WO2013100023A1 - Résine résistant à la chaleur, agent adhésif, couche adhésive isolante, séparateur, électrolyte solide, et accumulateur - Google Patents

Résine résistant à la chaleur, agent adhésif, couche adhésive isolante, séparateur, électrolyte solide, et accumulateur Download PDF

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WO2013100023A1
WO2013100023A1 PCT/JP2012/083811 JP2012083811W WO2013100023A1 WO 2013100023 A1 WO2013100023 A1 WO 2013100023A1 JP 2012083811 W JP2012083811 W JP 2012083811W WO 2013100023 A1 WO2013100023 A1 WO 2013100023A1
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resistant resin
heat
storage device
separator
electrode layer
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PCT/JP2012/083811
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English (en)
Japanese (ja)
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上羽悠介
澤田学
日比野幹
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株式会社村田製作所
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Publication of WO2013100023A1 publication Critical patent/WO2013100023A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a heat resistant resin, and more specifically, a heat resistant resin suitable for use in a separator or an insulating adhesive layer constituting an electricity storage device, an adhesive using the same, an insulating adhesive layer, a separator, a solid electrolyte
  • the present invention relates to a power storage device including a separator using the heat resistant resin and an insulating adhesive layer.
  • Examples of such a resin include (A) 10 to 40 parts by weight of a structural unit derived from a monomer in which a carbonate group is introduced into the epoxy group of a (meth) acrylate monomer having an epoxy group, and (B) 10 to 10 structural units derived from acrylonitrile.
  • (A ′) a structural unit derived from 35 to 99% by mass of (meth) acrylate with respect to the total mass of the acrylic polymer;
  • the structural unit 1 derived from the (meth) acrylate represented by the general formula (1) is 1 to 99 mol%
  • the structural unit 2 having an epoxy group represented by the general formula (2) is 1 to 99 mol%.
  • An acrylic polymer having a weight average molecular weight of 1,000 to 100,000 has been proposed (see Patent Document 7).
  • D 1 is a porous film having a D 2 / D 1 value of 0.15 or less, where the second largest value is D 2, and uses a nitrogen-containing aromatic polymer as a heat-resistant resin. It has been proposed (see Patent Document 8).
  • Patent Documents 1 to 7 a copolymer made of an acrylic acid derivative or a methacrylic acid derivative made of various monomers is used as a binder for the separator.
  • References 1 to 7 do not mention the composition of an acrylic binder having a particularly high heat resistance.
  • the binder resin is decomposed at high temperatures such as reflow.
  • the decomposition product of the binder is vaporized due to high temperature, which may cause a problem that the package internal pressure is increased and the package is deformed.
  • the present invention solves the above-mentioned problems, does not thermally decompose even at reflow soldering temperature (260 ° C.), can maintain the given shape and structure, and is compatible with surface mounting by reflow soldering.
  • the inventors have studied a resin material having sufficient oxidation resistance with respect to the positive electrode potential and sufficient reduction resistance with respect to the negative electrode potential used in the electricity storage device, and has developed acrylic acid or acrylic resin.
  • acid esters homopolymers and copolymers having methacrylic acid or methacrylic acid esters as constituent monomers, those satisfying a predetermined condition are sufficient in oxidation resistance with respect to the positive electrode potential used in the electricity storage device, and the negative electrode It has been found that it has sufficient reduction resistance against electric potential and has thermal decomposition resistance that does not thermally decompose even at a reflow temperature (eg, 260 ° C.). And based on this knowledge, further experiment and examination were carried out, and the present invention was completed.
  • a reflow temperature eg, 260 ° C.
  • the heat resistant resin of the present invention is It is characterized by containing at least one of the following (a) and (b) as a main component.
  • R 1 represented by the chemical formula (1) has at least one carbon, the R 1 is bonded to the ester bond represented by the chemical formula (1) and the carbon, and the carbon (hereinafter referred to as the carbon bonded to the ester bond).
  • acrylic acid esters and "carbon of 1-position of R 1") is a primary or secondary, or a homopolymer or co-R 1 represented by the chemical formula (1) is a constituent monomer of acrylic acid is hydrogen
  • Polymer (b) A copolymer having at least one of acrylic acid ester and acrylic acid and at least one of methacrylic acid ester and methacrylic acid as a constituent monomer, wherein the constituent monomer is R represented by chemical formula (1) 1 has at least one carbon, R 1 is bonded by the carbon ester bond represented by the chemical formula (1), acrylic acid ester carbon at the 1-position of R 1 is a primary or secondary, methacrylic Ester, formula (1) are shown acrylate R 1 is hydrogen, a methacrylic acid, a copolymer mol% of the sum of methacrylic acid esters and methacrylic acid constituting the copolymer is not more than 30% [In the formula (1), R is H or CH 3 : R 1 is H or a chemical species having at least one carbon]
  • the heat-resistant resin of the present invention is At least one homopolymer included in the group of homopolymers defined in (a), At least one copolymer included in the group of copolymers defined in (a) above, It may be a mixture of at least two selected from the group consisting of at least one copolymer included in the group of copolymers defined in (b).
