WO2017154449A1 - Électrolyte de gel et son procédé de préparation - Google Patents

Électrolyte de gel et son procédé de préparation Download PDF

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WO2017154449A1
WO2017154449A1 PCT/JP2017/004554 JP2017004554W WO2017154449A1 WO 2017154449 A1 WO2017154449 A1 WO 2017154449A1 JP 2017004554 W JP2017004554 W JP 2017004554W WO 2017154449 A1 WO2017154449 A1 WO 2017154449A1
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matrix polymer
gel electrolyte
electrolyte
carbonate
polymer
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PCT/JP2017/004554
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English (en)
Japanese (ja)
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圭介 渡辺
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株式会社クレハ
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Priority claimed from JP2016053140A external-priority patent/JP6829943B2/ja
Application filed by 株式会社クレハ filed Critical 株式会社クレハ
Priority to CN201780004567.8A priority Critical patent/CN108370067B/zh
Priority to EP17762793.2A priority patent/EP3429018A4/fr
Priority to KR1020187016225A priority patent/KR101942835B1/ko
Priority to US16/067,869 priority patent/US20190348711A1/en
Publication of WO2017154449A1 publication Critical patent/WO2017154449A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • 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 gel electrolyte and a method for preparing the same, and more particularly to a gel electrolyte including a non-aqueous electrolyte in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent and a matrix polymer, and a method for preparing the gel electrolyte.
  • batteries have attracted attention as a power source for small portable devices such as smartphones, and a power source for electric vehicles and hybrid vehicles.
  • lithium ion batteries having a small volume and a large capacity are attracting particular attention.
  • Patent Document 1 discloses a gel polymer electrolyte for a lithium ion secondary battery using a gel composition containing a terpolymer of vinylidene fluoride, hexafluoropropene and chlorotrifluoroethylene and a lithium salt-soluble organic solvent. ing.
  • the gel electrolyte usually contains a non-aqueous electrolyte and a polymer.
  • the polymer itself constituting the gel electrolyte does not directly contribute to the battery capacity. Therefore, it is preferable that the amount of the polymer present in the gel electrolyte is small.
  • the gel electrolyte contains a large amount of non-aqueous electrolyte compared to the polymer, that is, when the polymer concentration in the gel electrolyte is relatively low, the gel strength decreases, and consequently the gel state is reduced. It cannot be maintained. If the gel state cannot be maintained, the non-aqueous electrolyte leaks to the outside of the battery, resulting in a problem relating to reliability such as the battery firing.
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a gel electrolyte capable of maintaining a gel state with a polymer concentration lower than usual.
  • the gel electrolyte according to the present invention is a gel electrolyte comprising a non-aqueous electrolyte solution in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent, and a matrix polymer.
  • a copolymer containing vinylidene fluoride units and fluorine atom-containing monomer units as repeating units and the melting point T m of the matrix polymer is the concentration C (mass%) of the matrix polymer contained in the gel electrolyte. ) Within the range satisfying the following formula (I).
  • a method for preparing a gel electrolyte according to the present invention is a method for preparing a gel electrolyte comprising a non-aqueous electrolyte solution in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent and a matrix polymer. And the non-aqueous electrolyte so that the melting point T m of the matrix polymer and the concentration C (% by mass) of the matrix polymer contained in the gel electrolyte satisfy the following formula (I): It has the structure which mixes the said matrix polymer.
  • the present invention it is possible to provide a gel electrolyte in which the concentration of the matrix polymer is lower than usual and the gel state can be maintained.
  • the gel electrolyte according to the present invention is a gel electrolyte containing a non-aqueous electrolyte solution in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent and a matrix polymer, wherein the matrix polymer includes a vinylidene fluoride unit and a fluorine.
  • T m of the matrix polymer is expressed by the following formula (concentration C) (% by mass) of the matrix polymer contained in the gel electrolyte: I) T m ⁇ 145-C (I) (In formula (I), 0.1 ⁇ C ⁇ 30.) It is within the range that satisfies.
  • the copolymer containing a vinylidene fluoride unit and a fluorine atom-containing monomer unit as a repeating unit is a vinylidene fluoride and a fluorine atom-containing monomer used as a monomer when polymerizing the copolymer, It is a copolymer containing a structure derived from vinylidene fluoride and a structure derived from a fluorine atom-containing monomer as repeating units.
