WO2002040594A1 - Materiau conducteur d'ions contenant un compose a faible poids moleculaire combine possedant une partie capable de se lier a l'hydrogene - Google Patents

Materiau conducteur d'ions contenant un compose a faible poids moleculaire combine possedant une partie capable de se lier a l'hydrogene Download PDF

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WO2002040594A1
WO2002040594A1 PCT/JP2001/009921 JP0109921W WO0240594A1 WO 2002040594 A1 WO2002040594 A1 WO 2002040594A1 JP 0109921 W JP0109921 W JP 0109921W WO 0240594 A1 WO0240594 A1 WO 0240594A1
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tetrakis
hydroxyphenyl
group
ethane
ion
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PCT/JP2001/009921
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English (en)
Japanese (ja)
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Satoru Abe
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Nippon Soda Co., Ltd.
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Priority to AU2002212765A priority Critical patent/AU2002212765A1/en
Priority to JP2002543597A priority patent/JP4100616B2/ja
Publication of WO2002040594A1 publication Critical patent/WO2002040594A1/fr

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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
    • 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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • An ion-conductive polymer having a hydrogen-bonding functional group or an ion-conductive cyclic compound having a hydrogen-bonding functional group in a repeating unit in the polymer main chain is composed of a low-molecular-weight compound having a hydrogen-bonding site and hydrogen.
  • polyether is polyethylene oxide or polypropylene oxide.
  • W represents (CH 2 ) n or! A monophenylene group, and n represents 02 or 3, X represents a hydroxyl group, a carboxyl group, or an amino group which may have a substituent, and RR 2 is a hydrogen atom, a C1-C6 alkyl group, or a phenyl which may be substituted. Represents a group, a halogen atom or a C1-C6 alkoxy group.
  • Y represents a hydroxyl group, an amino group, a carboxyl group, or a nitro group
  • R 3 represents a hydrogen atom, a C 1 -C 6 alkyl group, or a halogen atom.
  • Z represents a hydroxyl group, an amino group, a carboxyl group, or a nitro group
  • R 4 represents a hydrogen atom, a C 1 -C 6 alkyl group, or a halogen atom.
  • the ion conductive material according to claim 10, wherein the low molecular compound having a hydrogen bonding site is a tetraxaryl-based metal salt compound represented by the general formula (4).
  • V is, represents (CH 2) m or p- phenylene group, m is 0, 1, 2 or 3, ⁇ ⁇ 2, ⁇ 3 or Upsilon 4 are each a hydrogen atom or Represents an alkali metal atom, at least one of ⁇ 2 , ⁇ 3 or ⁇ 4 represents a hydrogen atom and an alkali metal atom, and R 5 and R 6 are each a hydrogen atom, a C 1 -C 6 alkyl group, Represents a phenyl group, a halogen atom or a C1-C6 alkoxy group which may be substituted.
  • lithium salt is lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imidate or lithium trifluoromethanesulfonate.
  • the present invention relates to ion conductive materials suitable for batteries and other electrochemical device materials, and in particular, to polymers in the polymer backbone such as polyethylene oxide (PEO) and polypropylene oxide (PP 0).
  • an ion conductive cyclic compound having a hydrogen bonding functional group such as an ion conductive polymer having a hydrogen bonding functional group or a crown ether derivative is hydrogen bonded to a low molecular compound having a hydrogen bonding site.
  • the present invention relates to an ion conductive material characterized by containing a compound having a hydrogen bonding site or a low molecular weight compound having the hydrogen bonding site.
  • the present invention relates to an ion conductive material containing a compound into which a metal salt site has been introduced. Further, the present invention relates to a lithium secondary battery using the ion conductive material for a solid electrolyte of a lithium secondary battery.
  • organic solid electrolytes composed mainly of polymers are excellent in flexibility, light weight, elasticity, thin film moldability, processability, transparency, etc., and are used for high-energy batteries for electric vehicles, IC cards, etc. Applications such as thin built-in batteries are considered.
  • polyethylene oxa Lee de or Poripuropi Renokisai polyether polymer compounds such as de lithium sulfonate Lee Mi-de, Application Benefits Furuorome data Nsuruhon Sanli lithium, L i C 1 0 4, etc.
