in the same manner as in reaction formula 1-3 to obtain (methylsilanediyl)bis((trimethylsilyl)sulfamoyl fluoride, and the obtained (methylsilanediyl)bis((trimethylsilyl)sulfamoyl fluoride (38.5 g, 0.1 mol) and Pt(O)-1 were reacted. ,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(O)) catalyst and allyl (fluorosulfonyl) sulfamoyl fluoride (44.2 g, 0.2 mol) were dissolved and dropped into 50 ml of tetrahydrofuran. After reflux at 65°C for 8 hours under a nitrogen atmosphere, it was cooled to room temperature, and then activated carbon was added. After stirring and filtering, toluene was evaporated under reduced pressure to obtain the product ((3-(bis(fluorosulfonyl)amino)propyl)(methyl)silanediyl)bis((trimethylsilyl)sulfamoyl fluoride) (Compound 4-3).

[0642] 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); 13 C NMR (300MHz, CDCl3): -1.2, 4.1, 17.3, 25.2, 33.3; 19 F NMR (CDCl3): ppm-78.8 (s).

[0643] [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]triazasilane-1-yl]-ethanone (Compound 5-1)

[0644] [Reaction formula 5-1]

[0645]

[0646] 2,2,4,4,6,6-hexamethyl-[1,3,5,2,4,6]triaziridosilane (3.84 g, 17.5 mmol) was reacted with triethylamine (2.0 g, 20 mmol) and trifluoroacetic anhydride (3.7 g, 17.6 mmol) as in reaction formula 1-1 to obtain the product 2,2,2-trifluoro-1-[2,2,4,4,6,6-hexamethyl-3.5-bis-(2,2,2-trifluoro-acetyl)-1-[1,3,5,2,4,4,6,6-hexamethyl-3.5-bis-(2,2,2-trifluoro-acetyl)-1-[1,3,5,2,4,4,6,6-hexamethyl-3.5-bis-(2,2,2-trifluoro-acetyl)-1-[1,3,5,2,4,4,6,6-hexamethyl-

[0647] yl)-[1,3,5,2,4,6]triazasilane-1-yl]-ethanone (Compound 5-1).

[0648] 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).

[0649] [Example 5-2]: Synthesis of 2,2,4,4,6,6-hexamethyl-1,3,5-tris-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilane (Compound 5-2)

[0650] [Reaction formula 5-2]

[0651]

[0652] 2,2,4,4,6,6-hexamethyl-[1,3,5,2,4,6]triazasilane (3.84 g, 17.5 mmol), triethylamine (6.0 g, 60 mmol) and trifluoromethanesulfonic anhydride (15 g, 54 mmol) were reacted by the same method as reaction formula 1-2 to obtain the product 2,2,4,4,6,6-hexamethyl-1,3,5-tris-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilanheterocyclohexane (compound 5-2).

[0653] 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).

[0654] [Example 5-3]: Synthesis of 2,2,4,4,6,6-hexamethyl-1,3,5-tris-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilane (Compound 5-3)

[0655] [Reaction 5-3]

[0656]

[0657] 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 the same manner as in Reaction Formula 1-2 to obtain the product 2,2,4,4,6,6-hexamethyl-1,3,5-tris-trifluoromethanesulfonyl-[1,3,5,2,4,6]triazasilanheterocyclohexane (Compound 5-3).

[0658] 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).

[0659] Example 6. Production of ion conductive film (1)

[0660] The anion receptor compound 1-1 (0.25 g) prepared in Example 1-1 was mixed with ethoxylated bisphenol A dimethacrylate of Chemical Formula 16 (purchased from Aldrich, Mw=1,700, "BIS-15m", 0.25 g), poly(ethylene glycol) dimethyl ether (Mw=350, "PEGDME 300", 0.5 g) and lithium trifluoromethanesulfonyl imide (Li(CF3SO2)2N, 0.7809 g) as a crosslinking agent. Dimethylphenylacetophenone (DMPA, 0.0075 g) was added to the mixture, and the mixture solution was coated on a conductive glass substrate and then exposed to ultraviolet light of 350 nm wavelength for 30 minutes under a nitrogen atmosphere. A solid polymer film was manufactured by the illumination.