  • the matrix polymer used for the gel electrolyte in the present embodiment is a copolymer (that is, a vinylidene fluoride copolymer) containing vinylidene fluoride units and fluorine atom-containing monomer units as repeating units.
  • the concentration of the matrix polymer in the gel electrolyte is 0.1% by mass or more and 30% by mass or less.
  • a preferable lower limit of the concentration of the matrix polymer in the gel electrolyte is 0.5% by mass or more, and a more preferable lower limit is 1.0% by mass or more.
  • a suitable upper limit is 20 mass% or less, and a more suitable upper limit is 15 mass% or less.
  • the melting point T m of the matrix polymer is represented by the following formula (I) T m ⁇ 145-C (I)
  • a matrix polymer that satisfies the above is used as the matrix polymer in the present embodiment.
  • the melting point T m of a matrix polymer can be measured by a conventionally known measuring method, for example, it can be measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the weight average molecular weight of the matrix polymer is preferably 100,000 to 3,000,000, more preferably 200,000 to 2,000,000, and still more preferably 300,000 to 1,500,000.
  • the fluorine atom-containing monomer in the present embodiment is a compound containing a fluorine atom, and a compound that can be used as a monomer component in polymerization is intended.
  • Fluorine atom-containing monomers include, but are not limited to, compounds having a structure in which fluorine is directly bonded to sp2 carbon, such as hexafluoropropylene (HFP) and chlorotrifluoroethylene (CTFE), trifluoromethyl acrylate, vinyl triflate. Examples thereof include fluoromethyl ether and trifluoroethylene.
  • the fluorine atom-containing monomer in the present embodiment include hexafluoropropylene (HFP) and chlorotrifluoroethylene (CTFE).
  • HFP and CTFE are also referred to as “fluorine monomer (A)”.
  • the matrix polymer in the present embodiment may include only one type of fluorine atom-containing monomer as the above-described fluorine atom-containing monomer, or may include two or more types of fluorine atom-containing monomers.
  • the matrix polymer in the present embodiment is provided with the retention of the nonaqueous electrolyte solution by controlling the crystallinity by including a fluorine atom-containing monomer (for example, the above-described fluorine-based monomer (A)).
  • the matrix polymer in this embodiment should just contain the repeating unit of a vinylidene fluoride unit and a fluorine atom containing monomer unit, and may further contain the other repeating unit.
  • Other repeating units include repeating units derived from unsaturated dibasic acids (hereinafter referred to as unsaturated dibasic acid units) and repeating units derived from unsaturated dibasic acid monoesters (hereinafter referred to as unsaturated dibasic acid monoesters). Unit).
  • the matrix polymer may contain both unsaturated dibasic acid units and unsaturated dibasic acid monoester units, or may contain either one.
  • the content of other repeating units in the matrix polymer in the present embodiment is particularly limited as long as the basic physical properties as a copolymer including a vinylidene fluoride unit and a fluorine atom-containing monomer unit as a repeating unit are not impaired. There is no limitation.
  • Examples of the unsaturated dibasic acid that forms the unsaturated dibasic acid unit in the matrix polymer in the present embodiment include unsaturated disulfonic acid and unsaturated dicarboxylic acid.
  • Examples of the unsaturated dicarboxylic acid include fumaric acid, (anhydrous) maleic acid and citraconic acid. Of these, (anhydrous) maleic acid and citraconic acid are preferred.
  • the matrix polymer in this embodiment contains an unsaturated dibasic acid unit, it may contain only one type of unsaturated dibasic acid unit, or may contain two or more types of unsaturated dibasic acid units.
  • the content of the unsaturated dibasic acid in the matrix polymer in the present embodiment is particularly limited as long as the basic physical properties as a copolymer containing a vinylidene fluoride unit and a fluorine atom-containing monomer unit as a repeating unit are not impaired. There is no.
  • Examples of the unsaturated dibasic acid monoester that forms the unsaturated dibasic acid monoester unit in the matrix polymer in the present embodiment include unsaturated disulfonic acid monoesters and unsaturated dicarboxylic acid monoesters. It is done.
  • Examples of the unsaturated dicarboxylic acid monoester include fumaric acid monomethyl ester, fumaric acid monoethyl ester, maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, and citraconic acid monoethyl ester.
  • the matrix polymer in this embodiment contains an unsaturated dibasic acid monoester unit, it may contain only one type of unsaturated dibasic acid monoester unit, or two or more types of unsaturated dibasic acid monoesters Units may be included.
