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WO2006129991A1 - Anion receptor and electrolyte using the same - Google Patents

Anion receptor and electrolyte using the same Download PDF

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Publication number
WO2006129991A1
WO2006129991A1 PCT/KR2006/002161 KR2006002161W WO2006129991A1 WO 2006129991 A1 WO2006129991 A1 WO 2006129991A1 KR 2006002161 W KR2006002161 W KR 2006002161W WO 2006129991 A1 WO2006129991 A1 WO 2006129991A1
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tegmp
pegmpc
tegmpc
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tfsa
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PCT/KR2006/002161
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French (fr)
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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Publication of WO2006129991A1 publication Critical patent/WO2006129991A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a novel anion receptor, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which is added to enhance ionic conductivity and cation transference number of electrolytes, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the anion receptors.
  • a novel anion receptor which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side
  • Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base.
  • These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li + ) by coordinating electron- rich anions around to interfere with forming ion pairs between the anions and the lithium cations.
  • the first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 146 (2000) 9).
  • aza-ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of anode materials.
  • aza-ethers are unstable to LiPF 6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, chemically and thermally unstable LiPF 6 is in equilibrium with solid LiF and PF 5 gas even at room temperature, and production of PF 5 gas makes the equilibrium moved towards generating PF 5 gas.
  • LiPF 6 (s) ⁇ ⁇ LiF (S) + PF 5 (g)
  • PF 5 has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electrons, e.g., oxygen or nitrogen. Meanwhile, PF 5 , a relatively strong Lewis acid, is known to attack electron pairs. Due to high electron density, aza-ethers are promptly attached by PF 5 (J. Power Sources, 104 (2002) 260). This is a major drawback to commercialize aza-ether compounds. To resolve this problem, McBreen et al. synthesized an anion receptor comprising boron as an electron deficient atom substituted by an electron withdrawing group using the same means (J. Electrochem.
  • solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances.
  • a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M.
  • a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor.
  • a solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10 ⁇ 8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted.
  • Li order to increase motility of molecular chains the crystalline area existing in the polymer structure should be minimized while the amorphous area therein should be expanded.
  • a research to achieve such has been and is under way by using a siloxane having a flexible molecular chain (Marcromol. Chem. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6845) as a main chain, or by introducing PAO having a relatively short molecular length as a side branch (Electrochem. Acta, 34 (1989) 635).
  • net-shaped solid polymer electrolytes are prepared by introducing at least one crosslmkable functional group to the PAO as a terminal group.
  • ionic conductivity of such electrolytes at room temperature is as low as 10 "5 ⁇ 10 "4 S/cm which is not suitable for use in lithium batteries operating at room temperature conditions, so continuous researches have been made to improve the ionic conductivity.
  • This problem was resolved by Abraham et al. who introduced polyethylene oxide with low molecular weight into a vinylidenhexafluoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978).
  • the CF 3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF 3 .
  • a C-O-C- functional group is formed and the main chain of the polymer therein is cut off.
  • CH 3 produced by chain scission together with the CF 3 radical attack the chain or break a C-O bond.
  • a Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated.
  • an object of the present invention to provide a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which enhances ionic conductivity and cation transference number of electrolytes containing it, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes.
  • R 1 and R 2 independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting Of -SO 2 CF 3 , -CN, -F, -Cl, -COCF 3 and -SO 2 CN, but do not both simultaneously represent a hydrogen atom;
  • R 3 represents a hydrogen atom or a cyano group
  • R 5 and R 6 independently represents a hydrogen atom or a methyl group
  • R 7 and the other R 7 in the formula each independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxyl group
  • Y and Z independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, and q are integers from O to 1000, respectively; and r and s are integers from 0 to 20, respectively, whose sum is at least 1.
  • the compound of the Formula 1 functions as an anion receptor in an electrolyte and preferred examples of the compound include C 4 -4TFSA; C 4 -4TFSI; C 4 -2TFSA-2TEGMP; C 4 -2TFSA-2PEGMP; Q-2TFSA-2TEGMPC; C 4 -2TFSA-2PEGMPC; C 4 -2TFSA-2CN; C 4 -2TFSA-2CPP; C 4 -2TFSA-TEGMP-CPP; C 4 -2TFSA-PEGMP-CPP; C 4 -2TFSA- TEGMPC-CPP; C 4 -2TFSA-PEGMPC-CPP; C 4 -2TFSA-CN-CPP; C 4 -2TFSA-TEGMP-CN; C 4 -2TFSA-PEGMP-CN; Q-2TFSA-TEGMPC-CN; C 4 -2TFSA-PEGMP-CN; C 4 -2TFSA- TEGMP-PEGMPC; C 4 -2TFS A-PEGMP-PEGMPC; C 4
  • TFSA-DFA-TFAC-PEGMPC C 4 -TFSA-DFA-TFAC-CN; C 4 -TFSA-DFA-TFAC-CPP;
  • TFSA-DCN-DCA-CPP C 4 -TFSA-DFA-DCA-TEGMP; C 4 -TFSA-DFA-DCA-PEGMP;
  • DCN-DCA-TFAC DCN-DCA-TFAC; C 4 -TFSA-DFA-DCA-TFAC; C 4 -TFSA-DCN-DFA-DCA or C 4 -DCN-
  • the nonaqueous liquid electrolyte and a gel or solid polymer electrolyte of the present invention comprises at least one of the novel anion receptors represented by the Formula 1 , which is composed of a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups.
  • the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number.
  • nitrogen in the amine becomes electron deficient by electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 and -SO 2 CN, and forms electrically neutral complexes with anions of alkali metal salts. In this manner, the dissociation of alkali metal salts into ions is promoted.
  • electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 and -SO 2 CN
  • the anionic receptor represented by the Formula 1 can be synthesized by any known method.
  • the compound of the Formula 1 can be synthesized by hydrosilylating a compound represented by the following Formula 2 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate.
  • Formula 2 the starting material
  • allyl trifluoro sulfonamide polyalkylene glycol allyl ether
  • allyl cyanide allyl propylene carbonate
  • the present invention provides electrolytes containing the anion receptor represented by the compound of the Formula 1 , and the electrolytes comprise nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.
  • the nonaqueous liquid electrolyte of the present invention comprises (i) an anion receptor of the Formula 1 ; (ii) a nonaqueous solvent; and (iii) an alkali metal ion containing substance.
  • the present invention provides a gel polymer electrolyte, which comprises (i) an anion receptor of the Formula 1; (ii) a polymer support; (iii) a nonaqueous solvent; and (iv) an alkali metal ion containing substance.
  • the present invention provides a solid polymer electrolyte, which comprises (i) an anion receptor of the Formula 1 ; (ii) a polymer selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.
  • the solid polymer electrolyte may further include one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
  • the nonaqueous solvent used for the electrolyte includes 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-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,
  • the alkali metal ion containing substance includes LiSO 3 CF 3 , LiCOOC 2 Fs, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiSbF 6 , LiI, LiBr, LiCl or a mixture thereof.
  • PAN polyacrylonitrile
  • PVDF polyvinylidenfluoride
  • the net-shaped, comb-shaped or branched polymer compounds used in the solid polymer electrolyte but flexible inorganic polymers or linear polyethers are preferred examples.
  • the crosslinkable polymer compound a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl is used.
  • the flexible inorganic polymer is preferably polysiloxane or polyphosphagen, and the linear polyether is preferably a polyalkylene oxide.
  • crosslinkable polymer compound examples include bisphenol A ethoxylate dimethacrylate represented by the following Formula 3 or TA-IO represented by the following Formula 4 disclosed in Korean Patent Registration No. 10-0419864: [Formula 3]
  • polyalkyleneglycol dialkylether or a nonaqueous solvent contained in the solid polymer electrolyte is used as a plasticizer.
  • the polyalkyleneglycol dialkylether include polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibuthylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether.
  • PEGDME polyethyleneglycol dimethylether
  • polyethyleneglycol diethylether polyethyleneglycol dipropylether
  • polyethyleneglycol dibutylether polyethyleneglycol diglycidy
  • the solid polymer electrolyte contains a crosslmkable polymer compound, it further comprises a curing initiator.
  • a photocuring initiator As for the curing initiator, a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used.
  • Preferred examples of the photocuring initiator is selected from the group consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, ⁇ -methyl bezoin ethyl ether, benzoin phenyl ether,
  • DMPA dimethoxyphenyl acetophenone
  • t-butylperoxypivalate ethyl benzoin ether
  • isopropyl benzoin ether ⁇ -methyl bezoin ethyl ether
  • benzoin phenyl ether benzoin phenyl ether
  • heat-curing initiator examples include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
  • the electrolyte of the present invention preferably contains 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.
  • the gel polymer electrolyte of the present invention preferably contains 5 - 40 parts by weight of the polymer support.
  • the solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of a polymer compound selected from the net-shaped, comb-shaped and branched polymer compounds, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator.
  • the solid polymer electrolyte of the present invention preferably contains 10 - 50 parts by weight of one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
  • the present invention provides an electrochemical cell containing the above anion receptor.
  • a cell using the liquid or gel polymer electrolyte of the present invention is composed of an anode, a cathode, and a separator, while a cell using the solid polymer electrolyte is composed of an anode and a cathode.
  • a cathode and an anode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing cathodes and anodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
  • the cathode is made of a material selected from the group that consists of lithium;
  • lithium alloys such as Li-Al, Li-Si, or Li-Cd
  • lithium-carbon intercalation compounds lithium-graphite intercalation compounds
  • lithium metal oxide intercalation compounds such as Li x WO 2 or LiMoO 2
  • lithium metal sulfide intercalation compounds such as Li-Al, Li-Si, or Li-Cd
  • LiTiS 2 LiTiS 2 ; mixtures thereof; and mixtures of these and alkali metals.
  • the anode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
  • a primary cell composed of a nonaqueous liquid electrolyte containing the anion receptor of the present invention is composed of: (i) a cathode made of a material selected from the group consisting of lithium, lithium alloys, lithium-carbon intercalation compounds, lithium-graphite intercalation compounds, lithium metal oxide intercalation compounds, mixtures thereof, and alkali metals;
  • an anode made of a material selected from the group consisting of transition metal oxides, transition metal chalcogenides, poly(carbondisulf ⁇ de)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and oxychlorides, such as, SO 2 , CuO, CuS, Ag 2 CrO 4 , 1 2 , PbI 2 , PbS, SOCl 2 , V 2 O 5 , MoO 3 , MnO 2 and polycarbon monofluoride (CF) n ;
  • a secondary cell composed of a nonaqueous liquid electrolyte
  • containing the anion receptor of the present invention is composed of:
  • a cathode containing lithium metals or materials capable of reversibly reacting with lithium metal including: lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as Li x WO 2 or LiMoO 2 ; and lithium metal
  • sulfide intercalation compounds such as LiTiS 2 ;
  • an anode containing transition metal oxides capable of intercalating lithium such as, Li 2 5 V 6 Oi 3 , Li 1-2 V 2 Os, LiCoO 2 , LiNiO 2 , LiNi i -x M x O 2 (wherein M is Co, Mg, Al or Ti), LiMn 2 O 4 or LiMnO 2 and the like; transition metal halides; or chalcogenides, such as, LiNbSe 3 , LiTiS 2 , LiMoS 2 and the like; (iii) a nonaqueous liquid electrolyte described above; and
  • the secondary cell composed of a gel polymer electrolyte containing the anion receptor of the present invention comprises a gel polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell composed of the above nonaqueous liquid electrolyte.
  • the secondary cell composed of a solid polymer electrolyte containing the anion receptor of the present invention comprises a solid polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell
  • the present invention provides a polymer electrolyte film (membrane) using an electrolyte of the present invention.
  • a preparation method of a gel or solid polymer electrolyte film (membrane) containing the components of the present invention is as follows:
  • a nonaqueous solvent, an anion receptor of the Formula 1 and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
  • a polymer support is then added to the solution and mixed together. If necessary, heat can be applied to completely dissolve the polymer support in the solution.
  • a composite mixture for preparing a gel polymer electrolyte film is made.
  • the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron rays, UV rays or
  • an anion receptor or polyalkyleneglycol dialkylether or a nonaqueous solvent and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. Then, a net-shaped, branched or comb-shaped polymer compound or a crosslinkable polymer compound is added to the solution and is mixed together. If necessary, heat can be applied to completely dissolve the net-shaped, branched or comb-shaped polymer compound in the solution.
  • a curing initiator can be added to the solution when the crosslinkable polymer is used, hi this manner, a composite mixture for preparing a solid polymer electrolyte film is made.
  • the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness.
  • the coated substrate is dried, exposed to electron rays, UV rays
  • Another example of the preparation method for a film is as follows. After the support substrate is coated with the composite mixture, a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a gel or solid polymer electrolyte film.
  • FIG. 1 is a graph showing a relation between ionic conductivities and temperature changes in solid polymer electrolytes of the present invention and of comparative examples (Experimental example 4);
  • FIG. 2 is a graph showing lithium cycling performance of cells of the present invention and of comparative examples (Experimental example 5).
  • Anion receptors (Example 13 - 47) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1 and 7-12 in the weight ratio shown in Table 1 below. [Table 1]
  • Anion receptors (Example 48 - 88) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3 and 7-12 in the weight ratio shown in Table 2 below. [Table 2] C 4 -2 DCN -
  • Anion receptors (Example 89 - 129) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4 and 7-12 in the weight ratio shown in Table 3 below. [Table 3]
  • Anion receptors (Example 130 - 170) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5 and 7-12 in the weight ratio shown in Table 4 below. [Table 4]
  • Anion receptors (Example 171 - 211) of the Formula 1 of the present invention were prepared using the procedures described in Examples 6 and 7-12 in the weight ratio shown in Table 5 below. [Table 5]
  • Anion receptors (Example 212 - 227) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3 and 7-12 in the weight ratio shown in Table 6 below. [Table 6]
  • Anion receptors (Example 228 - 243) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4 and 7-12 in the weight ratio shown in Table 7 below. [Table 7]
  • Anion receptors (Example 244 - 259) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5 and 7-12 in the weight ratio shown in Table 8 below. [Table 8]
  • Anion receptors (Example 260 - 275) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 6 and 7-12 in the weight ratio shown in Table 9 below. [Table 9]
  • Anion receptors (Example 276 - 291) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
  • Anion receptors (Example 292 - 307) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 5 and 7-12 in the weight ratio shown in Table 11 below. [Table 11]
  • Anion receptors (Example 308 - 323) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 6 and 7-12 in the weight ratio shown in Table 12 below. [Table 12]
  • Anion receptors (Example 324 - 339) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 5 and 7-12 in the weight ratio shown in Table 13 below. [Table 13]
  • Anion receptors (Example 340 - 355) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 6 and 7-12 in the weight ratio shown in Table 14 below. [Table 14]
  • Anion receptors (Example 356 - 371) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5, 6 and 7-12 in the weight ratio shown in Table 15 below. [Table 15]
  • Anion receptors (Example 372 - 377) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 6 and 7-12 in the weight ratio shown in Table 16 below. [Table 16]
  • Anion receptors (Example 378 - 383) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 6 and 7-12 in the weight ratio shown in Table 17 below. [Table 17]
  • Anion receptors (Example 384 - 389) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5, 6 and 7-12 in the weight ratio shown in Table 18 below. [Table 18]
  • Anion receptors (Example 390 - 395) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 5 and 7-12 in the weight ratio shown in Table 19 below. [Table 19]
  • Anion receptors (Example 396 - 401) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 5 and 7-12 in the weight ratio shown in Table 20 below. [Table 20]
  • Anion receptors (Example 402 - 407) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4 and 7-12 in the weight ratio shown in Table 21 below. [Table 21]
  • Anion receptors (Example 408 - 412) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4, 5 and 6 in the weight ratio shown in Table 22 below. [Table 22]
  • Example 414 Manufacture of Conductive Thin Film (2) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor Q-4TFSA obtained from Example 1 was replaced by 1.5g of C 4 -4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
  • Example 415 Manufacture of Conductive Film (3) The same procedure of Example 413 was repeated, with TA- 10 of the Formula 4 instead of the compound of the Formula 3 used as a crosslinking agent to prepare a solid polymer electrolyte.
