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WO2020071056A1 - Composition de pâte, matériau d'électrode pour batteries secondaires, électrode pour batteries secondaires et batterie secondaire - Google Patents

Composition de pâte, matériau d'électrode pour batteries secondaires, électrode pour batteries secondaires et batterie secondaire

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Publication number
WO2020071056A1
WO2020071056A1 PCT/JP2019/035239 JP2019035239W WO2020071056A1 WO 2020071056 A1 WO2020071056 A1 WO 2020071056A1 JP 2019035239 W JP2019035239 W JP 2019035239W WO 2020071056 A1 WO2020071056 A1 WO 2020071056A1
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WO
WIPO (PCT)
Prior art keywords
formula
group
secondary battery
electrode
polyamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/035239
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English (en)
Japanese (ja)
Inventor
遼太 山地
知己 北川
小林　正典
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Chemical Corp
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JFE Chemical Corp
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Filing date
Publication date
Application filed by JFE Chemical Corp filed Critical JFE Chemical Corp
Priority to CN201980003864.XA priority Critical patent/CN111263992B/zh
Priority to JP2020505930A priority patent/JP7011039B2/ja
Publication of WO2020071056A1 publication Critical patent/WO2020071056A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 paste composition, an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery.
  • Secondary batteries typified by lithium ion secondary batteries are recognized for their advantages of light weight, high operating voltage, high energy density, and long life, and are also expected to be applied to transportation equipment such as automobiles and aircraft. At present, demands for space saving, durability, high voltage, high energy density, and high safety are becoming higher.
  • PVDF polyvinylidene fluoride resin
  • NMP N-methyl-pyrrolidone
  • Patent Document 1 discloses “a positive electrode plate and a negative electrode plate; a separator disposed between the positive electrode plate and the negative electrode plate to form a storage region; and an electrolyte solution filled in the storage region.
  • a lithium battery comprising: a thermal activation protection film provided on a material surface of the positive electrode plate or the negative electrode plate; and when the temperature of the lithium battery rises to the thermal activation temperature of the thermal activation protection film, the thermal activation A lithium battery, wherein the protective film performs a cross-linking reaction to prevent thermal runaway, and the thermal operating temperature is from 80 ° C. to 280 ° C. ”(claim 1).
  • the thermal protection film in this lithium battery utilizes a thermal cross-linking reaction between a vinyl group derived from bismaleimide and an amino group derived from barbituric acid.
  • a positive electrode active material or a negative electrode is used. It is said that the thermal runaway is prevented by covering the active material with the thermal protection film.
  • the electrode plate paste composition is premised on using an organic solvent as a dispersion medium.
  • An object of the present invention is to provide a paste composition capable of manufacturing a secondary battery having high safety against overheating. Another object of the present invention is to provide an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery, which are highly safe against heating.
  • the present inventors have conducted intensive studies to solve the above problems, a specific tetracarboxylic acid ester, a specific polyamine, a secondary battery active material, and a paste composition containing an aqueous medium, The inventors have learned that a secondary battery which is an aqueous dispersion liquid, can be prepared in a relatively short time (several hours), and has high safety against overheating can be manufactured, and the present invention has been completed.
  • a paste composition comprising a hemiacetal ester derivative represented by the formula (1), a polyamine represented by the formula (2), an active material for a secondary battery, and an aqueous medium.
  • n is 0 or 1
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom or a monovalent organic group.
  • X may be bonded to form a cyclic structure, and X is a tetravalent organic group.
  • n 0, R 2 and R 4 or R 4 and R 5 combine with each other to form a six-membered aromatic carbon ring which may have a substituent. You may.
  • m is an integer of 2 or more
  • Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond.
  • the hemiacetal ester derivative is a 2,3-dihydrofuran derivative represented by the formula (1-1), a 3,4-dihydro-2H-pyran derivative represented by the formula (1-2),
  • the paste composition according to the above [1] which is at least one selected from the group consisting of a 1-benzofuran derivative represented by the formula (1-3).
  • R 1 , R 2 , R 4 , R 5 and X have the same meanings as R 1 , R 2 , R 4 , R 5 and X in the above formula (1), respectively. is there.
  • R 1 , R 2 , R 3 , R 4 , R 5 and X are each R 1 , R 2 , R 3 , R 4 , R 5 in the above formula (1).
  • X have the same meaning.
  • R 1 , R 2 and X have the same meanings as R 1 , R 2 and X in the above formula (1), respectively.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and are bonded to each other to form a cyclic structure. Is also good.
  • An electrode material for a secondary battery comprising a hemiacetal ester derivative represented by the formula (1), a polyamine represented by the formula (2), and an active material for a secondary battery.
  • n 0 or 1
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom or a monovalent organic group.
  • X may be bonded to form a cyclic structure, and X is a tetravalent organic group.