  • the heat resistant resin of the present invention preferably has a thermal decomposition temperature exceeding 260 ° C. According to the present invention, it is possible to realize a heat-resistant resin having a thermal decomposition temperature exceeding 260 ° C. By using this heat-resistant resin, for example, by forming a separator or an insulating adhesive layer, reflow soldering It is possible to obtain an electricity storage device that supports surface mounting by attaching.
  • the heat-resistant resin has the basic requirements of the present invention, for example, by controlling the ratio of acrylic resin and methacrylic resin, or by selecting an appropriate side chain structure
  • the pyrolysis temperature can easily be raised above 260 ° C.
  • the HOMO of the constituent monomer is preferably ⁇ 8.40 eV or less.
  • the heat-resistant resin of the present invention is used as, for example, a binder resin for a positive electrode of an electricity storage device, it is necessary to have oxidation resistance because it is exposed to an oxidizing atmosphere, but is not exposed to a reducing atmosphere, In particular, since reduction resistance is not required, it is not necessary to define LUMO. Therefore, when the HOMO of the constituent monomer is ⁇ 8.40 eV or less, it can be used without any particular problem for a positive electrode binder resin of an electricity storage device having a relatively low operating positive electrode potential.
  • the HOMO of the constituent monomer is more preferably ⁇ 10.71 eV or less.
  • the storage device such as a lithium ion secondary battery or an electric double layer capacitor having a high operating positive electrode potential is used. It can also be used as a positive electrode binder resin.
  • the LUMO of the constituent monomer is more preferably 2.77 eV or more.
  • an electricity storage device such as a lithium ion secondary battery or an electric double layer capacitor having a low operating negative electrode potential It can also be used as a negative electrode binder resin.
  • the constituent monomers preferably have a HOMO of ⁇ 8.40 eV or less and a LUMO of 2.70 eV or more.
  • the constituent monomers have the requirements that the HOMO is ⁇ 8.40 eV or less and the LUMO is 2.70 eV or more, since both the oxidation resistance and the reduction resistance are provided, the electricity storage device having a relatively low energy density
  • the heat-resistant resin of the present invention can be used for the separator and the insulating adhesive layer that are bonded to both the negative electrode and the positive electrode that constitute the material.
  • the constituent monomers have a HOMO of 10.71 eV or less and a LUMO of 2.77 eV or more.
  • a separator constituting a power storage device such as a lithium ion secondary battery or an electric double layer capacitor having a high energy density
  • the heat resistant resin of the present invention can be used for the insulating adhesive layer.
  • the heat resistant resin of this invention can be set as the structure which mix
  • inorganic fine particles for example, it becomes possible to impart high liquid content, so that when the heat-resistant resin of the present invention is used for a separator or an insulating adhesive layer of an electricity storage device, the production of the electricity storage device is performed.
  • the electrolyte solution is injected and impregnated into a laminate formed by laminating the positive electrode layer and the negative electrode layer via the separator and the insulating adhesive layer, the time required for the impregnation is shortened and the productivity is improved. It becomes possible to make it.
  • the addition of inorganic fine particles increases the elasticity of separators, insulating adhesive layers, etc., and can improve reliability by preventing deformation due to external forces and the accompanying short circuit caused by contact between the positive and negative electrode layers. it can.
  • the heat-resistant resin of the present invention is preferably used for an electricity storage device, and is preferably used for an electricity storage device that supports mounting by reflow soldering.
  • the heat-resistant resin of the present invention has sufficient heat resistance, and when used in an electricity storage device that supports mounting by reflow soldering, it is possible to perform efficient mounting and reliability. Can be provided.
  • a heat-resistant resin having oxidation resistance and / or reduction resistance with the requirements of HOMO and LUMO it forms important elements that constitute an electricity storage device such as a binder for electrodes, a separator, and an insulating adhesive layer. It can use suitably as a material for doing.
  • the adhesive of the present invention is characterized by using the above heat-resistant resin of the present invention.
  • the positive electrode layer and the negative electrode layer are laminated so as to face each other via the insulating adhesive layer in a predetermined region, and face each other via a separator in the other predetermined region.
