Additive and crosslinking agent, and non-aqueous liquid electrolyte and gel-type or solid polymer electrolyte containing same

Abstract

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

Description

Additives and crosslinking agents and non-aqueous liquid electrolytes and gel-type or solid polymer electrolytes containing the same

[0001] The present invention relates to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, and more specifically, to a novel additive and a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte containing the same, which improves the electrochemical stability, thermal stability, flame retardancy, and lifespan of an alkali metal battery using an electrolyte to which the same is added, and is composed of a siloxane compound comprising an amine group substituted with an electron-withdrawing functional group, or an isocyanate group, a boronate pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, or a diethyl phosphate group.

[0002] To meet the demand for high-capacity, high-output, and long-life power storage devices as power sources for advanced industries such as robots and UAM (Urban Air Mobility) and to expand the use of eco-friendly electric vehicles in response to global warming and the depletion of fossil fuels, there is a need for such devices. Various studies are being conducted focusing on cathode, anode, separator, and electrolyte materials to improve lithium-ion batteries as power sources for these products. Among the component materials that determine the performance of these power sources, the electrolyte significantly affects not only itself but also the performance of the electrode. If the electrolytes used in conventional lithium-ion batteries are used as is, there is a problem where electrochemical stability rapidly deteriorates due to reactions and degradation between the electrode and the electrolyte during long-term charging and discharging. Furthermore, in the case of electric vehicles or ESS (Energy Storage Systems) equipped with multiple battery packs, the risk of fire caused by ignition resulting from battery damage due to physical damage, overcharging, or over-discharging is emerging as a major social issue. As part of efforts to overcome the problems associated with these electrolytes, research on anion acceptors is underway, and anion acceptors enhance anion stability through Lewis acid-salt interactions. Anion acceptors are compounds containing electron-deficient atoms (nitrogen or boron) that facilitate the movement of anions and lithium cations by coordinating electron-rich anions around them. The first known compounds as anion acceptors are aza-ethers composed of cyclic or linear amides, in which the nitrogen atom of an amine group substituted by a perfluoroalkylsulfonyl substituent is made electron-deficient, allowing it to interact appropriately with electron-rich anions through Coulomb attraction. (J. Electrochem. Soc., 143(1996)3825, 146(2000)9).However, these aza-ethers exhibit limited solubility in polar solvents adopted as typical non-aqueous electrolytes, and it has been found that the electrochemical stability window of the electrolyte with added LiCl salts does not meet the 4.0 V required for commercially available cathode materials, and is unstable in LiPF6 (J. Electrochem. Solid-State Lett., 5(2002) A248). That is, LiPF6 is chemically and thermally unstable and is in equilibrium with solid LiF and gaseous PF5 even at room temperature, and the generation of this gaseous product PF5 further tilts the equilibrium toward the formation of PF5.

[0003] LiF6(s) ↔ LiF(s) + PF5(g)

[0004] In non-aqueous solvents, PF5 tends to initiate a series of reactions, such as ring-opening polymerization or the breaking of ether bonds composed of atoms with non-covalent electron pairs, such as oxygen or nitrogen. As a strong Lewis acid, PF5 attacks electron pairs, and the high electron density of aza-ether causes it to be subjected to immediate attack by PF5. (J. Power Sources, 104(2002)260).

[0005] The object of the present invention is to provide a novel additive or crosslinking agent that improves the electrochemical stability, thermal stability, flame retardancy, and lifespan of an alkali metal battery using an electrolyte to which the same is added, and is composed of a siloxane compound comprising an amine group substituted with an electron-withdrawing functional group, or an isocyanate group, a boronate pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethyl phosphate group, or an oxypyrrolidin-2,5-dione group.

[0006] Another objective of the present invention is to provide a non-aqueous liquid electrolyte, a gel-type or solid polymer electrolyte with one or more of the novel additives or crosslinking agents described above added.

[0007] Another objective of the present invention is to provide an electrochemical cell using an electrolyte to which the novel additive or crosslinking agent described above has been added.

[0008] To achieve the above objective, the present invention provides an additive or crosslinking agent for a non-aqueous liquid electrolyte and a gel-type or solid polymer electrolyte represented by the following chemical formulas 1 to 3, which comprises a siloxane compound comprising an amine group substituted with an electron-withdrawing functional group, or an isocyanate group, a boronic acid pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethyl phosphate group, or an oxypyrrolidin-2,5-dione group.

[0009]

[0010] In the above chemical formula 1,

[0011] R1 is a hydrogen atom or a functional group selected from an isocyanate group, a boronic acid pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethyl phosphate group, and an oxypyrrolidin-2,5-dione group;

[0012] R2 and R3 are each independently electron-withdrawing functional groups selected from hydrogen atoms or -SO2CF3, -SO2CH2F, -SO2CHF2, -CN, -F, -Cl, -COCF3, BF3K and -SO2CN, and R2 and R3 do not simultaneously become hydrogen atoms, and

[0013] R4 is a hydrogen atom or a methyl group;

[0014] n and o are integers from 0 to 1000, and the sum of n and o is not 0.

[0015]

[0016] In the above chemical formula 2,

[0017] R1, R2, R3, R4, n and o are the same as in Chemical Formula 1 above.

[0018] The compounds of the above chemical formulas 1 and 2 can serve as additives in the electrolyte.

[0019]

[0020] In the above chemical formula 3,

[0021] R1, R2, R3, R4, n and o are the same as in Chemical Formula 1 above;

[0022] R5 is -CH2-, or And;

[0023] p is an integer from 0 to 100;

[0024] R6 is a hydrogen atom or a methyl group.

[0025] The compound of Chemical Formula 3 above can serve as an additive or crosslinking agent in the electrolyte.

[0026] The non-aqueous liquid electrolyte and gel-type or solid polymer electrolyte of the present invention contain one or more additives or crosslinking agents composed of siloxane compounds containing amine groups or isocyanate groups, boronate pinacol ester groups, butylate groups, hexanoate groups, heptanoate groups, cyclohexanopropionate groups, diethyl phosphate groups, and oxypyrrolidin-2,5-dione groups substituted with electron-withdrawing functional groups as in Formulas 1 to 3 above.