  • Alkali metal salt complex The body is known. However, although the composite is solid and can be formed into a film, the ionic conductivity required by the alternating impedance method is extremely low, about 1 O — TCSZ cn (25 ° C). Unavailable.
  • a low-molecular-high-molecular complex utilizing hydrogen bond interaction with a low molecule is known.
  • a compound containing polyethylene oxide and hydroquinone, resorcinol, or p-ditrophenol as a component compound [Macromol. Symp., Vol. 114, p51 (1997)] is disclosed. I have. However, there is no description that these compounds can be used as an ion conductive material such as a solid electrolyte by adding a Li salt or the like.
  • the present invention relates to a polymer solid electrolyte having flexibility that cannot be obtained by a conventional covalent bond by utilizing a hydrogen bond between poly (ethylene glycol) bis (carboxymethyl) ether and a nitrogen-containing heterocyclic compound such as virazine.
  • Japanese Patent Application Laid-Open No. 2000-100424 is disclosed.
  • the present invention utilizes a hydrogen bond with a polymer having a hydrogen bonding site at the polymer terminal, and the present invention material utilizing a hydrogen bond with a hydrogen-bonding functional group in a repeating unit in a polymer main chain. Is different.
  • its ionic conductivity is lower than that of poly (ethylene glycol) bis (carboxymethyl) ether alone, so it has not been put to practical use. Disclosure of the invention:
  • An object of the present invention is to provide an ion conductive material which can be easily prepared, has excellent heat resistance and workability, and has a high ion conductivity at room temperature.
  • the present invention has found that an ion conductive polymer having a hydrogen bonding functional group or an ion conductive polymer having a hydrogen bonding functional group in a repeating unit in a polymer main chain.
  • a hydrogen bond with a low-molecular compound having a hydrogen bonding site By forming a hydrogen bond with a low-molecular compound having a hydrogen bonding site, a cyclic compound was found to be extremely effective not only for controlling the chain structure of the polymer but also for improving the ionic conductivity.
  • the electronic material of the present invention can provide a good thin film having excellent smoothness and homogeneity, and can significantly improve the heat resistance of the thin film, and have completed the present invention.
  • an ion conductive polymer having a hydrogen bonding functional group or an ion conductive cyclic compound having a hydrogen bonding functional group in a repeating unit in a polymer main chain has a hydrogen bonding site.
  • the ion-conductive material according to claim 1 wherein the ion-conductive material is characterized by containing a compound that has formed a hydrogen bond with a low-molecular compound (claim 1), or is used as a solid electrolyte for a lithium secondary battery. (Claim 2) or the ion conductive material (Claim 3) according to Claims 1 and 2, wherein the ion conductive polymer having a hydrogen bonding functional group is a polyether. 4.
  • the ion conductive material according to claim 3 which is lenoxide or polypropylene oxide (claim 4) or the ion conductive cyclic compound having a hydrogen bonding functional group is a cyclic ether.
  • the ion conductive material according to claim 1, wherein the low molecular compound having a hydrogen bonding site is a tetrakisaryl compound represented by the general formula (1).
  • W represents (CH 2 ) n or p-phenylene group, and n represents 0, 1, 2 or
  • X represents a hydroxyl group, a carboxyl group, or an amino group which may have a substituent
  • RR 2 is a hydrogen atom, a C1-C6 alkyl group, or an optionally substituted phenyl, respectively.
  • Y represents a hydroxyl group, an amino group, a carboxyl group, or a nitro group
  • R 3 represents a hydrogen atom, a C 1 -C 6 alkyl group, or a halogen atom.
  • the ion conductive material according to any one of claims 1 to 6, wherein the low molecular weight compound having a hydrogen bonding site is a meta-substituted hydroxybenzene derivative compound represented by the general formula (3).
  • Z represents a hydroxyl group, an amino group, a carboxyl group, or a nitro group
  • R 4 represents a hydrogen atom, a C 1 -C 6 alkyl group, or a halogen atom.
  • [Claim 9] or the low molecular weight compound having a hydrogen binding site is a compound having at least one or more alkali metal salt sites.
  • the ion conductive material according to (10), wherein the low molecular weight compound having a hydrogen bonding site is a tetrakisaryl-based alkali metal salt compound represented by the general formula (4).
