WO2006129992A1 - Anion receptor and electrolyte using the same - Google Patents
Anion receptor and electrolyte using the same Download PDFInfo
- Publication number
- WO2006129992A1 WO2006129992A1 PCT/KR2006/002162 KR2006002162W WO2006129992A1 WO 2006129992 A1 WO2006129992 A1 WO 2006129992A1 KR 2006002162 W KR2006002162 W KR 2006002162W WO 2006129992 A1 WO2006129992 A1 WO 2006129992A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tegmp
- tegmpc
- pegmpc
- cpp
- tfsa
- Prior art date
Links
Classifications
-
- 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
- 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
-
- 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
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- Y02E60/10—Energy storage using batteries
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 linear 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
- 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) Z 35 ⁇ 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
- 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. Armand in 1978.
- a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor.
- PEO polyethylene oxide
- LiNaO 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. In 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.
- 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 linear 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.
- Ri and R 2 each 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 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group
- R 8 and the other R 8 in the formula independently represents an alkyl, an alkenyl, an alkyl halide, and an alkenyl halide;
- Y and Z each independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, q and t 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 L 4 -4TFSA; L 4 -4TFSI; L 4 -2TFSA-2TEGMP; L 4 -2TFSA-2PEGMP; L 4 -2TFSA-2TEGMPC; L 4 -2TFSA-2PEGMPC; L 4 -2TFSA-2CN; L 4 -
- TEGMP-PEGMPC L 4 -2TFSA-PEGMP-PEGMPC; L 4 -2TFSA-TEGMPC-PEGMPC; L 4 - 2TFSA-TEGMP-TEGMPC; L 4 -2TFSA-PEGMP-TEGMPC; L 4 -2TFSA-TEGMP-TEGMP;
- L 4 -TFSA-TEGMP-CN-CPP L 4 -TFSA-PEGMP-CN-CPP; L 4 -TFSA-TEGMPC-CN-CPP;
- PEGMPC-CPP PEGMPC-CPP; L 4 -TFSA-TEGMPC-PEGMPC-CPP; L 4 -TFSA-TEGMP-TEGMPC-CPP; L 4 -TFSA-PEGMP-TEGMPC-CPP; L 4 -TFSA-TEGMP-PEGMP-CPP; L 4 -TFSA-TEGMP- PEGMPC-CN; L 4 -TFSA-PEGMP-PEGMPC-CN; L 4 -TFSA-TEGMPC-PEGMPC-CN; L 4 - TFSA-TEGMP-TEGMPC-CN; L 4 -TFSA-PEGMP-TEGMPC-CN; L 4 -TFSA-TEGMP-TEGMPC-CN; L 4 -TFSA-TEGMP-TEGMPC-CN; L 4 -TFSA-TEGMP-TEGMPC-CN; L 4 -TFSA-TEGMP-
- TEGMPC TEGMPC; L 4 -DCN-DCA-TEGMP-TEGMP; L 4 -2DCN-2TFAC; L 4 -DCN-TFAC-TEGMP- CPP; L 4 -DCN-TFA-PEGMP-CPP; L 4 -DCN-TFAC-TEGMPC-CPP; L 4 -DCN-TFAC- PEGMPC-CPP; L 4 -DCN-TFAC-CN-CPP; L 4 -DCN-TFAC-TEGMP-CN; L 4 -DCN-TF AC- PEGMP-CN; L 4 -DCN-TFAC-TEGMPC-CN; L 4 -DCN-TFAC-PEGMPC-CN; L 4 -DCN- DCA-TEGMP-PEGMPC; L 4 -DCN-DCA-PEGMP-PEGMPC; L 4 -DCN-DCA-TEGMPC-
- PEGMPC PEGMPC; L 4 -DCN-DCA-TEGMP-TEGMPC; L 4 -DCN-DCA-PEGMP-TEGMPC; L 4 - DCN-DCA-TEGMP-TEGMP; L 4 -2DFA-2DCA; L 4 -DFA-DCA-TEGMP-CPP; L 4 -DFA- DCA-PEGMP-CPP; L 4 -DFA-DCA-TEGMPC-CPP; L 4 -DFA-DCA-PEGMPC-CPP; L 4 - DFA-DCA-CN-CPP; L 4 -DFA-DCA-TEGMP-CN; L 4 -DFA-DCA-PEGMP-CN; L 4 -DFA-DCA-PEGMP-CN; L 4 -DFA-DCA-PEGMP-CN; L 4 -DFA-DCA-PEGMP-CN; L 4 -DFA-DCA-PEGMP-CN; L 4 -
- 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 linear 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.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Y, Z, n, o, p, q, r, s, and t are defined as in the compound of 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.
- 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)
- polyalkyleneglycol dialkylether 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,
- 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.
- polyalkyleneglycol dialkylether examples 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
- the solid polymer electrolyte contains a crosslinkable polymer compound
- it further comprises a curing initiator.
- a 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 DMPA, t-butylperoxypivalate, ethyl DMPA, t-butylperoxypivalate, ethyl DMPA, t-butylperoxypivalate, ethyl
- benzoin ether isopropyl benzoin ether, ⁇ -methyl bezoin ethyl 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
- 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:
- 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(carbondisulfide)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 ;
- transition metal oxides transition metal chalcogenides
- poly(carbondisulfide)polymers organic disulfide redox polymers
- polyaniline organic disulfide/polyaniline complexes
- oxychlorides such as, SO 2 , CuO, CuS, Ag 2 CrO 4 , 1 2 , PbI 2 , PbS, SOCl 2 , V 2 O 5
- 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 O 5 , 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;
- 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.
- 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, hi 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
- 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.
- 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
- Another example of the preparation method for a film is as follows.
- 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); and 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]
- 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
- 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 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]
- 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]
- 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 413 The same procedure of Example 413 was repeated, with the exception that 3.Og of the anion receptor L 4 -4TFSA obtained from Example 1 was replaced by 1.5g of L 4 -4TFSA and 1.5g of the anion receptor L 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
- Example 415 Manufacture of Conductive Thin Film (3)
- Example 413 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 L 4 -4TFSA obtained from Example 1 was replaced by 1.5g of L 4 -4TFSA and 1.5g of the anion receptor L 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
- Example 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
- 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
- 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]
- 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
- Example 2 0.015g of the anion receptor L 4 -4TFSI obtained from Example 2 was mixed with l.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
- 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
- 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 L 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 L 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, hi 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.
- small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc.
- electronic equipments e.g., camcorders
- large capacity lithium polymer secondary cells used in power storage systems for power equalization and electric vehicles.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Disclosed is a novel anion receptor and electrolytes containing the same. A novel anion receptor is a linear 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 linear 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) Z35=^ 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) Al 460).