[0661] Example 7. Production of ion conductive film (2)

[0662] The anion receptor compound 1-2 (0.25 g) prepared in Example 1-2 and lithium trifluoromethanesulfonyl imide (0.7234 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0663] Example 8. Production of ion conductive film (3)

[0664] The anion receptor compound 1-3 (0.25 g) prepared in Example 1-3 and lithium trifluoromethanesulfonyl imide (0.7499 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenyl acetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0665] Example 9. Production of ion conductive film (4)

[0666] The anion receptor compound 1-4 (0.25 g) prepared in Example 1-4 and lithium trifluoromethanesulfonyl imide (0.6597 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenyl acetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0667] Example 10. Production of ion conductive film (5)

[0668] The anion receptor compound 1-5 (0.25 g) prepared in Example 1-5 and lithium trifluoromethanesulfonyl imide (0.6237 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0669] Example 11. Production of ion conductive film (6)

[0670] The anion receptor compound 1-6 (0.25 g) prepared in Example 1-6 and lithium trifluoromethanesulfonyl imide (0.6109 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0671] Example 12. Production of ion conductive film (7)

[0672] The anion receptor compound 1-7 (0.25 g) prepared in Example 1-7 and lithium trifluoromethanesulfonyl imide (0.6128 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0673] Example 13. Production of ion conductive film (8)

[0674] The anion receptor compound 1-8 (0.25 g) prepared in Example 8 and lithium trifluoromethanesulfonyl imide (0.6134 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0675] Example 14. Production of ion conductive film (9)

[0676] The anion receptor compound 1-9 (0.25 g) prepared in Example 1-9 and lithium trifluoromethanesulfonyl imide (0.6159 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0677] Example 15. Manufacturing of ion conductive film (10)

[0678] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-10 and lithium trifluoromethanesulfonyl imide (0.6143 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0679] Example 16. Production of ion conductive thin film (11)

[0680] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-11 and lithium trifluoromethanesulfonyl imide (0.6142 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0681] Example 17. Manufacturing of ion conductive film (12)

[0682] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-12 and lithium trifluoromethanesulfonyl imide (0.6138 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0683] Example 18. Manufacturing of ion conductive film (13)

[0684] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-13 and lithium trifluoromethanesulfonyl imide (0.6145 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0685] Example 19. Manufacturing of ion conductive film (14)

[0686] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-14 and lithium trifluoromethanesulfonyl imide (0.6189 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0687] Example 20. Manufacturing of ion conductive film (15)

[0688] The anion receptor compound 1-10 (0.25 g) prepared in Example 1-15 and lithium trifluoromethanesulfonyl imide (0.6195 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0689] Example 21. Manufacturing of ion conductive film (16)

[0690] The anion receptor compound 2-1 (0.25 g) prepared in Example 2-1 and lithium trifluoromethanesulfonyl imide (0.4548 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenyl acetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0691] Example 22. Manufacturing of ion conductive film (17)

[0692] The anion receptor compound 2-2 (0.25 g) prepared in Example 2-2 and lithium trifluoromethanesulfonyl imide (0.4846 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0693] Example 23. Manufacturing of ion conductive film (18)

[0694] The anion receptor compound 2-2 (0.25 g) prepared in Example 2-3 and lithium trifluoromethanesulfonyl imide (0.4837 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0695] Example 24. Manufacturing of ion conductive film (19)

[0696] The anion receptor compound 3-1 (0.25 g) prepared in Example 3-1 and lithium trifluoromethanesulfonyl imide (0.4530 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0697] Example 25. Manufacturing ion-conductive film (20)

[0698] The anion receptor compound 3-2 (0.25 g) prepared in Example 3-2 and lithium trifluoromethanesulfonyl imide (0.4877 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0699] Example 26. Manufacturing of ion conductive film (21)

[0700] The anion receptor compound 3-3 (0.25 g) prepared in Example 3-3 and lithium trifluoromethanesulfonyl imide (0.4867 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0701] Example 27. Manufacturing of ion conductive film (22)