  • Example 416 Manufacture of Conductive Thin Film (2) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor Q-4TFSA obtained from Example 1 was replaced by 1.5g of C 4 -4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
  • Example 415 Manufacture of Conductive Film (3) The same procedure
  • Example 413 Manufacture of Conductive Thin Film (4) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor C 4 -4TFSA obtained from Example 1 was replaced by 1.5g of Q-4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte. Examples 417 - 431. Manufacture of Conductive Thin Film (5 - 19)
  • Example 413 The same procedure of Example 413 was repeated, with the exception that compositions of compounds used are as shown in the following Table 23 to prepare a solid polymer electrolyte. Comparative Examples 1 - 2. Manufacture of Film without Anion Receptors (1 - 2)
  • Example 413 The same procedure of Example 413 was repeated using the compositions of compounds shown in the following Table 23 to prepare a solid polymer electrolyte. As shown in Table 23, polymer electrolytes of Comparative Examples do not contain anion receptors. [Table 23]
  • Ionic conductivities of the solid polymer electrolyte films obtained from the above examples were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium-copper foil, photohardened, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance. To manufacture the band shaped electrodes, masking tapes having a width between 0.5mm and 2mm were adhered to the center of a conductive glass (ITO) at intervals of 0.5 - 2mm, etched in an etching solution, washed and dried.
  • ITO conductive glass
  • Ionic conductivity of the solid polymer electrolyte film thusly obtained was measured at a temperature of 3O 0 C. Results are shown in Table 24. According to Table 24, ionic conductivity of the film of Example 418 is greater than that of the film of Example 417. Similarly, ionic conductivity of Example 420 is greater than that of Example 419. These results prove that ionic conductivity improves proportionally to the concentration of anion receptors. [Table 24]
  • Ionic conductivity measurement results of polymer films of the Examples 422 and 423 at a temperature of 3O 0 C are shown in the following Table 25.
  • the test was carried out using the same procedure described in Experimental Example 1 to find out conditions for maximizing ion conductivities of polymer films, hi particularly, plasticizers and anion receptors were used together to make polymer films. It turned out that Example 2 which used both anion receptors and plasticizers exhibited superior ionic conductivity to that of Example 1 which used anion receptors only. [Table 25]
  • Example 413 The same procedure in Example 413 was repeated to manufacture solid polymer electrolyte films using anion receptors obtained from Examples 3 - 7, 11, 12 and 28. Using the same procedure described in Experimental Example 1, ionic conductivities of the films were measured. The measurement results are shown in the following Table 26. As shown in Table 26, the results proved that solid polymer electrolytes containing various anion receptors exhibited superior ionic conductivities. [Table 26]
  • Ionic conductivities of films obtained from Comparative Examples 1 and 2 without anion receptors were measured using the same procedure described in Experimental Example 1. Ionic conductivity measurement results of the solid polymer electrolyte films at a temperature of 3O 0 C are shown in Table 27. Comparing the measurement results shown in Table 27 with the measurement results shown in Tables 24 - 26, one can find out that ionic conductivities of films without anion receptors are very low. [Table 27]
  • Example 431 Manufacture of Cell Using Liquid Electrolyte with Anion Receptors
  • 0.015g of the anion receptor C 4 -4TFSI obtained from Example 2 was mixed with 1.Og of an organic solvent EC/DMC/EMC (1:1:1, IM LiPF 6 ).
  • a polypropylene separator impregnated with the above solution was inserted between a LiCoO 2 anode and a graphite carbon cathode in a dry room (humidity below 3%) and vacuum-sealed to assemble a cell.
  • the LiCoO 2 anode was prepared by coating an aluminum foil with a mixture of 94wt% LiCoO 2 (manufactured by Nippon Chemical Industry), 3wt% of acetylene black, and 3wt% of polyvinylidenfluoride (PVDF).
  • Comparative Example 3 Manufacture of Cell Using Liquid Electrolyte without Anion Receptors The same procedure described in Example 431 was repeated, with the exception that the separator impregnated with an organic solvent EC/DMC/DEC (1:1 :1, IM LiPF 6 ) only was inserted between a LiCoO 2 anode and a graphite carbon cathode. Experimental Example 5. Cell Lithium Cycling Performance and Efficiency Test Lithium cycling performance and efficiency of cells manufactured in Example 431 of the present invention and Comparative Example 3 were tested at room temperature using Maccor 4000. Charging and discharging were carried out to 0.2, 0.5 and 1C, respectively. The cells were charged and discharged anywhere between 3.0V and 4.2V at a predetermined current density of 0.6mA/cm (charging) and 1.5mA/cm (discharging) with respect to a LiCoO 2 counter electrode.
  • FIG. 2 graphically shows a comparison between discharge capacities with respect to the number of cyclings of cells manufactured using electrolytes inclusive of the anion receptor C 4 -4TFSI (Example 2) and those of cells manufactured using electrolytes exclusive of the anion receptor. As shown in FIG. 2, it turned out that the cells manufactured using electrolytes of the anion receptor C 4 -4TFSI exhibited higher capacity and superior stability.
  • the novel anion receptor of the present invention can be used as an additive to enhance lithium cycling performance and efficiency of liquid electrolytes for high capacity lithium-ion batteries and cells.
  • the polymer electrolytes containing the novel anion receptor offer substantially enhanced ionic conductivities and electrochemical stabilities at room temperature, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all

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Abstract

Disclosed is a novel anion receptor and electrolytes containing the same. A novel anion receptor is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups. When the anion receptor is added to the electrolyte, ionic conductivity and cation transference number of electrolytes are enhanced, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes.

Description

ANION RECEPTOR AND ELECTROLYTE USING THE SAME
Field of the Invention
The present invention relates to a novel anion receptor, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which is added to enhance ionic conductivity and cation transference number of electrolytes, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the anion receptors.
Description of the Related Art Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base. These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li+) by coordinating electron- rich anions around to interfere with forming ion pairs between the anions and the lithium cations. The first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 146 (2000) 9). However, these aza- ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of anode materials. In addition, it has been discovered that aza-ethers are unstable to LiPF6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, chemically and thermally unstable LiPF6 is in equilibrium with solid LiF and PF5 gas even at room temperature, and production of PF5 gas makes the equilibrium moved towards generating PF5 gas.
LiPF6 (s) ^=^ LiF (S) + PF5 (g)
In a nonaqueous solvent, PF5 has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electrons, e.g., oxygen or nitrogen. Meanwhile, PF5, a relatively strong Lewis acid, is known to attack electron pairs. Due to high electron density, aza-ethers are promptly attached by PF5 (J. Power Sources, 104 (2002) 260). This is a major drawback to commercialize aza-ether compounds. To resolve this problem, McBreen et al. synthesized an anion receptor comprising boron as an electron deficient atom substituted by an electron withdrawing group using the same means (J. Electrochem. Soc, 145 (1998) 2813, 149 (2002) A1460). On the other hand, solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances. In 1975, a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M. Armand in 1978. Typically, a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor. One of the most well- known solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10~8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted. Li order to increase motility of molecular chains, the crystalline area existing in the polymer structure should be minimized while the amorphous area therein should be expanded. A research to achieve such has been and is under way by using a siloxane having a flexible molecular chain (Marcromol. Chem. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6845) as a main chain, or by introducing PAO having a relatively short molecular length as a side branch (Electrochem. Acta, 34 (1989) 635). According to another research in progress, net-shaped solid polymer electrolytes are prepared by introducing at least one crosslmkable functional group to the PAO as a terminal group. Unfortunately however, ionic conductivity of such electrolytes at room temperature is as low as 10"5~10"4 S/cm which is not suitable for use in lithium batteries operating at room temperature conditions, so continuous researches have been made to improve the ionic conductivity. This problem was resolved by Abraham et al. who introduced polyethylene oxide with low molecular weight into a vinylidenhexafluoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978). In addition, by adding lower molecular weight PEGDME (polyethyleneglycol demethylether) to a photocuring type crosslinking agent having a siloxane based main chain and a PEO side branch, the ionic conductivity was increased to 8x10~4 S/cm at room temperature under film forming conditions (J. Power Sources 119- 121 (2003) 448). However, cycling efficiency on a Ni electrode was about 53% at most mainly because the newly deposited lithium surface rapidly eroded, thereby passivating the electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). That is, according to Vincent, lithium metal reacts with a lithium salt as follows (Solid State Chem. 17 (1987) 145):
LiSO3CF3 + Li (s) → 2Li+ + SO3 2" + CF3-
The CF3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF3. In result, a =C-O-C- functional group is formed and the main chain of the polymer therein is cut off. At this time, CH3 produced by chain scission together with the CF3 radical attack the chain or break a C-O bond. A Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated.
Therefore, in order to solve the above-described problems, there is a need to develop a novel substance capable of resolving the electrochemical instability and the instability towards lithium salts and offering enhanced ionic conductivity by designing a compound which does not have an easily attackable nitrogen atom in the middle of a compound as in aza-ether compounds, or by replacing the PAO type plasticizer.