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. In 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 crosslinkable 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
8xlO"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 linear 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 linear 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]
CH3
wherein Ri and R2 each 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;
R5 and R6 independently represents a hydrogen atom or a methyl group; R7 and the other R7 in the formula independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group; R8 and the other R8 in the formula independently represents an alkyl, an alkenyl, an alkyl halide, and an alkenyl halide;
Y and Z each independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, q and t 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 L4-4TFSA; L4-4TFSI; L4-2TFSA-2TEGMP; L4-2TFSA-2PEGMP; L4-2TFSA-2TEGMPC; L4-2TFSA-2PEGMPC; L4-2TFSA-2CN; L4-
2TFSA-2CPP; L4-2TFSA-TEGMP-CPP; L4-2TFSA-PEGMP-CPP; L4-2TFSA-TEGMPC-
CPP; L4-2TFSA-PEGMPC-CPP; L4-2TFSA-CN-CPP; L4-2TFSA-TEGMP-CN; L4-
2TFSA-PEGMP-CN; L4-2TFSA-TEGMPC-CN; L4-2TFSA-PEGMPC-CN; L4-2TFSA-
TEGMP-PEGMPC; L4-2TFSA-PEGMP-PEGMPC; L4-2TFSA-TEGMPC-PEGMPC; L4- 2TFSA-TEGMP-TEGMPC; L4-2TFSA-PEGMP-TEGMPC; L4-2TFSA-TEGMP-TEGMP;
L4-TFSA-TEGMP-CN-CPP; L4-TFSA-PEGMP-CN-CPP; L4-TFSA-TEGMPC-CN-CPP;
L4-TFSA-PEGMPC-CN-CPP; L4-TFSA-TEGMP-PEGMPC-CPP; L4-TFSA-PEGMP-
PEGMPC-CPP; L4-TFSA-TEGMPC-PEGMPC-CPP; L4-TFSA-TEGMP-TEGMPC-CPP;
L4-TFSA-PEGMP-TEGMPC-CPP; L4-TFSA-TEGMP-PEGMP-CPP; L4-TFSA-TEGMP- PEGMPC-CN; L4-TFSA-PEGMP-PEGMPC-CN; L4-TFSA-TEGMPC-PEGMPC-CN; L4- TFSA-TEGMP-TEGMPC-CN; L4-TFSA-PEGMP-TEGMPC-CN; L4-TFSA-TEGMP-
PEGMP-CN; L4-TFSA-TEGMP-TEGMPC-PEGMPC; L4-TFSA-PEGMP-TEGMPC- PEGMPC; L4-TFSA-TEGMP-PEGMP-PEGMPC; L4-TFSA-TEGMP-PEGMP-TEGMPC; L4-4DCN; L4-2DCN-2TEGMP; L4-2DCN-2PEGMP; L4-2DCN-2TEGMPC; L4-2DCN- 2PEGMPC; L4-2DCN-2CN; L4-2DCN-2CPP; L4-2DCN-TEGMP-CPP; L4-2DCN- PEGMP-CPP; L4-2DCN-TEGMPC-CPP; L4-2DCN-PEGMPC-CPP; L4-2DCN-CN-CPP; L4-2DCN-TEGMP-CN; L4-2DCN-PEGMP-CN; L4-2DCN-TEGMPC-CN; L4-2DCN- PEGMPC-CN; L4-2DCN-TEGMP-PEGMPC; L4-2DCN-PEGMP-PEGMPC; L4-2DCN- TEGMPC-PEGMPC; L4-2DCN-TEGMP-TEGMPC; L4-2DCN-PEGMP-TEGMPC; L4- 2DCN-TEGMP-TEGMP; L4-DCN-TEGMP-CN-CPP; L4-DCN-PEGMP-CN-CPP; L4- DCN-TEGMPC-CN-CPP; L4-DCN-PEGMPC-CN-CPP; L4-DCN-TEGMP-PEGMPC- CPP; L4-DCN-PEGMP-PEGMPC-CPP; L4-DCN-TEGMPC-PEGMPC-CPP; L4-DCN- TEGMP-TEGMPC-CPP; L4-DCN-PEGMP-TEGMPC-CPP; L4-DCN-TEGMP-PEGMP- CPP; L4-DCN-TEGMP-PEGMPC-CN; L4-DCN-PEGMP-PEGMPC-CN; L4-DCN- TEGMPC-PEGMPC-CN; L4-DCN-TEGMP-TEGMPC-CN; L4-DCN-PEGMP-TEGMPC- CN; L4-DCN-TEGMP-PEGMP-CN; L4-DCN-TEGMP-TEGMPC-PEGMPC; L4-DCN- PEGMP-TEGMPC-PEGMPC; L4-DCN-TEGMP-PEGMP-PEGMPC; L4-DCN-TEGMP- PEGMP-TEGMPC; L4-4DFA; L4-2DFA-2TEGMP; L4-2DFA-2PEGMP; L4-2DFA- 2TEGMPC; L4-2DFA-2PEGMPC; L4-2DFA-2CN; L4-2DFA-2CPP; L4-2DFA-TEGMP- CPP; L4-2DFA-PEGMP-CPP; L4-2DFA-TEGMPC-CPP; L4-2DFA-PEGMPC-CPP; L4- 2DF A-CN-CPP; L4-2DF A-TEGMP-CN; L4-2DF A-PEGMP-CN; L4-2DF A-TEGMPC-CN; L4-2DF A-PEGMPC-CN; L4-2DFA-TEGMP-PEGMPC; L4-2DFA-PEGMP-PEGMPC; L4-
2DF A-TEGMPC-PEGMPC; L4-2DF A-TEGMP-TEGMPC; L4-2DF A-PEGMP-TEGMPC; L4-2DFA-TEGMP-TEGMP; L4-DFA-TEGMP-CN-CPP; L4-DFA-PEGMP-CN-CPP; L4- DFA-TEGMPC-CN-CPPJ L4-DFA-PEGMPC-CN-CPPJ L4-DFA-TEGMP-PEGMPC-CPP;
L4-DFA-PEGMP-PEGMPC-CPP; L4-DFA-TEGMPC-PEGMPC-CPP; L4-DFA-TEGMP- TEGMPC-CPP; L4-DFA-PEGMP-TEGMPC-CPP; L4-DFA-TEGMP-PEGMP-CPP; L4- DFA-TEGMP-PEGMPC-CN; L4-DFA-PEGMP-PEGMPC-CN; L4-DFA-TEGMPC- PEGMPC-CN; L4-DFA-TEGMP-TEGMPC-CN; L4-DFA-PEGMP-TEGMPC-CN; L4- DFA-TEGMP-PEGMP-CN; L4-DFA-TEGMP-TEGMPC-PEGMPC; L4-DFA-PEGMP- TEGMPC-PEGMPC; L4-DFA-TEGMP-PEGMP-PEGMPC; L4-DFA-TEGMP-PEGMP- TEGMPC; L4-4DCA; L4-2DCA-2TEGMP; L4-2DCA-2PEGMP; L4-2DCA-2TEGMPC; L4-2DCA-2PEGMPC; L4-2DCA-2CN; L4-2DCA-2CPP; L4-2DCA-TEGMP-CPP; L4- 2DCA-PEGMP-CPP; L4-2DCA-TEGMPC-CPP; L4-2DC A-PEGMPC-CPP; L4-2DCA- CN-CPP; L4-2DCA-TEGMP-CN; L4-2DCA-PEGMP-CN; L4-2DCA-TEGMPC-CN; L4-
2DCA-PEGMPC-CN; L4-2DCA-TEGMP-PEGMPC; L4-2DCA-PEGMP-PEGMPC; L4- 2DCA-TEGMPC-PEGMPC; L4-2DC A-TEGMP-TEGMPC; L4-2DCA-PEGMP-
TEGMPC; L4-2DCA-TEGMP-TEGMP; L4-DCA-TEGMP-CN-CPP; L4-DCA-PEGMP- CN-CPP; L4-DCA-TEGMPC-CN-CPP; L4-DCA-PEGMPC-CN-CPP; L4-DCA-TEGMP- PEGMPC-CPP; L4-DCA-PEGMP-PEGMPC-CPP; L4-DCA-TEGMPC-PEGMPC-CPP; L4-DCA-TEGMP-TEGMPC-CPP; L4-DCA-PEGMP-TEGMPC-CPP; L4-DCA-TEGMP- PEGMP-CPP; L4-DCA-TEGMP-PEGMPC-CN; L4-DCA-PEGMP-PEGMPC-CN; L4- DCA-TEGMPC-PEGMPC-CN; L4-DCA-TEGMP-TEGMPC-CN; L4-DCA-PEGMP- TEGMPC-CN; L4-DCA-TEGMP-PEGMP-CN; L4-DCA-TEGMP-TEGMPC-PEGMPC; L4-DCA-PEGMP-TEGMPC-PEGMPC; L4-DCA-TEGMP-PEGMP-PEGMPC; L4-DCA- TEGMP-PEGMP-TEGMPC; L4-4TFAC; L4-2TFAC-2TEGMP; L4-2TFAC-2PEGMP; L4-
2TFAC-2TEGMPC; L4-2TFAC-2PEGMPC; L4-2TFAC-2CN; L4-2TFAC-2CPP; L4- 2TF AC-TEGMP-CPP; L4-2TF AC-PEGMP-CPP; L4-2TFAC-TEGMPC-CPP; L4-2TFAC- PEGMPC-CPP; L4-2TFAC-CN-CPP; L4-2TFAC-TEGMP-CN; L4-2TFAC-PEGMP-CN; L4-2TF AC-TEGMPC-CN; L4-2TFAC-PEGMPC-CN; L4-2TFAC-TEGMP-PEGMPC; L4- 2TFAC-PEGMP-PEGMPC; L4^TFAC-TEGMPC-PEGMPC; L4-2TFAC-TEGMP- TEGMPC; L4-2TFAC-PEGMP-TEGMPC; L4-2TFAC-TEGMP-TEGMP; L4-TFAC- TEGMP-CN-CPP; L4-TFAC-PEGMP-CN-CPP; L4-TFAC-TEGMPC-CN-CPP; L4-TFAC- PEGMPC-CN-CPP; L4-TFAC-TEGMP-PEGMPC-CPP; L4-TFAC-PEGMP-PEGMPC- CPP; L4-TFAC-TEGMPC-PEGMPC-CPP; L4-TFAC-TEGMP-TEGMPC-CPP; L4-TFAC- PEGMP-TEGMPC-CPP; L4-TFAC-TEGMP-PEGMP-CPP; L4-TFAC-TEGMP-PEGMPC- CN; L4-TFAC-PEGMP-PEGMPC-CN; L4-TFAC-TEGMPC-PEGMPC-CN; L4-TFAC- TEGMP-TEGMPC-CN; L4-TFAC-PEGMP-TEGMPC-CN; L4-TFAC-TEGMP-PEGMP- CN; L4-TFAC-TEGMP-TEGMPC-PEGMPC; L4-TFAC-PEGMP-TEGMPC-PEGMPC; L4-TFAC-TEGMP-PEGMP-PEGMPC; L4-TFAC-TEGMP-PEGMP-TEGMPC; L4- 2TFSA-2DCN; L4-TFSA-DCN-TEGMP-CPP; L4-TFSA-DCN-PEGMP-CPP; L4-TFS A- DCN-TEGMPC-CPP; L4-TFSA-DCN-PEGMPC-CPP; L4-TFSA-DCN-CN-CPP; L4- TFSA-DCN-TEGMP-CN; L4-TFSA-DCN-PEGMP-CN; L4-TFSA-DCN-TEGMPC-CN; L4-TFSA-DCN-PEGMPC-CN; L4-TFSA-DCN-TEGMP-PEGMPC; L4-TFSA-DCN- PEGMP-PEGMPC; L4-TFSA-DCN-TEGMPC-PEGMPC; L4-TFSA-DCN-TEGMP- TEGMPC; L4-TFSA-DCN-PEGMP-TEGMPC; L4-TFSA-DCN-TEGMP-TEGMP; L4- 2TFSA-2DFA; L4-TFSA-DFA-TEGMP-CPP; L4-TFSA-DFA-PEGMP-CPP; L4-TFSA- DFA-TEGMPC-CPP; L4-TFSA-DFA-PEGMPC-CPP; L4-TFSA-DFA-CN-CPP; L4-TFSA- DFA-TEGMP-CN; L4-TFSA-DFA-PEGMP-CN; L4-TFSA-DFA-TEGMPC-CN; L4- TFSA-DFA-PEGMPC-CN; L4-TFSA-DFA-TEGMP-PEGMPC; L4-TFSA-DFA-PEGMP-