  • an insulating adhesive layer used in an electricity storage device having a structure in which the positive electrode layer and the negative electrode layer are bonded via the insulating adhesive layer Using a heat resistant resin in which HOMO of the constituent monomer is ⁇ 8.40 eV or less and LUMO is 2.70 eV or more, or HOMO of the constituent monomer is ⁇ 10.71 eV or less and LUMO is 2.77 eV or more. It is characterized by being manufactured.
  • the HOMO of the constituent monomer and the constituent monomer is ⁇ 8.40 eV or less
  • the LUMO is 2.70 eV or more
  • the HOMO of the constituent monomer is ⁇ 10.71 eV or less.
  • the positive electrode layer and the negative electrode layer are laminated so as to oppose each other via an insulating adhesive layer in a predetermined region, and so as to oppose each other via a separator in other predetermined regions.
  • the electricity storage device of the present invention has a structure in which a positive electrode layer and a negative electrode layer are stacked via a separator, and the positive electrode layer and the negative electrode layer in contact with the separator are directly bonded to the separator.
  • An electricity storage device with a body An electricity storage device comprising the separator of the present invention as the separator.
  • the electricity storage device of the present invention can be configured as one selected from the group consisting of a lithium ion secondary battery, a lithium ion capacitor, and an electric double layer capacitor.
  • the heat-resistant resin of the present invention has characteristics such as oxidation resistance and / or reduction resistance and heat resistance. Therefore, by using the heat-resistant resin of the present invention, the heat-resistant resin has good characteristics.
  • a highly reliable lithium ion secondary battery, a lithium ion capacitor, and an electric double layer capacitor can be provided.
  • the heat-resistant resin of the present invention having the above-mentioned configuration has heat resistance, and is generally not thermally decomposed even in the reflow soldering process, so that the structure is maintained, so that it can be used for surface mounting by reflow soldering. It can be suitably used as a resin for use in electrical storage devices such as the electric double layer capacitor, lithium ion secondary battery, lithium ion capacitor, sulfide solid state battery, oxide solid state battery, and thin film battery.
  • the fact that thermal decomposition does not occur even in the reflow soldering process is not limited to literally no thermal decomposition at all, and it causes deterioration of characteristics that are particularly problematic even after the reflow process. This means that it is as stable as possible.
  • the heat-resistant resin of the present invention has characteristics such as oxidation resistance and / or reduction resistance, heat resistance, etc., so that it is widely used for adhesives used in the manufacture of power storage devices. Can do.
  • the insulating adhesive layer of the present invention is the heat resistant resin of the present invention, wherein the constituent monomer has a HOMO of ⁇ 8.40 eV or less, a LUMO of 2.70 eV or more, or a constituent monomer has a HOMO of ⁇ Since it is produced using a heat-resistant resin having 10.71 eV or less and LUMO of 2.77 eV or more, the necessary heat resistance, oxidation resistance, reduction resistance as an insulating adhesive layer used in an electricity storage device Therefore, it is possible to provide a highly reliable power storage device that supports surface mounting by reflow soldering.
  • the separator of the present invention is a separator used for an electricity storage device including a laminate having a structure in which a positive electrode layer and a negative electrode layer are laminated via a separator, and a constituent monomer has a HOMO of ⁇ 8.40 eV.
  • LUMO is 2.70 eV or more, or it is produced using a heat-resistant resin whose constituent monomer has HOMO of ⁇ 10.71 eV or less and LUMO of 2.77 eV or more.
  • a separator used in the above it has necessary heat resistance, oxidation resistance, and reduction resistance, and can provide a highly reliable power storage device corresponding to surface mounting by reflow soldering.
  • the solid electrolyte of the present invention comprises a powdered electrolyte and the heat-resistant resin of the present invention (whether the constituent monomer has a HOMO of ⁇ 8.40 eV or less and a LUMO of 2.70 eV or more, or the constituent monomer has a HOMO of -10.71 eV or less and a LUMO having a heat resistance resin having a LUMO of 2.77 eV or more), it has heat resistance, oxidation resistance, reduction resistance, and excellent shape retention.
  • a solid electrolyte having high characteristics and reliability can be provided.
  • FIG. 7 is a diagram illustrating a process of punching the printed body of FIG. 6 into a predetermined shape, where (a) is a plan view showing the position of a cutting line of the printed body, and (b) is a positive electrode layer obtained by punching the printed body
  • FIG. 4C is a front sectional view showing a negative electrode layer obtained by punching a printed body.