Detailed Description of the Invention Technical Subject It is, therefore, an object of the present invention to provide a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which enhances ionic conductivity and cation transference number of electrolytes containing it, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes.
It is another object of the present invention to provide a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing at least one of the novel anion receptors.
It is still another object of the present invention to provide an electrochemical cell which uses an electrolyte containing the novel anion receptors.
Technical Solution To achieve the above objects and advantages, there is provided an anion receptor for use in a polymer electrolyte represented by the following Formula 1, which is composed of a cyclic siloxane compound having an amine substituted with electron withdrawing group, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups : [Formula 1]
Figure imgf000008_0001
wherein R1 and R2 independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting Of -SO2CF3, -CN, -F, -Cl, -COCF3 and -SO2CN, but do not both simultaneously represent a hydrogen atom;
R3 represents a hydrogen atom or a cyano group;
Figure imgf000008_0002
R5 and R6 independently represents a hydrogen atom or a methyl group; R7 and the other R7 in the formula each independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxyl group;
Y and Z independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, and q are integers from O to 1000, respectively; and r and s are integers from 0 to 20, respectively, whose sum is at least 1. The compound of the Formula 1 functions as an anion receptor in an electrolyte and preferred examples of the compound include C4-4TFSA; C4-4TFSI; C4-2TFSA-2TEGMP; C4-2TFSA-2PEGMP; Q-2TFSA-2TEGMPC; C4-2TFSA-2PEGMPC; C4-2TFSA-2CN; C4-2TFSA-2CPP; C4-2TFSA-TEGMP-CPP; C4-2TFSA-PEGMP-CPP; C4-2TFSA- TEGMPC-CPP; C4-2TFSA-PEGMPC-CPP; C4-2TFSA-CN-CPP; C4-2TFSA-TEGMP-CN; C4-2TFSA-PEGMP-CN; Q-2TFSA-TEGMPC-CN; C4-2TFSA-PEGMPC-CN; C4-2TFSA- TEGMP-PEGMPC; C4-2TFS A-PEGMP-PEGMPC; C4-2TFSA-TEGMPC-PEGMPC; C4- 2TFSA-TEGMP-TEGMPC; C4-2TFSA-PEGMP-TEGMPC; C4-2TFSA-TEGMP-TEGMP; C4-TFSA-TEGMP-CN-CPP; C4-TFSA-PEGMP-CN-CPP; C4-TFSA-TEGMPC-CN-CPP;
C4-TFSA-PEGMPC-CN-CPP; C4-TFSA-TEGMP-PEGMPC-CPP; C4-TFSA-PEGMP- PEGMPC-CPP; C4-TFSA-TEGMPC-PEGMPC-CPP; C4-TFSA-TEGMP-TEGMPC-CPP; C4-TFSA-PEGMP-TEGMPC-CPP; C4-TFSA-TEGMP-PEGMP-CPP; C4-TFSA-TEGMP- PEGMPC-CN; C4-TFSA-PEGMP-PEGMPC-CN; C4-TFSA-TEGMPC-PEGMPC-CN; C4- TFSA-TEGMP-TEGMPC-CN; C4-TFSA-PEGMP-TEGMPC-CN; C4-TFSA-TEGMP- PEGMP-CN; C4-TFSA-TEGMP-TEGMPC-PEGMPC; C4-TFSA-PEGMP-TEGMPC- PEGMPC; C4-TFSA-TEGMP-PEGMP-PEGMPC; C4-TFSA-TEGMP-PEGMP-TEGMPC; C4-4DCN; C4-2DCN-2TEGMP; C4-2DCN-2PEGMP; C4-2DCN-2TEGMPC; Q-2DCN- 2PEGMPC; C4-2DCN-2CN; C4-2DCN-2CPP; C4-2DCN-TEGMP-CPP; C4-2DCN- PEGMP-CPP; Q-2DCN-TEGMPC-CPP; C4-2DCN-PEGMPC-CPP; C4-2DCN-CN-CPP; C4-2DCN-TEGMP-CN; C4-2DCN-PEGMP-CN; C4-2DCN-TEGMPC-CN; C4-2DCN- PEGMPC-CN; Q-2DCN-TEGMP-PEGMPC; C4-2DCN-PEGMP-PEGMPC; Q-2DCN- TEGMPC-PEGMPC; C4-2DCN-TEGMP-TEGMPC; C4-2DCN-PEGMP-TEGMPC; C4- 2DCN-TEGMP-TEGMP; C4-DCN-TEGMP-CN-CPP; C4-DCN-PEGMP-CN-CPP; C4- DCN-TEGMPC-CN-CPP; C4-DCN-PEGMPC-CN-CPP; C4-DCN-TEGMP-PEGMPC- CPP; C4-DCN-PEGMP-PEGMPC-CPP; C4-DCN-TEGMPC-PEGMPC-CPP; C4-DCN- TEGMP-TEGMPC-CPP; C4-DCN-PEGMP-TEGMPC-CPP; Q-DCN-TEGMP-PEGMP- CPP; C4-DCN-TEGMP-PEGMPC-CN; C4-DCN-PEGMP-PEGMPC-CN; C4-DCN- TEGMPC-PEGMPC-CN; C4-DCN-TEGMP-TEGMPC-CN; C4-DCN-PEGMP-TEGMPC- CN; C4-DCN-TEGMP-PEGMP-CN; C4-DCN-TEGMP-TEGMPC-PEGMPC; C4-DCN- PEGMP-TEGMPC-PEGMPC; C4-DCN-TEGMP-PEGMP-PEGMPC; C4-DCN-TEGMP- PEGMP-TEGMPC; Q-4DFA; C4-2DFA-2TEGMP; C4-2DFA-2PEGMP; Q-2DFA- 2TEGMPC; C4-2DFA-2PEGMPC; C4-2DFA-2CN; C4-2DFA-2CPP; C4-2DF A-TEGMP- CPP; C4-2DFA-PEGMP-CPP; C4-2DFA-TEGMPC-CPP; C4-2DFA-PEGMPC-CPP; C4- 2DFA-CN-CPP; Q-2DF A-TEGMP-CN; C4-2DF A-PEGMP-CN; C4-2DF A-TEGMPC- CN; C4-2DFA-PEGMPC-CN; C4-2DFA-TEGMP-PEGMPC; Q-2DFA-PEGMP- PEGMPC; C4-2DFA-TEGMPC-PEGMPC; C4-2DFA-TEGMP-TEGMPC; C4-2DFA- PEGMP-TEGMPC; C4-2DFA-TEGMP-TEGMP; C4-DFA-TEGMP-CN-CPP; C4-DFA- PEGMP-CN-CPP; C4-DFA-TEGMPC-CN-CPP; C4-DFA-PEGMPC-CN-CPP; C4-DFA- TEGMP-PEGMPC-CPP; C4-DFA-PEGMP-PEGMPC-CPP; C4-DFA-TEGMPC- PEGMPC-CPP; C4-DFA-TEGMP-TEGMPC-CPP; C4-DFA-PEGMP-TEGMPC-CPP; C4- DFA-TEGMP-PEGMP-CPP; C4-DFA-TEGMP-PEGMPC-CN; C4-DFA-PEGMP- PEGMPC-CN; C4-DFA-TEGMPC-PEGMPC-CN; C4-DFA-TEGMP-TEGMPC-CN; C4- DFA-PEGMP-TEGMPC-CN; C4-DFA-TEGMP-PEGMP-CN; C4-DFA-TEGMP- TEGMPC-PEGMPC; C4-DFA-PEGMP-TEGMPC-PEGMPC; C4-DFA-TEGMP-PEGMP- PEGMPC; C4-DFA-TEGMP-PEGMP-TEGMPC; Q-4DCA; C4-2DCA-2TEGMP; C4- 2DCA-2PEGMP; C4-2DCA-2TEGMPC; C4-2DCA-2PEGMPC; C4-2DCA-2CN; C4- 2DCA-2CPP; C4-2DC A-TEGMP-CPP; C4-2DCA-PEGMP-CPP; C4-2DCA-TEGMPC- CPP; C4-2DCA-PEGMPC-CPP; C4-2DCA-CN-CPP; C4-2DCA-TEGMP-CN; C4-2DCA- PEGMP-CN; C4^DCA-TEGMPC-CN; C4-2DCA-PEGMPC-CN; C4-2DCA-TEGMP- PEGMPC; C4-2DCA-PEGMP-PEGMPC; C4-2DCA-TEGMPC-PEGMPC; C4-2DCA- TEGMP-TEGMPC; C4-2DC A-PEGMP-TEGMPC; C4-2DCA-TEGMP-TEGMP; C4-DCA-
TEGMP-CN-CPP; C4-DCA-PEGMP-CN-CPP; C4-DCA-TEGMPC-CN-CPP; C4-DCA- PEGMPC-CN-CPP; C4-DCA-TEGMP-PEGMPC-CPP; C4-DCA-PEGMP-PEGMPC-CPP; C4-DCA-TEGMPC-PEGMPC-CPP; C4-DCA-TEGMP-TEGMPC-CPP; C4-DCA-PEGMP- TEGMPC-CPP; C4-DCA-TEGMP-PEGMP-CPP; C4-DCA-TEGMP-PEGMPC-CN; C4- DCA-PEGMP-PEGMPC-CN; C4-DCA-TEGMPC-PEGMPC-CN; C4-DCA-TEGMP- TEGMPC-CN; C4-DCA-PEGMP-TEGMPC-CN; C4-DCA-TEGMP-PEGMP-CN; C4- DCA-TEGMP-TEGMPC-PEGMPC; C4-DCA-PEGMP-TEGMPC-PEGMPC; C4-DCA- TEGMP-PEGMP-PEGMPC; C4-DCA-TEGMP-PEGMP-TEGMPC; C4-4TFAC; C4- 2TFAC-2TEGMP; Q-2TFAC-2PEGMP; C4-2TFAC-2TEGMPC; C4-2TFAC-2PEGMPC; C4-2TFAC-2CN; Q-2TFAC-2CPP; C4-2TFAC-TEGMP-CPP; C4-2TFAC-PEGMP-CPP; C4-2TFAC-TEGMPC-CPP; C4-2TFAC-PEGMPC-CPP; C4-2TFAC-CN-CPP; C4-2TFAC- TEGMP-CN; C4-2TFAC-PEGMP-CN; Q-2TFAC-TEGMPC-CN; C4-2TF AC-PEGMPC- CN; C4-2TFAC-TEGMP-PEGMPC; C4-2TFAC-PEGMP-PEGMPC; C4-2TFAC- TEGMPC-PEGMPC; C4-2TF AC-TEGMP-TEGMPC; C4-2TFAC-PEGMP-TEGMPC; C4- 2TFAC-TEGMP-TEGMP; C4-TFAC-TEGMP-CN-CPP; C4-TFAC-PEGMP-CN-CPP; C4- TFAC-TEGMPC-CN-CPP; C4-TFAC-PEGMPC-CN-CPP; C4-TFAC-TEGMP-PEGMPC- CPP; C4-TFAC-PEGMP-PEGMPC-CPP; C4-TFAC-TEGMPC-PEGMPC-CPP; C4-TFAC- TEGMP-TEGMPC-CPP; C4-TFAC-PEGMP-TEGMPC-CPP; C4-TFAC-TEGMP- PEGMP-CPP; C4-TFAC-TEGMP-PEGMPC-CN; C4-TFAC-PEGMP-PEGMPC-CN; C4- TFAC-TEGMPC-PEGMPC-CN; C4-TFAC-TEGMP-TEGMPC-CN; C4-TFAC-PEGMP- TEGMPC-CN; C4-TFAC-TEGMP-PEGMP-CN; C4-TFAC-TEGMP-TEGMPC-PEGMPC; C4-TFAC-PEGMP-TEGMPC-PEGMPC; C4-TFAC-TEGMP-PEGMP-PEGMPC; C4-
TFAC-TEGMP-PEGMP-TEGMPC; Q-2TFSA-2DCN; C4-TFSA-DCN-TEGMP-CPP; C4- TFSA-DCN-PEGMP-CPP; C4-TFSA-DCN-TEGMPC-CPP; C4-TFSA-DCN-PEGMPC- CPP; C4-TFSA-DCN-CN-CPP; C4-TFSA-DCN-TEGMP-CN; C4-TFSA-DCN-PEGMP- CN; C4-TFSA-DCN-TEGMPC-CN; C4-TFSA-DCN-PEGMPC-CN; C4-TFSA-DCN- TEGMP-PEGMPC; C4-TFSA-DCN-PEGMP-PEGMPC; C4-TFSA-DCN-TEGMPC- PEGMPC; C4-TFSA-DCN-TEGMP-TEGMPC; C4-TFSA-DCN-PEGMP-TEGMPC; C4- TFSA-DCN-TEGMP-TEGMP; C4-2TFSA-2DFA; C4-TFSA-DFA-TEGMP-CPP; C4- TFSA-DFA-PEGMP-CPP; C4-TFSA-DFA-TEGMPC-CPP; C4-TFSA-DFA-PEGMPC- CPP; C4-TFSA-DFA-CN-CPP; C4-TFSA-DFA-TEGMP-CN; C4-TFSA-DFA-PEGMP- CN; C4-TFSA-DFA-TEGMPC-CN; C4-TFSA-DFA-PEGMPC-CN; C4-TFSA-DFA- TEGMP-PEGMPC; C4-TFSA-DFA-PEGMP-PEGMPC; C4-TFSA-DFA-TEGMPC- PEGMPC; C4-TFSA-DFA-TEGMP-TEGMPC; C4-TFSA-DFA-PEGMP-TEGMPC; C4- TFSA-DFA-TEGMP-TEGMP; C4-2TFSA-2DCA; C4-TFSA-DCA-TEGMP-CPP; C4- TFSA-DCA-PEGMP-CPP; C4-TFSA-DCA-TEGMPC-CPP; C4-TFSA-DCA-PEGMPC- CPP; C4-TFSA-DCA-CN-CPP; C4-TFSA-DCA-TEGMP-CN; C4-TFSA-DCA-PEGMP- CN; C4-TFSA-DCA-TEGMPC-CN; C4-TFSA-DCA-PEGMPC-CN; C4-TFSA-DCA- TEGMP-PEGMPC; C4-TFSA-DCA-PEGMP-PEGMPC; C4-TFSA-DCA-TEGMPC- PEGMPC; C4-TFSA-DCA-TEGMP-TEGMPC; C4-TFSA-DCA-PEGMP-TEGMPC; C4- TFSA-DCA-TEGMP-TEGMP; C4-2TFSA-2TFAC; C4-TFSA-TFAC-TEGMP-CPP; C4- TFSA-TFAC-PEGMP-CPP; C4-TFSA-TFAC-TEGMPC-CPP; C4-TFSA-TFAC- PEGMPC-CPP; C4-TFSA-TFAC-CN-CPP; C4-TFSA-TFAC-TEGMP-CN; C4-TFSA- TFAC-PEGMP-CN; C4-TFSA-TFAC-TEGMPC-CN; C4-TFSA-TFAC-PEGMPC-CN; C4- TFSA-TFAC-TEGMP-PEGMPC; C4-TFSA-TFAC-PEGMP-PEGMPC; C4-TFSA-TF AC- TEGMPC-PEGMPC; C4-TFSA-TFAC-TEGMP-TEGMPC; C4-TFSA-TFAC-PEGMP- TEGMPC; C4-TFSA-TFAC-TEGMP-PEGMP; C4-2DCN-2DFA; C4-DCN-DFA-TEGMP- CPP; C4-DCN-DFA-PEGMP-CPP; C4-DCN-DFA-TEGMPC-CPP; C4-DCN-DFA- PEGMPC-CPP; C4-DCN-DFA-CN-CPP; C4-DCN-DFA-TEGMP-CN; C4-DCN-DFA- PEGMP-CN; C4-DCN-DFA-TEGMPC-CN; C4-DCN-DFA-PEGMPC-CN; C4-DCN-DF A- TEGMP-PEGMPC; C4-DCN-DFA-PEGMP-PEGMPC; C4-DCN-DFA-TEGMPC- PEGMPC; C4-DCN-DFA-TEGMP-TEGMPC; C4-DCN-DFA-PEGMP-TEGMPC; C4- DCN-DFA-TEGMP-TEGMP; Q-2DCN-2DCA; C4-DCN-DCA-TEGMP-CPP; C4-DCN- DCA-PEGMP-CPP; C4-DCN-DCA-TEGMPC-CPP; C4-DCN-DCA-PEGMPC-CPP; C4- DCN-DCA-CN-CPP; C4-DCN-DCA-TEGMP-CN; C4-DCN-DCA-PEGMP-CN; C4-DCN- DCA-TEGMPC-CN; C4-DCN-DCA-PEGMPC-CN; C4-DCN-DCA-TEGMP-PEGMPC; C4-DCN-DCA-PEGMP-PEGMPC; C4-DCN-DCA-TEGMPC-PEGMPC; C4-DCN-DCA- TEGMP-TEGMPC; C4-DCN-DCA-PEGMP-TEGMPC; C4-DCN-DCA-TEGMP-TEGMP; Q-2DCN-2TFAC; C4-DCN-TFAC-TEGMP-CPP; C4-DCN-TFA-PEGMP-CPP; C4-DCN- TFAC-TEGMPC-CPP; C4-DCN-TFAC-PEGMPC-CPP; C4-DCN-TFAC-CN-CPP; C4- DCN-TFAC-TEGMP-CN; C4-DCN-TFAC-PEGMP-CN; C4-DCN-TFAC-TEGMPC-CN; C4-DCN-TFAC-PEGMPC-CN; C4-DCN-DCA-TEGMP-PEGMPC; C4-DCN-DCA- PEGMP-PEGMPC; C4-DCN-DCA-TEGMPC-PEGMPC; C4-DCN-DCA-TEGMP- TEGMPC; C4-DCN-DCA-PEGMP-TEGMPC; C4-DCN-DCA-TEGMP-TEGMP; C4- 2DFA-2DCA; C4-DFA-DCA-TEGMP-CPP; C4-DFA-DCA-PEGMP-CPP; C4-DF A-DCA- TEGMPC-CPP; C4-DFA-DCA-PEGMPC-CPP; C4-DFA-DCA-CN-CPP; C4-DFA-DCA- TEGMP-CN; C4-DFA-DCA-PEGMP-CN; C4-DFA-DCA-TEGMPC-CN; C4-DF A-DCA- PEGMPC-CN; C4-DFA-DCA-TEGMP-PEGMPC; C4-DFA-DCA-PEGMP-PEGMPC; C4- DFA-DCA-TEGMPC-PEGMPC; C4-DFA-DCA-TEGMP-TEGMPC; C4-DFA-DCA- PEGMP-TEGMPC; C4-DFA-DCA-TEGMP-TEGMP; C4-2DFA-2TFAC; C4-DFA- TFACTEGMP-CPP; C4-DFA-TFAC-PEGMP-CPP; C4-DFA-TFAC-TEGMPC-CPP; C4- DFA-TFAC-PEGMPC-CPP; C4-DFA-TFAC-CN-CPP; C4-DFA-TFAC-TEGMP-CN; C4- DFA-TFAC-PEGMP-CN; C4-DFA-TFAC-TEGMPC-CN; C4-DFA-TFAC-PEGMPC-CN;
C4-DFA-TFAC-TEGMP-PEGMPC; C4-DFA-TFAC-PEGMP-PEGMPC; C4-DFA-TF AC- TEGMPC-PEGMPC; C4-DFA-TFAC-TEGMP-TEGMPC; C4-DFA-TFAC-PEGMP- TEGMPC; C4-DFA-TFAC-TEGMP-TEGMP; Q-2DCA-2TFAC; C4-DCA-TFAC- TEGMP-CPP; C4-DCA-TFAC-PEGMP-CPP; C4-DCA-TFAC-TEGMPC-CPP; C4-DCA- TFAC-PEGMPC-CPP; C4-DCA-TFAC-CN-CPP; C4-DCA-TFAC-TEGMP-CN; C4-DCA- TFAC-PEGMP-CN; C4-DCA-TFAC-TEGMPC-CN; C4-DCA-TFAC-PEGMPC-CN; C4- DCA-TFAC-TEGMP-PEGMPC; C4-DCA-TFAC-PEGMP-PEGMPC; C4-DCA-TFAC- TEGMPC-PEGMPC; C4-DCA-TFAC-TEGMP-TEGMPC; C4-DCA-TFAC-PEGMP- TEGMPC; C4-DCA-TFAC-TEGMP-TEGMP; C4-TFSA-DCN-TFAC-TEGMP; C4-TFSA-
DCN-TFAC-PEGMP; C4-TFSA-DCN-TFAC-TEGMPC; C4-TFSA-DCN-TFAC-
PEGMPC; C4-TFSA-DCN-TFAC-CN; C4-TFSA-DCN-TFAC-CPP; C4-TFS A-DF A-
TFAC-TEGMP; C4-TFSA-DFA-TFAC-PEGMP; C4-TFSA-DFA-TFAC-TEGMPC; C4-
TFSA-DFA-TFAC-PEGMPC; C4-TFSA-DFA-TFAC-CN; C4-TFSA-DFA-TFAC-CPP;
C4-TFSA-DCA-TFAC-TEGMP; C4-TFSA-DCA-TFAC-PEGMP; C4-TFSA-DCA-TFAC-
TEGMPC; C4-TFSA-DCA-TFAC-PEGMPC; C4-TFSA-DCA-TFAC-CN; C4-TFSA-DCA- TFAC-CPP; C4-TFSA-DCN-DCA-TEGMP; C4-TFSA-DCN-DCA-PEGMP; C4-TFSA- DCN-DCA-TEGMPC; C4-TFSA-DCN-DCA-PEGMPC; C4-TFSA-DCN-DCA-CN; C4-
TFSA-DCN-DCA-CPP; C4-TFSA-DFA-DCA-TEGMP; C4-TFSA-DFA-DCA-PEGMP;
C4-TFSA-DFA-DCA-TEGMPC; C4-TFSA-DFA-DCA-PEGMPC; C4-TFSA-DF A-DCA- CN; C4-TFSA-DFA-DCA-CPP; C4-TFSA-DCN-DFA-TEGMP; C4-TFSA-DCN-DFA-
PEGMP; C4-TFSA-DCN-DFA-TEGMPC; C4-TFSA-DCN-DFA-PEGMPC; C4-TFSA-
DCN-DFA-CN; C4-TFSA-DCN-DFA-CPP; C4-TFSA-DCN-DFA-TFAC; C4-TFSA-
DCN-DCA-TFAC; C4-TFSA-DFA-DCA-TFAC; C4-TFSA-DCN-DFA-DCA or C4-DCN-
DFA-DCA-TFAC (see structural formulas of the following Examples).