[0027] Among the functional groups introduced as side branches, amine groups substituted with electron-withdrawing functional groups are used to increase electronegativity and cation mobility by promoting the dissociation of alkali metal salts. That is, as the nitrogen of the amine group becomes electron-deficient due to electron-withdrawing functional groups such as -SO2CF3, -SO2CH2F, -SO2CHF2, -CN, -F, -Cl, -COCF3, BF3K, and -SO2CN, it forms an electrically neutral complex with the anionic species of the alkali metal salt, thereby promoting the dissociation of the alkali metal salt. In addition, since the nitrogen atom, which is substituted with an electron-withdrawing functional group for the hydrogen atom of the amine group, is positioned only at the end of the hydrocarbon chain, it is possible to eliminate electrochemical instability, instability of lithium salts (especially LiPF6), and steric hindrance caused by the presence of a nitrogen atom susceptible to attack in the middle of the complex, as described in Aza-ethers in U.S. Patents No. 5,705,689 and No. 6,120,941. Furthermore, because the center of the nitrogen is more exposed and allows large anions to easily access it, it promotes the dissociation of the lithium salt and increases cation mobility, thereby enabling high ionic conductivity.

[0028] The additive or crosslinking agent represented by the above chemical formulas 1 to 3 according to the present invention can be synthesized by a known method.

[0029] For example, as shown in reaction schemes 1 and 2 below, compounds represented by the following chemical formulas 4 and 5 can be used as starting materials to synthesize a compound represented by the following chemical formula (1) by a hydrosylation reaction with allyl trifluorosulfonamide or allyl isocyanate, allyl boronate pinacol ester, allyl butylate, allyl hexanoate, allyl heptanoate, allyl cyclohexanopropionate, allyl diethyl phosphate, allyl oxypyrrolidin-2,5-dione, etc.

[0030] [Reaction Equation 1]

[0031]

[0032] [Reaction Equation 2]

[0033]

[0034] In the above reaction scheme 2, R1, R2, R3, R4, n, and o are each as defined in the above chemical formula 1.

[0035] [Reaction Equation 3]

[0036]

[0037] In the above reaction formula 3, R1, R2, R3, R4, n, and o are as defined in the above formula 1, and R5, R6, and p are as defined in the above formula 3.

[0038]

[0039] The present invention provides an electrolyte comprising an additive represented by a compound of Formula 1 and Formula 2 and a crosslinking agent represented by a compound of Formula 3, wherein the electrolyte may include a non-aqueous liquid electrolyte, a gel-type polymer electrolyte, and a solid polymer electrolyte.

[0040]

[0041] Specifically, in the present invention,

[0042] (i) an additive of the above chemical formula 1 or 2;

[0043] (ii) non-aqueous solvents; and

[0044] (iii) Provides a non-aqueous liquid electrolyte composed of a material containing alkali metal ions.

[0045] In addition to the present invention,

[0046] (i) an additive of the above chemical formula 1 or 2;

[0047] (ii) polymer support;

[0048] (iii) non-aqueous solvents; and

[0049] (iv) Provides a gel-type polymer electrolyte composed of an alkali metal ion-containing material.

[0050] And in the present invention, also,

[0051] (i) an additive of Formula 1 or Formula 2; or the additive comprising one or more compounds selected from polyalkylene glycol dialkyl ether and non-aqueous solvents;

[0052] (ii) a crosslinking agent of the above formula 3; or a crosslinkable polymer compound comprising a polymer compound selected from network, comb-shaped, and branched polymer compounds;

[0053] (iii) alkali metal ion-containing material; and

[0054] (vi) Provides a solid polymer electrolyte composed of a curing initiator.

[0055] At this time, the non-aqueous solvent used in the above electrolyte may be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolan, 1,3-dioxolan, 1,2-dimethoxyethane, dimethoxymethane, γ-butyrolactone, methyl formate, sulfolane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2-pyrrolidinone, or a mixture thereof;

[0056] The above alkali metal ion-containing material may be LiSO3CF3, LiCOOC2F5, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl, or a mixture thereof.

[0057] In addition, the polymer support used in the gel-type polymer electrolyte is not particularly limited, but a polyacrylonitrile (PAN)-based polymer or a polyvinylidene fluoride (PVDF)-hexafluoropropylene-based polymer may be used.

[0058] In addition, the network, comb-like, or branched polymer compounds used in the above-mentioned solid polymer electrolyte are not particularly limited, but may be composed of flexible inorganic polymers or linear polyethers, and as for the crosslinkable polymer compounds, may be those having a flexible inorganic polymer or linear polyether main chain as a basic framework and having functional groups such as acrylic, epoxy, trimethylsilyl, silanol, vinylmethyl, or divinyl monomethyl introduced at the ends.

[0059] In this case, the flexible inorganic polymer is preferably polysiloxane or polyphosphazene, and the linear polyether is preferably polyalkylene oxide.

[0060] Examples of the above-mentioned crosslinkable polymer compounds include bisphenol A ethoxylate dimethacrylate (Bis-15m) of Formula 7 below or TA-10 of Formula 8 below disclosed in Korean Registered Patent No. 10-0419864:

[0061]

[0062]

[0063] The polyalkylene glycol dialkyl ether or non-aqueous solvent that may be included in the above-mentioned solid polymer electrolyte acts as a plasticizer together with the additive of the present invention,

[0064] Examples of polyalkylene glycol dialkyl ethers include polyethylene glycol dimethyl ether (PEGDME), polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl ether; polypropylene glycol / polyethylene glycol copolymers with dibutyl ether ends; or polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymers with dibutyl ether ends.

[0065] In addition, the curable initiator included in the solid polymer electrolyte can be a photocurable initiator, a thermocurable initiator, or a mixture thereof.

[0066] The above photocurable initiator may use dimethylphenylacetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methyl benzoin ethyl ether, benzoin phenyl ether, α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, anthraquinone, thioxantone, isopropylthioxantone, chlorothioxantone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone, or a mixture thereof, and

[0067] The above-mentioned thermosetting initiator may use an azoisobutylonitrile-based compound, a peroxide-based compound, or a mixture thereof.

[0068] In the electrolyte of the present invention, it is preferable that the additive is contained in an amount of 0.01 to 86.5 parts by weight of the total composition, and the alkali metal ion-containing substance is contained in an amount of 3 to 60 parts by weight.

[0069] In the gel-type polymer electrolyte of the present invention, it is preferable to contain 5 to 40 parts by weight of the polymer support.