  • V represents (CH 2 ) m or p-phenylene group
  • m is 0, 1, 2 or 3
  • ⁇ ⁇ 2 , ⁇ 3 or ⁇ 4 is a hydrogen atom or Represents an alkali metal atom
  • at least one of ⁇ ⁇ 3 or ⁇ 4 represents a hydrogen atom and an alkali metal atom
  • R 5 and R 6 are each a hydrogen atom, a C1-C6 alkyl group, Represents a phenyl group, a halogen atom or a C1-C6 alkoxy group which may be substituted.
  • the ion conductive material contains an alkali metal salt.
  • the ion-conductive material according to claim 13 which is lithium midoate or lithium trifluoromethane sulfonate, or the ion-conductive material is solid.
  • the present invention relates to the ion-conductive material according to any one of claims 1 to 14 (claim 15).
  • a low molecular weight compound having a hydrogen bonding site used in the present invention a low molecular weight compound having a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group or the like may be used in the present invention.
  • a tetraxaryl compound represented by the general formula (1) a para- or meta-substituted hydroxybenzene derivative compound represented by the general formula (2) or (3)
  • a general formula (4) A tetrakisaryl-based alkali metal salt compound represented by the following formula is preferred.
  • W represents (CH 2 ) n or a p-phenylene group, and n represents 0, 1, 2 or 3.
  • RR 2 is a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, etc .; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an s-butyl group.
  • C 1 -C 6 alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t—C 1 -C 6 alkoxy group such as butoxy group; phenyl group which may have a substituent (as a substituent, a hydroxyl group; fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) Halogen atom; C 1 to C 6 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group And an alkyl group, etc.).
  • X represents a hydroxyl group, a carboxyl group, or an amino group which may have a substituent (substituents include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group) , S-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and other C1 to C6 alkyl groups.).
  • tetrakisaryl compounds used in the present invention include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-Methyl-1-hydroxyphenyl) ethane, 1,1,2,2-tetrax (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrax ( 3-chloro-1,4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis 3-Promo 4-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3,5-dibromo-14-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3 — T — butyl 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-t-butyl-4—hydroxypheny
  • Y and Z are a hydroxyl group, an amino group, a carboxyl group, and a nitro group
  • 1 3 and 1 4 is a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, c port Gen atom and an iodine atom; a methyl group, Echiru group, n- propyl group, isopropyl group, n- blanking Lil group, It represents a C1-C6 alkyl group such as s-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
  • a molecule of an ion conductive polymer having a hydrogen bonding functional group or an ion conductive cyclic compound having a hydrogen bonding functional group From the viewpoint of performance such as improvement of ionic conductivity and heat resistance due to the arrangement and accompanying ion conductivity, in particular, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2—te Thakis (3-methyl-1-hydroxyphenyl) ethane, 1,1,4,4—te Thakis (4—hydroxyphenyl) butane, 1,1,5,5—te thakis (4-hydroxyphenyl) Pentane, 1,1,2,2-Tetrakis (4-carboxyphenyl) ethane 1,1,2,2—Tetrakis (4-aminophenol) ethane is preferred.
  • an ion-conductive polymer or a hydrogen-bonding functional group having a hydrogen-bonding functional group is particularly preferred from the viewpoints of the molecular arrangement of the ion-conductive cyclic compound having the above and the performance such as improvement in ionic conductivity and heat resistance associated therewith.
  • V represents (CH 2 ) m or p-phenylene; n is 0, 1, 2 or 3;
  • Y ⁇ YY 3 or Y 4 is a hydrogen atom or a lithium atom, Na Application Benefits um atom, an alkali metal atom such as potassium ⁇ beam atoms, Upsilon Upsilon 2, when Upsilon 3 or Upsilon less of 4
  • R 5 and R 6 are each a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, a haegen atom such as an iodine atom, etc .; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group C 1 -C 6 alkyl groups such as s-butyl group, t-butyl group, n-pentyl group, n-hexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n —C 1 -C 6 alkoxy group such as butoxy group, t-butoxy group; phenyl group which may have a substituent (substituent is a hydroxyl group; fluorine atom, chlorine atom, bromine atom Halogen atoms such as iodine and iodine; methyl,
  • Examples of the tetrakisaryl-based alkali metal salt compound used in the present invention include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1,1,2,2-tetrakis. (3-Methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3 —Chloro-1-4-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis (3,5-dichloro-14-hydroxyphenyl) ethane, 1,1,2,2-Tetrakis 3-bromo-1-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-jib-mouth 4-hydroxyhydroxy) ethane, 1,1,2,2-tetrakis (3-t-butyl-1-hydroxyphenyl) ethane, 1,1,2,2-tetrakis 3,5-di-t
  • Examples of the alkali metal salt used in the present invention include lithium salts of organic acids, sodium salts, lithium salts, lithium salts of inorganic acids, and lithium salts of inorganic acids and sodium salts. And lithium salts, preferably lithium salts.