The nonaqueous liquid electrolyte and a gel or solid polymer electrolyte of the present invention comprises at least one of the novel anion receptors represented by the Formula 1 , which is composed of a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups.
Among the functional groups introduced as a side branch, the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number. In detail, nitrogen in the amine becomes electron deficient by electron withdrawing groups such as -SO2CF3, - CN, -F, -Cl, -COCF3 and -SO2CN, and forms electrically neutral complexes with anions of alkali metal salts. In this manner, the dissociation of alkali metal salts into ions is promoted. Unlike a family of aza-ether based compounds disclosed in U.S. Pat. Nos. 5,705,689 and 6,120,941 where an easily attackable nitrogen atom existing in the middle of a compound causes electrochemical instability and instability to lithium salts (especially, LiPF6) and steric hindrance, hydrogen atoms in the amine of the present invention make the nitrogen atom substituted with electron withdrawing groups be only in terminal position of the hydrocarbon chain, so more portion of the center of the nitrogen atom is exposed, easily attracting bulky anions thereto. In result, dissociation of lithium salt is enhanced, cation transference number is increased and thus, high ionic conductivity can be
achieved.
The anionic receptor represented by the Formula 1 can be synthesized by any known method.
For example, the compound of the Formula 1 can be synthesized by hydrosilylating a compound represented by the following Formula 2 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate. [Reaction Scheme 1]
Figure imgf000016_0001
formula 2
, Z (CH2CHO)I- -(CH2CHO)S-C H,
Rs Ro
iKC-I iO) — (
Figure imgf000016_0002
formula 1 wherein, R1, R2, R3, R4, R5, R6, R7, Y, Z, n, o, p, q, r, and s are defined as in the Formula 1.
The present invention provides electrolytes containing the anion receptor represented by the compound of the Formula 1 , and the electrolytes comprise nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.
In detail, the nonaqueous liquid electrolyte of the present invention comprises (i) an anion receptor of the Formula 1 ; (ii) a nonaqueous solvent; and (iii) an alkali metal ion containing substance.
In addition, the present invention provides a gel polymer electrolyte, which comprises (i) an anion receptor of the Formula 1; (ii) a polymer support; (iii) a nonaqueous solvent; and (iv) an alkali metal ion containing substance.
Moreover, the present invention provides a solid polymer electrolyte, which comprises (i) an anion receptor of the Formula 1 ; (ii) a polymer selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.
The solid polymer electrolyte may further include one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
The nonaqueous solvent used for the electrolyte includes 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-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,
dimethoxymethane, γ-butyrolactone, methyl formate, sulforane, acetonitrile, 3-methyl-2- oxazolidinone, N-methyl-2-pyrrolidinone or mixtures thereof. The alkali metal ion containing substance includes LiSO3CF3, LiCOOC2Fs, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl or a mixture thereof.
Although there is no limitation on the polymer support for use in the gel polymer
electrolyte, preferred examples include polyacrylonitrile (PAN) type polymers or polyvinylidenfluoride (PVDF)-hexafluoropropylene type polymers.
Also, there is no limitation on the net-shaped, comb-shaped or branched polymer compounds used in the solid polymer electrolyte, but flexible inorganic polymers or linear polyethers are preferred examples. As for the crosslinkable polymer compound, a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl is used.
The flexible inorganic polymer is preferably polysiloxane or polyphosphagen, and the linear polyether is preferably a polyalkylene oxide.
Examples of the crosslinkable polymer compound include bisphenol A ethoxylate dimethacrylate represented by the following Formula 3 or TA-IO represented by the following Formula 4 disclosed in Korean Patent Registration No. 10-0419864: [Formula 3]
Figure imgf000018_0001
Bis- 15m
[Formula 4]
Figure imgf000019_0001
TA-IO
Similar to the anion receptor of the present invention, polyalkyleneglycol dialkylether or a nonaqueous solvent contained in the solid polymer electrolyte is used as a plasticizer. Examples of the polyalkyleneglycol dialkylether include polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibuthylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether.
When the solid polymer electrolyte contains a crosslmkable polymer compound, it further comprises a curing initiator.
As for the curing initiator, a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used.
Preferred examples of the photocuring initiator is selected from the group consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl ether, benzoin phenyl ether,
α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-
methyl- 1-phenylpropane-l -on, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p- chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone and a mixture thereof.
Examples of the heat-curing initiator include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
More particularly, the electrolyte of the present invention preferably contains 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.
The gel polymer electrolyte of the present invention preferably contains 5 - 40 parts by weight of the polymer support.
The solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of a polymer compound selected from the net-shaped, comb-shaped and branched polymer compounds, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator. The solid polymer electrolyte of the present invention preferably contains 10 - 50 parts by weight of one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
In addition, the present invention provides an electrochemical cell containing the above anion receptor. Particularly, a cell using the liquid or gel polymer electrolyte of the present invention is composed of an anode, a cathode, and a separator, while a cell using the solid polymer electrolyte is composed of an anode and a cathode.
Here, a cathode and an anode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing cathodes and anodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
The cathode is made of a material selected from the group that consists of lithium;
lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as LixWO2 or LiMoO2; lithium metal sulfide intercalation compounds, such as
LiTiS2; mixtures thereof; and mixtures of these and alkali metals.
The anode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
The following now describes constitutional embodiments of the electrochemical cell of the present invention.
A primary cell composed of a nonaqueous liquid electrolyte containing the anion receptor of the present invention is composed of: (i) a cathode made of a material selected from the group consisting of lithium, lithium alloys, lithium-carbon intercalation compounds, lithium-graphite intercalation compounds, lithium metal oxide intercalation compounds, mixtures thereof, and alkali metals;
(ii) an anode made of a material selected from the group consisting of transition metal oxides, transition metal chalcogenides, poly(carbondisulfϊde)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and oxychlorides, such as, SO2, CuO, CuS, Ag2CrO4, 12, PbI2, PbS, SOCl2, V2O5, MoO3, MnO2 and polycarbon monofluoride (CF)n;
(iii) a nonaqueous liquid electrolyte described above; and (iv) a separator.
Manufacture of a cathode and an anode, and assembly of a cell can be achieved by
well-known methods.
In addition, a secondary cell composed of a nonaqueous liquid electrolyte
containing the anion receptor of the present invention is composed of:
(i) a cathode containing lithium metals or materials capable of reversibly reacting with lithium metal, including: lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as LixWO2 or LiMoO2; and lithium metal
sulfide intercalation compounds, such as LiTiS2;
(ii) an anode containing transition metal oxides capable of intercalating lithium, such as, Li2 5V6Oi3, Li1-2V2Os, LiCoO2, LiNiO2, LiNi i-xMxO2 (wherein M is Co, Mg, Al or Ti), LiMn2O4 or LiMnO2 and the like; transition metal halides; or chalcogenides, such as, LiNbSe3, LiTiS2, LiMoS2 and the like; (iii) a nonaqueous liquid electrolyte described above; and
(iv) a separator.
Manufacture of a cathode and an anode, and assembly of a cell can be achieved by well-known methods.
The secondary cell composed of a gel polymer electrolyte containing the anion receptor of the present invention comprises a gel polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell composed of the above nonaqueous liquid electrolyte.
The secondary cell composed of a solid polymer electrolyte containing the anion receptor of the present invention comprises a solid polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell
composed of the above nonaqueous liquid electrolyte.
Moreover, the present invention provides a polymer electrolyte film (membrane) using an electrolyte of the present invention. A preparation method of a gel or solid polymer electrolyte film (membrane) containing the components of the present invention is as follows:
First, in case of a gel polymer electrolyte, a nonaqueous solvent, an anion receptor of the Formula 1 and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. A polymer support is then added to the solution and mixed together. If necessary, heat can be applied to completely dissolve the polymer support in the solution. In this manner, a composite mixture for preparing a gel polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron rays, UV rays or
γ-rays, or heated to cause the hardening reaction, and a desired film is obtained.
In case of a solid polymer electrolyte, on the other hand, an anion receptor or polyalkyleneglycol dialkylether or a nonaqueous solvent and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. Then, a net-shaped, branched or comb-shaped polymer compound or a crosslinkable polymer compound is added to the solution and is mixed together. If necessary, heat can be applied to completely dissolve the net-shaped, branched or comb-shaped polymer compound in the solution. Meanwhile, a curing initiator can be added to the solution when the crosslinkable polymer is used, hi this manner, a composite mixture for preparing a solid polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron rays, UV rays
or γ-rays, or heated to cause the hardening reaction, and a desired film is obtained.
Another example of the preparation method for a film is as follows. After the support substrate is coated with the composite mixture, a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a gel or solid polymer electrolyte film.
Brief Description of the Drawings
FIG. 1 is a graph showing a relation between ionic conductivities and temperature changes in solid polymer electrolytes of the present invention and of comparative examples (Experimental example 4); and
FIG. 2 is a graph showing lithium cycling performance of cells of the present invention and of comparative examples (Experimental example 5).
Preferred Embodiments
A preferred embodiment of the present invention will be described herein below. It is also to be understood that examples herein are for the purpose of describing the present invention only, and are not intended to be limiting. Preparation Example 1 [Reaction Scheme 2]
Figure imgf000025_0001
Allyl-TFSA
1.Og of allylamine (17.5mmol) and 2.Og of triethylamine (20mmol) were mixed with 40ml of chloroform at -4O0C, and 5.Og of triflic anhydride (18mmol) was added dropwise to the mixture under nitrogen atmosphere. The solution was stirred at room temperature for four hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30ml of 4M NaOH, and washed with chloroform. Then, an organic extract was dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield N-Ally-C,C,C-trifluoro- methanesulfonamide (Allyl-TFSA) (see the Reaction Scheme 2). 1R NMR (300MHz, CDCl3): ppm 3.9 (m, 2H), 4.9 (s-broad, IH), 5.35 (m, 2H), 5.9
(m, IH); 19F NMR (CDCl3): ppm -77.9 (s)
Example 1 [Reaction Scheme 3]
Figure imgf000026_0001
D4H
,
F,
Figure imgf000026_0002
C 4-HTSA
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 10.3g of allyl-TFSA (0.055mol) obtained from Preparation Example 1 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4TFSA (see the Reaction Scheme 3). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.51(m, 2H), 1.49-1.54(m, 2H), 3.13-3.15(m, 2H), 5.64-5.68(m, IH)
Example 2 [Reaction Scheme 4]
Figure imgf000027_0001
I
Figure imgf000027_0002
( j 4 1 1 SI
49.8g of Q-4TFSA of Example 1 and 24.3g of triethylamine were dissolved in 100ml of chloroform -250C. Then, 62.1g of triflic anhydride was added dropwise to the reaction mixture under nitrogen atmosphere. The resulting solution was stirred at room temperature for 1 hour, and distilled water was poured therein to separate an organic layer. The organic layer thusly obtained was washed three times with distilled water. Then, an organic extract was dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield Q-4TFSI (see the Reaction Scheme 4).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.51(m, 2H), 1.49-1.54(m, 2H), 3.13-3.15(m, 2H)
Preparation Example 2 [Reaction Scheme 5]
.NH, CICN -CH2CHCH2NH2CI
Figure imgf000028_0001
Allylmonocyanamidc Allyldicyanamide
86g of cyanuric chloride (1.4mol) was dissolved in 150ml of cold anhydrous ether (-1O0C). A mixed solution of 57.1g of allylamine and 20ml of anhydrous ether was added thereto over 2 hours while keeping the temperature below -50C. The reaction mixture was set aside until room temperature for 12 hours. A white precipitate thusly produced was collected and washed once with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. Then, a mixed solution of 30.7g of cyanuric chloride (0.5mol) and 150ml of cold anhydrous ether (-150C) was added dropwise to the filtrate while stirring. At the same time, another mixed solution of 50.6g of triethylamine (0.5mol) and 150ml of anhydrous ether was added dropwise to the filtrate while keeping the temperature below -
1O0C. Stirring and cooling was continued for an additional 15 minutes and the temperature of the reaction mixture was raised to +1O0C. A precipitate was filtered and washed once with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. The ether solution was evaporated and the residue was fractionally distilled over a 15cm Vigreux column under nitrogen atmosphere. To obtain dicyanamide free of diethyl cyanamide, the crude product was distilled once more over the Vigreux column to yield allyldicyanamide (Allyl-DCN) (see the Reaction Scheme 5).