[0070] In the solid polymer electrolyte of the present invention, it is preferable to contain 1 to 95 parts by weight of a polymer compound selected from the crosslinking agent of compound 3 and the network, comb, and branched polymer compounds, and 0.01 to 5 parts by weight of a curing initiator.

[0071] In addition, the present invention provides an electrochemical cell containing the additive or crosslinking agent, wherein the cell using the liquid or gel-type polymer electrolyte of the present invention comprises a negative electrode, a positive electrode, and a separator, and the cell using the solid polymer electrolyte of the present invention comprises a negative electrode and a positive electrode.

[0072] The negative electrode and positive electrode used in the battery of the present invention may be manufactured according to the manufacturing method of the negative electrode and positive electrode used in conventional batteries, and the assembly of the battery may also be manufactured by the conventional method of assembling the negative electrode, positive electrode, and electrolyte.

[0073] A secondary battery comprising a gel-type polymer electrolyte containing the additive and crosslinking agent of the present invention is composed of the gel-type polymer electrolyte of the present invention together with a negative electrode, a positive electrode, and a separator used in a secondary battery composed of the non-aqueous liquid electrolyte.

[0074] A secondary battery comprising a solid polymer electrolyte containing the additive and crosslinking agent of the present invention is composed of the solid polymer electrolyte of the present invention, together with a negative electrode and a positive electrode used in a secondary battery composed of the non-aqueous liquid electrolyte.

[0075] In addition, the present invention provides a polymer electrolyte thin film using the electrolyte of the present invention.

[0076] A method for manufacturing a gel-type or solid polymer electrolyte thin film containing the components of the present invention will be described below.

[0077] First, in the case of a gel-type polymer electrolyte, a non-aqueous solvent, an additive of Formula 1 or 2, a crosslinking agent of Formula 3, and an alkali metal ion-containing substance are placed in a container in an appropriate mixing ratio, and the mixture is stirred with a stirrer to prepare a solution, after which a polymer support is added and mixed. When mixing the polymer support, if necessary, a predetermined amount of heat is applied to melt it to create a composition mixture for preparing the gel-type polymer electrolyte thin film of the present invention. The prepared solution is coated to an appropriate thickness onto a support substrate made of glass or polyethylene, or a commercial Mylar film. Then, the coated substrate is dried, exposed to electron beams, ultraviolet rays, or gamma rays, or heated to induce a curing reaction, thereby forming a thin film.

[0078] Next, in the case of a solid polymer electrolyte, first, an additive, polyalkylene glycol dialkyl ether, a non-aqueous solvent, and an alkali metal ion-containing substance are placed in a container in an appropriate mixing ratio, and the mixture is stirred with a stirrer to prepare a solution. Then, the crosslinking agent of the present invention or a network, branched, or comb-shaped polymer compound is added and mixed together. When mixing the network, branched, or comb-shaped polymer compound, a predetermined amount of heat is applied to melt it if necessary. In the case of a crosslinkable polymer compound, a curing initiator is added to this mixture and stirred to create a composition mixture for preparing the solid polymer electrolyte of the present invention. The prepared solution is coated to an appropriate thickness onto a support substrate made of glass or polyethylene, or a commercial Mylar film. Then, the coated substrate is dried, exposed to electron beams, ultraviolet rays, or gamma rays, or heated to induce a curing reaction, thereby forming a thin film.

[0079] Another method for manufacturing a thin film is as follows. A composition mixture is applied onto the support substrate, thickness control spacers are fixed to both ends of the support substrate, and then another support substrate is placed over it. Afterward, a curing reaction is carried out using the curing irradiator or heat source to produce a gel-type or solid polymer electrolyte thin film.

[0080] As described above, the liquid electrolyte using the novel anion acceptor of the present invention as an additive can provide an electrolyte with improved cycling performance and efficiency, and thus can be used as an electrolyte additive for high-capacity lithium-ion batteries. In addition, the polymer electrolyte containing the novel anion acceptor of the present invention can provide an electrolyte with significantly improved ionic conductivity and electrochemical stability at room temperature, and thus can be widely applied as a polymer electrolyte for small lithium polymer secondary batteries used in various electronic devices such as mobile phones, laptop computers, and camcorders, as well as for power storage devices for power leveling and electric vehicles.

[0081] Figure 1 is a graph showing the cycling performance of a liquid electrolyte using an additive according to Experimental Example 2, which is a preferred embodiment of the present invention.

[0082] The present invention will be explained in more detail below through the following examples. The following examples are intended to illustrate the present invention and do not limit the scope of the invention.

[0083] [Example 1]

[0084]

[0085] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, followed by the addition of a Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst, and dropwise addition of allyl isocyanate (4.57 g, 0.055 mol) dissolved in 50 ml of toluene. The mixture was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature. After adding activated carbon, the mixture was stirred and filtered, and then the toluene was evaporated under reduced pressure to obtain the product (C4-4NCO; 2,4,6,8-tetrakis(3-isocyanatopropyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane).

[0086] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.4(m, 8H), 3.47(m, 8H)

[0087] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 19.3, 22.9, 55.2, 122.7

[0088]

[0089] [Example 2]

[0090]

[0091] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.242 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and toluene was evaporated under reduced pressure to obtain the product (C4-4TMDOB; 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3-(4,4,5,5-tetramethyl-1,3,2-dioxaboloran-2-yl)propyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane).

[0092] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.57(m, 8H), 1.02(m, 8H), 1.4(m, 8H), 1.24(m, 48H)

[0093] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 4.7, 16.8, 24.7, 28.6, 88.5

[0094]

[0095] [Example 3]

[0096]

[0097] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylbutylate (7.05 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and then toluene was evaporated under reduced pressure to obtain the product (C4-4TB; (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrabutylate).

[0098] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.90 (s, 12H), 1.02(m, 8H), 1.6(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0099] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 13.5, 15.9, 18.4, 21.8, 36.1, 68.4, 173.1

[0100]

[0101] [Example 4]

[0102]

[0103] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylhexanoate (8.59 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The mixture was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and toluene was evaporated under reduced pressure to obtain the product (C4-4TH; (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrahexanoate).