  • (a) is a front sectional view showing a step of forming a laminate by laminating and adhering the positive electrode layer and the negative electrode layer shown in FIG. 7 with the surface on which the insulating adhesive layer is printed facing each other
  • FIG. 3 is a front sectional view showing the laminate obtained in (a). It is front sectional drawing which shows the electric double layer capacitor (cell) formed by accommodating the laminated body shown in FIG. 8 in a package, inject
  • R 1 represented by the chemical formula (1) has at least one carbon, R 1 is bonded to the ester bond represented by the chemical formula (1) and the carbon, and R 1 A homopolymer or copolymer having a constituent monomer of acrylic acid ester in which the carbon at the 1-position is primary or secondary, or acrylic acid in which R 1 is hydrogen represented by chemical formula (1), or (b ) A copolymer having at least one of acrylic acid ester and acrylic acid and at least one of methacrylic acid ester and methacrylic acid as a constituent monomer, wherein the constituent monomer has an R 1 of at least 1 in the chemical formula (1).
  • R 1 is bonded to the ester bond represented by the chemical formula (1) by the above carbon, and the carbon at the 1-position of R 1 is primary or secondary, or R represented by the chemical formula (1) acrylic acid 1 is hydrogen, meta An acrylic acid, those containing copolymer mol% of the sum of methacrylic acid esters and methacrylic acid constituting the copolymer is 30% or less, as major component.
  • R is H or CH 3 : R 1 is H or a chemical species having at least one carbon]
  • the heat-resistant resin of the present invention having the above-described structure has sufficient heat resistance, and maintains its structure without being thermally decomposed even in a normal reflow soldering process. This is for the reason described below.
  • R 1 represented by the chemical formula (1) has at least one carbon, and R 1 has the chemical formula (1 ) And the above-mentioned carbon and when the carbon at the 1-position of R 1 is primary or secondary, even at 260 ° C. of reflow soldering temperature (hereinafter “reflow temperature”) Side chains do not break down.
  • reflow temperature reflow soldering temperature
  • the methacrylic acid skeleton is more easily decomposed than the acrylic acid skeleton.
  • a homopolymer of a methacrylic acid ester is decomposed around 130 ° C. and cannot be used because it easily decomposes at a high temperature such as reflow.
  • an acrylic resin consisting only of an acrylic acid skeleton has high heat resistance that does not decompose at 260 ° C. Therefore, the heat resistant resin of the present invention can be constituted by using an acrylic resin.
  • an acrylic resin has a low glass transition temperature, and it is not always easy to obtain a heat-resistant resin (particularly an adhesive) having no tack. Therefore, the introduction of a methacrylic acid skeleton into the acrylic acid skeleton was studied so that a heat resistant resin having a high glass transition temperature could be obtained.
  • the thermal decomposability increases with the introduction of the methacrylic acid skeleton (the thermal decomposability decreases)
  • the sum of the mol% of methacrylic acid and methacrylic acid ester monomer constituting the polymer is 30% or less. In some cases, it was confirmed that it did not decompose even at a reflow temperature of 260 ° C. and showed sufficient heat resistance for reflow.
  • acrylic acid ester and methacrylic acid ester Since the reactivity of acrylic acid ester and methacrylic acid ester is relatively similar, they can be easily copolymerized. By selecting the monomer and copolymer composition ratio, a wide range of glass transition temperatures can be obtained. Can be designed. That is, it is a resin material that is very effective in that a resin design having a composition corresponding to the bonding temperature required for use as an adhesive material can be performed. For example, when an adhesive material having no instantaneous adhesiveness (tack) is required, it is possible to easily control the glass transition temperature by copolymerization so that the glass transition temperature becomes room temperature or higher.
  • tack instantaneous adhesiveness
  • heat-resistant resins using acrylic and methacrylic resins include fluororesins such as PTFE, PVDF, and PVDF-HFP (a copolymer of PVDF and hexafluoropropylene (HFP)), and engineering plastics such as polyimide and polyamide.
  • fluororesins such as PTFE, PVDF, and PVDF-HFP (a copolymer of PVDF and hexafluoropropylene (HFP)
  • engineering plastics such as polyimide and polyamide.
  • an acrylic resin and a methacrylic resin are advantageous in that they are cheaper than these.
  • high heat-resistant resins such as fluororesins such as PTFE, PVDF, PVDF-HFP (copolymer of PVDF and hexafluoropropylene (HFP)) as described above, engineering plastics such as polyimide and polyamide are highly stable.
  • fluororesins such as PTFE, PVDF, PVDF-HFP (copolymer of PVDF and hexafluoropropylene (HFP)
  • engineering plastics such as polyimide and polyamide are highly stable.
  • acrylic resins and methacrylic resins are soluble in many solvents, and not only can an inexpensive solvent be selected, but also a solvent according to the process can be selected. There are many options.
  • the side chain structures of acrylic resins and methacrylic resins are diverse and have different physical properties such as glass transition temperature, the degree of freedom in designing physical properties by selecting side chains is high.