1H NMR (300MHz, CDCl3): ppm 4.02 (m, 2H), 5.25 (m, 2H), 6.63 (m, IH)
Example 3 [Reaction Scheme 6]
Figure imgf000029_0001
C,-4DCN
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.9g of allyl-DCN (O.055mol) obtained from Preparation Example 2 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DCN (see the Reaction Scheme 6). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.48-0.52(m, 2H), 1.51-1.57(m, 2H),
3.17-3.19(m, 2H) Preparation Example 3 [Reaction Scheme 7]
Figure imgf000030_0001
Allyldifluoroamine
16.8g of allyl iodide (lOOmmol) and 35ml of tetrachloroethane were placed in a
100ml round flask connected to a glass manifold system having an expansion valve, and the entire system went through 3 freezing - defreezing cycles under vacuum to remove air therein. The system was then filled with 6.7Og of tetrafluorohydrazine (64mmol), and the mixture was heated at 6O0C for 2 hours. During the heating process, the pressure was dropped from the lowest 525mmHg to 368mmHg. When excess gas fraction was analyzed by mass spectroscopy, it was discovered that 5.63g of tetrafluorohydrazine (54mmol) was consumed. Obtained dark colored solution was treated with mercury to remove iodin therein. A substantially transparent solution thusly obtained was then distilled to yield allyldifluoroamine (allyl-DFA) (see the Reaction Scheme 7).
1H NMR (300MHz, CDCl3): ppm 4.26 (m, 2H), 5.37 (m, 2H), 5.97 (m, IH) ; 19F NMR (CDCl3): ppm -53.7 (s) Example 4 [Reaction Scheme 8]
Figure imgf000030_0002
C4-4DFΛ 3.Og of 2,4,6, 8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-DFA (O.055mol) obtained from Preparation Example 3 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-1, 3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DCN (see the Reaction Scheme 8).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.48-0.52(m, 2H), 1.51-1.57(m, 2H), 3.17-3.19(m, 2H)
Preparation Example 4 [Reaction Scheme 9]
Figure imgf000031_0001
Alumina
N,N-Dichloroallylamine
A mixture of 106g of chromatographic alumina and 4Og of N-chlorosuccinimide, a chlorinating agent (0.3mol) was packed into a reactor tube (60cm x 40cm). Then, the chlorinating agent was horizontally split between two pieces of quartz wool being 50cm apart from each other. 5.7g of allylamine which was precooled to -3O0C was slowly introduced into the system over 1 hour. Later, vapor was condensed in liquid nitrogen trap to yield N, N-dichloroallylamine (Allyl-DCA) (see the Reaction Scheme 9). 1H NMR (300MHz, CDCl3): ppm 5.2 (m, 2H), 5.4 (m, 2H), 5.95 (m, IH)
Example 5 [Reaction Scheme 10]
Figure imgf000032_0001
C ,-4IX Λ
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 6.9g of allyl-DCA (0.055mol) obtained from Preparation Example 4 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DCN (see the Reaction Scheme 10).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49-1.54(m, 2H), 3.13-3.15(m, 2H) Preparation Example 5 [Reaction Scheme 11]
Figure imgf000032_0002
N-ally!-2,2,2-tπfluoro-N-tπfluoroacetyl-dctamide 0.119g of allylamine (2.09mmol) and 0.49g of anhydrous trifluoroacetic acid (3.2mmol) were reacted with a mixed solution of 3ml of carbon tetrachloride and 0.637g of 2,6-di-tertiary-butyl-4-methyl-pyridine (3.1 lmmol) for four hours. Pyridinium triflate was
filtered and removed to yield N-allyl-2,2,2-trifluoro-N-trifluoroacetyl-acetamide (Allyl- TFAC) (see the Reaction Scheme 11).
1H NMR (300MHz, CDCl3): ppm 4.37 (m, 2H), 5.07-5.26 (m, 2H), 5.80 (m, IH) ) ;
19F NMR (CDCl3): ppm -71.3 (s) Example 6 [Reaction Scheme 12]
Figure imgf000033_0001
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 13.7g of allyl-TFAC (0.055mol) obtained from Preparation Example 5 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-1, 3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was reflux ed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4TFAC (see the Reaction Scheme 12). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49-1.54(m, 2H), 3.13-3.15(m, 2H) Preparation Example 6
[Reaction Scheme 13]
Figure imgf000034_0001
THGM 164Ac (ii --3) e PFXΪM350Ac <ιv=7.2)
6.Og of NaOH and tri(ethylene glycol)monomethylether (TEGMe, Mw=I 64.2) were put into 50ml THF dried over Na. A small amount of copper(II) chloride as a polymerization inhibitor was added thereto under nitrogen atmosphere, and 18.2g of allylbromide was then added dropwise. The reaction mixture was refluxed for 12 hours. 0 When the reaction was completed, extra NaOH and the product NaBr were filtered and the TFT was evaporated under reduced pressure. The residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH solution. An organic layer thusly obtained was dried over anhydrous MgSO4 and dried under vacuum to yield tri(ethylene glycol) monomethyl monoallyl ether [TEGMAe (n=3)] (see the Reaction 5 Scheme 13).
1H NMR (300MHz, CDCl3): 3.37 ppm (s, 3H), 3.54-3.67 (m, 12H), 4.02 (d, 2H), 5.25 (m, 2H); 13C NMR (300MHz, CDCl3): ppm 58.99, 69.41, 70.51, 70.61, 71.92, 72.18, 116.99, 134.78 Preparation Example 7 Under the same conditions as in Preparation Example 6, 43.8g of poly(ethylene glycol) monomethyl ether (PEGMe, Mw=350) and 18.2g of allylbromide were reacted to yield poly(ethylene glycol) monomethyl monoallyl ether [PEGMAe (n=7.2)] (see the
Reaction Scheme 13). 1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 4.14-4.18 (d, 2H), 5.25-5.50 (m, IH), 5.95-6.15(m, 2H); 13C NMR (300MHz, CDCl3): ppm 59.31, 69.73, 70.81, 70.88, 72.23, 72.50, 117.32, 135.09
Example 7 [Reaction Scheme 14]
Figure imgf000035_0001
D,H
Figure imgf000035_0002
C4-2TFSΛ-2TEGMP (n=3) C-2TFSA-2PF.GMP (n=7.2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 5.6g of TEGMAe (0.0275mol) obtained from Preparation Example 6 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room
temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-2TFSA-2TEGMP (see the Reaction Scheme 14).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m, 2H), 3.13-3.15(m, 2H), 3.31-3.60(m, 17H), 5.66-5.71(m, IH) Example 8
Under the same conditions as in Example 7, 3.Og of D4H, 5.1g of ally-TFSA obtained from Preparation Example 1, and 10.7g of PEGMAe obtained from Preparation Example 7 were reacted to yield C4-2TFSA-2PEGMP (see the Reaction Scheme 14).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m, 2H), 3.13-3.15(m, 2H), 3.31-3.59(m, 33.8H), 5.63-5.68(m, IH) Preparation Example 8 [Reaction Scheme 15]
Figure imgf000036_0001
TEGMCI (n=3) PEGMCI (n=7.2)
16.4g of tri(ethylene glycol)monomethylether (TEGMe) and 19.5g of 1,1- carbodiimidazole were put into 200ml THF dried over Na. The reaction ran at a temperature range of 40 - 5O0C for 5 - 6 hours under nitrogen atmosphere. When the reaction was completed, extra carbodiimidazole was filtered and extracted three times with chloroform or methylchloride and 5wt% NaOH solution. An organic layer was separated,
dried over anhydrous MgSO4 and dried under vacuum to yield tri(ethylene glycol) monomethyl ether carbonylimidazole [TEGMCI, n=3, Mw=258.2] (see the Reaction
Scheme 15). 1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 12H), 7.07 (s, IH),
7.44 (s, IH)
Preparation Example 9
Under the same conditions as in Preparation Example 8, 35.Og of poly(ethylene glycol) monomethyl ether (PEGMe) and 19.5g of 1,1-carbodiimidazole were reacted to yield poly(ethylene glycol) monomethyl ether carbonylimidazole (PEGMCI, n=7.2,
Mw=444) (see the Reaction Scheme 15).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 7.07 (s, IH),
7.44 (s, IH)
Preparation Example 10 [Reaction Scheme 16]
O
N v- ^ -i-,-N" L C U 0((LCnH21^CHH12UO))-nLCHH31 + /^ ■s^-' — "-^s-./' \_ Il
\^ " " ^ ^^ O C-O — (CH2CH2O)nCH,
TEGMAC (n=3) PEGMAC (n=7.2)
25.8g of TEGMCI obtained from Preparation Example 8 and 6.4g of allylalcohol were added into 50ml THF dried over Na. The reaction mixture was reflux ed for 24 hours under nitrogen atmosphere. When the reaction was completed, the THF was evaporated under reduced pressure and the residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH solution. An organic layer thusly separated was dried over anhydrous MgSO4 and dried under vacuum to yield TEGMAC (n=3, Mw=249.2) into which allyl carbonate was introduced (see the Reaction Scheme 16).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 12H), 4.63-4.61 (d,
2H), 5.39-5.24 (m, 2H), 5.99-5.89 (m, IH)
Preparation Example 11
Under the same conditions as in Preparation Example 10, 44.4g of PEGMCI obtained form Preparation Example 8 and 5.8g of allylalcohol were reacted to yield PEGMAC (n=7.2, Mw=435) (see the Reaction Scheme 16).
1R NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 4.63-4.61 (d, 2H), 5.39-5.24 (m, 2H), 5.99-5.89 (m, IH) Example 9 [Reaction Scheme 17]
Figure imgf000039_0001
TEGMAC (n=3)
I)4H PEGMAC (n=7 2)
I,
Figure imgf000039_0002
C4-2ΪTSΛ-2 H-CiMPC (n-J) C4-2 I ! SΛ-2P! GMPC (n=7 2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 6.99g of TEGMAC (0.0275mol) obtained from Preparation Example 10 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield Q-2TFSA-2TEGMPC (see the Reaction Scheme 17). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m, 2H), 3.13-3.15(m, 2H), 3.31-3.60(m, 17H), 5.64-5.68(m, IH)
Example 10
Under the same conditions as in Example 9, 3.0g of D4H, 5.1g of ally-TFSA obtained from Preparation Example 1, and 12.Og of PEGMAC obtained from Preparation Example 10 were reacted to yield C4-2TFSA-2PEGMPC (see the Reaction Scheme 17).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m, 2H), 3.13-3.15(m, 2H), 3.31-3.59(m, 33.8H), 5.63-5.68(m, IH) Example 11 [Reaction Scheme 18]
Figure imgf000041_0001
allyl cyanide
D4H
Figure imgf000041_0002
C4-2TFSA-2CN
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 1.8g of allyl cyanide (0.0275mol) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-1, 3-divinyl- 1,1,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-2TFSA-2CN (see the Reaction Scheme 18). 1H NMR (300MHz, CDCl3): ppm 0.15(s, 3H), 0.74(m, 2H), 1.71(m, 2H), 2.4(m, 2H), 5.63-5.68(m, IH) Preparation Example 12 [Reaction Scheme 19]
Figure imgf000042_0001
3-(allyloxy)-1 ,2-propandιol
Figure imgf000042_0002
384ml of diethyl carbonate, 192ml of 3-(allyloxy)-l,2-propanediol, and 32g (dry) of potassium carbonate were added into a 1,000ml round flask which was fitted with a magnetic stirring bar and a Dean Stark trap with a water cooled condenser in order to collect ethanol, one of the products. The reaction mixture was heated at 12O0C for 24 hours and the resulting ethanol was distilled. When the reaction was completed, the reaction mixture was cooled to room temperature and filtered, and a solid phase carbonate in the solution was removed. Meanwhile, the residue was vacuum distilled at a pressure of lOmmHg to yield (cyclic-allyloxy)methylethylene ester carboxylic acid (CAMEECA, Mw=I 58). Among the fractional distillates, a distillate obtained at a temperature of 150 - 1520C was chosen as a final product (see the Reaction Scheme 19).
