WO2007091867A1 - Nouveau composé de réticulation et électrolyte polymère solide faisant appel à ce composé - Google Patents

Nouveau composé de réticulation et électrolyte polymère solide faisant appel à ce composé Download PDF

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WO2007091867A1
WO2007091867A1 PCT/KR2007/000724 KR2007000724W WO2007091867A1 WO 2007091867 A1 WO2007091867 A1 WO 2007091867A1 KR 2007000724 W KR2007000724 W KR 2007000724W WO 2007091867 A1 WO2007091867 A1 WO 2007091867A1
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polymer electrolyte
reaction scheme
compounds
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/188—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 crosslinker compound, and a crosslinkable solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer 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 a gel or solid polymer electrolyte containing the novel crosslinker.
  • 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.
  • a solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10 "8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted.
  • ionic conductivity of such electrolytes at room temperature is as low as lO ⁇ -lO "4 S/cm, which may have poor mechanical properties when they were formed into films.
  • Abraham et al. introduced polyethylene oxide with low molecular weight into a vinylidenhexaf ⁇ uoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978).
  • the CF 3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF 3 .
  • a C-O-C- 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. Therefore, there is a need to develop a novel substance which replaces the PAO type plasticizer having the above drawbacks.
  • 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, 147 (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 cathode materials.
  • aza- ethers are unstable to LiPF 6 (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.
  • 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 electron, e.g., oxygen or nitrogen.
  • PF 5 a relatively strong Lewis acid, is known to attack electron pairs (J. Power Sources, 104 (2002) 260). Due to high electron density, aza-ethers are promptly attached by PF 5 . 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 attacked nitrogen or oxygen atom in the middle
  • an object of the present invention to provide a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer 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.
  • a crosslinker represented by the following Formula 1 : [Formula 1] wherein R 1 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 , -BF 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 4 is a hydrogen atom
  • R 5 and R 6 independently represents a hydrogen atom or a methyl group
  • R 7 and the other R 7 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group
  • Rg and the other R 8 in the formula 1 independently represents an alkyl, an alkenyl,
  • R 9 represents a hydrogen atom or a methyl group
  • R 1O represents -CH 2 -, R 11 and the other R 11 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide;
  • Y and Z each independently represent -O-, -S-, -CO-, -OCO-, -OCOO- or -COO-;
  • n is an integer from 1 to 100;
  • o, p, q, t and u are integers from O to 100, respectively;
  • r and s are integers from O to 20, respectively, whose sum is at least 1 ;
  • v represents integer from 1 to 6;
  • w represents integer from O to 4.
  • the compound represented by the Formula 1 has a main structure of methyl siloxane polymer 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 the compound has two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain.
  • 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 , -BF 3 and -SO 2 CN, and forms electrically neutral complexes with anions of alkali metal salts.
  • electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 , -BF 3 and -SO 2 CN
  • the compound of Formula 1 can be easily approached by bulky and soft anion such as trifluoromethane sulfone imide since the center of the nitrogen atom is exposed, therefore dissociation of lithium salt is promoted, the complex can be formed more effectively. As a result, alkali metal cationic mobility is increased and thus, high ionic conductivity can be achieved.
  • polyalkylene oxide group, cyano group and propylene carbonate group and the like also include atoms with high electronegativity such as oxygen and nitrogen, and thus enhance ionic conductivity by increasing alkali metal cationic mobility.
  • the crosslinker of the present invention comprises flexible polymethyl siloxane polymer as a main chain, therefore complements mechanical properties such as drawing and bending properties, and also contains amine substituted with electron withdrawing groups, polyalkylene oxide group, cyano group and propylene carbonate group as a side branch to improve compatibility of plasticizer added in order to enhance ionic conductivity.