[0702] The anion receptor compound 4-1 (0.25 g) prepared in Example 4-1 and lithium trifluoromethanesulfonyl imide (0.4877 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0703] Example 28. Manufacturing of ion conductive film (23)

[0704] The anion receptor compound 4-2 (0.25 g) prepared in Example 4-2 and lithium trifluoromethanesulfonyl imide (0.4879 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0705] Example 29. Manufacturing of ion conductive film (24)

[0706] The anion receptor compound 4-3 (0.25 g) prepared in Example 4-3 and lithium trifluoromethanesulfonyl imide (0.4897 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0707] Example 30. Manufacturing of ion conductive film (25)

[0708] The anion receptor compound 5-1 (0.25 g) prepared in Example 5-1 and lithium trifluoromethanesulfonyl imide (0.4894 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenyl acetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0709] Example 31. Manufacturing of ion-conductive thin film (26)

[0710] The anion receptor compound 5-2 (0.25 g) prepared in Example 5-2 and lithium trifluoromethanesulfonyl imide (0.4889 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenyl acetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0711] Example 32. Manufacturing of ion-conductive thin film (27)

[0712] The anion receptor compound 5-3 (0.25 g) prepared in Example 5-3 and lithium trifluoromethanesulfonyl imide (0.4884 g) were mixed with ethoxylated bisphenol A dimethacrylate, poly(ethylene glycol) dimethyl ether, and dimethylphenylacetophenone of Chemical Formula 16 as a crosslinking agent in the same amounts as in Example 6. A solid polymer film was prepared in the same manner as in Example 6.

[0713] [Table 1]

[0714]

[0715]

[0716] Comparative Example 1. Preparation of a film without anion receptors

[0717] As shown in Table 1, a solid polymer film was produced by the same method as in Example 6 using the composition of the compounds used. As shown in Table 1, the polymer electrolyte of the comparative example did not contain an anion receptor.

[0718] Experimental Examples 1 to 28. Ionic Conductivity Experiment

[0719] The ion conductivity of the solid polymer electrolyte membranes produced in Examples 6 to 32 and Comparative Example 1 was measured. The ion conductivity was measured by the following method.

[0720] The solid polymer electrolyte composition is coated on a strip-type conductive glass substrate or lithium copper foil, then photocured and fully dried, and the AC impedance between the strip-type or sandwich-type electrodes is measured in a nitrogen atmosphere, and the measured value is analyzed with a frequency response analyzer to resolve the complex impedance obtained by the above method.

[0721] The strip electrode is manufactured and used by attaching a masking tape with a width of 0.5-2 mm to the center of a conductive glass (ITO) at intervals of about 0.5-2 mm, and then etching it in an etching solution, followed by cleaning and drying. The ionic conductivity of the manufactured solid polymer electrolyte film was measured at a temperature of 30°C, and the results are shown in Table 2 below.

[0722] [Table 2]

[0723]

[0724]

[0725] From the above results, it can be seen that the solid polymer electrolyte containing anion receptors shows higher ionic conductivity than the solid polymer electrolyte without anion receptors.

[0726] Example 33. Fabrication of a battery using a liquid electrolyte containing an anion receptor

[0727] The anion receptor compound 1-1 (AR-8B, 0.015 g) prepared in Example 1-1 and the anion receptor compound 3-1 (AR-7, 0.015 g) prepared in Example 3-1 were mixed with an organic solvent EC / DMC / EMC (1:1:1, 1M LiPF6) (1.0 g). In a dry room (humidity: within 3%), a polypropylene separator impregnated with the above mixture solution was inserted between the NMC ternary positive electrode and the graphite carbon negative electrode, and vacuum sealed to assemble the battery.

[0728] Comparative Example 2. Fabrication of a battery using a liquid electrolyte without an anion receptor

[0729] The battery was manufactured by assembling a separator impregnated with 1.0 g of an organic solvent EC / DMC / DEC (1:1:1, 1 M LiPF6), an NMC ternary positive electrode, and a graphite carbon negative electrode in the same manner as in Example 33.