PEGMPC; L4-TFSA-DFA-TEGMPC-PEGMPC; L4-TFSA-DFA-TEGMP-TEGMPC; L4- TFSA-DFA-PEGMP-TEGMPC; L4-TFSA-DFA-TEGMP-TEGMP; L4-2TFSA-2DCA; L4- TFSA-DCA-TEGMP-CPP; L4-TFSA-DCA-PEGMP-CPP; L4-TFSA-DCA-TEGMPC-
CPP; L4-TFSA-DCA-PEGMPC-CPP; L4-TFSA-DCA-CN-CPP; L4-TFSA-DCA-TEGMP-
CN; L4-TFSA-DCA-PEGMP-CN; L4-TFSA-DCA-TEGMPC-CN; L4-TFSA-DCA- PEGMPC-CN; L4-TFSA-DCA-TEGMP-PEGMPC; L4-TFSA-DCA-PEGMP-PEGMPC; L4-TFSA-DCA-TEGMPC-PEGMPC; L4-TFSA-DCA-TEGMP-TEGMPC; L4-TFSA- DCA-PEGMP-TEGMPC; L4-TFSA-DCA-TEGMP-TEGMP; L4-2TFSA-2TFAC; L4- TFSA-TFAC-TEGMP-CPP; L4-TFSA-TFAC-PEGMP-CPP; L4-TFSA-TFAC-TEGMPC- CPP; L4-TFSA-TFAC-PEGMPC-CPP; L4-TFSA-TFAC-CN-CPP; L4-TFS A-TFAC- TEGMP-CN; L4-TFSA-TFAC-PEGMP-CN; L4-TFSA-TFAC-TEGMPC-CN; L4-TFSA- TFAC-PEGMPC-CN; L4-TFSA-TFAC-TEGMP-PEGMPC; L4-TFSA-TFAC-PEGMP- PEGMPC; L4-TFSA-TFAC-TEGMPC-PEGMPC; L4-TFSA-TFAC-TEGMP-TEGMPC; L4-TFSA-TFAC-PEGMP-TEGMPC; L4-TFSA-TFAC-TEGMP-PEGMP; L4-2DCN- 2DFA; L4-DCN-DFA-TEGMP-CPP; L4-DCN-DFA-PEGMP-CPP; L4-DCN-DF A- TEGMPC-CPP; L4-DCN-DFA-PEGMPC-CPP; L4-DCN-DFA-CN-CPP; L4-DCN-DFA- TEGMP-CN; L4-DCN-DFA-PEGMP-CN; L4-DCN-DFA-TEGMPC-CN; L4-DCN-DFA- PEGMPC-CN; L4-DCN-DFA-TEGMP-PEGMPC; L4-DCN-DFA-PEGMP-PEGMPC; L4- DCN-DFA-TEGMPC-PEGMPC; L4-DCN-DFA-TEGMP-TEGMPC; L4-DCN-DFA- PEGMP-TEGMPC; L4-DCN-DFA-TEGMP-TEGMP; L4-2DCN-2DCA; L4-DCN-DCA- TEGMP-CPP; L4-DCN-DCA-PEGMP-CPP; L4-DCN-DCA-TEGMPC-CPP; L4-DCN- DCA-PEGMPC-CPP; L4-DCN-DCA-CN-CPP; L4-DCN-DCA-TEGMP-CN; L4-DCN- DCA-PEGMP-CN; L4-DCN-DCA-TEGMPC-CN; L4-DCN-DCA-PEGMPC-CN; L4- DCN-DCA-TEGMP-PEGMPC; L4-DCN-DCA-PEGMP-PEGMPC; L4-DCN-DCA-
TEGMPC-PEGMPC; L4-DCN-DCA-TEGMP-TEGMPC; L4-DCN-DCA-PEGMP-
TEGMPC; L4-DCN-DCA-TEGMP-TEGMP; L4-2DCN-2TFAC; L4-DCN-TFAC-TEGMP- CPP; L4-DCN-TFA-PEGMP-CPP; L4-DCN-TFAC-TEGMPC-CPP; L4-DCN-TFAC- PEGMPC-CPP; L4-DCN-TFAC-CN-CPP; L4-DCN-TFAC-TEGMP-CN; L4-DCN-TF AC- PEGMP-CN; L4-DCN-TFAC-TEGMPC-CN; L4-DCN-TFAC-PEGMPC-CN; L4-DCN- DCA-TEGMP-PEGMPC; L4-DCN-DCA-PEGMP-PEGMPC; L4-DCN-DCA-TEGMPC-
PEGMPC; L4-DCN-DCA-TEGMP-TEGMPC; L4-DCN-DCA-PEGMP-TEGMPC; L4- DCN-DCA-TEGMP-TEGMP; L4-2DFA-2DCA; L4-DFA-DCA-TEGMP-CPP; L4-DFA- DCA-PEGMP-CPP; L4-DFA-DCA-TEGMPC-CPP; L4-DFA-DCA-PEGMPC-CPP; L4- DFA-DCA-CN-CPP; L4-DFA-DCA-TEGMP-CN; L4-DFA-DCA-PEGMP-CN; L4-DFA- DCA-TEGMPC-CN; L4-DFA-DCA-PEGMPC-CN; L4-DFA-DCA-TEGMP-PEGMPC; L4-DFA-DCA-PEGMP-PEGMPC; L4-DFA-DCA-TEGMPC-PEGMPC; L4-DFA-DCA- TEGMP-TEGMPC; L4-DFA-DCA-PEGMP-TEGMPC; L4-DFA-DCA-TEGMP-TEGMP; L4-2DFA-2TFAC; L4-DFA-TFACTEGMP-CPP; L4-DFA-TFAC-PEGMP-CPP; L4-DFA- TFAC-TEGMPC-CPP; L4-DFA-TFAC-PEGMPC-CPP; L4-DFA-TFAC-CN-CPP; L4- DFA-TFAC-TEGMP-CN; L4-DFA-TFAC-PEGMP-CN; L4-DFA-TFAC-TEGMPC-CN; L4-DFA-TFAC-PEGMPC-CN; L4-DFA-TFAC-TEGMP-PEGMPC; L4-DFA-TFAC- PEGMP-PEGMPC; L4-DFA-TFAC-TEGMPC-PEGMPC; L4-DFA-TFAC-TEGMP- TEGMPC; L4-DFA-TFAC-PEGMP-TEGMPC; L4-DFA-TFAC-TEGMP-TEGMP; L4- 2DCA-2TFAC; L4-DCA-TFAC-TEGMP-CPP; L4-DCA-TFAC-PEGMP-CPP; L4-DCA- TFAC-TEGMPC-CPP; L4-DCA-TFAC-PEGMPC-CPP; L4-DCA-TFAC-CN-CPP; L4- DCA-TFAC-TEGMP-CN; L4-DCA-TFAC-PEGMP-CN; L4-DCA-TFAC-TEGMPC-CN; L4-DCA-TFAC-PEGMPC-CN; L4-DCA-TFAC-TEGMP-PEGMPC; L4-DCA-TFAC- PEGMP-PEGMPC; L4-DCA-TFAC-TEGMPC-PEGMPC; L4-DCA-TFAC-TEGMP-
TEGMPC; L4-DCA-TFAC-PEGMP-TEGMPC; L4-DCA-TFAC-TEGMP-TEGMP; L4- TFSA-DCN-TFAC-TEGMP; L4-TFSA-DCN-TFAC-PEGMP; L4-TFSA-DCN-TFAC-
TEGMPC; L4-TFSA-DCN-TFAC-PEGMPC; L4-TFSA-DCN-TFAC-CN; L4-TFSA-DCN- TFAC-CPP; L4-TFSA-DFA-TFAC-TEGMP; L4-TFSA-DFA-TFAC-PEGMP; L4-TFSA- DFA-TFAC-TEGMPC; L4-TFSA-DFA-TFAC-PEGMPC; L4-TFSA-DFA-TFAC-CN; L4- TFSA-DFA-TFAC-CPP; L4-TFSA-DCA-TFAC-TEGMP; L4-TFSA-DCA-TFAC- PEGMP; L4-TFSA-DCA-TFAC-TEGMPC; L4-TFSA-DCA-TFAC-PEGMPC; L4-TFSA- DCA-TFAC-CN; L4-TFSA-DCA-TFAC-CPP; L4-TFSA-DCN-DCA-TEGMP; L4-TFSA- DCN-DCA-PEGMP; L4-TFSA-DCN-DCA-TEGMPC; L4-TFSA-DCN-DCA-PEGMPC; L4-TFSA-DCN-DCA-CN; L4-TFSA-DCN-DCA-CPP; L4-TFSA-DFA-DCA-TEGMP; L4- TFSA-DFA-DCA-PEGMP; L4-TFSA-DFA-DCA-TEGMPC; L4-TFSA-DFA-DCA- PEGMPC; L4-TFSA-DFA-DCA-CN; L4-TFSA-DFA-DCA-CPP; L4-TFSA-DCN-DFA- TEGMP; L4-TFSA-DCN-DFA-PEGMP; L4-TFSA-DCN-DFA-TEGMPC; L4-TFSA- DCN-DFA-PEGMPC; L4-TFSA-DCN-DFA-CN; L4-TFSA-DCN-DFA-CPP; L4-TFSA- DCN-DFA-TFAC; L4-TFSA-DCN-DCA-TFAC; L4-TFSA-DFA-DCA-TFAC; L4-TFSA- DCN-DFA-DCA; or L4-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 linear 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]
\
(2)
(I )
wherein, R1, R2, R3, R4, R5, R6, R7, R8, Y, Z, n, o, p, q, r, s, and t are defined as in the compound of 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]
Bis- 15m
[Formula 4]
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 crosslinkable 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(carbondisulfide)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 2V2O5, 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, hi 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]
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).