  • the high heat-resistant resins described above do not have as many types of constituent monomers as acrylic resins and methacrylic resins, and the design range of characteristics and physical properties is narrow. Also from this point, acrylic resins and methacrylic resins are superior to other heat resistant resins.
  • acrylic resins and methacrylic resins have high oxidation resistance and reduction resistance that do not decompose even in high energy density power storage devices such as lithium ion secondary batteries.
  • the inventors examined the oxidation resistance and reduction resistance of various resin materials, and when many of acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester polymers are used in power storage devices. It was discovered that the required oxidation resistance and reduction resistance were satisfied.
  • acrylic acid, acrylic acid ester, methacrylic acid, a homopolymer of methacrylic acid ester, a copolymer thereof or the like Use a mixture.
  • a monomer (constituent monomer) that can be used to obtain a homopolymer, a copolymer, or a mixture thereof is defined by the values of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital).
  • the heat-resistant resin of the present invention is intended for use in power storage devices such as lithium ion secondary batteries, electric double layer capacitors, lithium ion capacitors, sulfide solid state batteries, oxide solid state batteries, and thin film batteries. .
  • power storage devices such as lithium ion secondary batteries, electric double layer capacitors, lithium ion capacitors, sulfide solid state batteries, oxide solid state batteries, and thin film batteries.
  • the values of HOMO and LUMO are used as indicators of oxidation resistance and reduction resistance.
  • Table 1 Table 2A, Table 2B, Table 3A, Table 3B show HOMO values and LUMO values obtained by calculation for various resin materials.
  • Table 1 shows HOMO values and LUMO values of polyolefin resin, CMC (carboxymethylcellulose), PVDF (polyvinylidene fluoride), acrylic acid ester, and methacrylic acid ester.
  • Tables 2A and 2B show HOMO values and LUMO values of acrylic acid, acrylic acid ester and acrylamide
  • Tables 3A and 3B show HOMO values of methacrylic acid, methacrylic acid ester and methacrylamide. , Shows the LUMO value.
  • the side chains shown in Table 2A, Table 2B, Table 3A, and Table 3B correspond to the portion of —O—R 1 shown in Formula (1). That is, the chemical species bonded to the carbonyl group of the chemical formula represented by formula (1) was defined as a side chain.
  • the quantum chemistry calculation program Gaussian 03 was used to obtain the HOMO value and the LUMO value.
  • the molecular structure was optimized to determine the stable structure of the molecule.
  • the energy levels of HOMO and LUMO were calculated using the stable structure.
  • the conditions in each calculation are as follows. In the structural optimization calculation, B3LYP method was used, and 3-21G * was used as the basis function of atomic orbitals.
  • the Hartree-Fock method was used to calculate the energy levels of HOMO and LUMO, and 6-311G was used as the basis function of atomic orbitals.
  • monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester are used for separators of lithium ion batteries, and polyolefin-based polymer resins that are known not to be decomposed even in contact with the positive electrode Compared with (polyethylene, polypropylene), it has lower or equivalent HOMO (the smaller the value of HOMO, the less it is oxidized) (see Table 1, Table 2A, 2B, Table 3A, 3B).
  • LUMO has a higher value than CMC (carboxymethylcellulose) and PVDF (polyvinylidene fluoride) widely used for a binder of a negative electrode layer of a lithium ion battery (the larger the LUMO value, the more difficult it is reduced). (See Table 1, Tables 2A and 2B, Tables 3A and 3B).
  • the polymer and copolymer used in the heat-resistant resin of the present invention are those obtained by polymerization or copolymerization of monomers having the above HOMO and LUMO values.
  • the polymer also has the same oxidation resistance and reduction resistance as the monomer.
  • the heat resistant resin of the present invention it is not always necessary to define both HOMO and LUMO of the constituent monomers.
  • the member using the heat-resistant resin of the present invention is a separator or an electrolyte part, since they are disposed between and in contact with the positive electrode and the negative electrode, both oxidation resistance and reduction resistance are provided. I need it.
  • the resin used in the electricity storage device has a HOMO of ⁇ 8.40 eV or less and a LUMO of 2.70 eV or more.
  • This value is based on polyacrylamide.
  • Polyacrylamide is used in power storage devices with relatively low energy density, for example, by adding it to the electrolyte of lead acid batteries or manganese dry batteries. Therefore, if it has a value of HOMO and LUMO comparable to those of polyacrylamide, it can be used as a resin for an electricity storage device having a relatively low energy density.
  • HOMO is ⁇ 10.71 eV or less and LUMO is 2.77 eV or more.