[0104] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.90 (s, 12H), 1.02(m, 8H), 1.29(m, 8H), 1.31(m, 8H), 1.6(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0105] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 14.1, 15.9, 21.8, 22.4, 31.2, 33.9, 68.4, 173.1

[0106]

[0107] [Example 5]

[0108]

[0109] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylheptanoate (9.36 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (C4-4THP; (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetraheptanoate) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0110] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.88 (s, 12H), 1.02(m, 8H), 1.29(m, 16H), 1.31(m, 8H), 1.60(m, 8H), 1.64(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0111] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 14.1, 15.9, 21.8, 22.7, 25.0, 28.7, 31.5, 68.4, 173.1

[0112]

[0113] [Example 6]

[0114]

[0115] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylcyclohexapropionate (10.80 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and then toluene was evaporated under reduced pressure to obtain the product (C4-4CH; (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrakis(2-cyclohexylacetate)).

[0116] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.60(m, 8H), 2.07(m, 4H), 2.21(m, 8H), 4.13(m, 8H), 149.15(m, 4H), 152.13(m, 8H), 153.14(m, 8H)

[0117] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 15.9, 21.8, 25.5, 26.0, 33.0, 34.6, 68.4, 173.1

[0118]

[0119] [Example 7]

[0120]

[0121] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and 1-(allyloxy)pyrrolidine-2,5-dione (8.53 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and toluene was evaporated under reduced pressure to obtain the product (C4-4OPDO; 1,1',1'',1'''-(((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(oxy))tetrakis(pyrrolidine-2,5-dione)).

[0122] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.5(m, 8H), 2.64(m, 48H), 3.53(m, 8H)

[0123] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 14.1, 21.6, 25.7, 72.1, 169.0

[0124]

[0125] [Example 8]

[0126]

[0127] 2,4,6,8-trimethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allyl diethyl phosphate (10.68 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product octaethyl (C4-4PS; ((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(phosphate)) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0128] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.29(m, 24H), 1.7(m, 8H), 4.04(m, 16H), 4.07(m, 8H)

[0129] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 16.3, 16.6, 21.4, 64.4, 67.0

[0130]

[0131] [Example 9]

[0132]

[0133] 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and N-allyl-2,2,2-trifluoroacetamide (8.42 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (C-4TFAc; N,N',N'',N'''-((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoroacetamide)) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere, cooling to room temperature, adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0134] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.6(m, 8H), 3.42(m, 8H), 8.03(m, 4H)

[0135] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 22.7, 43.2, 116.2, 157.3

[0136]

[0137] [Example 10]

[0138]

[0139] 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (3.0 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide (13.70 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (C4-4(di-TFAc); N,N',N'',N'''-((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere, cooling to room temperature, adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0140] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 1.02(m, 8H), 1.6(m, 8H), 4.40(m, 8H)

[0141] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 22.7, 25.4, 44.9, 115.7, 156.1

[0142]

[0143] [Example 11]

[0144]

[0145] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allyl isocyanate (4.57 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4NCO; 3,5,7,9-tetrakis(3-isocyanatopropyl)-1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0146] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.4(m, 8H), 3.47(m, 8H)

[0147] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 19.3, 22.9, 55.2, 122.7

[0148]

[0149] [Example 12]

[0150]

[0151] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.242 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4TMDOB; 1,1,1,3,5,7,9,11,11,11-decamethyl-3,5,7,9-tetrakis(3-(4,4,5,5-tetramethyl-1,3,2-dioxaboloran-2-yl)propyl)hexasiloxane) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0152] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 0.57(m, 8H), 1.02(m, 8H), 1.4(m, 8H), 1.24(m, 48H)

[0153] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 4.7, 16.8, 24.7, 28.6, 88.5

[0154]

[0155] [Example 13]

[0156]

[0157] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylbutylate (7.05 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and then toluene was evaporated under reduced pressure to obtain the product (C4-4TB; (1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl)tetrabutylate).

[0158] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21 (s, 18H), 0.90(m, 12H), 1.02(m, 8H), 1.6(m, 8H), 1.79(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0159] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 13.5, 15.9, 18.4, 21.8, 36.1, 68.4, 173.1

[0160]

[0161] [Example 14]

[0162]

[0163] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, followed by the addition of a Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst, and dropwise addition of allylhexanoate (8.59 g, 0.055 mol) dissolved in 50 ml of toluene. The mixture was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature; then, activated carbon was added, the mixture was stirred and filtered, and the toluene was evaporated under reduced pressure to obtain the product L4-4TH; (1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl)tetrahexaoate) was obtained.

[0164] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 0.90 (s, 12H), 1.02(m, 8H), 1.29(m, 8H), 1.31(m, 8H), 1.6(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0165] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 14.1, 15.9, 21.8, 22.4, 31.1, 33.9, 68.4, 173.1

[0166]

[0167] [Example 15]

[0168]

[0169] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylheptanoate (9.36 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4THP; (1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl)tetraheptanoate) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0170] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 0.88 (s, 12H), 1.02(m, 8H), 1.29(m, 16H), 1.31(m, 8H), 1.60(m, 8H), 1.64(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0171] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 14.1, 15.9, 21.8, 22.7, 25.0, 28.7, 31.5, 33.9, 68.4, 173.1

[0172]

[0173] [Example 16]

[0174]

[0175] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allylcyclohexapropionate (10.80 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4CH; (1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl)tetrakis(3-cyclohexylpropionate)) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0176] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.27(m, 8H), 1.43(m, 12H), 1.47(m, 4H), 1.52(m, 8H), 1.53(m, 8H), 1.60(m, 8H), 1.64(m, 8H), 2.32(m, 8H), 4.13(m, 8H)

[0177] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 15.9, 21.8, 25.8, 26.0, 33.3, 34.6, 68.4, 173.1

[0178]

[0179] [Example 17]

[0180]

[0181] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and 1-(allyloxy)pyrrolidine-2,5-dione (8.533 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4OPDO; 1,1',1'',1''-(((1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(oxy))tetrakis(pyrrolidine-2,5-dione)) was obtained by refluxing at 110 °C for 8 hours under a nitrogen atmosphere and cooling to room temperature, then adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0182] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.5(m, 8H), 2.64(m, 16H), 3.53(m, 8H)

[0183] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 14.1, 21.6, 25.7, 72.1, 169.0

[0184]

[0185] [Example 18]

[0186]

[0187] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and allyl diethyl phosphate (10.68 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere and cooled to room temperature, then activated carbon was added, stirred, filtered, and then toluene was evaporated under reduced pressure to obtain the product (L4-4PS; (1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl)octaethyltetrakis(phosphate)).