1H 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]
1 ,-41 I SI
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 10.3g of allyl- TFSA (0.055mol) 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 L4-4TFSA (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]
Il ,(
L, 4TFSA L4 4TTSI
57.9g of L4-4TFSA of Example 1 and 24.3g of triethylamine were dissolved in 100ml of chloroform and kept at -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 L4-4TFSI (see the Reaction Scheme 4).
1K 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, ClCN
Λllylmonocyananmle Λllyldicyanamide
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]
I 1C
L_,-4DCN 4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390)
(0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.9g of allyl-DCN (0.055mol) obtained from Preparation Example 2 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)- 1,3-divinyl-l, 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 L4-4DCN (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]
Ally ldi fluoroamine
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]
1, CH,
I.J-4DI Λ
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-DFA (0.055mol) 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- 1,1, 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 L4-4DCN (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]
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). 1K NMR (300MHz, CDCl3): ppm 5.2 (m, 2H), 5.4 (m, 2H), 5.95 (m, IH)
Example 5 [Reaction Scheme 10]
I,C
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 6.9g of allyl-DCN (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)- 1,3-divinyl-l, 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 L4-4DCA (see the Reaction Scheme 10). 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 5 [Reaction Scheme 11]
N-dllyl-l^^-tπfluoio-N-tiifluorodcetyl-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]
I1
\ , 4 I PAC
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 13.7g of allyl- TFAC (O.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- 1,1,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at 1100C 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 L4-4TFAC (see the Reaction Scheme 12).
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 6 [Reaction Scheme 13]
HO- -(( 1 I2CHiO)11C! .0(CH2CH2O)11CH3
THGM I 64Ae (n=3) PEGV1350Λe (n=-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. When the reaction was completed, extra NaOH and the product NaBr were filtered and the THF 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 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]
,0(CHXH1O)11CH., trimethylsUane terminated PMHS
TEGMAc (Ii=?) PEGMAc (n=7.2)
L4-2TFSA-2TEGMP (n=3 ) L4-2TFSA-2PEGMP (π=7.2)
4.8g of trimethylsilyl teπninated polymethylhydrosiloxane (PMHS) (Mw ca.390) (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 11O0C 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 L4- 2TFSA-2TEGMP (see the Reaction Scheme 14, n=3).
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, 4.8g of PMHS, 5.1g of ally-TFSA, and 10.7g of PEGMAe obtained from Preparation Example 7 were reacted to yield L4-2TFSA- 2PEGMP (see the Reaction Scheme 14, n=7.2).
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]
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, n=3).
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, n=7.2).
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]
TEGMΛC (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 refluxed 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, n=3). 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 (Mw=435) (see the Reaction Scheme 16, n=7.2).
1H 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]
π<
,,,(
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (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, 6.9g 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 L4-
2TFSA-2TEGMPC (see the Reaction Scheme 17, n=3).
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, 4.8g of PMHS, 5.1g of ally-TFSA obtained from Preparation Example 1, and 12.Og of PEGMAC obtained from Preparation Example 10 were reacted to yield L4-2TFSA-2PEGMPC (see the Reaction Scheme 17,
n=7.2).
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]
SO2Cf,
/
CH, CH, C H,
Pt(O)
AUyI-TFSA
H,C — Si θ4-S θ4— Si CH, THF
CH, H CH, trimethylsilane terminated PMHS allyl cyanide
1-4-2TFSA-2CN
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (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)-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 L4-2TFSA-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]
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]
SO2CF3
/
L4-2TFSA-2CPP
4.8g of trimethylsilyl terminated polymethylhydrosiloxane (PMHS) (Mw ca.390) (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 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 L4- 2TFSA-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]
TEGMPC-
34 3.4 g 6.O g 2.2 g
PEGMPC-
CPP
L4-TFSA-
TEGMP-
35 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
L4-TFSA-
PEGMP-
36 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
L4-TFSA-
TEGMP-
37 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
L4-TFSA-
TEGMP-
38 2.8 g 6.O g 0.9 g
PEGMPC-
CN
L4-TFSA-
PEGMP-
39 5.4 g 6.O g 0.9 g
PEGMPC-
CN
L4-TFSA- TEGMPC-
40 3.4 g 6.O g 0.9 g PEGMPC-
CN
L4-TFSA-
TEGMP-
41 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
L4-TFSA-
PEGMP-
42 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
L4-TFSA-
43 2.8 g 5.4 g 0.9 g TEGMP-
PEGMP-CN
L4-TFSA-
TEGMP-
44 2.8 g 3.4g 0.6 g
TEGMPC-
PEGMPC
L4-TFSA-
PEGMP-
45 5.4 g 3.4 g 0.6 g
TEGMPC-
PEGMPC
L4-TFSA- TEGMP-
46 2.8 g 5.4 g 0.6 g PEGMP- PEGMPC
L4-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]
PEGMPC
L4-2 DCN -
65 3.4 g 6.Og TEGMPC-
PEGMPC
L4-2 DCN -
66 2.8 g 3.4 ; TEGMP-
TEGMPC
L4-2 DCN -
67 5.4 g 3.4 g PEGMP-
TEGMPC
L4-2 DCN -
68 2.8 g 5.4 g TEGMP-
TEGMP
L4- DCN -
69 1.48 g 2.8 g 0.9 g 2.2 g TEGMP-
CN-CPP
L4- DCN -
70 5.4 g 0.9 g 2.2 g PEGMP-
CN-CPP
L4- DCN -
71 3-4 g 0.9 g 2.2 g TEGMPC-
CN-CPP
L4- DCN -
72 6.O g 0.9 g 2.2 g PEGMPC-
CN-CPP
L4- DCN -
TEGMP-
73 2.8 g 6.O g 2.2 g
PEGMPC-
CPP
L4- DCN -
PEGMP-
74 5.4 g 6.O g 2.2 g
PEGMPC-
CPP
L4- DCN - TEGMPC-
75 3.4 g 6.O g 2.2 g PEGMPC-
CPP
L4- DCN -
TEGMP-
76 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
L4- DCN -
PEGMP-
77 5.4 g 3-4 g 2.2 g
TEGMPC-
CPP
L4- DCN - TEGMP-
78 2.8 g 5.4 g 2.2 g PEGMP-
CPP
L4- DCN - TEGMP-
79 2.8 g 6.O g 0.9 g PEGMPC-
CN
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]
111 5.4 g 0.9 g 2.2 g PEGMP-
CN-CPP
L4- DFA -
112 3.4 g 0.9 g 2.2 g TEGMPC-
CN-CPP
L4- DFA -
113 6.O g 0.9 g 2.2 g PEGMPC-
CN-CPP
L4- DFA -
TEGMP-
114 2.8 g 6.O g 2.2 g
PEGMPC-