[0730] Experimental Example 29: Lithium Cycle Performance Experiment

[0731] The lithium cycle performance and efficiency of the batteries manufactured in Example 33 of the present invention and Comparative Example 2 were measured at room temperature using a charge and discharge test device (Maccor 4000). Charging and discharging were performed at 1C. The battery was charged at 0.6 mA / cm 2 (Charging), 1.5mA / cm 2 The charge and discharge were performed at a constant current density (discharge) between 3.0 V and 4.2 V.

[0732] The capacity retention rates at high temperature (60° C.) related to the elapsed time of batteries manufactured using an electrolyte containing the anion receptor compound 1-1 of the present invention and an electrolyte not containing the anion receptor compound 1-1 of the present invention were compared. Figure 1 As shown. Using anion receptor compound 1-1 ( Figure 1 AR-7) and anion receptor compound 3-1 ( Figure 1 The battery using the electrolyte containing no anion receptor compound (AR-8B) showed significantly higher capacity retention rate than the battery using the electrolyte containing no anion receptor compound (Ref).

[0733] Therefore, the above results show that by using anion receptors, the capacity retention rate at high temperature is high and the internal resistance increase rate is low, thereby extending the battery life and stabilizing it at high temperatures.

[0734] In addition, the present invention provides a battery in which the spent electrolyte in a used battery for electric vehicles (waste battery) is replaced with an electrolyte to which the above-mentioned anion receptor is added so that the battery can be reused.

[0735] Hereinafter, a method for producing a reusable battery by replacing and filling a novel electrolyte including the anion receptor of the present invention will be described.

[0736] The method for manufacturing a reusable battery of the present invention comprises the following steps: preparing waste batteries; removing waste electrolytes and other impurities in the waste batteries; and injecting the novel electrolyte of the present invention into the waste batteries for regeneration.

[0737] The step of removing spent electrolyte and other impurities from spent batteries may be performed in a dry room or in an inert atmosphere.

[0738] Alternatively, the step of removing spent electrolyte and other impurities in spent batteries may be performed under vacuum conditions.

[0739] In the step of injecting new electrolyte into the waste battery for regeneration, a method of injecting the new electrolyte into the waste battery and then vibrating the battery at a certain temperature may be used, and the certain temperature may be 20°C to 50°C.

[0740] If we explain the method of recycling waste batteries in more detail, waste batteries for electric vehicles have a high risk of explosion and fire when they are charged, so after the charged current is completely discharged, it may be necessary to separate the battery pack and separate it into individual battery cells. The charging and discharging capacities of each discharged battery cell can be evaluated using a charger and discharger, and the cells can be graded according to the capacity.

[0741] For example, the battery cells are divided into those with a capacity of 80% or more, 68% to 80%, and 68% or less, and the battery cells with a capacity of 68% or less, which have greatly decreased, are targeted for the regeneration process.

[0742] After the battery cells with reduced capacity are completely discharged, holes are opened in each battery cell in a dry room or inert atmosphere, and the existing electrolyte and the generated gas and impurities are removed by vacuum. Thereafter, an electrolyte containing an additive that can restore performance is injected into the battery cell and the holes are blocked. By shaking the battery cell for a period of time at a certain temperature (25°C to 50°C), the electrolyte is evenly distributed to activate the positive / negative active materials and increase the activity of Li ions, thereby restoring the capacity of the battery.

[0743] Hereinafter, the method for producing a reusable battery using an electrolyte according to the present invention will be described in detail.

[0744] Example 34. Manufacturing a reusable battery

[0745] (1) Prepare waste batteries

[0746] In this embodiment, after disassembling the module in the battery pack running on the electric bus and separating it into unit battery cells, the battery cells classified as less than 12Ah (less than 68% compared to the initial capacity) are discharged to 2.5V at 0.5C based on the discharge capacity. Thereafter, in an inert atmosphere in a dry room or a glove box, holes are punched in the battery cells using a syringe and vacuumed to remove the existing waste electrolyte and the generated gas and impurities before use.

[0747] (2) Reassembling and activating the battery cells

[0748] The novel electrolyte of the present invention is injected by a syringe, and the temperature is maintained at 25 to 30°C after the hole is sealed. After aging treatment by shaking left and right, a current of 0.1C rate (2.1A) is applied, and the battery is charged to 4.2V at a constant current, and then charged at a constant voltage of 4.2V to reach a current value of 0.01C (0.21A).