  • the content of the unsaturated dibasic acid monoester in the matrix polymer in the present embodiment is within a range that does not impair the basic physical properties of the copolymer containing vinylidene fluoride units and fluorine atom-containing monomer units as repeating units. There is no particular limitation.
  • the gel electrolyte in the present embodiment has a functional group such as a carboxy group of the unsaturated dibasic acid as a matrix polymer. By containing in, it becomes easy to gelatinize by the hydrogen bond between functional groups.
  • Method for preparing matrix polymer As a method for preparing the matrix polymer in the present embodiment, conventionally known methods and conditions can be used other than the method and conditions described below.
  • the melting point of the matrix polymer according to the above formula (I) and the concentration (mass%) of the matrix polymer in the gel electrolyte are determined.
  • T m ⁇ 135 is determined by substituting 10 for C in formula (I)
  • the lower limit of the melting point of the matrix polymer is determined to be 135 ° C. can do. That is, once the matrix polymer concentration in the gel electrolyte is determined, the lower limit of the melting point of the matrix polymer satisfying the formula (I) can be determined under the concentration condition.
  • the melting point of the matrix polymer may be determined in advance, and the concentration of the vinylidene fluoride copolymer in the gel electrolyte satisfying the formula (I) may be determined under the melting point condition.
  • a vinylidene fluoride copolymer that satisfies the determined melting point may be manufactured.
  • the melting point of the vinylidene fluoride copolymer mainly depends on the amount of the fluorine atom-containing monomer (for example, fluorine-based monomer (A)) contained and the method of introducing it. Therefore, in order to prepare a matrix polymer having a desired melting point, first, the amount of fluorine atom-containing monomer contained in the matrix polymer is determined.
  • the melting point of a copolymer (vinylidene fluoride copolymer) obtained by copolymerizing a fluorine atom-containing monomer (for example, a fluorine-based monomer (A)) and vinylidene fluoride is the charging ratio of the fluorine atom-containing monomer and vinylidene fluoride. It depends on. When the introduction method of the fluorine atom-containing monomer is the same, the melting point of the copolymer becomes lower than that of the homopolymer of vinylidene fluoride as the ratio of the fluorine atom-containing monomer to vinylidene fluoride increases.
  • the method for introducing the fluorine atom-containing monomer is set.
  • the method for introducing a fluorine atom-containing monomer that is a factor for determining the melting point of the vinylidene fluoride copolymer include the timing of the introduction of the fluorine atom-containing monomer in the synthesis of the vinylidene fluoride copolymer and the manner of introduction. However, it is not limited to these.
  • timing of the introduction of the fluorine atom-containing monomer and the manner of introduction include, for example, introducing the fluorine atom-containing monomer dividedly, continuously, or collectively.
  • a person skilled in the art can easily produce a vinylidene fluoride copolymer having a desired melting point based on the above-described technical contents and technical common sense in this technical field.
  • the non-aqueous electrolyte used for the gel electrolyte in the present embodiment is prepared by dissolving a lithium-containing electrolyte in a non-aqueous solvent.
  • a conventionally known non-aqueous electrolyte used for obtaining a gel electrolyte can be used.
  • the gel electrolyte preferably contains 70 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass of the nonaqueous electrolyte solution per 100 parts by mass of the gel electrolyte.
  • lithium-containing electrolyte examples include lithium salt electrolytes.
  • a conventionally known lithium salt can be used as the lithium salt.
  • lithium-containing electrolytes include LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiCl, LiBr, LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiC (CF 3 SO 2 ) 3, and the like.
  • a lithium containing electrolyte used for the non-aqueous electrolyte in this embodiment only 1 type of lithium containing electrolyte may be used, and 2 or more types of lithium containing electrolyte may be used.
  • the concentration of the lithium-containing electrolyte in the nonaqueous electrolytic solution is preferably 0.1 to 3 mol / dm 3 , and more preferably 0.5 to 2 mol / dm 3 .
  • Nonaqueous solvent As the non-aqueous solvent used in the non-aqueous electrolyte in the present embodiment, a conventionally known non-aqueous solvent can be used.
  • non-aqueous solvents include organic solvents, specifically, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl butyl carbonate. , ⁇ -butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, methyl propionate, and ethyl propionate.