CPP
L4- DFA -
PEGMP-
115 5.4 g 6.O g 2.2 g
PEGMPC-
CPP
L4- DFA - TEGMPC-
116 3.4 g 6.0 ; 2.2 g PEGMPC-
CPP
L4- DFA -
TEGMP-
117 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
L4- DFA -
PEGMP-
118 5.4 g 3.4 : 2.2 ]
TEGMPC-
CPP
L4- DFA - TEGMP-
119 2.8 g 5.4 g 2.2 g PEGMP-
CPP
L4- DFA - TEGMP-
120 2.8 g 6.O g 0.9 g PEGMPC-
CN
L4- DFA -
PEGMP-
121 5.4 g 6.O g 0.9 g
PEGMPC-
CN
L4- DFA - TEGMPC-
122 3.4 g 6.O g 0.9 g PEGMPC-
CN
L4- DFA -
TEGMP-
123 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
L4- DFA -
PEGMP-
124 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
L4- DFA -
125 2.8 g 5.4 g 0.9 g TEGMP-
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]
TEGMPC-
157 3.4 g 6.O g 2.2 g
PEGMPC-
CPP
L4- DCA -
TEGMP-
158 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
L4- DCA -
PEGMP-
159 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
L4- DCA -
TEGMP-
160 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
L4- DCA - TEGMP-
161 2.8 g 6.0 ι 0.9 g PEGMPC-
CN
L4- DCA -
PEGMP-
162 5.4 g 6.O g 0.9 g
PEGMPC-
CN
L4- DCA - TEGMPC-
163 3.4 g 6.O g 0.9 g PEGMPC-
CN
L4- DCA -
TEGMP-
164 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
L4- DCA -
PEGMP-
165 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
L4- DCA -
166 2.8 g 5.4 g 0.9 g TEGMP-
PEGMP-CN
L4- DCA-
TEGMP-
167 2.8 g 3.4g 0.6 g
TEGMPC-
PEGMPC
L4- DCA-
PEGMP-
168 5.4 g 3.4 g 0.6 g
TEGMPC-
PEGMPC
L4- DCA - TEGMP-
169 2.8 g 5.4 i 0.6 ι PEGMP- PEGMPC
L4- DCA - TEGMP-
170 2.8 g 5.4 ; 3.4 g PEGMP- TEGMPC
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]
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]
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]
DFA-
234 2.8 g 0.9 g TEGMP-
CN
L4- TFSA-
DFA-
235 5.4 g 0.9 g PEGMP-
CN
L4- TFSA-
DFA-
236 3.4 g 0.9 g TEGMPC
-CN
L4- TFSA-
DFA-
237 6.O g 0.9 ; PEGMPC
-CN
L4- TFSA-
DFA -
238 2.8 g 6.O g TEGMP- PEGMPC
L4- TFSA-
DFA-
239 5.4 g 6.O g PEGMP- PEGMPC
L4- TFSA-
DFA-
240 3.4 g 6.Og TEGMPC
PEGMPC
L4- TFSA-
DFA-
241 2.8 g 3.4 g TEGMP- TEGMPC
L4- TFSA-
DFA-
242 5.4 g 3.4 g PEGMP- TEGMPC
L4- TFSA-
DFA-
243 2.8 g 5.4 g TEGMP- TEGMP
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]
Product
Example Reagent Code
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]
4.8 g 10.3 g TFSA
L4-4
13.7 g TFAC
L4-2
260 5.15 g 6.85 g TFSA-2
TFAC
L4- TFSA-
TFAC-
261 2.58 g 3.43 g 2.8 g 2.2 g
TEGMP-
CPP
L4- TFSA-
TFAC-
262 5.4 g 2.2 g
PEGMP-
CPP
L4- TFSA-
TFAC-
263 3.4 g 2.2 g
TEGMPC
-CPP
L4- TFSA-
TFAC-
264 6.O g 2.2 g
PEGMPC
-CPP
L4- TFSA-
265 0.9 g 2.2 g TFAC - CN-CPP
L4- TFSA-
TFAC-
266 2.8 g 0.9 g
TEGMP-
CN
L4- TFSA-
TFAC-
267 5.4 g 0.9 g
PEGMP-
CN
L4- TFSA-
TFAC-
268 3.4 ; 0.9 g TEGMPC
-CN
L4- TFSA-
TFAC-
269 6.O g 0.9 g PEGMPC
-CN
L4- TFSA-
TFAC-
270 2.8 g 6.O g
TEGMP-
PEGMPC
L4- TFSA-
TFAC-
271 5.4 g 6.O g
PEGMP-
PEGMPC
L4- TFSA-
TFAC-
272 3.4 ; 6.Og TEGMPC
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]
DFA-
282 2.8 g 0.9 g TEGMP-
CN
L4- DCN-
DFA-
283 5.4 g 0.9 g PEGMP-
CN
L4- DCN-
DFA-
284 3.4 g 0.9 g TEGMPC
-CN
L4- DCN-
DFA-
285 6.O g 0.9 g PEGMPC
-CN
L4- DCN-
DFA-
286 2.8 g 6.O g TEGMP- PEGMPC
L4- DCN-
DFA-
287 5.4 g 6.O g PEGMP- PEGMPC
L4- DCN-
DFA-
288 3.4 g 6.Og TEGMPC
PEGMPC
L4- DCN-
DFA -
289 2.8 g 3.4 g TEGMP- TEGMPC
L4- DCN-
DFA -
290 5.4 g 3.4 g PEGMP- TEGMPC
L4- 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]
Product
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]
314 2.8 g 0.9 g TEGMP-
CN
L4-DCN- TFAC-
315 5.4 g 0.9: PEGMP-
CN
L4-DCN-
TFAC-
316 3.4 g 0.9 g
TEGMPC
-CN
L4-DCN-
TFAC-
317 6.Og 0.9 g
PEGMPC
-CN
L4- DCN-
TFAC-
318 2.8 g 6.Og
TEGMP-
PEGMPC
L4- DCN-
TFAC-
319 5.4 g 6.Og
PEGMP-
PEGMPC
L4- DCN-
TFAC-
320 3.4 g 6.Og TEGMPC
PEGMPC
L4- DCN-
TFAC-
321 2.8 g 3.4 g
TEGMP-
TEGMPC
L4- DCN-
TFAC-
322 5.4 g 3.4 g
PEGMP-
TEGMPC
L4- 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]
Product
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]
346 2.8 g 0.9 g TEGMP-
CN
L4-DFA- TFAC -
347 5.4 g 0.9 g PEGMP-
CN
L4-DFA-
TFAC -
348 3.4 g 0.9 g
TEGMPC
-CN
L4-DFA-
TFAC -
349 6.O g 0.9 g
PEGMPC
-CN
L4-DFA-
TFAC -
350 2.8 g 6.O g
TEGMP-
PEGMPC
L4-DFA-
TFAC -
351 5.4 g 6.O g
PEGMP-
PEGMPC
L4-DFA-
TFAC -
352 3.4 g 6.Og TEGMPC
PEGMPC
L4-DFA-
TFAC -
353 2.8 g 3.4 g
TEGMP-
TEGMPC
L4-DFA-
TFAC -
354 5.4 g 3.4 g
PEGMP-
TEGMPC
L4-DFA- TFAC -
355 2.8 g 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]
Product
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]
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]
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]
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]
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]
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]
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]
Example 413. Manufacture of Conductive Thin Film (1)
3.0g of the anion receptor L4-4TFSA obtained from Example 1 was mixed with 2g of bisphenol A ethoxylate dimethacrylate (Bis- 15m) of the Formula 3 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.Og of the anion receptor L4-4TFSA obtained from Example 1 was replaced by 1.5g of L4-4TFSA and 1.5g of the anion receptor L4-4TFSI obtained from Example 2 to prepare a solid polymer electrolyte. Example 415. Manufacture of Conductive Thin 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 L4-4TFSA obtained from Example 1 was replaced by 1.5g of L4-4TFSA and 1.5g of the anion receptor L4-4TFSI 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]
Experimental Example 1. Ionic Conductivity Test (1) - Ionic Conductivities Depending on Amount of Used Anion Receptors
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]
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]
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]
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]
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 L4-4TFSI obtained from Example 2 was mixed with l.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/cm2 (charging) and 1.5mA/cm2 (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 L4-4TFSI (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 L4-4TFSI 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, hi 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
1. A compound represented by the Formula 1 : [Formula 1]
wherein Ri and R2 each 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;
R7 and the other R7 in the formula independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group;
R8 and the other R8 in the formula independently represents an alkyl, an alkenyl, an alkyl halide, and an alkenyl halide;
Y and Z each independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, q and t are integers from O to 1000, respectively; and r and s are integers from O to 20, respectively, whose sum is at least 1.