[0749] Comparative Example 3: Production of Reusable Batteries

[0750] It was prepared in the same manner as in Example 34 except that a non-aqueous electrolyte containing 1 M LiPF6 in a mixed solvent of EC:EMC:DMC in a volume ratio of 3:3:4 was used without additional additives.

[0751] Experimental Example 30. Evaluation of Reusable Batteries

[0752] The constant current discharge capacity of the battery manufactured in Example 34 was evaluated using a charger and discharger in the range of 3.0 to 4.2 V at a current value of 0.1 C (2.1 A). As a result, the discharge capacity recovered from 6.2 Ah to 14.8 Ah.

[0753] On the other hand, the evaluation results of the battery manufactured in Comparative Example 3 showed that although the discharge capacity increased from 6.2 Ah capacity to 10.5 Ah capacity, sufficient capacity was not restored.

[0754] In addition, the present invention provides the following solidified electrolyte, which uses the electrolyte of the present invention to operate a normal lithium-ion battery to a certain temperature (preferably 70°C), and then quickly (within 5 to 10 minutes) hardens and stops the operation of the battery when the temperature reaches above a certain temperature (preferably 130°C) in order to prevent the risk of fire caused by a sharp rise in the battery temperature due to thermal runaway of the battery.

[0755] Next, a method for producing a solid electrolyte including an anion receptor of the present invention will be described.

[0756] For the solidified electrolyte, first, a composition mixed solution for producing the solidified electrolyte of the present invention was prepared by adding an anion receptor, a crosslinking agent, a hardening initiator, and a polymerization inhibitor to an electrolyte solution and stirring, as shown in Table 3 below.

[0757] Hereinafter, an example of manufacturing a solidified electrolyte composition mixed solution and the results of a hardening experiment will be described in detail.

[0758] Comparative Example 4. Preparation of solidified electrolyte

[0759] 0.24 g of the anion receptor compound 1-1 prepared in Example 1 and 6.15 g of triethylene glycol dimethacrylate (purchased from Aldrich, "TEGDA") of Chemical Formula 17 as a crosslinking agent were mixed in 60 g of an electrolyte solution (EC:EMC:DMC=3:3:4, LiPF61 mol / L). 0.01 g of an initiator Luperox TBEC (purchased from Aldrich) was added to the mixture to prepare a cured electrolyte.

[0760] Comparative Example 5. Preparation of solidified electrolyte

[0761] A solidified electrolyte was prepared by mixing 6.06 g of a crosslinking agent (TEGDA) with the anion receptor compound 1-1, an electrolyte solution, and an initiator in the same amounts as in Comparative Example 3.

[0762] Comparative Example 6. Preparation of solidified electrolyte

[0763] A solidified electrolyte was prepared by mixing 6.04 g of a crosslinking agent (TEGDA) with the anion receptor compound 1-1, an electrolyte solution, and an initiator in the same amounts as in Comparative Example 3.

[0764] Comparative Example 7. Preparation of solidified electrolyte

[0765] A solidified electrolyte was prepared by mixing 6.00 g of a crosslinking agent (TEGDA) with the anion receptor compound 1-1, an electrolyte solution, and an initiator in the same amounts as in Comparative Example 3.

[0766] Comparative Example 8. Preparation of solidified electrolyte

[0767] A solidified electrolyte was prepared by mixing 5.40 g of a crosslinking agent (TEGDA) with the anion receptor compound 1-1, an electrolyte solution, and an initiator in the same amounts as in Comparative Example 3.

[0768] Comparative Example 9. Preparation of solidified electrolyte

[0769] A solidified electrolyte was prepared by mixing 4.50 g of a crosslinking agent (TEGDA) with the anion receptor compound 1-1, an electrolyte solution, and an initiator in the same amounts as in Comparative Example 3.