[0188] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.29(m, 24H), 1.7(m, 8H), 4.04(m, 16H), 4.07(m, 8H)

[0189] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 16.3, 16.6, 21.4, 64.4, 67.0

[0190]

[0191] [Example 19]

[0192]

[0193] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and N-allyl-2,2,2-trifluoroacetamide (8.42 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product (L4-4TFAc; N,N',N'',N'''-((1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoroacetamide)) was obtained by refluxing at 110°C for 8 hours under a nitrogen atmosphere, cooling to room temperature, adding activated carbon, stirring, filtering, and then evaporating toluene under reduced pressure.

[0194] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.6(m, 8H), 3.42(m, 8H), 8.03(m, 4H)

[0195] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 22.7, 28.1, 43.2, 116.2, 157.3

[0196]

[0197] [Example 20]

[0198]

[0199] 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane (5.04 g, 0.0125 mol) was dissolved in 50 ml of toluene, then Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt(0)) catalyst was added, and N-allyl-2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide (13.70 g, 0.055 mol) dissolved in 50 ml of toluene was added dropwise. The product was refluxed at 110 °C for 8 hours under a nitrogen atmosphere, cooled to room temperature, then activated carbon was added and stirred and filtered, and then toluene was evaporated under reduced pressure to obtain the product (L4-4(di-TFAc); N,N',N'',N'''-((1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane-3,5,7,9-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide)).

[0200] 1 H NMR (300 MHz, CDCl3): ppm 0.14(s, 12H), 0.21(m, 18H), 1.02(m, 8H), 1.6(m, 8H), 4.40(m, 8H)

[0201] 13 C NMR (300 MHz, CDCl3): ppm 4.5, 5.8, 22.7, 25.4, 44.9, 115.7, 156.1

[0202]

[0203] [Preparation Example 1]

[0204]

[0205] (Step : 1)

[0206] 1,1,3,3-tetramethyldisiloxane (D2) (3.0 g) was dissolved in 50 ml of toluene in a 3-neck flask, Pt (0) catalyst was added, and 3-(allyloxy)propane-1,2-diol (7.1 g) dissolved in 50 ml of toluene was added dropwise. The mixture was refluxed at 110 °C for 12 hours under a nitrogen atmosphere, cooled to room temperature, then activated carbon was added and stirred, filtered, and then evaporated under reduced pressure to obtain 3,3'-(((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(oxy))bis(propane-1,2-diol).

[0207] 1 H-NMR (300 MHz, CDCl3): ppm 0.21(m, 12H), 1.02(m, 4H), 1.5(m, 4H), 3.37(m, 4H), 3.40~3.65(m, 4H), 3.58(m, 2H), 3.63(m, 2H), 3.65(m, 2H)

[0208] 13 C-NMR (300 MHz, CDCl3): ppm 6.2, 20.2, 20.7, 63.8, 70.7, 72.8, 73.8

[0209] (Step: 2)

[0210] In a three-necked flask, the above 3,3'-(((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(oxy))bis(propane-1,2-diol) (20.0 g) and triethylamine (20.74 g) were dissolved in 100 ml of THF, and then methacryloyl chloride (21.2 g) dissolved in 100 ml of THF was added dropwise while stirring at 0 °C. After reacting for about 2 hours, the precipitate was filtered out and distilled under reduced pressure. The yellow, viscous liquid product was dissolved in chloroform and extracted several times with water. The chloroform layer was separated, dried with MgSO4, and then evaporated under reduced pressure to obtain D2-1,3-di(propoxy-6,7-propane dimethacrylate) (TaD2).

[0211] 1H-NMR (300 MHz, CDCl3): ppm 0.21(m, 12H), 1.02(m, 4H), 1.5(m, 4H), 2.01(m, 12H), 3.37(s, 4H), 3.48~3.73(m, 4H), 4.51~4.26(m, 4H), 4.88(m, 2H), 6.40(m, 12H), 6.48(m, 12H)

[0212] 13 C-NMR (300 MHz, CDCl3): ppm 6.2, 17.9, 20.2, 20.7, 62.5, 71.2, 73.5, 125.2, 136.0, 167.

[0213]

[0214] [Example 21]

[0215]

[0216] 5.73 g of 2,4,6,8-tetrakis(3-isocyanatopropyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane from Example 1 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) from Preparation Example 1 were placed in a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of a saturated aqueous solution of Na2SO4, and then washed with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4NCO was obtained by vacuum evaporation.

[0217] 1H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.4(m, 8H), 1.5(m, 4H), 2.01(m, 12H), 3.48(m, 2H), 3.73(m, 2H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0218] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 17.9, 19.3, 20.2, 20.7, 22.9, 55.2, 62.5, 70.6, 71.2, 125.2, 136.0, 167.2

[0219]

[0220] [Example 22]

[0221]

[0222] 9.12 g of 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (9.12 g) from Example 2 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) from Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of saturated aqueous Na2SO4 solution, and then washed with a 5 wt% aqueous Na2CO3 solution until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4TMDOB was obtained by vacuum evaporation.

[0223] 1H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 0.57(m, 8H), 1.02(m, 12H), 1.24(m, 48H), 1.5(m, 4H), 2.01(m, 12H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0224] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 4.7, 5.3, 6.2, 14.3, 16.5, 16.8, 17.9, 20.7, 24.6, 28.6, 62.5, 69.6, 70.6, 71.2, 73.5, 88.2, 88.5, 125.2, 136.0, 167.2

[0225]

[0226] [Example 23]

[0227]

[0228] 7.53 g of 2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrabutylate of Example 3 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) of Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of a saturated aqueous solution of Na2SO4, and then washed with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4TB was obtained by vacuum evaporation.

[0229] 1H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 0.90(m, 12H), 1.02(m, 12H), 1.5(m, 4H), 1.6(m, 8H), 1.79(m, 8H), 2.01(m, 12H), 2.32(m, 8H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.13(m, 8H), 4.26(m, 2H), 4.51(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0230] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 13.5, 15.9, 17.9, 18.4, 21.8, 36.1, 62.5, 68.4, 70.6, 125.2, 136.0, 167.2, 173.1

[0231]

[0232] [Example 24]

[0233]

[0234] 8.65 g of (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrahexanoate from Example 4 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) from Preparation Example 1 were placed in a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of saturated aqueous Na2SO4 solution, and then washed with a 5 wt% aqueous Na2CO3 solution until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4TH was obtained by vacuum evaporation.