  • the crosslinker of the present invention has a structure containing two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain, therefore it makes the solid polymer electrolyte form three dimensional net-shaped structure after crosslinking.
  • the crosslinker represented by the Formula 1 can be synthesized by any known method.
  • the compound of the Formula 1 can be synthesized by: hydrosilylating a polymethylcyclo polysiloxane (D t+n+o+ p + qH) represented by the following Formula 3 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate to synthesize the compound represented
  • the present invention provides gel polymer electrolytes and solid polymer electrolytes containing the crosslinker represented by Formula 1.
  • the present invention provides a gel polymer electrolyte, which comprises (i) a crosslinker of the Formula 1 ; (ii) a nonaqueous solvent; (iii) an anion receptor; (iv) a curing initiator; and (v) an alkali metal ion containing substance.
  • a solid polymer electrolyte which comprises (i) a crosslinker of the Formula 1; (ii) plasticizer; (iii) a curing initiator; and (iv) an alkali metal ion containing substance.
  • 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 gel polymer electrolytes of the present invention use the anion receptor, for example, linear or cyclic siloxane compounds having 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; linear or cyclic hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; or aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups and the like.
  • the anion receptor for example, linear or cyclic siloxane compounds having 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; linear or cyclic hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; or aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups and the like.
  • the alkali metal ion containing substance includes LiSO 3 CF 3 , LiCOOC 2 Fs, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiSbF 6 , LiI, LiBr, LiCl or a mixture thereof.
  • the gel polymer electrolyte contains 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 benzoin ether, isopropyl benzoin ether, ⁇ -methyl bezoin ethyl ether, benzoin phenyl ether,
  • DMPA dimethoxyphenyl acetophenone
  • t-butylperoxypivalate ethyl benzoin ether
  • isopropyl benzoin ether ⁇ -methyl bezoin ethyl ether
  • benzoin phenyl ether benzoin phenyl ether
  • heat-curing initiator examples include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
  • the solid polymer electrolyte of the present invention may contain plasticizer in order to enhance conductivity by elevating dissociation of metal salts and conductivity of lithium ion.
  • the plasticizer may include one or combination selected from the group consisting of an anion receptor, a polyalkyleneglycol dialkylether and a
  • the present invention may use the anion receptor such as linear of cyclic siloxane compound, linear hydrocarbon compounds and aromatic hydrocarbon compound having amine substituted with electron withdrawing groups in order to solve the problems caused by low molecular weight polyethyleneglycol dimethylether (PEGDME) used for enhancing conductivity.
  • anion receptor such as linear of cyclic siloxane compound, linear hydrocarbon compounds and aromatic hydrocarbon compound having amine substituted with electron withdrawing groups
  • polyalkyleneglycol dialkylether which is used as other plasticizer
  • polyethyleneglycol dimethylether PEGDME
  • polyethyleneglycol diethylether polyethyleneglycol dipropylether
  • polyethyleneglycol dibutylether polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether
  • polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated with dibutylether.
  • the gel polymer electrolyte of the present invention preferably contains 1 - 40 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of the nonaqueous solvent, 0 - 30 parts by weight of the anion receptor, 3 - 60 parts by weight of the alkali metal ion containing substance, and 0.5 - 5 parts by weight of a curing initiator.
  • the solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of one or more substance(s) selected from the anion receptor, polyalkyleneglycol dialkylether, nonaqueous solvent and mixtures thereof, 3 — 60 parts by weight of the alkali metal ion containing substance, and
  • the present invention provides an electrochemical cell comprising the gel polymer electrolyte or solid polymer electrolyte containing the above crosslinker, a cathode and an anode.
  • an electrochemical cell comprising the gel polymer electrolyte or solid polymer electrolyte containing the above crosslinker, a cathode and an anode.
  • a cathode is composed of a cathode, an anode, and a separator, while a cell using the solid polymer electrolyte is composed of a cathode and an anode.
  • an anode and a cathode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing anodes and cathodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
  • the anode 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 ; mixtures thereof; and mixtures of these and alkali metals.