[0770] Comparative Example 10. Preparation of solidified electrolyte

[0771] 0.30 g of the anion receptor compound 1-1 prepared in Example 1 and 8.40 g of triethylene glycol dimethacrylate (purchased from Aldrich, "TEGDA") as a crosslinking agent were mixed in 60 g of an electrolyte solution (EC:EMC:DMC=3:3:4, LiPF61 mol / L). 0.01 g of an initiator Luperox TBEC (purchased from Aldrich) and 1.2 mg of a polymerization inhibitor 4-methoxyphenol were added to the mixture to prepare a solidified electrolyte.

[0772] Example 35. Preparation of solidified electrolyte

[0773] 0.33 g of the anion receptor compound 1-1 prepared in Example 1 and 9.23 g of triethylene glycol dimethacrylate (purchased from Aldrich, "TEGDA") as a crosslinking agent were mixed in 60 g of an electrolyte solution (EC:EMC:DMC=3:3:4, LiPF61 mol / L). 0.01 g of an initiator Luperox TBEC (purchased from Aldrich) and 1.2 mg of a polymerization inhibitor 4-methoxyphenol (purchased from Aldrich) were added to the mixture to prepare a solidified electrolyte.

[0774] [Table 3]

[0775] *Additives = cross-linker + anion receptor

[0776]

[0777]

[0778] Experimental Example 31. Hardening experiment of solidified electrolyte (1)

[0779] The solidified electrolyte solutions prepared in Comparative Examples 4 to 9 were placed in 50 ml round flasks, and then the hardening time at 50° C., 70° C., 90° C., 110° C., and 130° C. in a nitrogen atmosphere was observed and measured with naked eyes.

[0780] The measurement results of Comparative Examples 4 to 9 are shown in Table 4 below.

[0781] [Table 4]

[0782]

[0783] (In the above table, X means unhardened and O means hardened)

[0784] As shown in Table 4, Comparative Examples 4 to 6 all hardened at temperatures between 50°C and 130°C, and therefore could not be used as curing agents. In addition, Comparative Examples 7 to 9 did not harden at temperatures between 50°C and 130°C, indicating that they could not be used as curing agents either.

[0785] As shown in Table 4, hardening occurs only when the total additive content reaches at least 12.33%.

[0786] Experimental Example 32. Hardening experiment of solidified electrolyte (2)

[0787] The hardening times of the solidified electrolyte solutions prepared in Comparative Example 10 and Example 35 were respectively measured in the same manner as in Experimental Example 31.

[0788] The measurement results of Comparative Example 10 and Example 35 are shown in Table 5 below.

[0789] [Table 5]

[0790]

[0791] (In the above table, X means unhardened and O means hardened)

[0792] As shown in Table 5, Example 35 does not harden at a temperature below 70°C, but hardens rapidly within 5 minutes at a high temperature of 130°C, and can therefore be used as a curing agent. In contrast, Comparative Example 10 hardens even at a temperature below 70°C, indicating that it cannot be used as a curing agent.

[0793] As shown in Table 3, in both Example 35 and Comparative Example 10, when 1.2 mg of polymerization inhibitor was added respectively, as shown in Example 35, the total content of the additives must be at least 13.74% to prevent hardening at temperatures below 70°C and thus be used as a curing agent.

[0794] As described above, the liquid electrolyte using the novel anion receptor according to the embodiment as an additive can provide an electrolyte that improves the lithium cycle performance and efficiency, and can therefore be used as an electrolyte additive for high-capacity lithium-ion batteries. In addition, the polymer electrolyte containing the novel anion receptor of the present invention can provide an electrolyte with significantly improved ionic conductivity and electrochemical stability at room temperature, so it can be widely used not only as a polymer electrolyte for small lithium polymer secondary batteries suitable for various electronic devices such as mobile phones, laptop computers and portable video cameras, but also as a polymer electrolyte for large-capacity lithium polymer secondary batteries used in power storage devices for power averaging and electric vehicles. In addition, above a certain temperature (130°C), it hardens rapidly within 5 minutes and stops the battery from operating, thereby providing a solidified electrolyte that prevents the battery from being in danger of fire due to a sharp rise in temperature due to thermal runaway. Recently, fire accidents have frequently occurred in such solidified electrolytes, and it is expected that the demand for not only batteries for electric vehicles that are urgently needed to ensure safety in use, but also power storage devices will also expand significantly.