[0235] 1H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 0.90(m, 12H), 1.02(m, 12H), 1.29(m, 8H), 1.31(m, 8H), 1.5(m, 4H), 1.6(m, 8H), 1.64(m, 8H), 2.01(m, 12H), 2.32(m, 8H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.13(m, 8H), 4.26(m, 2H), 4.51(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0236] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 14.1, 15.9, 17.9, 20.2, 20.7, 21.8, 31.1, 31.2, 33.9, 62.5, 68.4, 70.6, 125.2, 136.0, 167.2, 173.1

[0237]

[0238] [Example 25]

[0239]

[0240] 9.21 g of (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetraheptanoate from Example 5 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) from Preparation Example 1 were placed in a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of a saturated aqueous solution of Na2SO4, and then washed with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4THP was obtained by vacuum evaporation.

[0241] 1 H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 0.88(m, 12H), 1.02(m, 12H), 1.29(m, 8H), 1.31(m, 8H), 1.5(m, 4H), 1.6(m, 8H), 1.64(m, 8H), 2.01(m, 12H), 2.32(m, 8H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.13(m, 8H), 4.26(m, 2H), 4.51(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0242] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 14.1, 15.9, 17.9, 20.2, 20.7, 21.8, 25.0, 33.9, 62.5, 68.4, 70.6, 125.2, 136.0, 167.2, 173.1

[0243]

[0244] [Example 26]

[0245]

[0246] 9.70 g of (2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl)tetrakis(2-cyclohexanoate) from Example 6 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) from Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of a saturated aqueous solution of Na2SO4, and then washed with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4CH was obtained by vacuum evaporation.

[0247] 1 H-NMR (300 MHz, CDCl3) : ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.27(m, 4H), 1.43(m, 8H), 1.49(m, 4H), 1.5(m, 4H), 1.53(m, 8H), 1.6(m, 8H), 2.01(m, 12H), 2.07(m, 4H), 2.21(m, 8H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.13(m, 8H), 4.26(m, 2H), 4.51(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0248] 13 C-NMR(300 MHz, CDCl3) : ppm 4.5, 6.2, 15.9, 17.9, 20.2, 20.7, 21.8, 25.5, 26.0, 33.0, 34.6, 39.4, 62.5, 68.4, 70.6, 71.2, 73.5, 125.2, 136.0, 167.2, 173.1

[0249]

[0250] [실시예 27]

[0251]

[0252] 1,1',1'',1'''-(((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(oxy))tetrakis(pyrrolidine-2,5-dione) (8.61 g) of Example 7 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) of Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added and the mixture was stirred for 1 hour. 150 ml of chloroform and 90 ml of saturated aqueous Na2SO4 were added to the reaction product, and then neutralized with a 5 wt% aqueous Na2CO3 solution until neutralized. MgSO4 was added to the neutralized reaction product and stirred, after which the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4OPDO was obtained by vacuum evaporation.

[0253] 1 H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.5(m, 12H), 2.64(m, 16H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0254] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 14.1, 17.9, 20.2, 20.7, 70.6, 71.2, 72.1, 73.5, 125.2, 136.0, 167.2

[0255]

[0256] [Example 28]

[0257]

[0258] 10.17 g of octaethyl ((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(phosphate)) of Example 8 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) of Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added, and the mixture was stirred for 1 hour. The reaction product was then mixed with 150 ml of chloroform and 90 ml of saturated aqueous solution of Na2SO4, and then washed with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction mixture and stirred, then the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4PS was obtained by vacuum evaporation.

[0259] 1 H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.29(m, 24H), 1.5(m, 4H), 1.7(m, 8H), 2.01(m, 12H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.04(m, 16H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0260] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 16.3, 16.6, 17.9, 20.2, 20.7, 21.4, 64.4, 70.6, 71.2, 73.5, 125.2, 136.0, 167.2

[0261]

[0262] [Example 29]

[0263]

[0264] 8.53 g of N,N',N'',N'''-((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoroacetamide) of Example 9 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) of Preparation Example 1 were added to a 3-neck flask, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added and the mixture was stirred for 1 hour. 150 ml of chloroform and 90 ml of saturated aqueous Na2SO4 were added to the reaction product, and then neutralized with a 5 wt% aqueous Na2CO3 solution until neutralized. MgSO4 was added to the neutralized reaction product and stirred, after which the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4TFAc was obtained by vacuum evaporation.

[0265] 1 H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.5(m, 4H), 1.6(m, 8H), 2.01(m, 12H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H), 8.03(m, 4H)

[0266] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 17.9, 20.2, 20.7, 22.7, 28.1, 43.2, 62.5, 70.6, 71.2, 116.2, 125.2, 136.0, 157.3, 167.2

[0267]

[0268] [Example 30]

[0269]

[0270] In a 3-neck flask, 12.37 g of N,N',N'',N'''-((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilicane-2,4,6,8-tetrayl)tetrakis(propane-3,1-diyl))tetrakis(2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide) of Example 10 and 6.71 g of D2-1,3-di(propoxy-6,7-propanedimethacrylate) of Preparation Example 1 were added, 0.1 ml of fuming sulfuric acid was added dropwise, and the mixture was stirred at 30–35 °C for 6 hours. 0.1 ml of distilled water was added and the mixture was stirred for 1 hour. 150 ml of chloroform and 90 ml of saturated aqueous solution of Na2SO4 were added to the reaction product, and then neutralized with a 5 wt% aqueous solution of Na2CO3 until neutralized. MgSO4 was added to the neutralized reaction product and stirred, after which the precipitate was filtered through filter paper, 100 ppm of hydroquinone was added as a polymerization inhibitor, and Ta-4(di-TFAc) was obtained by vacuum evaporation.