2. The compound of claim 1 is selected from the group consisting of: L4-4TFSA; L4-4TFSI; L4-2TFSA-2TEGMP; L4-2TFSA-2PEGMP; L4-2TFSA-2TEGMPC; L4-2TFSA-2PEGMPC; L4-2TFSA-2CN; L4-2TFSA-2CPP; L4-2TFSA-TEGMP-CPP; L4- 2TFSA-PEGMP-CPP; L4-2TFSA-TEGMPC-CPP; L4-2TFSA-PEGMPC-CPP; L4-2TFSA- CN-CPP; L4-2TFSA-TEGMP-CN; L4-2TFSA-PEGMP-CN; L4-2TFSA-TEGMPC-CN; L4- 2TFSA-PEGMPC-CN; L4-2TFSA-TEGMP-PEGMPC; L4-2TFSA-PEGMP-PEGMPC; L4- 2TFSA-TEGMPC-PEGMPC; L4-2TFSA-TEGMP-TEGMPC; L4-2TFSA-PEGMP- TEGMPC; L4-2TFSA-TEGMP-TEGMP; L4-TFSA-TEGMP-CN-CPP; L4-TFSA-PEGMP- CN-CPP; L4-TFSA-TEGMPC-CN-CPP; L4-TFSA-PEGMPC-CN-CPP; L4-TFS A- TEGMP-PEGMPC-CPP; L4-TFSA-PEGMP-PEGMPC-CPP; L4-TFSA-TEGMPC- PEGMPC-CPP; L4-TFSA-TEGMP-TEGMPC-CPP; L4-TFSA-PEGMP-TEGMPC-CPP; L4-TFSA-TEGMP-PEGMP-CPP; L4-TFSA-TEGMP-PEGMPC-CN; L4-TFSA-PEGMP- PEGMPC-CN; L4-TFSA-TEGMPC-PEGMPC-CN; L4-TFSA-TEGMP-TEGMPC-CN; L4- TFSA-PEGMP-TEGMPC-CN; L4-TFSA-TEGMP-PEGMP-CN; L4-TFSA-TEGMP- TEGMPC-PEGMPC; L4-TFSA-PEGMP-TEGMPC-PEGMPC; L4-TFSA-TEGMP- PEGMP-PEGMPC; L4-TFSA-TEGMP-PEGMP-TEGMPC; L4-4DCN; L4-2DCN- 2TEGMP; L4-2DCN-2PEGMP; L4-2DCN-2TEGMPC; L4-2DCN-2PEGMPC; L4-2DCN- 2CN; L4-2DCN-2CPP; L4-2DCN-TEGMP-CPP; L4-2DCN-PEGMP-CPP; L4-2DCN- TEGMPC-CPP; L4-2DCN-PEGMPC-CPP; L4-2DCN-CN-CPP; L4-2DCN-TEGMP-CN; L4-2DCN-PEGMP-CN; L4-2DCN-TEGMPC-CN; L4-2DCN-PEGMPC-CN; L4-2DCN- TEGMP-PEGMPC; L4-2DCN-PEGMP-PEGMPC; L4-2DCN-TEGMPC-PEGMPC; L4- 2DCN-TEGMP-TEGMPC; L4-2DCN-PEGMP-TEGMPC; L4-2DCN-TEGMP-TEGMP; L4-DCN-TEGMP-CN-CPP; L4-DCN-PEGMP-CN-CPP; L4-DCN-TEGMPC-CN-CPP; L4- DCN-PEGMPC-CN-CPP; L4-DCN-TEGMP-PEGMPC-CPP; L4-DCN-PEGMP- PEGMPC-CPP; L4-DCN-TEGMPC-PEGMPC-CPP; L4-DCN-TEGMP-TEGMPC-CPP; L4-DCN-PEGMP-TEGMPC-CPP; L4-DCN-TEGMP-PEGMP-CPP; L4-DCN-TEGMP- PEGMPC-CN; L4-DCN-PEGMP-PEGMPC-CN; L4-DCN-TEGMPC-PEGMPC-CN; L4- DCN-TEGMP-TEGMPC-CN; L4-DCN-PEGMP-TEGMPC-CN; L4-DCN-TEGMP- PEGMP-CN; L4-DCN-TEGMP-TEGMPC-PEGMPC; L4-DCN-PEGMP-TEGMPC- PEGMPC; L4-DCN-TEGMP-PEGMP-PEGMPC; L4-DCN-TEGMP-PEGMP-TEGMPC; L4-4DFA; L4-2DFA-2TEGMP; L4-2DFA-2PEGMP; L4-2DFA-2TEGMPC; L4-2DFA- 2PEGMPC; L4-2DFA-2CN; L4-2DFA-2CPP; L4-2DF A-TEGMP-CPP; L4-2DF A-PEGMP- CPP; L4-2DF A-TEGMPC-CPP; L4-2DFA-PEGMPC-CPP; L4-2DFA-CN-CPP; L4-2DFA- TEGMP-CN; L4-2DF A-PEGMP-CN; L4-2DFA-TEGMPC-CN; L4-2DFA-PEGMPC-CN; L4-2DFA-TEGMP-PEGMPC; L4-2DFA-PEGMP-PEGMPC; L4-2DFA-TEGMPC- PEGMPC; L4-2DFA-TEGMP-TEGMPC; L4-2DFA-PEGMP-TEGMPC; L4-2DFA- TEGMP-TEGMP; L4-DFA-TEGMP-CN-CPP; L4-DFA-PEGMP-CN-CPP; L4-DFA- TEGMPC-CN-CPP; L4-DFA-PEGMPC-CN-CPP; L4-DFA-TEGMP-PEGMPC-CPP; L4- DFA-PEGMP-PEGMPC-CPP; L4-DFA-TEGMPC-PEGMPC-CPP; L4-DFA-TEGMP- TEGMPC-CPP; L4-DFA-PEGMP-TEGMPC-CPP; L4-DFA-TEGMP-PEGMP-CPP; L4- DFA-TEGMP-PEGMPC-CN; L4-DFA-PEGMP-PEGMPC-CN; L4-DFA-TEGMPC- PEGMPC-CN; L4-DFA-TEGMP-TEGMPC-CN; L4-DFA-PEGMP-TEGMPC-CN; L4- DFA-TEGMP-PEGMP-CN; L4-DFA-TEGMP-TEGMPC-PEGMPC; L4-DFA-PEGMP- TEGMPC-PEGMPC; L4-DFA-TEGMP-PEGMP-PEGMPC; L4-DFA-TEGMP-PEGMP- TEGMPC; L4-4DCA; L4-2DCA-2TEGMP; L4-2DCA-2PEGMP; L4-2DCA-2TEGMPC; L4-2DCA-2PEGMPC; L4-2DCA-2CN; L4-2DCA-2CPP; L4-2DCA-TEGMP-CPP; L4- 2DCA-PEGMP-CPP; L4-2DCA-TEGMPC-CPP; L4-2DCA-PEGMPC-CPP; L4-2DCA- CN-CPP; L4-2DCA-TEGMP-CN; L4-2DCA-PEGMP-CN; L4-2DCA-TEGMPC-CN; L4- 2DCA-PEGMPC-CN; L4-2DCA-TEGMP-PEGMPC; L4-2DCA-PEGMP-PEGMPC; L4- 2DCA-TEGMPC-PEGMPC; L4-2DCA-TEGMP-TEGMPC; L4-2DCA-PEGMP- TEGMPC; L4-2DCA-TEGMP-TEGMP; L4-DCA-TEGMP-CN-CPP; L4-DCA-PEGMP- CN-CPP; L4-DCA-TEGMPC-CN-CPP; L4-DCA-PEGMPC-CN-CPP; L4-DCA-TEGMP- PEGMPC-CPP; L4-DCA-PEGMP-PEGMPC-CPP; L4-DCA-TEGMPC-PEGMPC-CPP; L4-DCA-TEGMP-TEGMPC-CPP; L4-DCA-PEGMP-TEGMPC-CPP; L4-DCA-TEGMP- PEGMP-CPP; L4-DCA-TEGMP-PEGMPC-CN; L4-DCA-PEGMP-PEGMPC-CN; L4- DCA-TEGMPC-PEGMPC-CN; L4-DCA-TEGMP-TEGMPC-CN; L4-DCA-PEGMP- TEGMPC-CN; L4-DC A-TEGMP-PEGMP-CN; L4-DCA-TEGMP-TEGMPC-PEGMPC; L4-DCA-PEGMP-TEGMPC-PEGMPC; L4-DCA-TEGMP-PEGMP-PEGMPC; L4-DCA- TEGMP-PEGMP-TEGMPC; L4-4TFAC; L4-2TFAC-2TEGMP; L4-2TFAC-2PEGMP; L4- 2TFAC-2TEGMPC; L4-2TFAC-2PEGMPC; L4-2TFAC-2CN; L4-2TFAC-2CPP; L4- 2TF AC-TEGMP-CPP; L4-2TF AC-PEGMP-CPP; L4-2TFAC-TEGMPC-CPP; L4-2TFAC- PEGMPC-CPP; L4-2TF AC-CN-CPP; L4-2TF AC-TEGMP-CN; L4-2TF AC-PEGMP-CN; L4-2TF AC-TEGMPC-CN; L4-2TFAC-PEGMPC-CN; L4-2TFAC-TEGMP-PEGMPC; L4- 2TFAC-PEGMP-PEGMPC; L4-2TFAC-TEGMPC-PEGMPC; L4-2TFAC-TEGMP- TEGMPC; L4-2TFAC-PEGMP-TEGMPC; L4-2TFAC-TEGMP-TEGMP; L4-TFAC- TEGMP-CN-CPP; L4-TFAC-PEGMP-CN-CPP; L4-TFAC-TEGMPC-CN-CPP; L4-TFAC- PEGMPC-CN-CPP; L4-TFAC-TEGMP-PEGMPC-CPP; L4-TFAC-PEGMP-PEGMPC- CPP; L4-TFAC-TEGMPC-PEGMPC-CPP; L4-TFAC-TEGMP-TEGMPC-CPP; L4-TFAC- PEGMP-TEGMPC-CPP; L4-TFAC-TEGMP-PEGMP-CPP; L4-TFAC-TEGMP-PEGMPC- CN; L4-TFAC-PEGMP-PEGMPC-CN; L4-TFAC-TEGMPC-PEGMPC-CN; L4-TFAC- TEGMP-TEGMPC-CN; L4-TFAC-PEGMP-TEGMPC-CN; L4-TFAC-TEGMP-PEGMP- CN; L4-TFAC-TEGMP-TEGMPC-PEGMPC; L4-TFAC-PEGMP-TEGMPC-PEGMPC;