  • R 2 and R 4 or R 4 and R 5 combine with each other to form a six-membered aromatic carbon ring which may have a substituent. You may.
  • m is an integer of 2 or more
  • Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond.
  • the hemiacetal ester derivative is a 2,3-dihydrofuran derivative represented by the formula (1-1), a 3,4-dihydro-2H-pyran derivative represented by the formula (1-2),
  • the electrode material for a secondary battery according to the above [4] which is at least one member selected from the group consisting of a 1-benzofuran derivative represented by the formula (1-3).
  • R 1 , R 2 , R 4 , R 5 and X have the same meanings as R 1 , R 2 , R 4 , R 5 and X in the above formula (1), respectively. is there.
  • R 1 , R 2 , R 3 , R 4 , R 5 and X are each R 1 , R 2 , R 3 , R 4 , R 5 in the above formula (1).
  • X have the same meaning.
  • R 1 , R 2 and X have the same meanings as R 1 , R 2 and X in the above formula (1), respectively.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and are bonded to each other to form a cyclic structure. Is also good.
  • a secondary battery electrode comprising the secondary battery electrode material according to any one of [4] to [6].
  • a paste composition which is a water-based dispersion liquid, can be prepared in a relatively short time (several hours), and can produce a secondary battery having high safety against overheating.
  • the present invention can provide an electrode material for a secondary battery, an electrode for a secondary battery, and a secondary battery, which are highly safe against heating.
  • FIG. 1 is a schematic cross-sectional view of a battery used in Examples.
  • a range represented by “to” includes both ends of the range.
  • a range represented by “AB” includes A and B.
  • the hemiacetal ester derivative, the polyamine, and the active material for a secondary battery are in a mixed state, and for a secondary battery, Active material is not coated.
  • vinyl ether is eliminated from the hemiacetal ester derivative, tetracarboxylic acid reacts with polyamine, and the active material for a secondary battery is coated with polyimide.
  • the electrodes are not broken, and ignition, explosion, and the like of the secondary battery are prevented.
  • the paste composition of the present invention includes a hemiacetal ester derivative represented by the following formula (1) (hereinafter, may be referred to as a “hemiacetal ester derivative (1)”) and a polyamine represented by the formula (2). (Hereinafter sometimes referred to as “polyamine (2)”), an active material for a secondary battery, and an aqueous medium.
  • the hemiacetal ester derivative (1) is a compound represented by the formula (1).
  • One or more hemiacetal ester derivatives (1) can be included in the paste composition of the present invention.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom or a monovalent organic group.
  • the halogen atom is not particularly limited, and is preferably at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and more preferably a fluorine atom.
  • the monovalent organic group is not particularly limited and is preferably a monovalent hydrocarbon group, and is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group and an aryl group. It is more preferably at least one kind, more preferably an alkyl group, further preferably an alkyl group having 1 to 3 carbon atoms (C 1-3 alkyl group), and more preferably a methyl group. More preferred.
  • examples of the C 1-3 alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group (2-propyl group).
  • a hydrogen atom may be substituted by a halogen atom or a hydroxyl group.
  • the halogen atom is not particularly limited, and is preferably at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and more preferably a fluorine atom.
  • the monovalent organic group does not include a functional group reactive with an amino group or a carboxy group.
  • the group reactive with the amino group includes, for example, a carboxy group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, and a halogenocarbonyl group, but are not limited thereto.
  • the functional group reactive with a carboxy group include, but are not limited to, an amino group, a hydroxy group, a carboxy group, and a vinyloxy group.
  • R 1 , R 2 , R 3 , R 4 and R 5 may combine with each other to form a cyclic structure.
  • the cyclic structure is not particularly limited, and examples thereof include an aromatic hydrocarbon ring which may have a substituent and an alicyclic hydrocarbon ring which may have a substituent.
  • R 2 and R 4 or R 4 and R 5 may combine with each other to form a six-membered aromatic carbon ring which may have a substituent.
  • X is a tetravalent organic group.
  • the tetravalent organic group include compounds having a basic skeleton of a chain hydrocarbon such as ethylene and propane; compounds having a basic skeleton of a cyclic hydrocarbon such as cyclohexane; and aromatic hydrocarbons such as benzene and naphthalene.
  • a group in which four hydrogen atoms have been removed is exemplified. However, it is not limited to these.
  • the tetravalent organic group does not include a functional group having reactivity with an amino group.
  • the group reactive with the amino group includes, for example, a carboxy group, a carboxylic anhydride group, a carbonyl group, an aldehyde group, and a halogenocarbonyl group, but are not limited thereto.
  • the carboxy group bonded to X in the formula (1) may be ionized to form a carboxylate anion.