  • non-aqueous solvent used in the non-aqueous electrolysis solution in the present embodiment only one type of non-aqueous solvent may be used, or at least two or more types of non-aqueous solvents may be used. You may use the mixed solvent mixed.
  • the melting point T m of the matrix polymer and the concentration C (mass%) of the matrix polymer contained in the gel electrolyte are represented by the following formula (I): T m ⁇ 145-C (I) (In formula (1), 0.1 ⁇ C ⁇ 30.) What is necessary is just to include mixing a non-aqueous electrolyte and a matrix polymer so that it may satisfy
  • the method for preparing the gel electrolyte in the present embodiment will be described in detail below.
  • the means for mixing the non-aqueous electrolyte and the matrix polymer to form a gel electrolyte is not particularly limited, but in one aspect of the gel electrolyte preparation method in the present embodiment, the matrix polymer is dissolved. Further, a volatile organic solvent for mixing is used for mixing to obtain a gel electrolyte. That is, as one aspect, a step of mixing a matrix polymer, a non-aqueous electrolyte, and a volatile organic solvent for dissolving the matrix polymer, and then volatilizing the volatile organic solvent from the obtained mixture. After that, a film-like gel electrolyte is obtained.
  • a matrix polymer and a volatile organic solvent for dissolving the matrix polymer are mixed to prepare a solution in which the vinylidene fluoride copolymer is dissolved.
  • the solution and the non-aqueous electrolyte are mixed.
  • a film-like gel electrolyte is obtained through a step of volatilizing a volatile organic solvent from the obtained mixture.
  • the mixing in these embodiments is usually performed under heating conditions, preferably at 40 to 150 ° C.
  • the step of volatilizing the volatile organic solvent is preferably performed at 0 to 100 ° C., more preferably at 15 to 60 ° C.
  • Non-aqueous electrolysis is performed so that the concentration of the matrix polymer in the gel electrolyte finally obtained in this manner is in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 20% by mass.
  • the liquid and the matrix polymer are mixed.
  • volatile organic solvent in the present embodiment, a solvent having a high vapor pressure at a relatively low temperature, being easily volatilized, and well dissolving the matrix polymer is preferable.
  • volatile organic solvents include tetrahydrofuran, methyltetrahydrofuran, acetone, methyl ethyl ketone, 1,3-dioxolane, cyclohexanone, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, but are not necessarily limited thereto. Absent.
  • the addition amount of the volatile organic solvent used in the method of the present embodiment may be an amount that can sufficiently dissolve the matrix polymer, and may be appropriately adjusted according to the matrix polymer.
  • organic solvents such as propylene carbonate, ethylene carbonate, and dimethyl carbonate can be used as the solvent for the matrix polymer. Therefore, when these solvents are employed as the nonaqueous solvent used in the nonaqueous electrolytic solution, it is also possible to prepare a gel electrolyte without using a volatile organic solvent separately.
  • a lithium-containing electrolyte may be added and further dissolved in a solution in which the matrix polymer is dissolved in these non-aqueous solvents.
  • the matrix polymer and the lithium-containing electrolyte may be simultaneously dissolved in these nonaqueous solvents.
  • the gel electrolyte is obtained by swelling the film with a non-aqueous electrolyte. You can also.
  • the gel electrolyte according to the present invention can be used as a member in a nonaqueous electrolyte battery.
  • the nonaqueous electrolyte battery here is a battery having a configuration in which a gel electrolyte is provided between a positive electrode and a negative electrode. Examples of such a non-aqueous electrolyte battery include, but are not limited to, a lithium ion secondary battery.
  • a conventionally well-known method can be used as a preparation method of a nonaqueous electrolyte battery.
  • the gel electrolyte according to the present invention is a gel electrolyte comprising a non-aqueous electrolyte solution in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent, and a matrix polymer.
  • a copolymer containing vinylidene fluoride units and fluorine atom-containing monomer units as repeating units and the melting point T m of the matrix polymer is the concentration C (mass%) of the matrix polymer contained in the gel electrolyte. ) Within the range satisfying the following formula (I).
  • the copolymer preferably further includes at least one of a repeating unit derived from an unsaturated dibasic acid and a repeating unit derived from an unsaturated dibasic acid monoester.
  • the unsaturated dibasic acid and the unsaturated dibasic acid monoester are an unsaturated dicarboxylic acid and an unsaturated dicarboxylic acid monoester, respectively.