1H NMR (300MHz, CDCl3): ppm 3.66 (m, 2H), 4.05 (d, 2H), 4.48 (m, 2H), 4.818 (m, IH), 5.25 (m, 2H), 5.86(m, IH) Example 12 [Reaction Scheme 20]
Figure imgf000043_0001
( A 2 I FSA 2C Pl>
3.Og of 2,4,6, 8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 4.3g of CAMEECA (0.0275mol) obtained from Preparation Example 12 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was reflux ed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-2TFS A-2CPP (see the Reaction Scheme 20). 1H NMR (300MHz, CDCl3): ppm 0.19(s, 3H), 0.62(m, 2H), 1.70(m, 2H), 3.5 l(m, 2H), 3.74(m, 2H), 4.37(m, 2H), 4.96(s, IH), 5.64-5.68(m, IH) Examples 13 - 47
Anion receptors (Example 13 - 47) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1 and 7-12 in the weight ratio shown in Table 1 below. [Table 1]
Figure imgf000044_0001
Figure imgf000045_0001
C4-TFSA-
TEGMP-
37 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4-TFSA-
TEGMP-
38 2.8 g 6.O g 0.9 g
PEGMPC-
CN
C4-TFSA-
PEGMP-
39 5.4 g 6.O g 0.9 g
PEGMPC-
CN
C4-TFSA- TEGMPC-
40 3.4 g 6.O g 0.9 PEGMPC-
CN
C4-TFSA-
TEGMP-
41 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
C4-TFSA-
PEGMP-
42 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
C4-TFSA- TEGMP-
43 2.8 g 5.4 g 0.9 g PEGMP-
CN
C4-TFSA-
TEGMP-
44 2.8 g 3.4g 0.6 g
TEGMPC-
PEGMPC
C4-TFSA-
PEGMP-
45 5.4 g 3.4 g 0.6 g
TEGMPC-
PEGMPC
C4-TFSA- TEGMP-
46 2.8 g 5.4 g 0.6 g PEGMP- PEGMPC
C4-TFSA- TEGMP-
47 2.8 g 5.4 g 3.4 g PEGMP- TEGMPC
Examples 48 - 88
Anion receptors (Example 48 - 88) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3 and 7-12 in the weight ratio shown in Table 2 below. [Table 2]
Figure imgf000047_0001
C4-2 DCN -
67 5.4 g 3.4 g PEGMP-
TEGMPC
C4-2 DCN -
68 2.8 g 5.4 g TEGMP-
TEGMP C4- DCN -
69 1.48 g 2.8 g 0.9 g 2.2 g TEGMP-
CN-CPP C4- DCN -
70 5.4 g 0.9 g 2.2 g PEGMP-
CN-CPP C4- DCN -
71 3.4 g 0.9 g 2.2 g TEGMPC-
CN-CPP C4- DCN -
72 6.O g 0.9 g 2.2 PEGMPC-
CN-CPP C4- DCN -
TEGMP-
73 2.8 g 6.O g 2.2 g PEGMPC-
CPP C4- DCN -
PEGMP-
74 5.4 g 6.O g 2.2 g PEGMPC-
CPP
C4- DCN - TEGMPC-
75 3.4 g 6.O g 2.2 g PEGMPC-
CPP C4- DCN -
TEGMP-
76 2.8 g 3.4 g 2.2 g TEGMPC-
CPP C4- DCN -
PEGMP-
77 5.4 g 3.4 g 2.2 g TEGMPC-
CPP C4- DCN -
TEGMP-
78 2.8 g 5.4 g 2.2 g
PEGMP-
CPP C4- DCN -
TEGMP-
79 2.8 g 6.O g 0.9 g PEGMPC-
CN C4- DCN -
PEGMP-
80 5.4 g 6.O g 0.9 g PEGMPC-
CN
C4- DCN -
TEGMPC-
81 3.4 g 6.O g 0.9 g
PEGMPC-
CN
Figure imgf000049_0001
Examples 89 - 129
Anion receptors (Example 89 - 129) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4 and 7-12 in the weight ratio shown in Table 3 below. [Table 3]
Figure imgf000049_0002
C4-2 DFA
92 12.O g
2PEGMP C
C4-2 DFA
93 1.8 g -2CN
C4-2 DFA
94 4.3 g -2CPP
C4-2 DFA
95 2.8 g 2.2 g -TEGMP- CPP
C4-2 DFA
96 5.4 g 2.2 g -PEGMP- CPP
C4-2 DFA
97 3.4 g 2.2 g
TEGMPC
-CPP C4-2 DFA
98 6.O g 2.2 g
PEGMPC
-CPP C4-2 DFA
99 0.9 g 2.2 g -CN-CPP
C4-2 DFA
100 2.8 g 0.9 g -TEGMP-
CN
C4-2 DFA
101 5.4 g 0.9 g -PEGMP-
CN C4-2 DFA
102 3.4 g 0.9 g
TEGMPC
-CN C4-2 DFA
103 6.O g 0.9 g
PEGMPC
-CN
C4-2 DFA
104 2.8 g 6.O g -TEGMP- PEGMPC C4-2 DFA
105 5.4 g 6.O g -PEGMP- PEGMPC C4-2 DFA
106 3.4 g 6.Og TEGMPC
PEGMPC C4-2 DFA
107 2.8 g 3.4 g -TEGMP- TEGMPC C4-2 DFA
108 5.4 g 3.4 g -PEGMP- TEGMPC
Figure imgf000051_0001
Figure imgf000052_0001
Example 130 - 170
Anion receptors (Example 130 - 170) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5 and 7-12 in the weight ratio shown in Table 4 below. [Table 4]
Figure imgf000052_0002
Figure imgf000053_0001
C4- DCA -
TEGMP-
155 2.8 g 6.O g 2.2 g
PEGMPC-
CPP
C4- DCA -
PEGMP-
156 5.4 g 6.O g 2.2 g
PEGMPC-
CPP
C4- DCA - TEGMPC-
157 3.4 g 6.O g 2.2 g PEGMPC-
CPP
C4- DCA -
TEGMP-
158 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCA -
PEGMP-
159 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCA - TEGMP-
160 2.8 g 5.4 g 2.2 g PEGMP-
CPP
C4- DCA -
TEGMP-
161 2.8 g 6.O g 0.9 g
PEGMPC-
CN
C4- DCA -
PEGMP-
162 5.4 g 6.O g 0.9 g
PEGMPC-
CN
C4- DCA - TEGMPC-
163 3.4 g 6.O g 0.9 g PEGMPC-
CN
C4- DCA -
TEGMP-
164 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
C4- DCA -
PEGMP-
165 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
C4- DCA - TEGMP-
166 2.8 g 5.4 g 0.9 g PEGMP-
CN
C4- DCA-
TEGMP-
167 2.8 g 3.4g 0.6 g
TEGMPC-
PEGMPC
C4- DCA-
PEGMP-
168 5.4 g 3.4 g 0.6 g
TEGMPC-
PEGMPC
Figure imgf000055_0001
Examples 171 - 211
Anion receptors (Example 171 - 211) of the Formula 1 of the present invention were prepared using the procedures described in Examples 6 and 7-12 in the weight ratio shown in Table 5 below. [Table 5]
Figure imgf000055_0002
Figure imgf000056_0001
C4- TFAC -
TEGMP-
201 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4- TFAC -
TEGMP-
202 2.8 g 6.O g 0.9
PEGMPC-
CN
C4- TFAC -
PEGMP-
203 5.4 g 6.O g 0.9 g
PEGMPC-
CN
C4- TFAC - TEGMPC-
204 3.4 g 6.O g 0.9 g PEGMPC-
CN
C4- TFAC -
TEGMP-
205 2.8 g 3.4 g 0.9 !
TEGMPC-
CN
C4- TFAC -
PEGMP-
206 5.4 g 3.4 g 0.9 i
TEGMPC-
CN
C4- TFAC -
207 2.8 g 5.4 g 0.9 i TEGMP-
PEGMP-CN
C4- TFAC- TEGMP-
208 2.8 g 3.4g 0.6 g
TEGMPC- PEGMPC
C4- TFAC- PEGMP-
209 5.4 g 3.4 g 0.6 g
TEGMPC- PEGMPC
C4- TFAC - TEGMP-
210 2.8 g 5.4 g 0.6 g PEGMP- PEGMPC
C4- TFAC - TEGMP-
211 2.8 g 5.4 g 3.4 g PEGMP- TEGMPC
Examples 212 - 227
Anion receptors (Example 212 - 227) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3 and 7-12 in the weight ratio shown in Table 6 below. [Table 6]
Figure imgf000058_0001
Figure imgf000059_0001
Examples 228 - 243
Anion receptors (Example 228 - 243) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4 and 7-12 in the weight ratio shown in Table 7 below. [Table 7]
Figure imgf000059_0002
Figure imgf000060_0001
Figure imgf000061_0001
Examples 244 - 259
Anion receptors (Example 244 - 259) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5 and 7-12 in the weight ratio shown in Table 8 below. [Table 8]
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Examples 260 - 275
Anion receptors (Example 260 - 275) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 6 and 7-12 in the weight ratio shown in Table 9 below. [Table 9]
Figure imgf000063_0002
Figure imgf000064_0001
Figure imgf000065_0001
Examples 276 - 291
Anion receptors (Example 276 - 291) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
Figure imgf000065_0002
C4- DCN- DFA-
280 6.0g 2.2 g
PEGMPC -CPP
C4- DCN-
281 0.9 g 2.2 g DFA -CN-
CPP
C4- DCN-
DFA-
282 2.8 g 0.9 g TEGMP-
CN
C4- DCN-
DFA-
283 5.4 g 0.9 g
PEGMP-
CN
C4- DCN-
DFA-
284 3.4 g 0.9 g TEGMPC
-CN
C4- DCN-
DFA-
285 6.Og 0.9 g PEGMPC
-CN
C4- DCN-
DFA-
286 2.8 g 6.Og TEGMP- PEGMPC
C4- DCN-
DFA-
287 5.4 g 6.Og PEGMP- PEGMPC
C4- DCN-
DFA-
288 3.4 g 6.Og TEGMPC
PEGMPC
C4- DCN-
DFA-
289 2.8 g 3.4 g TEGMP- TEGMPC
C4- DCN-
DFA-
290 5.4 g 3.4 g PEGMP- TEGMPC
C4- DCN-
DFA-
291 2.8 g 5.4 g TEGMP-
TEGMP
Examples 292 - 307
Anion receptors (Example 292 - 307) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 5 and 7-12 in the weight ratio shown in Table 11 below. [Table 11]
Figure imgf000067_0001
Figure imgf000068_0001
Examples 308 - 323
Anion receptors (Example 308 - 323) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 6 and 7-12 in the weight ratio shown in Table 12 below. [Table 12]
Figure imgf000068_0002
C4-DCN-
313 0.9 g 2.2 g TFAC- CN-CPP
C4-DCN-
TFAC-
314 2.8 g 0.9 g
TEGMP-
CN
C4-DCN- TFAC-
315 5.4 g 0.9 g PEGMP-
CN
C4-DCN-
TFAC-
316 3.4 g 0.9 g
TEGMPC
-CN
C4-DCN-
TFAC-
317 6.Og 0.9 g
PEGMPC
-CN
C4- DCN-
TFAC-
318 2.8 g 6.Og
TEGMP-
PEGMPC
C4- DCN-
TFAC-
319 5.4 g 6.Og
PEGMP-
PEGMPC
C4- DCN-
TFAC-
320 3.4 g 6.Og TEGMPC
PEGMPC
C4- DCN-
TFAC-
321 2.8 g 3.4 g
TEGMP-
TEGMPC
C4- DCN-
TFAC-
322 5.4 g 3.4 g
PEGMP-
TEGMPC
C4- DCN- TFAC-
323 2.8 g 5.4 g
TEGMP- TEGMP
Examples 324 - 339
Anion receptors (Example 324 - 339) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 5 and 7-12 in the weight ratio shown in Table 13 below. [Table 13]
Figure imgf000070_0001
Figure imgf000071_0001
Examples 340 - 355
Anion receptors (Example 340 - 355) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 6 and 7-12 in the weight ratio shown in Table 14 below. [Table 14]
Figure imgf000071_0002
C4-DFA-
345 0.9 g 2.2 g TFAC- CN-CPP
C4-DFA- TFAC-
346 2.8 g 0.9 g TEGMP-
CN
C4-DFA- TFAC-
347 5.4 g 0.9 g PEGMP-
CN
C4-DFA-
TFAC-
348 3.4 g 0.9 g
TEGMPC
-CN
C4-DFA-
TFAC-
349 6.Og 0.9 g
PEGMPC
-CN
C4-DFA-
TFAC-
350 2.8 g 6.Og
TEGMP-
PEGMPC
C4-DFA-
TFAC-
351 5.4 g 6.Og
PEGMP-
PEGMPC
C4-DFA-
TFAC-
352 3.4 g 6.OE TEGMPC
PEGMPC
C4-DFA-
TFAC-
353 2.8 g 3.4 g
TEGMP-
TEGMPC
C4-DFA-
TFAC-
354 5.4 g 3.4 g
PEGMP-
TEGMPC
C4-DFA- TFAC-
355 2.8 i 5.4 g TEGMP- TEGMP
Examples 356 - 371
Anion receptors (Example 356 - 371) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5, 6 and 7-12 in the weight ratio shown in Table 15 below. [Table 15]
Figure imgf000073_0001
Figure imgf000074_0001
Examples 372 - 377
Anion receptors (Example 372 - 377) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 6 and 7-12 in the weight ratio shown in Table 16 below. [Table 16]
Figure imgf000074_0002
Figure imgf000075_0001
Examples 378 - 383
Anion receptors (Example 378 - 383) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 6 and 7-12 in the weight ratio shown in Table 17 below. [Table 17]
Figure imgf000075_0002
Figure imgf000076_0001
Examples 384 - 389
Anion receptors (Example 384 - 389) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5, 6 and 7-12 in the weight ratio shown in Table 18 below. [Table 18]
Figure imgf000076_0002
Figure imgf000077_0001
Examples 390 - 395
Anion receptors (Example 390 - 395) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 5 and 7-12 in the weight ratio shown in Table 19 below. [Table 19]
Figure imgf000077_0002
Figure imgf000078_0001
Examples 396 - 401
Anion receptors (Example 396 - 401) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 5 and 7-12 in the weight ratio shown in Table 20 below. [Table 20]
Figure imgf000078_0002
Figure imgf000079_0001
Examples 402- 407
Anion receptors (Example 402 - 407) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4 and 7-12 in the weight ratio shown in Table 21 below. [Table 21]
Figure imgf000079_0002
Figure imgf000080_0001
Examples 408 - 412
Anion receptors (Example 408 - 412) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4, 5 and 6 in the weight ratio shown in Table 22 below. [Table 22]
Figure imgf000080_0002
Figure imgf000081_0001
Example 413. Manufacture of Conductive Thin Film (1)
3.0g of the anion receptor C4-4TFSA obtained from Example 1 was mixed with 2g of bisphenol A ethoxylate dimethacrylate (Bis- 15m) of the formula (III) used as a crosslinking agent, 5g of poly(ethylene glycol) dimethyl ether (Mw=300, PEGDME 300), and 0.06g of dimethoxyphenyl acetophenone (DMPA). To this mixture, 2.4Og of lithium trifluoromethane sulfonimide (Li(CF3SO2)2N) was added. Then, the resulting solution was coated onto a conductive glass substrate and exposed to 350nm UV rays for 30 minutes under nitrogen atmosphere. With this radiation, a solid polymer electrolyte was prepared. Example 414. Manufacture of Conductive Thin Film (2) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor Q-4TFSA obtained from Example 1 was replaced by 1.5g of C4-4TFSA and 1.5g of the anion receptor C4-4TFSI obtained from Example 2 to prepare a solid polymer electrolyte. Example 415. Manufacture of Conductive Film (3) The same procedure of Example 413 was repeated, with TA- 10 of the Formula 4 instead of the compound of the Formula 3 used as a crosslinking agent to prepare a solid polymer electrolyte. Example 416. Manufacture of Conductive Thin Film (4) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor C4-4TFSA obtained from Example 1 was replaced by 1.5g of Q-4TFSA and 1.5g of the anion receptor C4-4TFSI obtained from Example 2 to prepare a solid polymer electrolyte. Examples 417 - 431. Manufacture of Conductive Thin Film (5 - 19)
The same procedure of Example 413 was repeated, with the exception that compositions of compounds used are as shown in the following Table 23 to prepare a solid polymer electrolyte. Comparative Examples 1 - 2. Manufacture of Film without Anion Receptors (1 - 2)
The same procedure of Example 413 was repeated using the compositions of compounds shown in the following Table 23 to prepare a solid polymer electrolyte. As shown in Table 23, polymer electrolytes of Comparative Examples do not contain anion receptors. [Table 23]
Figure imgf000082_0001
Figure imgf000083_0001
Depending on Amount of Anion Receptors Used
Ionic conductivities of the solid polymer electrolyte films obtained from the above examples were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium-copper foil, photohardened, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance. To manufacture the band shaped electrodes, masking tapes having a width between 0.5mm and 2mm were adhered to the center of a conductive glass (ITO) at intervals of 0.5 - 2mm, etched in an etching solution, washed and dried. Ionic conductivity of the solid polymer electrolyte film thusly obtained was measured at a temperature of 3O0C. Results are shown in Table 24. According to Table 24, ionic conductivity of the film of Example 418 is greater than that of the film of Example 417. Similarly, ionic conductivity of Example 420 is greater than that of Example 419. These results prove that ionic conductivity improves proportionally to the concentration of anion receptors. [Table 24]
Figure imgf000084_0001
Experimental Example 2. Ionic Conductivity Test (2) - Ionic Conductivities of Anion Receptors Containing Plasticizers
Ionic conductivity measurement results of polymer films of the Examples 422 and 423 at a temperature of 3O0C are shown in the following Table 25. The test was carried out using the same procedure described in Experimental Example 1 to find out conditions for maximizing ion conductivities of polymer films, hi particularly, plasticizers and anion receptors were used together to make polymer films. It turned out that Example 2 which used both anion receptors and plasticizers exhibited superior ionic conductivity to that of Example 1 which used anion receptors only. [Table 25]
Figure imgf000084_0002
Figure imgf000085_0001
Experimental Example 3. Ionic Conductivity Test (3) - Ionic Conductivities Depending on Kind of Anion Receptors
The same procedure in Example 413 was repeated to manufacture solid polymer electrolyte films using anion receptors obtained from Examples 3 - 7, 11, 12 and 28. Using the same procedure described in Experimental Example 1, ionic conductivities of the films were measured. The measurement results are shown in the following Table 26. As shown in Table 26, the results proved that solid polymer electrolytes containing various anion receptors exhibited superior ionic conductivities. [Table 26]
Figure imgf000085_0002
Comparative Experimental Example 1. Ionic Conductivities of Solid Polymer Electrolytes without Anion Receptors
Ionic conductivities of films obtained from Comparative Examples 1 and 2 without anion receptors were measured using the same procedure described in Experimental Example 1. Ionic conductivity measurement results of the solid polymer electrolyte films at a temperature of 3O0C are shown in Table 27. Comparing the measurement results shown in Table 27 with the measurement results shown in Tables 24 - 26, one can find out that ionic conductivities of films without anion receptors are very low. [Table 27]
Figure imgf000086_0001
Experimental Example 4. Ionic Conductivity Test (4) - Ionic Conductivities Depending on Temperature
The same procedure described in Experimental Example 1 was repeated to measure ionic conductivities of films obtained from Example 421 (TC-2TF10) and Comparative Example 2 (TA-IO(S)) according to a change in temperature. The measurement results are shown in FIG. 1. Example 431. Manufacture of Cell Using Liquid Electrolyte with Anion Receptors
0.015g of the anion receptor C4-4TFSI obtained from Example 2 was mixed with 1.Og of an organic solvent EC/DMC/EMC (1:1:1, IM LiPF6). A polypropylene separator impregnated with the above solution was inserted between a LiCoO2 anode and a graphite carbon cathode in a dry room (humidity below 3%) and vacuum-sealed to assemble a cell. The LiCoO2 anode was prepared by coating an aluminum foil with a mixture of 94wt% LiCoO2 (manufactured by Nippon Chemical Industry), 3wt% of acetylene black, and 3wt% of polyvinylidenfluoride (PVDF).