L4-TFAC-TEGMP-PEGMP-PEGMPC; L4-TFAC-TEGMP-PEGMP-TEGMPC; L4- 2TFSA-2DCN; L4-TFSA-DCN-TEGMP-CPP; L4-TFSA-DCN-PEGMP-CPP; L4-TFSA- DCN-TEGMPC-CPP; L4-TFSA-DCN-PEGMPC-CPP; L4-TFSA-DCN-CN-CPP; L4- TFSA-DCN-TEGMP-CN; L4-TFSA-DCN-PEGMP-CN; L4-TFSA-DCN-TEGMPC-CN; L4-TFSA-DCN-PEGMPC-CN; L4-TFSA-DCN-TEGMP-PEGMPC; L4-TFSA-DCN- PEGMP-PEGMPC; L4-TFSA-DCN-TEGMPC-PEGMPC; L4-TFSA-DCN-TEGMP- TEGMPC; L4-TFSA-DCN-PEGMP-TEGMPC; L4-TFSA-DCN-TEGMP-TEGMP; L4- 2TFSA-2DFA; L4-TFSA-DFA-TEGMP-CPP; L4-TFSA-DFA-PEGMP-CPP; L4-TFSA- DFA-TEGMPC-CPP; L4-TFSA-DFA-PEGMPC-CPP; L4-TFSA-DFA-CN-CPP; L4-TFS A- DFA-TEGMP-CN; L4-TFSA-DFA-PEGMP-CN; L4-TFSA-DFA-TEGMPC-CN; L4- TFSA-DFA-PEGMPC-CN; L4-TFSA-DFA-TEGMP-PEGMPC; L4-TFSA-DFA-PEGMP- PEGMPC; L4-TFSA-DFA-TEGMPC-PEGMPC; L4-TFSA-DFA-TEGMP-TEGMPC; L4- TFSA-DFA-PEGMP-TEGMPC; L4-TFSA-DFA-TEGMP-TEGMP; L4-2TFSA-2DCA; L4- TFSA-DCA-TEGMP-CPP; L4-TFSA-DCA-PEGMP-CPP; L4-TFSA-DCA-TEGMPC- CPP; L4-TFSA-DCA-PEGMPC-CPP; L4-TFSA-DCA-CN-CPP; L4-TFSA-DCA-TEGMP- CN; L4-TFSA-DCA-PEGMP-CN; IΛ-TFSA-DCA-TEGMPC-CN; L4-TFSA-DCA- PEGMPC-CN; L4-TFSA-DCA-TEGMP-PEGMPC; L4-TFSA-DCA-PEGMP-PEGMPC; L4-TFSA-DCA-TEGMPC-PEGMPC; L4-TFSA-DCA-TEGMP-TEGMPC; L4-TFSA- DCA-PEGMP-TEGMPC; L4-TFSA-DCA-TEGMP-TEGMP; L4-2TFSA-2TFAC; L4- TFSA-TFAC-TEGMP-CPP; L4-TFSA-TFAC-PEGMP-CPP; L4-TFSA-TFAC-TEGMPC- CPP; L4-TFSA-TFAC-PEGMPC-CPP; L4-TFSA-TFAC-CN-CPP; L4-TFSA-TFAC- TEGMP-CN; L4-TFSA-TFAC-PEGMP-CN; L4-TFSA-TFAC-TEGMPC-CN; L4-TFSA- TFAC-PEGMPC-CN; L4-TFSA-TFAC-TEGMP-PEGMPC; L4-TFSA-TFAC-PEGMP- PEGMPC; L4-TFSA-TFAC-TEGMPC-PEGMPC; L4-TFSA-TFAC-TEGMP-TEGMPC;
L4-TFSA-TFAC-PEGMP-TEGMPC; L4-TFSA-TFAC-TEGMP-PEGMP; L4-2DCN- 2DFA; L4-DCN-DFA-TEGMP-CPP; L4-DCN-DFA-PEGMP-CPP; L4-DCN-DFA- TEGMPC-CPP; L4-DCN-DFA-PEGMPC-CPP; L4-DCN-DFA-CN-CPP; L4-DCN-DFA- TEGMP-CN; L4-DCN-DFA-PEGMP-CN; L4-DCN-DFA-TEGMPC-CN; L4-DCN-DFA- PEGMPC-CN; L4-DCN-DFA-TEGMP-PEGMPC; L4-DCN-DFA-PEGMP-PEGMPC; L4- DCN-DFA-TEGMPC-PEGMPC; L4-DCN-DFA-TEGMP-TEGMPC; L4-DCN-DFA- PEGMP-TEGMPC; L4-DCN-DFA-TEGMP-TEGMP; L4-2DCN-2DCA; L4-DCN-DCA- TEGMP-CPP; L4-DCN-DCA-PEGMP-CPP; L4-DCN-DCA-TEGMPC-CPP; L4-DCN- DCA-PEGMPC-CPP; L4-DCN-DCA-CN-CPP; L4-DCN-DCA-TEGMP-CN; L4-DCN- DCA-PEGMP-CN; L4-DCN-DCA-TEGMPC-CN; L4-DCN-DCA-PEGMPC-CN; L4- DCN-DCA-TEGMP-PEGMPC; L4-DCN-DCA-PEGMP-PEGMPC; L4-DCN-DCA- TEGMPC-PEGMPC; L4-DCN-DCA-TEGMP-TEGMPC; L4-DCN-DCA-PEGMP- TEGMPC; L4-DCN-DCA-TEGMP-TEGMP; L4-2DCN-2TFAC; L4-DCN-TFAC-TEGMP- CPP; L4-DCN-TFA-PEGMP-CPP; L4-DCN-TFAC-TEGMPC-CPP; L4-DCN-TF AC- PEGMPC-CPP; L4-DCN-TFAC-CN-CPP; L4-DCN-TFAC-TEGMP-CN; L4-DCN-TFAC- PEGMP-CN; L4-DCN-TFAC-TEGMPC-CN; L4-DCN-TFAC-PEGMPC-CN; L4-DCN- DCA-TEGMP-PEGMPC; L4-DCN-DCA-PEGMP-PEGMPC; L4-DCN-DCA-TEGMPC- PEGMPC; L4-DCN-DCA-TEGMP-TEGMPC; L4-DCN-DCA-PEGMP-TEGMPC; L4- DCN-DCA-TEGMP-TEGMP; L4-2DFA-2DCA; L4-DFA-DCA-TEGMP-CPP; L4-DFA- DCA-PEGMP-CPP; L4-DFA-DCA-TEGMPC-CPP; L4-DFA-DCA-PEGMPC-CPP; L4- DFA-DCA-CN-CPP; L4-DFA-DCA-TEGMP-CN; L4-DFA-DCA-PEGMP-CN; L4-DFA- DCA-TEGMPC-CN; L4-DFA-DCA-PEGMPC-CN; L4-DFA-DCA-TEGMP-PEGMPC; L4-DFA-DCA-PEGMP-PEGMPC; L4-DFA-DCA-TEGMPC-PEGMPC; L4-DFA-DCA- TEGMP-TEGMPC; L4-DFA-DCA-PEGMP-TEGMPC; L4-DFA-DCA-TEGMP-TEGMP; L4-2DFA-2TFAC; L4-DFA-TFACTEGMP-CPP; L4-DFA-TFAC-PEGMP-CPP; L4-DFA- TFAC-TEGMPC-CPP; L4-DFA-TFAC-PEGMPC-CPP; L4-DFA-TFAC-CN-CPP; L4-
DFA-TFAC-TEGMP-CN; L4-DFA-TFAC-PEGMP-CN; L4-DFA-TFAC-TEGMPC-CN; L4-DFA-TFAC-PEGMPC-CN; L4-DFA-TFAC-TEGMP-PEGMPC; L4-DFA-TFAC- PEGMP-PEGMPC; L4-DFA-TFAC-TEGMPC-PEGMPC; L4-DFA-TFAC-TEGMP- TEGMPC; L4-DFA-TFAC-PEGMP-TEGMPC; L4-DFA-TFAC-TEGMP-TEGMP; L4- 2DCA-2TFAC; L4-DCA-TFAC-TEGMP-CPP; L4-DCA-TFAC-PEGMP-CPP; L4-DCA- TFAC-TEGMPC-CPP; L4-DCA-TFAC-PEGMPC-CPP; L4-DCA-TFAC-CN-CPP; L4- DCA-TFAC-TEGMP-CN; L4-DCA-TFAC-PEGMP-CN; L4-DCA-TFAC-TEGMPC-CN; L4-DCA-TFAC-PEGMPC-CN; L4-DCA-TFAC-TEGMP-PEGMPC; L4-DCA-TFAC- PEGMP-PEGMPC; L4-DCA-TFAC-TEGMPC-PEGMPC; L4-DCA-TFAC-TEGMP- TEGMPC; L4-DCA-TFAC-PEGMP-TEGMPC; L4-DCA-TFAC-TEGMP-TEGMP; L4- TFSA-DCN-TFAC-TEGMP; L4-TFSA-DCN-TFAC-PEGMP; L4-TFSA-DCN-TFAC- TEGMPC; L4-TFSA-DCN-TFAC-PEGMPC; L4-TFSA-DCN-TFAC-CN; L4-TFS A-DCN- TFAC-CPP; L4-TFSA-DFA-TFAC-TEGMP; L4-TFSA-DFA-TFAC-PEGMP; L4-TFSA- DFA-TFAC-TEGMPC; L4-TFSA-DFA-TFAC-PEGMPC; L4-TFSA-DFA-TFAC-CN; L4- TFSA-DFA-TFAC-CPP; L4-TFSA-DCA-TFAC-TEGMP; L4-TFSA-DCA-TFAC- PEGMP; L4-TFSA-DCA-TFAC-TEGMPC; L4-TFSA-DCA-TFAC-PEGMPC; L4-TFSA- DCA-TFAC-CN; L4-TFSA-DCA-TFAC-CPP; L4-TFSA-DCN-DCA-TEGMP; L4-TFSA- DCN-DCA-PEGMP; L4-TFSA-DCN-DCA-TEGMPC; L4-TFSA-DCN-DCA-PEGMPC; L4-TFSA-DCN-DCA-CN; L4-TFSA-DCN-DCA-CPP; L4-TFSA-DFA-DCA-TEGMP; L4- TFSA-DFA-DCA-PEGMP; L4-TFSA-DFA-DCA-TEGMPC; L4-TFSA-DFA-DCA- PEGMPC; L4-TFSA-DFA-DCA-CN; L4-TFSA-DFA-DCA-CPP; L4-TFSA-DCN-DFA- TEGMP; L4-TFSA-DCN-DFA-PEGMP; L4-TFSA-DCN-DFA-TEGMPC; L4-TFSA- DCN-DFA-PEGMPC; L4-TFSA-DCN-DFA-CN; L4-TFSA-DCN-DFA-CPP; L4-TFSA- DCN-DFA-TFAC; L4-TFSA-DCN-DCA-TFAC; L4-TFSA-DFA-DCA-TFAC; L4-TFSA- DCN-DFA-DCA; and L4-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 compound of claim 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 compound of claim 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(SO2CFs)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 polyethers.