  • Examples of the lithium salt of an acid include lithium acetate, lithium trifluoroacetate, lithium benzoate, lithium trifluoromethansulfonate, lithium p-toluenesulfonate, and bis (trifluoromethylsulfonyl).
  • Li Furuorome Chirusuruhoniru such as carbon Sanli lithium and the like
  • Li Furuorome Chirusuruhoniru is a lithium salts of inorganic acids, for example, L i N 0 3, L i SCN, L i C 1 0 4, L i BF 4, L i PF 6, L i A s F have L i S b F 6, and the like.
  • Preferred lithium salts among these are lithium bis (trifluoromethylsulfonyl) imidate, lithium lithium trifluoromethansulfonate, and tris (trifluoromethylsulfonyl) carbonic acid.
  • Lithium salts such as L i PF 6.
  • the ion-conductive polymer used in the present invention may be any of polyethers, polyalcohols, polyamines, polyacrylic acids, polyesters, polysulfides, and polyvinyl heterocycles. Any one or more of polymers having conventionally known ion-conducting ability and a hydrogen-bonding functional group that can be classified can be selected and used, regardless of homopolymer or copolymer.
  • an ion-conductive polymer that forms a molecular compound with the trakisaryl-based alkali metal salt compound.
  • examples of such a polymer include polyoxymethylene, polyethylene oxide, polyethylene glycol, polybutylene glycol, polytetramethylenoxide, polyoxymethylene alkyl ether, and polyethers.
  • Polyesters include poly y3-propionlactone, polyethylene succinate, polyethylene adipate, polyvinyl alcohol as polyalcohols, vinyl alcohol-vinyl pyrrolidone copolymer, and polyamines Polyethyleneimine, poly (N-methyl) ethyleneimine, polyacrylic acid as polyacrylic acid, polymethacrylic acid mono-oxetylene copolymer, and polysulfide as polyethylene sulfide Polyvinyl sulfide and polyvinyl heterocycles can be exemplified by polyvinyl borolidone.
  • the ion-conductive polymer used in the present invention includes a tetraxaryl-based compound represented by the general formula (1), and a para- and meta-hydrid represented by the general formulas (2) and (3).
  • a tetraxaryl-based compound represented by the general formula (1) and a para- and meta-hydrid represented by the general formulas (2) and (3).
  • the molecular weight of the roxybenzene derivative as long as it forms a molecular compound with the tetraxaryl-based alkali metal salt compound represented by the general formula (4). From the viewpoints of performance such as formation and associated organization, chemical stabilization, and thin film moldability, those having a molecular weight in the range of 200 to 2,000, 000 are particularly preferably used.
  • the ion-conductive cyclic compound used in the present invention includes 12-crown-4-ether derivative, 15-crown-5-ether derivative, 18-crown-6-ether derivative, 21-crown 1 7-ether, 2 4 —crown 1-8—ether, benzo 1 1 2—crown 4—ether derivative, dibenzo 1 2—crown 1—ether derivative, benzo—1 5— crown 1—5 —ether Derivatives, dibenzo-15-crown-15-ether derivatives, benzo18-crown-16-ether derivatives, dibenzo-18-crown-16-ether derivatives, benzo-12-21-crown-7-ether derivatives, Dibenzo-21-crown-7-ether derivative, benzo-24-crown-18-ether derivative, dibenzo124-crown-18-ether derivative, tribenzo -18-crown-16-ether derivative, tetrabenzo-124-crown-8- ether derivative, etc., Cranether ether derivative, monoaza-12-crown14
  • the ion-conductive material of the present invention can be used as an ion-conductive polymer having a hydrogen-bonding functional group or an ion-conductive cyclic compound having a hydrogen-bonding functional group as described above.