  • the values of HOMO and LUMO are determined based on the resin currently used in the lithium ion secondary battery. That is, the HOMO value was set to ⁇ 10.71 eV or less in consideration of the HOMO of polypropylene, which is a general separator material, and the LUMO value was set to 2.77 eV or more in the positive electrode layer and the negative electrode layer. This is in consideration of the LUMO of PVDF, which is a binder material that can be used for any of these (see Tables 1, 2A, 2B, and 3A, 3B).
  • acrylic resin and methacrylic resin were prepared, and the thermal decomposition temperature was examined.
  • polymethyl acrylate has heat resistance that does not decompose even at 260 ° C., but polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polymethacrylic acid having a methacrylic acid skeleton. It was confirmed that the decomposition of n-butyl (PBMA) started at 130 ° C.
  • the rate of temperature increase is 10 ° C./min.
  • the power storage device passes through a reflow furnace set to a predetermined temperature. Therefore, the time of exposure to high temperature is short, and the temperature rise and fall are also performed quickly. Therefore, when judging whether or not thermal decomposition has occurred using the weight loss rate under the above TG measurement conditions as an index, weight loss If the rate is up to about 2%, it is considered appropriate to judge that there is no problem of thermal decomposition. This is the same when the thermal decomposition resistance is evaluated from the results shown in FIGS.
  • the copolymer was synthesized as follows. A 1-liter separable flask equipped with a nitrogen gas inlet tube, a reflux device, a thermometer, and a stirring function was charged with 198.5 g of methanol and 0.82 g of azobisisobutyronitrile and stirred, and nitrogen gas was bubbled. While warming to 63 ° C. Then, 180 g of methyl acrylate and methyl methacrylate mixed in the above proportions were added dropwise to the flask over 2 hours using a dropping funnel. After completion of the dropwise addition, 0.41 g of azobisisobutyronitrile and 7.6 g of methanol were added and heated for 2 hours, then heated to 65 ° C.
  • the copolymer was synthesized as follows. A 1-liter separable flask equipped with a nitrogen gas inlet tube, a reflux device, a thermometer, and a stirring function was charged with 198.5 g of methanol and 0.82 g of azobisisobutyronitrile and stirred while continuously bubbling nitrogen gas. Warmed to 63 ° C. Then, 180 g of methyl acrylate and cyclohexyl acrylate mixed at the following ratios were added dropwise to the flask with a dropping funnel over 2 hours. After completion of the dropwise addition, 0.41 g of azobisisobutyronitrile and 7.6 g of methanol were added and heated for 2 hours, then heated to 65 ° C. and heated for 2 hours to obtain a polymer solution (resin solution).
  • the mixing ratio of said methyl acrylate and cyclohexyl acrylate is a molar ratio, respectively.
  • the produced polymer was dried overnight in an oven at 130 ° C. to remove the solvent. After removing the solvent, TG measurement was performed in the same manner as described in [1] above, and the thermal decomposition temperature was measured. The result of TG measurement is shown in FIG.
  • R 1 represented by the chemical formula (1) has at least one carbon, R 1 is bonded to the ester bond represented by the chemical formula (1) by the carbon, and the carbon at the 1-position of R 1 is primary. Or satisfying the requirement that acrylic acid ester that is secondary or acrylic acid in which R 1 represented by chemical formula (1) is hydrogen is used as a constituent monomer, (b) a copolymer having at least one of acrylic acid ester and acrylic acid and at least one of methacrylic acid ester and methacrylic acid as a constituent monomer, wherein the constituent monomer has R 1 represented by chemical formula (1) It has at least one carbon, and R 1 is bonded to the ester bond represented by the chemical formula (1) by the carbon, and the carbon at the 1-position of R 1 is primary or secondary, or the chemical formula (1) When reflow soldering is performed by satisfying the requirement that the R 1 shown is acrylic acid or methacrylic acid in which hydrogen is present, and the sum of mol% of methacrylic acid ester and methacrylic acid constitu
  • Example 2 in order to evaluate the heat-resistant resin of the present invention, a separator (ceramic separator) using a polyacrylic acid ester (polymethyl acrylate) having a heat-resistant composition having the requirements of the present invention as a binder resin. And an electric double layer capacitor (cell) having an insulating adhesive layer using a copolymer of methyl acrylate and ethyl acrylate as a binder resin, and the obtained electric double layer capacitor (cell) It was passed through a reflow furnace and the electrical characteristics before and after that were investigated.
  • CMC2260 carboxymethylcellulose
  • aqueous polyacrylate resin solution 38.8% by weight
  • methyl acrylate was dropped into the flask with a dropping funnel over 2 hours. After completion of dropping, 0.41 g of azobisisobutyronitrile and 7.6 g of methanol were added and heated for 2 hours, and then heated to 65 ° C. and heated for 2 hours to obtain a polymer (methyl polyacrylate) solution. .