  • the carboxylate anion part (—COO ⁇ ) of the hemiacetal ester derivative represented by the formula (1) and the aminium cation part (—NH 3 + ) of the polyamine (2) in the paste composition of the present invention and a salt structure as shown in the following formula.
  • n, R 1, R 2 , R 3, R 4, R 5 and X are each, n in formula (1), R 1, R 2, R 3, R 4, R 5 and X Has the same meaning as
  • the method for producing the hemiacetal ester derivative (1) is not particularly limited.
  • a tetracarboxylic acid represented by the formula (B) is added to the unsaturated carbon-carbon bond of the cyclic unsaturated ether compound represented by the formula (A). Is added.
  • R 1 , R 2 , R 3 , R 4 and R 5 in the formula (A) and X in the formula (B) represent n, R 1 , R 2 , R in the formula (1), respectively. 3 have the same meanings as R 4, R 5 and X.
  • R 1 in the above formula has the same meaning as R 1 in formula (1).
  • the hemiacetal ester bond thus formed has resistance to hydrolysis, and hardly causes deprotection of the carboxy group due to elimination of the protective group of the carboxy group. Therefore, the stability of the hemiacetal ester derivative (1) in an aqueous medium is high, and as a result, the storage stability of the paste composition of the present invention is excellent.
  • the paste composition of the present invention is preferable for an electrode.
  • hemiacetal ester derivative (1) examples include a 2,3-dihydrofuran derivative represented by the following formula (1-1) and a 3,4-dihydro-furan derivative represented by the following formula (1-2).
  • Preferable examples include at least one selected from the group consisting of a 2H-pyran derivative and a 1-benzofuran derivative represented by the following formula (1-3).
  • the hemiacetal ester derivative (1) is not limited to the specific examples described below.
  • R 1, R 2, R 4, R 5 and X are respectively the same meaning as R 1, R 2, R 4 , R 5 and X in the formula (1).
  • R 1 , R 2 , R 4 and R 5 are preferably all hydrogen atoms.
  • R 1, R 2, R 3, R 4, R 5 and X are each, R 1 in the formula (1), R 2, R 3, R 4, R 5 and X Has the same meaning as In the formula (1-2), R 1 , R 2 , R 3 , R 4 and R 5 are preferably all hydrogen atoms.
  • (1-benzofuran derivative) Another specific example of the hemiacetal ester derivative (1) is a 1-benzofuran derivative represented by the formula (1-3).
  • n 0 in the formula (1), and R 4 and R 5 are bonded to each other to form a six-membered aromatic carbon ring which may have a substituent. Applicable if you do.
  • R 1 , R 2 and X have the same meanings as R 1 , R 2 and X in the formula (1), respectively.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and may be bonded to each other to form a cyclic structure. Good.
  • the halogen atom, the monovalent organic group and the cyclic structure are as described for R 1 and R 2 .
  • R 1 , R 2 , R 6 , R 7 , R 8 and R 9 are preferably all hydrogen atoms.
  • the polyamine (2) is a compound represented by the formula (2).
  • One or more polyamines (2) can be included in the paste composition of the present invention.
  • m is an integer of 2 or more
  • Y is an m-valent organic group or an m-valent organic silicon group containing a siloxane bond.
  • the primary amino group is directly bonded to a carbon atom.
  • the amino group (—NH 2 ) of the polyamine (2) may be an aminium cation (—NH 3 + ).
  • the upper limit of m is not particularly limited, but is preferably 2000, and more preferably 600.
  • the lower limit of m is, for example, 2, preferably 8, more preferably 20, and still more preferably 50.
  • Organic polyamine In the present specification, among the polyamines (2), the polyamine (2) in which Y is an m-valent organic group is particularly referred to as an organic polyamine.
  • Examples of the m-valent organic group include compounds having a basic skeleton of a chain hydrocarbon such as ethylene and propane; compounds having a basic skeleton of a cyclic hydrocarbon such as cyclohexane; and aromatic hydrocarbons such as benzene and naphthalene.
  • a compound having a benzophenone skeleton such as benzophenone; a compound having a diphenyl ether skeleton such as diphenyl ether; a compound having a diphenyl sulfone skeleton such as diphenyl sulfone; a compound having a biphenyl skeleton such as biphenyl; And a group from which m hydrogen atoms have been removed.
  • a chain hydrocarbon such as ethylene and propane
  • compounds having a basic skeleton of a cyclic hydrocarbon such as cyclohexane
  • aromatic hydrocarbons such as benzene and naphthalene.
  • the m-valent organic group preferably does not include a group having reactivity with a carboxy group.
  • examples of the group having reactivity with a carboxy group include, but are not limited to, an amino group, a hydroxy group, a carboxy group, and a vinyloxy group.
  • organic polyamine examples include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3 ' -Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenyl s
  • organic polyamine at least one kind selected from the group consisting of a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group in which a part or all of the hydrogen atoms on the aromatic ring of the exemplified organic polyamine is included May be used.