  • a trakisaryl compound or a para- or methyl-substituted hydroxybenzene derivative represented by the general formula (2) or (3) is directly mixed with an alkali metal salt or in an organic solvent.
  • a tetraxaryl-based alkali metal salt compound represented by the general formula (4) it can be obtained by a similar method without adding an alkali metal salt.
  • a complex comprising an ion-conductive polymer or an ion-conductive cyclic compound and a tetraxaryl-based compound or a para- or meta-substituted hydroxybenzene derivative
  • this is formed into an alkali metal salt. It is manufactured by doping an ion carrier by a known method of immersion treatment in an organic solvent in which is dissolved.
  • the reaction of a tetraxaryl compound or a para- or meta-substituted hydroxybenzene derivative with two or more ion-conductive polymers or ion-conductive cyclic compounds results in four components. It is also possible to obtain an ion conductive material composed of the above-mentioned multiple components.
  • the amount of the tetraxaryl-based compound represented by the general formula (1) and the amount of the para- or meta-substituted hydroxybenzene derivative compound represented by the general formula (2) or (3) is as follows. More specifically, the amount is 1 to 99 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the ion conductive polymer having a hydrogen bonding site.
  • the amount of the metal salt used is appropriately determined depending on the ion conductivity of the target solid electrolyte of low molecular weight one polymer or cyclic compound. And 15 to 20 in molar ratio
  • FIG. 1 shows 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (TEP) and polyethylene oxide (PEO) (average molecular weight of 200,000 and
  • FIG. 13 is a diagram showing a 13 C—CP / MAS solid NMR spectrum (measured at 27 ° C. with a rotor rotation frequency of 3.5 kHz) of a composite made of lithium perchlorate.
  • FIG. 2 shows P-nitrophenol (PNP), PEO (average molecular weight 100,000) and lithium bis (trifluoromethylsulfonyl) imid (L i TFSI) of Example 4 of the present invention.
  • FIG. 13 is a diagram showing a 13 C—CP / MAS-solid-state NMR spectrum (measured at 27 ° C. with a rotor rotation frequency of 3.5 kHz) of a complex consisting of)).
  • Figure 3 is a (one 1 8 C r - 6) TEP and 1 8-crown one 6-ether of Example 5 of the present invention and preparative Li Furuorome data Nsuruhon lithium acid (L i CF a S 0 3 ) or al FIG.
  • Example 1 The ionic conductivity of the ionic conductive material shown in the following examples was measured by a normal complex impedance method.
  • Example 1 The ionic conductivity of the ionic conductive material shown in the following examples was measured by a normal complex impedance method.
  • Example 1 resorcinol (RES) 1.1 mm ⁇ 1 (0.125 g) was added in place of ⁇ ⁇ ⁇ [, and the composition ratio of RES and EO unit was 1:10 (mol Ratio)], and membrane formation and ionic conductivity were evaluated in the same manner as in Example 1. Ionic conductivity that put in 3 0 ° C is 5. A 2 0 X 1 0- 6 [S / cm].
  • RES resorcinol
  • Example 1 p-nitrophenol (PNP) 1.1 mm 01 (0.125 g) was added instead of TEP, and the composition ratio of PNP to EO unit was 1:20 ( Molar ratio)], and film formation and ionic conductivity were evaluated in the same manner as in Example 1. Ion conductivity at 3 0 ° C is 6. was 6 0 X 1 0- 6 [S / cm].
  • PNP p-nitrophenol
  • TEP-1-OL i a compound in which one of the four hydroxyl groups of TEP was converted to 0 L i.
  • Example 2 Except that TEP was not added in Example 1, film formation and ionic conductivity were evaluated in the same manner as in Example 1. Ion conductivity at 30 ° C is 4. Atsuta at 41 X 1 0- 8 [S / cm]. The film melted at around 65 ° C. Comparative Example 2
  • Example 5 film formation and ion conductivity were evaluated in the same manner as in Example 5.
  • the ionic conductivity at 30 ° C. was 1.2 1 X 1 (J— 7 [S / cm]).
  • the present invention relates to an ion conductive polymer having a hydrogen bonding functional group in a repeating unit in a polymer main chain such as polyethylene oxide, polypropylene oxide, or the like.