[0271] 1 H-NMR (300 MHz, CDCl3): ppm 0.14(m, 12H), 0.21(m, 12H), 1.02(m, 12H), 1.5(m, 4H), 1.6(m, 8H), 2.01(m, 12H), 3.37(m, 4H), 3.48(m, 2H), 3.73(m, 2H), 4.26(m, 2H), 4.51(m, 2H), 4.88(m, 2H), 6.40(m, 4H), 6.48(m, 4H)

[0272] 13 C-NMR (300 MHz, CDCl3): ppm 4.5, 6.2, 17.9, 20.2, 20.7, 22.7, 25.4, 44.9, 62.5, 70.6, 71.2, 115.7, 125.2, 136.0, 156.1, 167.2

[0273] [Preparation Example 2]

[0274] <Conductive Thin Film Fabrication 1>

[0275] 3.0 g of the additive C4-4NCO prepared in Example 1 was mixed with the crosslinking agent Ta-4NCO (2 g), poly(ethylene glycol) dimethyl ether (Mw=300, "PEGDME 300", 5 g), and dimethylphenyl acetophenone (DMPA, 0.06 g) prepared in Example 21. Lithium trifluoromethanesulfonimide (Li(CF3SO2)2N, 2.40 g) was added to this mixture, the mixture solution was applied to a conductive glass substrate, and then exposed to ultraviolet light with a wavelength of 350 nm for 30 minutes under a nitrogen atmosphere. A solid polymer electrolyte was prepared by this light irradiation. In addition, a solid polymer electrolyte was prepared in the same manner using the additive C4-4NCO prepared in Example 1 and the additive L4-4NCO prepared in Example 11 (1.5 g each).

[0276]

[0277] [Experimental Example 1]: Ionic conductivity

[0278] (1) Ion conductivity experiment according to additive usage

[0279] Using the additive C4-4NCO prepared in Example 1 according to the present invention, a solid polymer electrolyte thin film was prepared to have the compositions shown in Tables 1 and 2 below, and its ionic conductivity was measured. The ionic conductivity was measured by the following method. The solid polymer electrolyte composition was applied onto a band-type conductive glass substrate or lithium-copper foil, photocured, and sufficiently dried. Then, the AC impedance between the band-type or sandwich-type electrodes was measured under a nitrogen atmosphere, and the complex impedance was determined by analyzing the measured values ​​using a frequency response analyzer. The band-type electrode was prepared and used by attaching a masking tape with a width of 0.5-2 mm to the center of the conductive glass (ITO) at intervals of approximately 0.5-2 mm, immersing it in an etching solution to etch it, and then washing and drying it. The results of measuring the ionic conductivity of the prepared solid polymer electrolyte thin film at room temperature (30 ℃) are shown in Tables 1 and 2. From the following results, it was confirmed that the ionic conductivity improves as the concentration of the additive of the present invention increases.

[0280] Ta-4NCOC4-4NCOLi(CF3SO2)2NDMPAσ (S / cm)1.000 g0.112 g0.520 g0.030 g7.45ⅹ10 -5 1.000 g0.430 g0.556 g0.030 g2.54ⅹ10 -4

[0281] Ta-4NCOC4-4NCO / L4-4NCOLi(CF3SO2)2NDMPAσ (S / cm)1.000 g0.056 / 0.056 g0.515 g0.030 g9.62ⅹ10 -5 1.000 g0.215 / 0.215 g0.541 g0.030 g2.73ⅹ10 -4

[0282]

[0283] (2) Ionic conductivity of an additive containing a plasticizer (PEGDMe300)

[0284] Solid polymer electrolyte thin films were prepared using the additive and plasticizer according to the present invention to have the compositions shown in Tables 3 and 4 below, and their ionic conductivity was measured. In this experiment, the conditions under which the ionic conductivity is maximized while the film is formed were investigated by using the additive together with the plasticizer. As a result, when the additive of Example 11 was mixed and used, superior ionic conductivity was observed compared to when the additive of Example 1 according to the present invention was used alone.

[0285]

[0286] Ta-4NCOPEGDMe 300C4-4NCOLi(CF3SO2)2NDMPAσ (S / cm)1.000 g2.500 g1.500 g2.110 g0.030 g7.45ⅹ10 -4

[0287] Ta-4NCOPEGDMe 300C4-4NCO / L4-4NCOLi(CF3SO2)2NDMPAσ (S / cm)1.000 g2.500 g0.750 g / 0.750 g2.085 g0.030 g1.78ⅹ10 -3

[0288]

[0289] (3) Ionic conductivity according to the type of additive

[0290] Solid polymer electrolyte thin films were prepared using the additives of Examples 2 to 10 and 12 to 20 according to the present invention in the same manner as in Preparation Example 2, and the ionic conductivity was measured in the same manner as in Experimental Example 1. The results are shown in Table 5 below. As shown in Table 5 below, the solid polymer electrolyte prepared with the additives according to the present invention also exhibited excellent ionic conductivity.

[0291] Additives (Content: 1.5 g) Ta-4 NCOPEG DMe 300 Li (CF3 SO2) 2 ND MPAσ (S / ㎝) C4-4 TM DOB 1.000 g 2.500 g 2.278 g 0.030 g 2.12 × 10 -4 C4-4TB1.738 g1.62×10 -4C4-4TH2.117 g1.98×10 -4 C4-4THP2.307 g2.16×10 -4 C4-4CH2.662 g2.48×10 -4 C4-4OPDO2.103 g1.95×10 -4 C4-4PS2.632 g2.45×10 -4 C4-4TFAc 2.075 g 1.93 × 10⁻⁶ -4 C4-4(di-TFAc)3.377 g 3.14 × 10⁻⁶ -4 L4-4TMDOB3.141 g2.93×10 -4 L4-4TB2.471 g2.30x10 -4 L4-4TH2.944 g2.74×10 -4 L4-4THP3.176 g2.96×10 -4 L4-4CH3.602 g3.35×10 -4 L4-4OPDO2.927 g2.72×10 -4 L4-4PS3.567 g3.32×10 -4 L4-4TFAc2.893 g2.69 × 10⁻⁶ -4 L4-4(di-TFAc)4.436 g 4.12 × 10⁻⁶ -4

[0292]

[0293] Comparative Example 1. Ionic conductivity of a solid polymer electrolyte without additives

[0294] A solid polymer electrolyte thin film was prepared without additives and had the composition as shown in Table 6 below, and its ionic conductivity was measured. The ionic conductivity was measured using the same method as in Test Example 1.

[0295] Table 6 shows the results of measuring the ionic conductivity of the manufactured solid polymer electrolyte thin film at room temperature (30 ℃).