  • the fluorine atom-containing monomer unit is preferably a repeating unit derived from hexafluoropropylene or chlorotrifluoroethylene.
  • the non-aqueous solvent is ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl butyl carbonate, ⁇ -butyrolactone. 1,2-dimethoxyethane, 1,2-diethoxyethane, methyl propionate or ethyl propionate, or a mixed solvent in which at least two of these are mixed is preferable.
  • a method for preparing a gel electrolyte according to the present invention is a method for preparing a gel electrolyte comprising a non-aqueous electrolyte solution in which a lithium-containing electrolyte is dissolved in a non-aqueous solvent and a matrix polymer. And the non-aqueous electrolyte so that the melting point T m of the matrix polymer and the concentration C (% by mass) of the matrix polymer contained in the gel electrolyte satisfy the following formula (I): It has the structure which mixes the said matrix polymer.
  • ⁇ Confirmation method of gelation> The gelation by the matrix polymer was confirmed by the inversion method. Specifically, after heating and dissolving a predetermined amount of matrix polymer in a non-aqueous electrolyte, the mixture is allowed to cool to room temperature, and the container containing the gel electrolyte is turned upside down as appropriate to change the flow state of the contents. Check. Those whose contents did not flow within 3 days were determined to be gelled, and those whose gelation could not be confirmed within 3 days were determined not to gel.
  • Example 1 [Method for preparing matrix polymer] In an autoclave with an internal volume of 2 liters, 1060 g of ion exchange water, 0.62 g of Metrose SM-100, 50% by mass of di-i-propyl peroxydicarbonate-1,1,2,2-tetrafluoroethyl-2 2.18 g of 2,2-trifluoroethyl ether solution, 390 g of vinylidene fluoride, 20 g of hexafluoropropylene, and 2.06 g of monomethyl maleate were charged. The mixture was heated to 29 ° C. over 1 hour and polymerized while maintaining 29 ° C. for a total of 42.8 hours from the start of the temperature increase.
  • polymer A After completion of the polymerization, the polymer slurry was heat treated at 95 ° C. for 60 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a polymer powder.
  • the polymerization rate was 80%.
  • the polymer obtained here will be referred to as polymer A below.
  • the powdered polymer A is preheated at 200 ° C. for 30 seconds using a press molding machine (AYSR-5 manufactured by Shindo Metal Industry Co., Ltd.), and after preheating, it is heated and pressed at a cylinder pressure of 10 MPa. The sheet was formed into a sheet shape. Thereafter, a 10 mg sheet was cut out from the molded sheet to obtain a melting point measurement sample. The melting point was measured by raising and lowering the temperature at a rate of 10 ° C./min in the range of 30 ° C. to 230 ° C. using a differential thermal scanning calorimeter (DSC1 manufactured by METTLER TOLEDO). As a result, the melting point (T m ) of the polymer A was 157 ° C.
  • Example 2 In the matrix polymer preparation method of Example 1, the copolymerization ratio of VDF (vinylidene fluoride), HFP (hexafluoropropylene), and MMM (monomethyl maleate) was adjusted so that the melting point of the matrix polymer was 153 ° C. As a result, a polymer B was obtained. And the gelation test similar to Example 1 was implemented except having used the polymer B as a matrix polymer.
  • VDF vinyllidene fluoride
  • HFP hexafluoropropylene
  • MMM monomethyl maleate
  • Example 3 In the method for preparing the matrix polymer in Example 1, polymer C was obtained by adjusting the copolymerization ratio of VDF, HFP, and MMM so that the melting point of the matrix polymer was 143 ° C. And the gelation test similar to Example 1 was implemented except having used the polymer C as a matrix polymer.
  • Example 4 In the matrix polymer preparation method of Example 1, polymer D was obtained by adjusting the copolymerization ratio of VDF and HFP so that the melting point of the matrix polymer was 169 ° C. without using MMM. And the gelation test similar to Example 1 was implemented except having used the polymer D as a matrix polymer and having made the matrix polymer density
  • Example 5 The same gelation test as in Example 4 was performed except that the matrix polymer concentration was 5% by mass.
  • Example 6 A gelation test similar to that of Example 4 was performed except that the matrix polymer concentration was 10% by mass.
  • Example 7 A gelation test similar to that of Example 4 was performed except that the matrix polymer concentration was 20% by mass.