  • separator layer slurry 100 g of spherical alumina powder (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size (D50) 0.3 ⁇ m) and 80 g of NMP as a solvent were charged into a 500 ml pot. Furthermore, PSZ grinding media having a diameter of 5 mm were placed, and the mixture was dispersed by mixing at 150 rpm for 16 hours using a rolling ball mill.
  • the synthesized polymethyl acrylate binder solution (40 wt% NMP solution) was put into the pot and mixed at 150 rpm for 4 hours using a rolling ball mill to prepare a separator layer slurry of 80% PVC.
  • pigment volume concentration PVC (Pigment Volume Concentration) is a value calculated
  • PVC (volume of inorganic fine particles) / (volume of inorganic fine particles + volume of binder resin) ⁇ 100 (1)
  • Volume of inorganic fine particles weight of inorganic fine particles / density of inorganic fine particles
  • Volume of binder resin weight of binder resin / density of binder resin
  • a binder solution of a copolymer of methyl acrylate and ethyl acrylate (40 wt% NMP solution) was put into the pot and mixed for 4 hours at 150 rpm using a rolling ball mill, and an insulating property of PVC 40% An adhesive layer slurry was prepared.
  • FIGS. 6 (a) and 6 (b) Coating of insulating adhesive layer slurry Using a # 500 mesh screen printing plate with a plate thickness of 5 ⁇ m, the insulating adhesive layer slurry prepared by the above method is shown in FIGS. 6 (a) and 6 (b). As shown in the figure, coating is performed on the positive electrode current collector layer 111 (negative electrode current collector layer 121) in the region surrounding the separator layer 113 (123), followed by drying at 120 ° C. for 30 minutes. An insulating adhesive layer 114 (124) having a thickness of 3 ⁇ m was formed in the surrounding region.
  • the positive electrode layer 115 includes a positive electrode current collector layer 111, a positive electrode active material layer 112 formed on the surface thereof, a separator layer 113, and an insulating adhesive layer 114.
  • the negative electrode layer 125 includes a negative electrode current collector layer 121, a negative electrode active material layer 122 formed on the surface thereof, a separator layer 123, and an insulating adhesive. Layer 124.
  • a lid 70a and a base portion 70b on which a positive electrode package electrode 61 and a negative electrode package electrode 62 are formed so as to wrap around from both ends to the lower surface side are provided.
  • a package 70 is prepared.
  • the lid body 70a and the base portion 70b those made of liquid crystal polymer are used.
  • a conductive adhesive containing gold as conductive particles is applied to the positive electrode side and negative electrode side extraction electrodes (electrode tabs) 116 and 126 of the laminate 106 by dipping.
  • the laminated body 106 is disposed inside the base portion 70b of the package 70 so that the applied conductive adhesive is connected to the positive electrode package electrode 61 and the negative electrode package electrode 62, and heated at 170 ° C. for 10 minutes.
  • the conductive adhesive 108 was cured.
  • the stacked body 106 is accommodated in the package 70, and the positive electrode side electrode tab 116 and the negative electrode side electrode tab 126 of the stacked body 106 are connected to the positive electrode package electrode via the conductive adhesive 108.
  • the structure connected to 61 and the negative electrode package electrode 62 was obtained.
  • the separator of the electric double layer capacitor and the insulating adhesive layer are formed of the heat resistant resin of the present invention.
  • the electricity storage device that can use the heat resistant resin of the present invention. Is not limited to electric double layer capacitors, but can also be applied to lithium ion secondary batteries, lithium ion capacitors, and the like.
  • each of the lithium ion secondary battery and the lithium ion capacitor has a structure in which a positive electrode layer and a negative electrode layer are laminated via a separator layer or an insulating adhesive layer and are housed in an outer packaging material together with an electrolytic solution.
  • the material containing the heat resistant resin of this invention can be used for these separators and an insulating contact bonding layer.
  • a lithium ion secondary battery or a lithium ion capacitor the thing of the following structures is illustrated, for example.
  • a lithium ion secondary battery for example, an aluminum foil is used as a positive electrode current collector layer, and an electrode in which a mixture layer containing a lithium composite oxide is provided on the aluminum foil as a positive electrode active material layer is used as a positive electrode layer.
  • the negative electrode current collector layer for example, a copper foil is used, and an electrode in which a mixture layer containing graphite is provided as a negative electrode active material layer on the copper foil is used as the negative electrode layer.
  • the positive electrode layer and the negative electrode layer are laminated via a separator and an insulating adhesive layer using the heat-resistant resin of the present invention as in the above-described example, and a laminate is formed, for example.