[0296] Crosslinking agent Li(CF3SO2)2NDMPAσ (S / ㎝)Bis-15 mTa-41.000 g-0.507 g0.030 g4.62×10 -6 -1.000 g0.151 g0.030 g7.93ⅹ10 -6

[0297]

[0298] Example 31. Cell manufacturing using a liquid electrolyte containing the additive of the present invention

[0299] The additive C4-4NCO (0.005 g) prepared in Example 1 was mixed with the organic solvent EC / DMC / EMC (1:1:1, 1M LiPF6) (1.0 g). A cell was assembled in a dry room (humidity: 3% or less) by vacuum sealing a polypropylene separator impregnated with the above mixture solution between a LiCoO2 anode and a graphite carbon cathode. The LiCoO2 anode was prepared by coating a mixture of 94 wt.% LiCoO2 (Nippon Chemical Industry), 3 wt.% acetylene black, and 3 wt.% polyvinylidene fluoride (PVDF) onto aluminum foil.

[0300]

[0301] Comparative Example 2. Cell fabrication using a liquid electrolyte containing commercial additives

[0302] A cell was prepared by assembling a separator impregnated with 0.01 g of commercial additive VC mixed in organic solvent EC / DMC / DEC (1:1:1, 1M LiPF6), a LiCoO2 anode, and a graphite carbon cathode in the same manner as in Example 31.

[0303] Experimental Example 2. Lithium Cycling Performance and Efficiency Experiment

[0304] The lithium cycling performance and efficiency of the cells prepared in Example 31 and Comparative Example 2 of the present invention were measured at room temperature using a charge-discharge test apparatus (Maccor 4000). Charging and discharging were performed at 0.2, 0.5, and 1 C. The cell showed 0.6 mA / cm² with respect to the LiCoO2 counter electrode. 2 (Charging), 1.5 mA / cm 2 It was charged and discharged between 3.0 V and 4.2 V with a constant current density of (discharge).

[0305] Figure 1 shows a comparison of the discharge capacity at 60°C with respect to the number of cycles of cells manufactured using an electrolyte containing the additive C4-4NCO of the present invention and an electrolyte containing the commercial additive VC. The cell using the electrolyte containing the anion acceptor C4-4NCO exhibits not only a higher capacity but also superior stability compared to the cell using the electrolyte containing the commercial additive VC.

Claims

1. A compound represented by any one of the following chemical formulas 1 to 3: [Chemical Formula 1] In the above chemical formula 1, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethylphosphate group, and an oxypyrrolidin-2,5-dione group; R2 and R3 are hydrogen atoms or -COCF3, where either R2 or R3 is a hydrogen atom, and R4 is a methyl group; n is an integer from 1 to 1000, o is 0, and the sum of n and o is not 0, and the compound of the above chemical formula 1 can act as an additive in an electrolyte. [Chemical Formula 2] In the above chemical formula 2, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethylphosphate group, and an oxypyrrolidin-2,5-dione group; R2 and R3 are hydrogen atoms or -COCF3, where either R2 or R3 is a hydrogen atom, and R4 is a methyl group; n is an integer from 1 to 1000, o is 0, and the sum of n and o is not 0, and the compound of Chemical Formula 2 above can act as an additive in an electrolyte. [Chemical Formula 3] In the above chemical formula 3, R1 is a hydrogen atom or a functional group selected from an isocyanate group, a boronic acid pinacol ester group, a butylate group, a hexanoate group, a heptanoate group, a cyclohexanopropionate group, a diethyl phosphate group, and an oxypyrrolidin-2,5-dione group; R2 and R3 are each independently electron-withdrawing functional groups selected from hydrogen atoms or -SO2CF3, -SO2CH2F, -SO2CHF2, -CN, -F, -Cl, -COCF3, BF3K and -SO2CN, and R2 and R3 do not simultaneously become hydrogen atoms, and R4 is a hydrogen atom or a methyl group; n and o are integers from 0 to 1000, respectively, and the sum of n and o is not 0; R5 is -CH2-, or And; p is an integer from 0 to 100; R6 is a hydrogen atom or a methyl group, and the compound of Chemical Formula 3 can act as an additive or crosslinking agent in the electrolyte.

2. In Paragraph 1, The compound represented by the above chemical formula 1 is any one selected from C4-4NCO; C4-4TB; C4-4TH; C4-4THP; C4-4CH; C4-4OPDO; and C4-4PS; The compound represented by the above chemical formula 2 is any one selected from L4-4NCO; L4-4TB; L4-4TH; L4-4THP; L4-4CH; L4-4OPDO; L4-4PS; A compound represented by the above chemical formula 3 is characterized by being selected from Ta-4NCO; Ta-4TMDOB; Ta-4TB; Ta-4TH; Ta-4THP; Ta-4CH; Ta-4OPDO; Ta-4PS; Ta-4TFAc; and Ta-4(di-TFAc).

3. An electrolyte comprising a compound represented by any one of the chemical formulas 1 to 3 of claim 1.

4. In Paragraph 3, The above electrolyte is characterized by being selected from the group consisting of non-aqueous liquid electrolytes, gel-type polymer electrolytes, and solid polymer electrolytes.

5. (i) A compound represented by any one of the chemical formulas 1 to 3 of claim 1 as an additive; (ii) non-aqueous solvents; and (iii) A non-aqueous liquid electrolyte characterized by containing an alkali metal ion-containing substance.

6. (i) A compound represented by any one of the chemical formulas 1 to 3 of claim 1 as an additive; (ii) polymer support; (iii) non-aqueous solvents; and (iv) A gel-type polymer electrolyte characterized by containing an alkali metal ion-containing substance.

7. (i) a compound represented by any one of the chemical formulas 1 to 3 of claim 1 as an additive; or the compound of claim 1 as an additive comprising one or more compounds selected from polyalkylene glycol dialkyl ether and non-aqueous solvents; (ii) a polymer compound selected from network, comb-shaped, and branched polymer compounds or a crosslinkable polymer compound; (iii) A solid polymer electrolyte characterized by containing an alkali metal ion-containing substance.

8. An electrochemical cell comprising a cathode, an anode, and an electrolyte of claim 3.

9. An electrochemical cell manufactured using the non-aqueous liquid electrolyte of claim 5.

10. A gel-type polymer battery manufactured using the gel-type polymer electrolyte of claim 6.

11. A solid polymer battery manufactured using the solid polymer electrolyte of claim 7.

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