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 dimethyl ether (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 5V6O13, Lii.2V2O5, 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 disulfide/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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2005-0047802 | 2005-06-03 | ||
KR20050047802 | 2005-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006129992A1 true WO2006129992A1 (en) | 2006-12-07 |
Family
ID=37481871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2006/002162 WO2006129992A1 (en) | 2005-06-03 | 2006-06-05 | Anion receptor and electrolyte using the same |
Country Status (2)
Country | Link |
---|---|
KR (1) | KR20080009313A (en) |
WO (1) | WO2006129992A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010277827A (en) * | 2009-05-28 | 2010-12-09 | Sony Corp | Nonaqueous electrolyte, positive electrode, and nonaqueous electrolyte secondary battery using the nonaqueous electrolyte and the positive electrode |
CN102746514A (en) * | 2012-08-01 | 2012-10-24 | 苏州大学 | Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof |
CN102807674A (en) * | 2012-09-05 | 2012-12-05 | 苏州大学 | Hyperbranched polysiloxane-modified polyaniline and preparation method thereof |
WO2013113593A1 (en) * | 2012-01-31 | 2013-08-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polar functionalized oligomers, polymer compound having blended polar functionalized oligomers, method for production thereof, and use thereof |
JP2014186957A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic battery using the same |
US8906546B2 (en) | 2010-10-29 | 2014-12-09 | Samsung Electronics Co., Ltd. | Non-aqueous electrolyte and lithium air battery including the same |
JP2016091663A (en) * | 2014-10-30 | 2016-05-23 | 三菱自動車工業株式会社 | Lithium secondary battery and electric vehicle |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR19990006136A (en) * | 1997-06-30 | 1999-01-25 | 김영환 | EPROM Diagnosis |
JPH11302383A (en) * | 1998-04-16 | 1999-11-02 | Kanegafuchi Chem Ind Co Ltd | Polysiloxane having cyclic carbonate group on side chain and its production |
KR20030040618A (en) * | 2001-11-15 | 2003-05-23 | 한국화학연구원 | New Cross-linker, and Cross-linkable Solid polymer Electrolytes using the same |
JP2003197030A (en) * | 2001-12-25 | 2003-07-11 | Daiso Co Ltd | Polymer solid electrolytic and battery |
-
2006
- 2006-06-05 KR KR1020077028341A patent/KR20080009313A/en not_active Application Discontinuation
- 2006-06-05 WO PCT/KR2006/002162 patent/WO2006129992A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR19990006136A (en) * | 1997-06-30 | 1999-01-25 | 김영환 | EPROM Diagnosis |
JPH11302383A (en) * | 1998-04-16 | 1999-11-02 | Kanegafuchi Chem Ind Co Ltd | Polysiloxane having cyclic carbonate group on side chain and its production |
KR20030040618A (en) * | 2001-11-15 | 2003-05-23 | 한국화학연구원 | New Cross-linker, and Cross-linkable Solid polymer Electrolytes using the same |
JP2003197030A (en) * | 2001-12-25 | 2003-07-11 | Daiso Co Ltd | Polymer solid electrolytic and battery |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010277827A (en) * | 2009-05-28 | 2010-12-09 | Sony Corp | Nonaqueous electrolyte, positive electrode, and nonaqueous electrolyte secondary battery using the nonaqueous electrolyte and the positive electrode |
US8906546B2 (en) | 2010-10-29 | 2014-12-09 | Samsung Electronics Co., Ltd. | Non-aqueous electrolyte and lithium air battery including the same |
WO2013113593A1 (en) * | 2012-01-31 | 2013-08-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polar functionalized oligomers, polymer compound having blended polar functionalized oligomers, method for production thereof, and use thereof |
CN102746514A (en) * | 2012-08-01 | 2012-10-24 | 苏州大学 | Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof |
CN102746514B (en) * | 2012-08-01 | 2014-02-26 | 苏州大学 | Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof |
CN102807674A (en) * | 2012-09-05 | 2012-12-05 | 苏州大学 | Hyperbranched polysiloxane-modified polyaniline and preparation method thereof |
JP2014186957A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic battery using the same |
JP2016091663A (en) * | 2014-10-30 | 2016-05-23 | 三菱自動車工業株式会社 | Lithium secondary battery and electric vehicle |
Also Published As
Publication number | Publication date |
---|---|
KR20080009313A (en) | 2008-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006129991A1 (en) | Anion receptor and electrolyte using the same | |
KR101265345B1 (en) | Cyclic Carbonate-Modified Siloxane Process for Producing the Same Non-Aqueous Electrolytic Solution Secondary Battery and Capacitor | |
US11489198B2 (en) | Nonaqueous electrolyte compositions comprising silyl oxalates | |
CN106795184B (en) | Functionalized silane, electrolyte composition comprising same, and electrochemical device | |
JP4438956B2 (en) | Non-aqueous electrolyte and secondary battery using the same | |
WO2006129992A1 (en) | Anion receptor and electrolyte using the same | |
KR101265334B1 (en) | Non-aqueous electrolytic solution secondary battery and electrochemical capacitor | |
JP2006137741A (en) | Cyclic carbonate-modified organic silicon compound and non-aqueous electrolyte solution including the same, secondary cell and capacitor | |
WO2007126262A1 (en) | Anion receptor, and electrolyte using the same | |
WO2014059709A1 (en) | Organohalogen silane containing polyether chain and use thereof in non-aqueous lithium ion battery electrolyte | |
WO2006101328A1 (en) | Cyclic siloxane-based compounds and solid polymer electrolyte composition containing the same as a crosslinking agent | |
WO2014043981A1 (en) | Halogenosilane-functionalized carbonate electrolyte material, preparation method thereof and use in lithium ion battery electrolyte | |
JP4957888B2 (en) | Non-aqueous electrolyte, secondary battery and electrochemical capacitor | |
KR101424188B1 (en) | anion receptors, electrolyte containing anion receptors, lithium ion battery and lithium ion capacitor using the same | |
WO2007091867A1 (en) | Novel crosslinker and solid polymer electrolyte using the same | |
WO2007091817A1 (en) | Anion receptor, and electrolyte using the same | |
JP4910278B2 (en) | Non-aqueous electrolyte and battery using the same | |
KR100663686B1 (en) | Setting composition for a battery electrolyte | |
WO2007102705A1 (en) | Anion receptor and electrolyte using the same | |
KR100344910B1 (en) | Heat-Crosslinkable Polysiloxane Electrolytes Composition And Method For Preparing Solid Polymer Electrolytic Film By Using The Same | |
US9221844B2 (en) | Metal bis(malonato) borate monomers, polymers and copolymers derived therefrom, methods of making the monomers and polymers, and articles derived therefrom | |
KR20070030682A (en) | Cyclic Carbonate-Modified Organosilicon Compound, Non-Aqueous Electrolytic Solution Comprising the Same, Secondary Battery and Capacitor | |
JP2002179800A (en) | Ion conductive polymer and ion conductor | |
KR20220120429A (en) | New anion receptor and electrolyte comprising same | |
CN117157795A (en) | Novel anion receptor and electrolyte comprising the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077028341 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 06768768 Country of ref document: EP Kind code of ref document: A1 |