Comparative Example 3. Manufacture of Cell Using Liquid Electrolyte without Anion Receptors The same procedure described in Example 431 was repeated, with the exception that the separator impregnated with an organic solvent EC/DMC/DEC (1:1 :1, IM LiPF6) only was inserted between a LiCoO2 anode and a graphite carbon cathode. Experimental Example 5. Cell Lithium Cycling Performance and Efficiency Test Lithium cycling performance and efficiency of cells manufactured in Example 431 of the present invention and Comparative Example 3 were tested at room temperature using Maccor 4000. Charging and discharging were carried out to 0.2, 0.5 and 1C, respectively. The cells were charged and discharged anywhere between 3.0V and 4.2V at a predetermined current density of 0.6mA/cm (charging) and 1.5mA/cm (discharging) with respect to a LiCoO2 counter electrode.
FIG. 2 graphically shows a comparison between discharge capacities with respect to the number of cyclings of cells manufactured using electrolytes inclusive of the anion receptor C4-4TFSI (Example 2) and those of cells manufactured using electrolytes exclusive of the anion receptor. As shown in FIG. 2, it turned out that the cells manufactured using electrolytes of the anion receptor C4-4TFSI exhibited higher capacity and superior stability.
Industrial Applicability
As described above, the novel anion receptor of the present invention can be used as an additive to enhance lithium cycling performance and efficiency of liquid electrolytes for high capacity lithium-ion batteries and cells. In addition, the polymer electrolytes containing the novel anion receptor offer substantially enhanced ionic conductivities and electrochemical stabilities at room temperature, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all
kinds of electronic equipments, e.g., camcorders, and large capacity lithium polymer secondary cells used in power storage systems for power equalization and electric vehicles.

Claims

What is claimed is:1. A compound represented by the following Formula 1 :
[Formula 1]
Figure imgf000089_0001
wherein R1 and R2 independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting of -SO2CF3, -CN, -F, -Cl, -COCF3 and -SO2CN, but do not both simultaneously represent a hydrogen atom;
R3 represents a hydrogen atom or a cyano group;
Figure imgf000089_0002
R5 and R6 independently represents a hydrogen atom or a methyl group; R7 and the other R7 in the formula each independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy 1 group; Y and Z independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, and q are integers from O to 1000, respectively; and r and s are integers from 0 to 20, respectively, whose sum is at least 1.
2. The compound of claim 1 is selected from the group consisting of: C4-4TFSA; Q-4TFSI; C4-2TFSA-2TEGMP; Q-2TFSA-2PEGMP; C4-2TFSA- 2TEGMPC; C4-2TFSA-2PEGMPC; C4-2TFSA-2CN; C4-2TFSA-2CPP; C4-2TFSA- TEGMP-CPP; Q-2TFSA-PEGMP-CPP; C4-2TFSA-TEGMPC-CPP; C4-2TFSA- PEGMPC-CPP; Q-2TFSA-CN-CPP; C4-2TFS A-TEGMP-CN; Q-2TFSA-PEGMP-CN; C4^TFSA-TEGMPC-CN; Q-2TFSA-PEGMPC-CN; Q-2TFSA-TEGMP-PEGMPC; C4- 2TFSA-PEGMP-PEGMPC; C4-2TFSA-TEGMPC-PEGMPC; Q-2TFSA-TEGMP- TEGMPC; C4-2TFSA-PEGMP-TEGMPC; C4-2TFSA-TEGMP-TEGMP; C4-TFSA- TEGMP-CN-CPP; C4-TFSA-PEGMP-CN-CPP; C4-TFSA-TEGMPC-CN-CPP; C4-TFSA- PEGMPC-CN-CPP; C4-TFSA-TEGMP-PEGMPC-CPP; C4-TFSA-PEGMP-PEGMPC- CPP; C4-TFSA-TEGMPC-PEGMPC-CPP; C4-TFSA-TEGMP-TEGMPC-CPP; C4-TFSA- PEGMP-TEGMPC-CPP; C4-TFSA-TEGMP-PEGMP-CPP; C4-TFSA-TEGMP-PEGMPC- CN; C4-TFSA-PEGMP-PEGMPC-CN; C4-TFSA-TEGMPC-PEGMPC-CN; C4-TFSA- TEGMP-TEGMPC-CN; C4-TFSA-PEGMP-TEGMPC-CN; C4-TFSA-TEGMP-PEGMP- CN; C4-TFSA-TEGMP-TEGMPC-PEGMPC; C4-TFSA-PEGMP-TEGMPC-PEGMPC; C4-TFSA-TEGMP-PEGMP-PEGMPC; C4-TFSA-TEGMP-PEGMP-TEGMPC; C4-4DCN; C4-2DCN-2TEGMP; C4-2DCN-2PEGMP; C4-2DCN-2TEGMPC; C4-2DCN-2PEGMPC; C4-2DCN-2CN; C4-2DCN-2CPP; C4-2DCN-TEGMP-CPP; C4-2DCN-PEGMP-CPP; C4- 2DCN-TEGMPC-CPP; C4-2DCN-PEGMPC-CPP; C4-2DCN-CN-CPP; C4-2DCN- TEGMP-CN; C4-2DCN-PEGMP-CN; C4-2DCN-TEGMPC-CN; C4-2DCN-PEGMPC-CN; C4-2DCN-TEGMP-PEGMPC; C4-2DCN-PEGMP-PEGMPC; Q-2DCN-TEGMPC- PEGMPC; Q-2DCN-TEGMP-TEGMPC; C4-2DCN-PEGMP-TEGMPC; Q-2DCN- TEGMP-TEGMP; C4-DCN-TEGMP-CN-CPP; C4-DCN-PEGMP-CN-CPP; C4-DCN- TEGMPC-CN-CPP; C4-DCN-PEGMPC-CN-CPP; C4-DCN-TEGMP-PEGMPC-CPP; C4- DCN-PEGMP-PEGMPC-CPP; C4-DCN-TEGMPC-PEGMPC-CPP; C4-DCN-TEGMP- TEGMPC-CPP; C4-DCN-PEGMP-TEGMPC-CPP; C4-DCN-TEGMP-PEGMP-CPP; C4- DCN-TEGMP-PEGMPC-CN; C4-DCN-PEGMP-PEGMPC-CN; C4-DCN-TEGMPC- PEGMPC-CN; C4-DCN-TEGMP-TEGMPC-CN; C4-DCN-PEGMP-TEGMPC-CN; C4- DCN-TEGMP-PEGMP-CN; C4-DCN-TEGMP-TEGMPC-PEGMPC; C4-DCN-PEGMP- TEGMPC-PEGMPC; C4-DCN-TEGMP-PEGMP-PEGMPC; C4-DCN-TEGMP-PEGMP- TEGMPC; C4-4DFA; C4-2DFA-2TEGMP; C4-2DFA-2PEGMP; C4-2DFA-2TEGMPC; C4-2DFA-2PEGMPC; C4-2DFA-2CN; C4-2DFA-2CPP; C4-2DFA-TEGMP-CPP; C4- 2DFA-PEGMP-CPP; C4-2DFA-TEGMPC-CPP; C4-2DFA-PEGMPC-CPP; C4-2DFA-CN- CPP; Q-2DFA-TEGMP-CN; C4-2DF A-PEGMP-CN; C4-2DFA-TEGMPC-CN; C4-2DFA- PEGMPC-CN; Q-2DFA-TEGMP-PEGMPC; C4-2DFA-PEGMP-PEGMPC; C4-2DFA- TEGMPC-PEGMPC; C4-2DF A-TEGMP-TEGMPC; Q-2DF A-PEGMP-TEGMPC; C4- 2DFA-TEGMP-TEGMP; C4-DFA-TEGMP-CN-CPP; C4-DFA-PEGMP-CN-CPP; C4- DFA-TEGMPC-CN-CPP; C4-DFA-PEGMPC-CN-CPP; C4-DFA-TEGMP-PEGMPC-CPP;
C4-DFA-PEGMP-PEGMPC-CPP; C4-DFA-TEGMPC-PEGMPC-CPP; C4-DFA-TEGMP- TEGMPC-CPP; C4-DFA-PEGMP-TEGMPC-CPP; C4-DFA-TEGMP-PEGMP-CPP; C4- DFA-TEGMP-PEGMPC-CN; C4-DFA-PEGMP-PEGMPC-CN; C4-DFA-TEGMPC- PEGMPC-CN; C4-DFA-TEGMP-TEGMPC-CN; C4-DFA-PEGMP-TEGMPC-CN; C4- DFA-TEGMP-PEGMP-CN; C4-DFA-TEGMP-TEGMPC-PEGMPC; C4-DFA-PEGMP- TEGMPC-PEGMPC; C4-DFA-TEGMP-PEGMP-PEGMPC; C4-DFA-TEGMP-PEGMP- TEGMPC; C4-4DCA; C4-2DCA-2TEGMP; C4-2DCA-2PEGMP; C4-2DCA-2TEGMPC; C4-2DCA-2PEGMPC; C4-2DCA-2CN; C4-2DCA-2CPP; C4-2DCA-TEGMP-CPP; C4- 2DCA-PEGMP-CPP; C4-2DC A-TEGMPC-CPP; C4-2DCA-PEGMPC-CPP; Q-2DCA- CN-CPP; C4-2DCA-TEGMP-CN; C4-2DCA-PEGMP-CN; C4-2DCA-TEGMPC-CN; C4- 2DCA-PEGMPC-CN; C4-2DCA-TEGMP-PEGMPC; C4-2DCA-PEGMP-PEGMPC; C4- 2DCA-TEGMPC-PEGMPC; C4-2DCA-TEGMP-TEGMPC; C4-2DCA-PEGMP- TEGMPC; C4-2DCA-TEGMP-TEGMP; C4-DCA-TEGMP-CN-CPP; C4-DCA-PEGMP- CN-CPP; C4-DCA-TEGMPC-CN-CPP; C4-DCA-PEGMPC-CN-CPP; C4-DCA-TEGMP- PEGMPC-CPP; C4-DCA-PEGMP-PEGMPC-CPP; C4-DCA-TEGMPC-PEGMPC-CPP; C4-DCA-TEGMP-TEGMPC-CPP; C4-DCA-PEGMP-TEGMPC-CPP; C4-DCA-TEGMP- PEGMP-CPP; C4-DCA-TEGMP-PEGMPC-CN; C4-DCA-PEGMP-PEGMPC-CN; C4- DCA-TEGMPC-PEGMPC-CN; C4-DCA-TEGMP-TEGMPC-CN; C4-DCA-PEGMP- TEGMPC-CN; C4-DCA-TEGMP-PEGMP-CN; C4-DCA-TEGMP-TEGMPC-PEGMPC; C4-DCA-PEGMP-TEGMPC-PEGMPC; C4-DCA-TEGMP-PEGMP-PEGMPC; C4-DCA- TEGMP-PEGMP-TEGMPC; Q-4TFAC; C4-2TFAC-2TEGMP; C4-2TFAC-2PEGMP; C4- 2TFAC-2TEGMPC; C4-2TFAC-2PEGMPC; C4-2TFAC-2CN; C4-2TFAC-2CPP; C4- 2TFAC-TEGMP-CPP; C4-2TFAC-PEGMP-CPP; C4-2TFAC-TEGMPC-CPP; C4-2TFAC- PEGMPC-CPP; C4-2TFAC-CN-CPP; C4-2TFAC-TEGMP-CN; C4-2TFAC-PEGMP-CN; C4-2TFAC-TEGMPC-CN; C4-2TFAC-PEGMPC-CN; C4-2TFAC-TEGMP-PEGMPC; C4- 2TFAC-PEGMP-PEGMPC; C4-2TFAC-TEGMPC-PEGMPC; C4-2TFAC-TEGMP- TEGMPC; C4-2TFAC-PEGMP-TEGMPC; C4-2TFAC-TEGMP-TEGMP; C4-TFAC- TEGMP-CN-CPP; C4-TFAC-PEGMP-CN-CPP; C4-TFAC-TEGMPC-CN-CPP; C4-TFAC- PEGMPC-CN-CPP; C4-TFAC-TEGMP-PEGMPC-CPP; C4-TFAC-PEGMP-PEGMPC- CPP; C4-TFAC-TEGMPC-PEGMPC-CPP; C4-TFAC-TEGMP-TEGMPC-CPP; C4-TF AC- PEGMP-TEGMPC-CPPi C4-TFAC-TEGMP-PEGMP-CPPi C4-TFAC-TEGMP-PEGMPC- CN; C4-TFAC-PEGMP-PEGMPC-CN; C4-TFAC-TEGMPC-PEGMPC-CN; C4-TFAC- TEGMP-TEGMPC-CN; C4-TFAC-PEGMP-TEGMPC-CN; C4-TFAC-TEGMP-PEGMP- CN; C4-TFAC-TEGMP-TEGMPC-PEGMPC; C4-TFAC-PEGMP-TEGMPC-PEGMPC; C4-TFAC-TEGMP-PEGMP-PEGMPC; C4-TFAC-TEGMP-PEGMP-TEGMPC; C4- 2TFSA-2DCN; C4-TFSA-DCN-TEGMP-CPP; C4-TFSA-DCN-PEGMP-CPP; C4-TFSA- DCN-TEGMPC-CPP; C4-TFSA-DCN-PEGMPC-CPP; C4-TFSA-DCN-CN-CPP; C4- TFSA-DCN-TEGMP-CN; C4-TFSA-DCN-PEGMP-CN; C4-TFSA-DCN-TEGMPC-CN; C4-TFSA-DCN-PEGMPC-CN; C4-TFSA-DCN-TEGMP-PEGMPC; C4-TFSA-DCN- PEGMP-PEGMPC; C4-TFSA-DCN-TEGMPC-PEGMPC; Q-TFSA-DCN-TEGMP- TEGMPC; C4-TFSA-DCN-PEGMP-TEGMPC; C4-TFSA-DCN-TEGMP-TEGMP; C4- 2TFSA-2DFA; C4-TFSA-DFA-TEGMP-CPP; C4-TFSA-DFA-PEGMP-CPP; C4-TFSA- DFA-TEGMPC-CPP; C4-TFSA-DFA-PEGMPC-CPP; C4-TFSA-DFA-CN-CPP; C4- TFSA-DFA-TEGMP-CN; C4-TFSA-DFA-PEGMP-CN; C4-TFSA-DFA-TEGMPC-CN; C4-TFSA-DFA-PEGMPC-CN; C4-TFSA-DFA-TEGMP-PEGMPC; C4-TFSA-DFA- PEGMP-PEGMPC; C4-TFSA-DFA-TEGMPC-PEGMPC; C4-TFSA-DFA-TEGMP- TEGMPC; C4-TFSA-DFA-PEGMP-TEGMPC; C4-TFSA-DFA-TEGMP-TEGMP; C4- 2TFSA-2DCA; C4-TFSA-DCA-TEGMP-CPP; C4-TFSA-DCA-PEGMP-CPP; C4-TFSA- DCA-TEGMPC-CPP; C4-TFSA-DCA-PEGMPC-CPP; C4-TFSA-DCA-CN-CPP; C4- TFSA-DCA-TEGMP-CN; C4-TFSA-DCA-PEGMP-CN; C4-TFSA-DCA-TEGMPC-CN; C4-TFSA-DCA-PEGMPC-CN; C4-TFSA-DCA-TEGMP-PEGMPC; C4-TFSA-DCA- PEGMP-PEGMPC; C4-TFSA-DCA-TEGMPC-PEGMPC; C4-TFSA-DCA-TEGMP- TEGMPC; C4-TFSA-DCA-PEGMP-TEGMPC; C4-TFSA-DCA-TEGMP-TEGMP; C4- 