  • Example 8> In the method for preparing the matrix polymer of Example 1, polymer E was obtained by adjusting the copolymerization ratio of VDF and HFP so that the melting point of the matrix polymer was 163 ° C. without using MMM. And the gelation test similar to Example 1 was implemented except having used the polymer E as a matrix polymer and having made the matrix polymer density
  • Example 9 A gelation test similar to that of Example 8 was performed except that the matrix polymer concentration was 5% by mass.
  • Example 10 A gelation test similar to Example 8 was performed except that the matrix polymer concentration was 10% by mass.
  • Example 11 A gelation test similar to Example 8 was performed except that the matrix polymer concentration was 20% by mass.
  • Example 12 In the method for preparing the matrix polymer of Example 1, polymer F was obtained by adjusting the copolymerization ratio of VDF and HFP so that the melting point of the matrix polymer was 154 ° C. without using MMM. And the gelation test similar to Example 1 was implemented except having used the polymer F as a matrix polymer and having made the matrix polymer density
  • Example 13> A gelation test similar to that of Example 12 was performed except that the matrix polymer concentration was set to 5% by mass.
  • Example 14 A gelation test similar to Example 12 was performed except that the matrix polymer concentration was 10% by mass.
  • Example 15 A gelation test similar to Example 12 was performed except that the matrix polymer concentration was 20% by mass.
  • Example 16> In the method for preparing the matrix polymer of Example 1, polymer G was obtained by adjusting the copolymerization ratio of VDF and HFP so that the melting point of the matrix polymer was 127 ° C. without using MMM. And the gelation test similar to Example 1 was implemented except having used the polymer G as a matrix polymer and having made the matrix polymer density
  • Example 17 In the method for preparing the matrix polymer of Example 1, CTFE (chlorotrifluoroethylene) was used instead of MMM and HFP, and the copolymerization ratio of VDF and CTFE was adjusted so that the melting point of the matrix polymer was 168 ° C. As a result, a polymer H was obtained. And the gelation test similar to Example 1 was implemented except having used the polymer H as a matrix polymer.
  • CTFE chlorotrifluoroethylene
  • Example 18 In the method for preparing the matrix polymer of Example 1, instead of MMM and HFP, CTFE was used, and polymer J was prepared by adjusting the copolymerization ratio of VDF and CTFE so that the melting point of the matrix polymer was 166 ° C. Obtained. And the gelation test similar to Example 1 was implemented except having used the polymer J as a matrix polymer.
  • Example 19 In the method for preparing the matrix polymer of Example 1, instead of HFP, CTFE was used, and the polymer K was prepared by adjusting the copolymerization ratio of VDF, CTFE, and MMM so that the melting point of the matrix polymer was 163 ° C. Obtained. And the gelation test similar to Example 1 was implemented except having used the polymer K as a matrix polymer.
  • Example 5 In the method for preparing the matrix polymer of Example 1, polymer M was obtained by adjusting the copolymerization ratio of VDF and HFP so that the melting point of the matrix polymer was 106 ° C. without using MMM. And the gelation test similar to Example 1 was implemented except having used the polymer M as a matrix polymer, and having made the matrix polymer density
  • FIG. 1 is a graph showing the relationship between the melting point of the matrix polymer and the concentration of the matrix polymer in Examples 1 to 19 and Comparative Examples 1 to 8.
  • the vertical axis represents the matrix polymer concentration C (% by mass) in the finally prepared mixture, and the horizontal axis represents the melting point T m (° C.) of the matrix polymer.
  • the numbers accompanying ⁇ or ⁇ indicate the numbers of the examples or comparative examples, respectively, ⁇ indicates that the finally adjusted mixture has gelled, and ⁇ indicates that the finally adjusted mixture It shows that it did not gel.
  • the dotted line in the graph of FIG. 1 has shown Formula (I) at the time of making an inequality sign into an equal sign.
  • the finally prepared mixture is a gel. It has become. That is, the finally adjusted mixture is a gel electrolyte.