  • a lithium ion secondary battery can be obtained by using 1 mol / l LiBF 4 dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate as an electrolytic solution (nonaqueous electrolytic solution).
  • lithium ion capacitor for example, an aluminum foil is used as the positive electrode current collector layer, and an electrode in which a mixture layer containing activated carbon is provided as a positive electrode active material layer on the aluminum foil is used as the positive electrode layer.
  • the negative electrode current collector layer for example, a copper foil is used, and an electrode provided with a mixture layer containing graphite as a negative electrode active material layer on the copper foil is used as a negative electrode layer, and lithium ions are further pre-doped into the negative electrode layer. To do.
  • a lithium ion capacitor can be obtained by using, as an electrolytic solution (nonaqueous electrolytic solution), 1 mol / l LiBF 4 dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate.
  • the heat resistant resin of the present invention can also be used for sulfide solid state batteries, oxide solid state batteries, thin film batteries and the like.
  • the present invention is not limited to the above-described embodiments and examples, and the types and combinations of constituent monomers constituting the heat-resistant resin, the blending ratio, the types and blending ratios of the inorganic fine particles, the configuration of the positive electrode layer and the negative electrode layer
  • materials, forming methods, specific configurations of power storage elements such as positive electrode layers, negative electrode layers, separators, insulating adhesive layers and the number of layers
  • types of electrolytes etc. It is possible to add deformation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

Cette invention concerne une résine résistant à la chaleur pour accumulateurs qui peut être utilisée en montage en surface par soudage par refusion. La résine selon l'invention utilise soit (a) un homopolymère ou un copolymère dont les monomères constitutifs sont un ester d'acide acrylique dans lequel R1 a au moins un carbone, R1 est lié par le carbone à une liaison ester, et le carbone lié par la liaison ester (ci-après, "carbone de la position 1 dans R1") est un carbone primaire ou secondaire, ou un acide acrylique dans lequel R1 est un atome d'hydrogène ; soit (b) un copolymère dont les monomères constitutifs sont un ester d'acide acrylique et/ou un acide acrylique et un ester d'acide méthacrylique et/ou un acide méthacrylique, dans lequel les monomères constitutifs sont un ester d'acide acrylique/ester d'acide méthacrylique dans lequel R1 a au moins un carbone, R1 est lié par le carbone à une liaison ester, et le carbone de la position 1 de R1 est un carbone primaire ou secondaire, ou un acide acrylique/acide méthacrylique dans lequel R1 est un atome d'hydrogène, et la somme de l'ester d'acide méthacrylique et de l'acide méthacrylique en pourcentage en moles est de 30 % ou moins.
PCT/JP2012/083811 2011-12-28 2012-12-27 Résine résistant à la chaleur, agent adhésif, couche adhésive isolante, séparateur, électrolyte solide, et accumulateur WO2013100023A1 (fr)

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CN106128778A (zh) * 2016-07-26 2016-11-16 胡英 一种全固态超级电容器及其制备方法
CN112259913A (zh) * 2020-09-25 2021-01-22 东莞维科电池有限公司 一种隔膜浆料及其制备方法与用途
JP7374134B2 (ja) 2018-09-28 2023-11-06 エルジー エナジー ソリューション リミテッド 電気化学素子用分離膜及びこれを製造する方法

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JP2002529891A (ja) * 1998-11-04 2002-09-10 ビーエーエスエフ アクチェンゲゼルシャフト 複合材料及び電気化学電池
JP2002161251A (ja) * 2000-11-28 2002-06-04 Hitachi Chem Co Ltd 接着フィルム、その製造方法及び接着方法
JP2011071128A (ja) * 2003-04-09 2011-04-07 Nitto Denko Corp 電池用セパレータのための接着剤担持多孔質フィルムとその利用
JP2007023145A (ja) * 2005-07-15 2007-02-01 Achilles Corp ポリ乳酸系樹脂軟質フィルム
WO2007023932A1 (fr) * 2005-08-26 2007-03-01 Kuraray Co., Ltd. Composition d'élastomère thermoplastique et article moulé composite fabriqué à partir de celle-ci
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JP2009132888A (ja) * 2007-11-05 2009-06-18 Hitachi Chem Co Ltd アクリル系エラストマー及びこれを用いた組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106128778A (zh) * 2016-07-26 2016-11-16 胡英 一种全固态超级电容器及其制备方法
JP7374134B2 (ja) 2018-09-28 2023-11-06 エルジー エナジー ソリューション リミテッド 電気化学素子用分離膜及びこれを製造する方法
CN112259913A (zh) * 2020-09-25 2021-01-22 东莞维科电池有限公司 一种隔膜浆料及其制备方法与用途

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