2TFSA-2TFAC; C4-TFSA-TFAC-TEGMP-CPP; C4-TFSA-TFAC-PEGMP-CPP; C4- TFSA-TFAC-TEGMPC-CPP; C4-TFSA-TFAC-PEGMPC-CPP; C4-TFSA-TFAC-CN- CPP; C4-TFSA-TFAC-TEGMP-CN; C4-TFSA-TFAC-PEGMP-CN; C4-TFSA-TFAC- TEGMPC-CN; C4-TFSA-TFAC-PEGMPC-CN; C4-TFSA-TFAC-TEGMP-PEGMPC; C4- TFSA-TFAC-PEGMP-PEGMPC; C4-TFSA-TFAC-TEGMPC-PEGMPC; C4-TFSA- TFAC-TEGMP-TEGMPC; C4-TFSA-TFAC-PEGMP-TEGMPC; C4-TFSA-TFAC- TEGMP-PEGMP; C4-2DCN-2DFA; C4-DCN-DFA-TEGMP-CPP; C4-DCN-DFA- PEGMP-CPP; C4-DCN-DFA-TEGMPC-CPP; C4-DCN-DFA-PEGMPC-CPP; C4-DCN- DFA-CN-CPP; C4-DCN-DFA-TEGMP-CN; C4-DCN-DFA-PEGMP-CN; C4-DCN-DFA- TEGMPC-CN; C4-DCN-DFA-PEGMPC-CN; C4-DCN-DFA-TEGMP-PEGMPC; C4- DCN-DFA-PEGMP-PEGMPC; C4-DCN-DFA-TEGMPC-PEGMPC; C4-DCN-DFA- TEGMP-TEGMPC; C4-DCN-DFA-PEGMP-TEGMPC; C4-DCN-DFA-TEGMP-TEGMP; Q-2DCN-2DCA; C4-DCN-DCA-TEGMP-CPP; C4-DCN-DCA-PEGMP-CPP; C4-DCN- DCA-TEGMPC-CPP; C4-DCN-DCA-PEGMPC-CPP; C4-DCN-DCA-CN-CPP; C4-DCN- DCA-TEGMP-CN; C4-DCN-DCA-PEGMP-CN; C4-DCN-DCA-TEGMPC-CN; C4-DCN- DCA-PEGMPC-CN; C4-DCN-DCA-TEGMP-PEGMPC; C4-DCN-DCA-PEGMP- PEGMPC; C4-DCN-DCA-TEGMPC-PEGMPC; C4-DCN-DCA-TEGMP-TEGMPC; C4- DCN-DCA-PEGMP-TEGMPC; C4-DCN-DCA-TEGMP-TEGMP; Q-2DCN-2TFAC; C4- DCN-TFAC-TEGMP-CPP; C4-DCN-TFA-PEGMP-CPP; C4-DCN-TFAC-TEGMPC-CPP; C4-DCN-TFAC-PEGMPC-CPP; C4-DCN-TFAC-CN-CPP; C4-DCN-TFAC-TEGMP-CN; C4-DCN-TFAC-PEGMP-CN; C4-DCN-TFAC-TEGMPC-CN; C4-DCN-TFAC-PEGMPC- CN; C4-DCN-DCA-TEGMP-PEGMPC; C4-DCN-DCA-PEGMP-PEGMPC; C4-DCN- DCA-TEGMPC-PEGMPC; C4-DCN-DCA-TEGMP-TEGMPC; C4-DCN-DCA-PEGMP- TEGMPC; C4-DCN-DCA-TEGMP-TEGMP; Q-2DFA-2DCA; C4-DFA-DCA-TEGMP- CPP; C4-DFA-DCA-PEGMP-CPP; C4-DFA-DCA-TEGMPC-CPP; C4-DFA-DCA- PEGMPC-CPP; C4-DFA-DCA-CN-CPP; C4-DFA-DCA-TEGMP-CN; C4-DFA-DCA- PEGMP-CN; C4-DFA-DCA-TEGMPC-CN; C4-DFA-DCA-PEGMPC-CN; C4-DFA-DCA- TEGMP-PEGMPC; C4-DFA-DCA-PEGMP-PEGMPC; Q-DFA-DCA-TEGMPC- PEGMPC; C4-DFA-DCA-TEGMP-TEGMPC; C4-DFA-DCA-PEGMP-TEGMPC; C4- DFA-DCA-TEGMP-TEGMP; C4-2DFA-2TFAC; C4-DFA-TFACTEGMP-CPP; C4-DFA- TFAC-PEGMP-CPP; C4-DFA-TFAC-TEGMPC-CPP; C4-DFA-TFAC-PEGMPC-CPP; C4-DFA-TFAC-CN-CPP; C4-DFA-TFAC-TEGMP-CN; C4-DFA-TFAC-PEGMP-CN; C4- DFA-TFAC-TEGMPC-CN; C4-DFA-TFAC-PEGMPC-CN; C4-DFA-TFAC-TEGMP- PEGMPC; C4-DFA-TFAC-PEGMP-PEGMPC; C4-DFA-TFAC-TEGMPC-PEGMPC; C4- DFA-TFAC-TEGMP-TEGMPC; C4-DFA-TFAC-PEGMP-TEGMPC; C4-DFA-TFAC- TEGMP-TEGMP; C4-2DCA-2TFAC; C4-DCA-TFAC-TEGMP-CPP; C4-DCA-TFAC- PEGMP-CPP; C4-DCA-TFAC-TEGMPC-CPP; C4-DCA-TFAC-PEGMPC-CPP; C4-DCA- TFAC-CN-CPP; C4-DCA-TFAC-TEGMP-CN; C4-DCA-TFAC-PEGMP-CN; C4-DCA- TFAC-TEGMPC-CN; C4-DCA-TFAC-PEGMPC-CN; C4-DCA-TFAC-TEGMP- PEGMPC; C4-DCA-TFAC-PEGMP-PEGMPC; C4-DCA-TFAC-TEGMPC-PEGMPC; C4- DCA-TFAC-TEGMP-TEGMPC; C4-DCA-TFAC-PEGMP-TEGMPC; C4-DCA-TFAC-
TEGMP-TEGMP; C4-TFSA-DCN-TFAC-TEGMP; C4-TFSA-DCN-TFAC-PEGMP; C4-
TFSA-DCN-TFAC-TEGMPC; C4-TFSA-DCN-TFAC-PEGMPC; C4-TFSA-DCN-TFAC-
CN; C4-TFSA-DCN-TFAC-CPP; C4-TFSA-DFA-TFAC-TEGMP; C4-TFSA-DFA-TFAC-
PEGMP; C4-TFSA-DFA-TFAC-TEGMPC; C4-TFSA-DFA-TFAC-PEGMPC; C4-TFSA-
DFA-TFAC-CN; C4-TFSA-DFA-TFAC-CPP; C4-TFSA-DCA-TFAC-TEGMP; C4-TFSA-
DCA-TFAC-PEGMP; C4-TFSA-DCA-TFAC-TEGMPC; C4-TFSA-DCA-TFAC- PEGMPC; C4-TFSA-DCA-TFAC-CN; C4-TFSA-DCA-TFAC-CPP; C4-TFSA-DCN- DCA-TEGMP; C4-TFSA-DCN-DCA-PEGMP; C4-TFSA-DCN-DCA-TEGMPC; C4- TFSA-DCN-DCA-PEGMPC; C4-TFSA-DCN-DCA-CN; C4-TFSA-DCN-DCA-CPP; C4-
TFSA-DFA-DCA-TEGMP; C4-TFSA-DFA-DCA-PEGMP; C4-TFSA-DFA-DCA-
TEGMPC; C4-TFSA-DFA-DCA-PEGMPC; C4-TFSA-DFA-DCA-CN; C4-TFSA-DFA-
DCA-CPP; C4-TFSA-DCN-DFA-TEGMP; C4-TFSA-DCN-DFA-PEGMP; C4-TFSA-
DCN-DFA-TEGMPC; C4-TFSA-DCN-DFA-PEGMPC; C4-TFSA-DCN-DFA-CN; C4-
TFSA-DCN-DFA-CPP; C4-TFSA-DCN-DFA-TFAC; C4-TFSA-DCN-DCA-TFAC; C4-
TFSA-DFA-DCA-TFAC; C4-TFSA-DCN-DFA-DCA and C4-DCN-DFA-DCA-TFAC.
3. An electrolyte comprising the compound of claim 1.
4. The electrolyte of claim 3, wherein the electrolyte is selected from the group consisting of nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.
5. A nonaqueous liquid electrolyte, comprising: (i) an anion receptor of the compound of claim 1; (ii) a nonaqueous solvent; and (iii) an alkali metal ion containing substance.
6. A gel polymer electrolyte, comprising: (i) an anion receptor of the Formula 1;
(ii) a polymer support; (iii) a nonaqueous solvent; and
(iv) an alkali metal ion containing substance.
7. A solid polymer electrolyte, comprising: (i) an anion receptor of the Formula 1 ;
(ii) a polymer compound selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.
8. The electrolyte of claim 7, wherein the solid polymer electrolyte further comprises the substance selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof .
9. The electrolyte of one of claims 5 to 8, wherein the nonaqueous solvent is selected from the group consisting of: ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-l,3-dioxolane,
1,3-dioxolane, 1,2-dimethoxyethane, dimethoxymethane, γ-butyrolactone, methyl formate, sulforane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2-pyrrolidinone and mixtures thereof.
10. The electrolyte of one of claims 5 to 7, wherein the alkali metal ion containing substance is selected from the group consisting of LiSO3CF3, LiCOOC2F5, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl, and a mixture thereof.
11. The electrolyte of claim 6, wherein the polymer support is polyacrylonitrile type polymer or polyvinylidenfluoride-hexafluoropropylene type polymer.
12. The electrolyte of claim 7, wherein the polymer selected from the group consisting of net-shaped, comb-shaped and branched polymer compounds are flexible inorganic polymers or linear poly ethers.
13. The electrolyte of claim 7, wherein the crosslinkable polymer is a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl.
14. The electrolyte of claim 12 or claim 13, wherein the flexible inorganic polymer is polysiloxane or polyphosphagen, and the linear polyether is a polyalkylene oxide.
15. The electrolyte of claim 8, wherein the polyalkyleneglycol dialkylether is selected from the group consisting of: polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibuthylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated with dibutylether.
16. The solid polymer electrolyte of claim 7, wherein the electrolyte further comprises a curing initiator when the electrolyte contains a crosslinkable polymer compound.
17. The electrolyte of claim 16, wherein the curing initiator is selected from the group consisting of: a photocuring initiator, a heat-curing initiator, and a mixture thereof.
18. The electrolyte of claim 17, wherein the photocuring initiator is selected from the group consisting of: dimethoxyphenyl acetophenone (DMPA), t-
butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl
ether, benzoin phenyl ether, α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-
dichloroacetophenone, 2-hydroxy-2-methyl-l-phenylpropane-l-on, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone, and a mixture thereof; and wherein the heat-curing initiator is selected from the group consisting of: azoisobutyrontrile compounds, peroxide compounds and mixtures thereof.
19. The electrolyte of one of claims 5 to 7, comprising 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.
20. The electrolyte of claim 6, comprising 5 - 40 parts by weight of the
polymer support.
21. The electrolyte of claim 7, comprising 10 - 95 parts by weight of a polymer compound selected from the group consisting of net-shaped, comb-shaped and branched polymer, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator.
22. The electrolyte of claim 8, comprising 10 - 50 parts by weight of the substance selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
23. An electrochemical cell comprising a cathode, an anode and the electrolyte of claim 3.
24. The electrochemical cell of claim 23, wherein the cathode is made of a material selected from the group that consists of lithium; lithium alloys; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds; lithium metal sulfide intercalation compounds; mixtures thereof; and mixtures of these and alkali metals, and wherein, the anode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
25. The electrochemical cell of claim 24, wherein the transition metal oxides is
selected from the group consisting of Li2 5V6Oi3, Li1 -2V2Os, LiCoO2, LiNiO2, LiMn2O4, LiMnO2, and LiNii-xMxO2 (wherein M is Co, Mg, Al or Ti); wherein the transition metal chalcogenides is selected from the group consisting
of: LiNbSe3, LiTiS2, and LiMoS2; wherein the organic disulfide redox polymers are prepared by reversible electrochemical dimerization/division or polymerization/dissociation; and wherein the organic disulfϊde/polyaniline complexes are mixtures of polyaniline and 2,5-dimercapto-l,3,4-thiadiazole.
26. A gel polymer electrolyte film manufactured using the gel polymer
electrolyte of claim 6.
27. A solid polymer electrolyte film manufactured using the solid polymer electrolyte of claim 7.
PCT/KR2006/002161 2005-06-03 2006-06-05 Anion receptor and electrolyte using the same WO2006129991A1 (en)

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