[0795] As described above, although the embodiments are described with the aid of limited figures, a person with general knowledge in the corresponding technical field can make various technical modifications and variations from the above description. For example, even if the described techniques are performed in a different order from the described method, and / or the described system, structure, device, circuit and other components are combined or combined in a different form from the described method, or are replaced or substituted by other components or equivalents, appropriate results can be achieved.

[0796] Therefore, other implementations, other embodiments, and equivalents to the patent claims are also within the scope of the claims.

[0797] Industrial Application Possibility

[0798] The present invention can not only provide a battery with significantly improved ion conductivity and electrochemical stability by using a novel silazane anion receptor compound and a liquid electrolyte (e.g., a non-aqueous liquid electrolyte), a gel-type or solid electrolyte (e.g., a gel-type polymer electrolyte or a solid polymer electrolyte, a solid sulfide-polymer electrolyte, a solid oxide-polymer electrolyte) containing the compound, but also provide a method for recycling waste batteries and a recycled battery by replacing the electrolyte.

Claims

1. A silazane anion receptor compound, It is characterized in that Selected from the group consisting of the following Chemical Formulas 1 to 5: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] In Chemical Formulas 1 to 5, (a) X is 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, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR' (R and R' are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR 3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR 3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), as well as (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 Selected from 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 electron-withdrawing functional groups, and l is an integer from 0 to 20), (b) Y is selected from as well as (R 2 , R 3 and R 4 are selected from 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 electron-withdrawing functional groups, but R 2 , R 3 and R 4 cannot be hydrogen atoms at the same time, and m and m' are integers from 0 to 20 respectively), (c)R 1 , R 2 and R 3 Selected from 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 electron-withdrawing functional groups, (d) n is an integer from 0 to 20.

2. The silazane anion receptor compound according to claim 1, It is characterized in that Chemical formula 1 is selected from The group formed; Chemical formula 2 free The group formed; Chemical formula 3 selected from The group formed; Chemical formula 4 choose free The group formed; Chemical formula 5 choose from The group composed of.

3. An electrolyte composition, It is characterized in that The invention comprises at least one of the silazane anion receptor compounds represented by Chemical Formula 1 to Chemical Formula 5 of claim 1.

4. The electrolyte composition according to claim 3, It is characterized in that Also included is 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 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, a linear or branched alkynyl group having 2 to 20 carbon atoms, -COR (R is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms), -OR (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -ROR' (R and R' are each a linear or branched alkyl group having 1 to 20 carbon atoms), -SiR 3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), -O-SiR 3 (R is a linear or branched alkyl group having 1 to 20 carbon atoms), as well as (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 Selected from 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 electron-withdrawing functional groups, and l is an integer from 0 to 20), (b) Y is selected from as well as (R 2 , R 3 and R 4 are selected from 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 electron-withdrawing functional groups, but R 2 , R 3 and R 4 cannot be hydrogen atoms at the same time, and m and m' are integers from 0 to 20 respectively), (c) W is 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, a linear or branched alkynyl group having 2 to 20 carbon atoms, (b) Y is selected from as well as (R 2 , R 3 and R 4 are selected from 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 electron-withdrawing functional groups, but R 2 , R 3 and R 4 cannot be hydrogen atoms at the same time, and m and m' are integers from 0 to 20 respectively), (d) R 1 and R 1 'are selected from hydrogen 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 electron-withdrawing functional groups, R 1 and R 1 'Cannot be a hydrogen atom in the same molecule at the same time, (e) n and q are each an integer from 0 to 20, (f) z is an integer from 1 to 20.

5. The electrolyte composition according to claim 4, It is characterized in that include: 0.01 to 40 wt % of one or more silazane 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, It is characterized in that The electrolyte composition forms a liquid, gel-type or solid electrolyte.

7. A solidified electrolyte, It is characterized in that Made from the electrolyte composition of claim 3 or 4.

8. A polymer electrolyte film, It is characterized in that Made from the electrolyte composition of claim 3 or 4.

9. A battery, It is characterized in that Comprising the solidified electrolyte of claim 7.

10. A reusable battery, It is characterized in that Comprising the solidified electrolyte of claim 7.

Images