  • 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 ; mixtures thereof; and mixtures of these and alkali metals.
  • the cathode 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.
  • transition metal oxides are Li 2 5 V 6 O 13 , Li 1 2 V 2 O 5 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiNi 1-x M x 0 2 (wherein M is Co, Mg, Al or Ti) and the like.
  • transition metal chalcogenides are LiNbSe 3 , LiTiS 2 , LiMoS 2 and the like.
  • the organic disulfide redox polymers are prepared by reversible electrochemical dimerization/scission or polymerization/depolymerization of the organic disulfide polymers.
  • the organic disulfide/polyaniline complexes are preferably mixtures of polyaniline and 2,5-dimercapto-l,3,4-thiadiazole.
  • the present invention provides a polymer electrolyte film using the gel polymer electrolyte or the solid polymer electrolyte of the present invention.
  • a preparation method of a gel or solid polymer electrolyte film containing the components of the present invention is as follows:
  • a nonaqueous solvent, an anion receptor and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
  • a crosslinker of the present invention is then added to the solution and mixed together.
  • 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 beams, UV rays or ⁇ -rays, or heated to cause the hardening reaction, and a desired film is obtained.
  • a plasticizer and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
  • a crosslinker compound of the present invention is added to the solution and mixed together.
  • a curing initiator is added to the solution, and 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
  • 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 solid polymer electrolyte film.
  • FIG. 1 is a graph showing a property of ionic conductivity of the solid polymer electrolytes of the present invention (Experimental example 3).
  • THF dried over Na.
  • the reaction mixture was refluxed for 24 hours under nitrogen atmosphere.
  • 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.
  • Preparation Examples 276 - 291 Compounds (Preparation Examples 276 - 291) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
  • Preparation Example 425 Preparation of Di-l,3-di(propane acrylate) (DaDi) (Step 1) 2.6g of 3-butene-l-ol instead of 3-allyloxy-l,2-propanediol and 3.Og of 1,1,3,3- tetramethyldisiloxane (D 2 , 0.0223 mol) were reacted under the same method as in (step 1) of Preparation Example 424 to obtain D 2 -l,3-di(propanol) (see the Reaction Scheme 29).
  • the crosslinker compound represented by Formula 1 is all of compounds synthesized by the same method described in the following Examples in combination of the monomer (Formula 4) in Reaction Scheme 1 prepared from Preparation Examples 1 to 423 and polymerization terminators substituted with acryl or phenyl acryl group in the Reaction Scheme 1 prepared from Preparation Examples 424 to 426, but are limited to the compounds prepared in the following Examples.
  • reaction products were added to 50ml of chloroform and 30ml of saturated aqueous Na 2 SO 4 solution, and neutralized and washed with 5 wt% of Na 2 CO 3 aqueous solution until neutrality was reached.
  • MgSO 4 was added to the neutralized reactants and the mixture was stirred.
  • the precipitates were filtered, hydroquinone (100 ppm) as a polymerization inhibitor was added thereto, and the resultant was evaporated under the reduced pressure to obtain Ta-0.86TFSI-10TEGMP (see
  • crosslinker compounds of Formula 1 (Examples 5 to 6) having a composition (weight ratio) shown in Table 24 were prepared by the same method as in Example 1. [Table 24]
  • Solid polymer electrolyte films were prepared having a composition shown in Table 25 by using the crosslinker Ta-xTFSI-y TEGMP of Examples 1 to 3 and the crosslinker of Ta-IOTEGMP of Comparative Example 1. Then, ionic conductivities of the solid polymer electrolyte films were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium- copper foil, photocured, 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.
  • Solid polymer electrolyte films were prepared having a composition shown in Table 26 by using the crosslinker Pha-xTFSI-yTEGMP of Examples 4 to 6. Then, ionic
  • Solid polymer electrolyte films were prepared having a composition shown in Table 27 by using the crosslinker Ta-2.58TFSI-10TEGMP of Example 3. Then, ionic
  • FIG. 1 shows a change of the ionic conductivities according to the temperature when the crosslinker Ta-2.58TFSI-10TEGMP and anion receptor C 4 -TFSI as a plasticizer were used.
  • the solid polymer electrolyte composition of the present invention has excellent mechanical properties such as drawing and bending properties owing to the skeletal structure of the added crosslinker, and offers substantially enhanced ionic conductivities at a room temperature to prepare the electrolyte thin film.
  • the electrolyte thin film of the present invention has good film-forming properties and electrochemical stabilities, 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.