  • a complex in which a hydrogen bonding functional group forms a hydrogen bond with a low molecular compound having a hydrogen bonding site may further include a lithium salt as an electrolyte or a low molecular compound having the above hydrogen bonding site.
  • a lithium salt an ion conductive material which is solid at room temperature and can be formed into a film or the like and has excellent heat resistance and good lithium ion conductivity can be easily provided.
  • the ion conductive material of the present invention has no problem of liquid leakage, has no corrosiveness, and the ion conductive polymer chain or the ring of the ion conductive cyclic compound is oriented in a specific direction by hydrogen bonding with a low molecular compound.
  • the thin film produced by the present invention has excellent heat resistance and mechanical stability compared with a thin film formed without using a low molecular compound having a hydrogen bonding site.
  • ionic conductivity is high, making it a solid electrolyte for electrochemical devices that can withstand long-term reliability.

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Abstract

L'invention concerne un matériau conducteur d'ions présentant une résistance à la chaleur et une aptitude au traitement excellentes, ainsi qu'une conductivité ionique élevée à température de laboratoire. Ce matériau comprend un polymère dont le squelette est constitué d'unités récurrentes renfermant des unités formées par liaison hydrogène entre un composé à faible poids moléculaire possédant une partie capable de se lier à l'hydrogène et un polymère conducteur d'ions ou un composé cyclique conducteur d'ions comprenant chacun un groupe fonctionnel capable de se lier à l'hydrogène. Les unités récurrentes comprennent, en outre, des unités qui sont un sel de métal alcalin ou des unités formées par conversion du composé à faible poids moléculaire possédant une partie capable de se lier à l'hydrogène en sel de métal alcalin. L'incorporation de ces unités récurrentes est extrêmement efficace non seulement dans la régulation de la structure en chaîne du polymère, mais aussi dans l'amélioration de la conductivité ionique.
PCT/JP2001/009921 2000-11-14 2001-11-13 Materiau conducteur d'ions contenant un compose a faible poids moleculaire combine possedant une partie capable de se lier a l'hydrogene WO2002040594A1 (fr)

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AU2002212765A AU2002212765A1 (en) 2000-11-14 2001-11-13 Ion-conductive material containing combined low-molecular compound having hydrogen bond part
JP2002543597A JP4100616B2 (ja) 2000-11-14 2001-11-13 水素結合部位を有する低分子化合物を複合化したイオン伝導性材料

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US7919570B2 (en) 2004-08-13 2011-04-05 Nippon Soda Co., Ltd. Multibranched polymer and method for producing the same
US8436103B2 (en) 2005-09-07 2013-05-07 Nippon Soda Co., Ltd. Star polymer and method of producing the same
JP2019110056A (ja) * 2017-12-19 2019-07-04 花王株式会社 蓄電デバイス電極用樹脂組成物
US10818913B2 (en) 2017-12-18 2020-10-27 Samsung Electronics Co, Ltd. Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery

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FR2960941B1 (fr) 2010-06-02 2014-11-14 Inst Francais Du Petrole Dispositif de separation de particules pour une boucle de combustion chimique

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EP0996029A2 (fr) * 1998-10-19 2000-04-26 Canon Kabushiki Kaisha Electrolyte gélifié, pile et élément électrochromique
JP2000273319A (ja) * 1999-03-29 2000-10-03 Hitachi Chem Co Ltd 疑似架橋型樹脂およびこの樹脂からなる成形品
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US7919570B2 (en) 2004-08-13 2011-04-05 Nippon Soda Co., Ltd. Multibranched polymer and method for producing the same
US8710165B2 (en) 2004-08-13 2014-04-29 Nippon Soda Co., Ltd. Multibranched polymer and method for producing the same
JP2006273890A (ja) * 2005-03-28 2006-10-12 Tokyo Institute Of Technology 異方性イオン伝導性高分子膜
US8436103B2 (en) 2005-09-07 2013-05-07 Nippon Soda Co., Ltd. Star polymer and method of producing the same
US10818913B2 (en) 2017-12-18 2020-10-27 Samsung Electronics Co, Ltd. Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery
JP2019110056A (ja) * 2017-12-19 2019-07-04 花王株式会社 蓄電デバイス電極用樹脂組成物

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