  • the present invention can be suitably used as a gel electrolyte in a nonaqueous electrolyte secondary battery.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

La présente invention concerne un électrolyte de gel qui a une faible concentration de polymère de matrice et qui peut maintenir un état de gel. Ce polymère de gel contient un polymère de matrice, et une solution électrolytique non aqueuse comprenant un électrolyte contenant du lithium dissous dans un solvant non aqueux, le polymère de matrice étant un copolymère comprenant des motifs de fluorure de vinylidène et des motifs de monomère contenant des atomes de fluor, et, pour la concentration C (% en masse) du polymère de matrice dans l'électrolyte de gel, la température de fusion Tm du polymère de matrice satisfait à l'équation Tm ≧ 145 - C (I) (Dans l'expression (I), 0,1 ≦ C ≦ 30).
PCT/JP2017/004554 2016-03-10 2017-02-08 Électrolyte de gel et son procédé de préparation WO2017154449A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780004567.8A CN108370067B (zh) 2016-03-10 2017-02-08 凝胶状电解质以及其制备方法
EP17762793.2A EP3429018A4 (fr) 2016-03-10 2017-02-08 Électrolyte de gel et son procédé de préparation
KR1020187016225A KR101942835B1 (ko) 2016-03-10 2017-02-08 겔상 전해질 및 이의 조제 방법
US16/067,869 US20190348711A1 (en) 2016-03-10 2017-02-08 Gel electrolyte and method for preparing same

Applications Claiming Priority (4)

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JP2016047547 2016-03-10
JP2016-047547 2016-03-10
JP2016053140A JP6829943B2 (ja) 2016-03-10 2016-03-16 ゲル状電解質およびその調製方法
JP2016-053140 2016-03-16

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WO2020090828A1 (fr) * 2018-10-31 2020-05-07 株式会社クレハ Électrolyte en gel et batterie secondaire à électrolyte non aqueux
US20200280094A1 (en) * 2017-09-18 2020-09-03 Blue Solutions Solid polymer electrolyte comprising a solvating polymer, a lithium salt and a selected halogenated polymer and battery comprising same
WO2022114044A1 (fr) * 2020-11-30 2022-06-02 株式会社クレハ Composition de copolymère de fluorure de vinylidène et son procédé de production, solution de dispersion de polymère, électrode pour batterie secondaire à électrolyte non aqueux, couche d'électrolyte pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
WO2022114039A1 (fr) * 2020-11-30 2022-06-02 株式会社クレハ Composition de polymère de fluorure de vinylidène et son procédé de production, composition de résine, mélange d'électrode, électrode contenant celles-ci, et leur procédé de production

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JP2009301833A (ja) * 2008-06-12 2009-12-24 Kureha Elastomer Co Ltd 架橋高分子固体電解質およびその製造方法
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JP2009301833A (ja) * 2008-06-12 2009-12-24 Kureha Elastomer Co Ltd 架橋高分子固体電解質およびその製造方法
WO2011096564A1 (fr) * 2010-02-05 2011-08-11 ダイキン工業株式会社 Film composite d'électrolyte en gel pour batterie secondaire et batterie secondaire
WO2014147955A1 (fr) * 2013-03-19 2014-09-25 ソニー株式会社 Batterie, couche d'électrolyte, bloc-batterie, appareil électronique, véhicule électrique, dispositif de stockage d'énergie, et système d'alimentation
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200280094A1 (en) * 2017-09-18 2020-09-03 Blue Solutions Solid polymer electrolyte comprising a solvating polymer, a lithium salt and a selected halogenated polymer and battery comprising same
US11804619B2 (en) * 2017-09-18 2023-10-31 Blue Solutions Solid polymer electrolyte including solvating polymer, lithium salt, and PVdF-HFP copolymer and battery including same
WO2020090828A1 (fr) * 2018-10-31 2020-05-07 株式会社クレハ Électrolyte en gel et batterie secondaire à électrolyte non aqueux
JPWO2020090828A1 (ja) * 2018-10-31 2021-06-10 株式会社クレハ ゲル状電解質および非水電解質二次電池
JP7042924B2 (ja) 2018-10-31 2022-03-28 株式会社クレハ ゲル状電解質および非水電解質二次電池
WO2022114044A1 (fr) * 2020-11-30 2022-06-02 株式会社クレハ Composition de copolymère de fluorure de vinylidène et son procédé de production, solution de dispersion de polymère, électrode pour batterie secondaire à électrolyte non aqueux, couche d'électrolyte pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
WO2022114039A1 (fr) * 2020-11-30 2022-06-02 株式会社クレハ Composition de polymère de fluorure de vinylidène et son procédé de production, composition de résine, mélange d'électrode, électrode contenant celles-ci, et leur procédé de production

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