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Abstract

L'invention concerne un nouveau composé de réticulation et un électrolyte polymère solide réticulable contenant ce composé. En particulier, l'invention concerne un nouveau composé de réticulation présentant un groupe acryle ou un groupe phénylacryle réticulable par traitement thermique ou par irradiation lumineuse au niveau de deux groupes terminaux et/ou dans une chaîne linéaire d'un polymère de méthyle siloxane présentant une amine substituée par des groupes de retrait d'électrons, ou au moins un élément parmi: un groupe d'oxyde de polyalkylène, un groupe cyano et un groupe de carbonate de propylène servant de ramification latérale, en plus de l'amine substituée par des groupes de retrait d'électrons. L'invention concerne également un électrolyte polymère solide ou en gel contenant le nouveau composé de réticulation. L'invention concerne encore une pile électrochimique contenant le composé de l'invention.
PCT/KR2007/000724 2006-02-09 2007-02-09 Nouveau composé de réticulation et électrolyte polymère solide faisant appel à ce composé WO2007091867A1 (fr)

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KR10-2006-0012530 2006-02-09
KR20060012530 2006-02-09

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WO2007091867A1 true WO2007091867A1 (fr) 2007-08-16

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Cited By (6)

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JP2011184333A (ja) * 2010-03-05 2011-09-22 Shin-Etsu Chemical Co Ltd 含フッ素有機ケイ素化合物及びその製造方法
US20120244427A1 (en) * 2009-12-09 2012-09-27 Nippon Shokubai Co., Ltd. Electrolyte material, and battery material and secondary battery using said electrolyte material
US20120283378A1 (en) * 2011-05-02 2012-11-08 Ricoh Company, Ltd., A silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink
WO2013113593A1 (fr) * 2012-01-31 2013-08-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Oligomères pourvus d'un groupe fonctionnel polaire, formulation complète pour polymères comportant un mélange d'oligomères pourvus d'un groupe fonctionnel polaire, leur procédé de préparation ainsi que leur utilisation
CN110915034A (zh) * 2017-11-20 2020-03-24 株式会社Lg化学 涂覆有导电聚合物的金属氧化物、包含它的用于电化学装置的电极和金属氧化物的制备方法
CN111370758A (zh) * 2020-03-16 2020-07-03 中山大学 一种基于本体增塑原理的聚合物固态电解质及其制备方法

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US4970012A (en) * 1988-12-16 1990-11-13 Nippon Oil Company, Ltd. Polymeric solid electrolytes and production process thereof
JPH0925384A (ja) * 1995-05-09 1997-01-28 Ricoh Co Ltd イオン伝導性高分子ゲル電解質および該電解質を含む二次電池
JPH11144524A (ja) * 1997-11-11 1999-05-28 Mitsui Chem Inc 高分子固体電解質

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Publication number Priority date Publication date Assignee Title
US4970012A (en) * 1988-12-16 1990-11-13 Nippon Oil Company, Ltd. Polymeric solid electrolytes and production process thereof
JPH0925384A (ja) * 1995-05-09 1997-01-28 Ricoh Co Ltd イオン伝導性高分子ゲル電解質および該電解質を含む二次電池
JPH11144524A (ja) * 1997-11-11 1999-05-28 Mitsui Chem Inc 高分子固体電解質

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120244427A1 (en) * 2009-12-09 2012-09-27 Nippon Shokubai Co., Ltd. Electrolyte material, and battery material and secondary battery using said electrolyte material
US9065150B2 (en) * 2009-12-09 2015-06-23 Nippon Shokubai Co., Ltd. Electrolyte material, and battery material and secondary battery using said electrolyte material
JP2011184333A (ja) * 2010-03-05 2011-09-22 Shin-Etsu Chemical Co Ltd 含フッ素有機ケイ素化合物及びその製造方法
US20120283378A1 (en) * 2011-05-02 2012-11-08 Ricoh Company, Ltd., A silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink
JP2013166908A (ja) * 2011-05-02 2013-08-29 Ricoh Co Ltd シリコーン化合物、該シリコーン化合物を用いた光硬化型液体インク及びその製造方法
US8871861B2 (en) * 2011-05-02 2014-10-28 Ricoh Company, Ltd. Silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink
WO2013113593A1 (fr) * 2012-01-31 2013-08-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Oligomères pourvus d'un groupe fonctionnel polaire, formulation complète pour polymères comportant un mélange d'oligomères pourvus d'un groupe fonctionnel polaire, leur procédé de préparation ainsi que leur utilisation
CN110915034A (zh) * 2017-11-20 2020-03-24 株式会社Lg化学 涂覆有导电聚合物的金属氧化物、包含它的用于电化学装置的电极和金属氧化物的制备方法
CN110915034B (zh) * 2017-11-20 2022-05-31 株式会社Lg化学 涂覆有导电聚合物的金属氧化物、包含它的用于电化学装置的电极和金属氧化物的制备方法
US11870062B2 (en) 2017-11-20 2024-01-09 Lg Energy Solution, Ltd. Metal oxide coated with conductive polymer, electrode for electrochemical device comprising the same, and method of producing the metal oxide
CN111370758A (zh) * 2020-03-16 2020-07-03 中山大学 一种基于本体增塑原理的聚合物固态电解质及其制备方法
CN111370758B (zh) * 2020-03-16 2022-04-05 中山大学 一种基于本体增塑原理的聚合物固态电解质及其制备方法

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