  • organic polyamine in addition to the exemplified organic polyamines, a polymer having two or more primary amino groups (—NH 2 ) in one molecule (a primary amino group having reactivity with a carboxy group) (Excluding those containing a group).
  • organic polyamines include polystyrene, polyacrylic acid, polyurethane, polyamide, polyimide, polyamideimide and the like whose main or side chains are modified with two or more primary amino groups.
  • at least one selected from the group consisting of polyacrylic acid, polyurethane, polyamide and polyamideimide is preferable.
  • the polymer having two or more primary amino groups in one molecule does not contain a group having reactivity with a carboxy group other than the primary amino group.
  • the group having reactivity with the carboxy group includes, for example, a hydroxy group, a carboxy group, and a vinyloxy group, but is not limited thereto.
  • the organic polyamine further comprises an ethynyl group, a benzocyclobuten-4'-yl group, a vinyl group, an allyl group, a cyano group, and an isopropenyl group, which are cross-linking points when a cross-linking reaction is performed after polyimide formation, according to the purpose.
  • Those obtained by introducing one or more selected from the group into some or all of the hydrogen atoms on the aromatic ring of the exemplified organic polyamine as a substituent may be used.
  • the organic polyamine can be appropriately selected depending on desired physical properties.
  • a rigid diamine such as p-phenylenediamine
  • the finally obtained polyimide can have a low expansion coefficient.
  • the rigid organic diamine include a diamine in which two amino groups are bonded to the same aromatic ring (aromatic diamine).
  • aromatic diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, And 1,4-diaminoanthracene.
  • Dendrimers of polyamines may be used.
  • organic polyamine an organic polyamine in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as a part of a substituent on separate aromatic rings.
  • organic polyamines include benzidine and toluidine.
  • organic polyamine an organic polyamine having a substituent on a benzene ring can also be used. These substituents are monovalent organic groups, but they may be bonded to each other. Specific examples of such organic polyamines include 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4'-diaminobiphenyl, isophthalic dihydrazide and the like.
  • an aminoethylated acrylic polymer or the like can be used as the organic polyamine other than those described above.
  • One preferred embodiment of the aminoethylated acrylic polymer is an acrylic polymer containing a primary amino group in which polyethyleneimine is grafted on a side chain.
  • the main chain of the aminoethylated acrylic polymer is a (meth) acrylic polymer formed from a monomer containing (meth) acrylate and (meth) acrylic acid.
  • One preferred embodiment of the aminoethylated acrylic polymer preferably has a plurality of primary amino groups.
  • the weight average molecular weight of the aminoethylated acrylic polymer is preferably from 5,000 to 100,000.
  • the aminoethylated acrylic polymer may form a salt such as a hydrohalide, for example, a hydrochloride or a hydrobromide.
  • a hydrohalide for example, a hydrochloride or a hydrobromide.
  • One preferred embodiment of the aminoethylated acrylic polymer is preferably water-soluble. Examples of commercially available aminoethyl acrylic polymer exhibiting water solubility, for example, POLYMENT (R) NK-100PM, POLYMENT (R) NK-200PM (all manufactured by Nippon Shokubai Co., Ltd.).
  • siloxane polyamine a polyamino compound in which Y is an m-valent organic silicon group containing a siloxane bond is referred to as a siloxane-based polyamine.
  • Examples of the m-valent organosilicon group containing a siloxane bond include, for example, those obtained by substituting m of the hydrogen atoms of a monovalent hydrocarbon group of an organosilicon compound represented by the following formula with a single bond.
  • k is an integer of 1 or more, and R 11 , R 12 , R 13 , R 14 , R 21 and R 22 each independently represent a monovalent hydrocarbon group, and k ⁇ 2.
  • R 21 may be the same or different, and a plurality of R 22 may be the same or different.
  • siloxane-based polyamine examples include 1,3-bis (3-aminopropyl) tetramethyldisiloxane. However, it is not limited to this.
  • the modulus of elasticity of the polyimide resin obtained by curing the paste composition of the present invention can be reduced, and the glass transition temperature can be adjusted.
  • Organic polyamine which can be used in combination with siloxane-based polyamine an aromatic polyamine is preferable from the viewpoint of heat resistance, and an aromatic diamine is more preferable.
  • an aromatic polyamine can be used.
  • an organic polyamine other than the aromatic diamine can be used in combination depending on the desired physical properties.
  • an organic polyamine an aliphatic polyamine is preferable, and an aliphatic diamine is more preferable.
  • One or more aliphatic diamines can be used.
  • the amount of the organic polyamine other than the aromatic polyamine is preferably not more than 60 mol% of the total amount of the organic polyamine, more preferably not more than 40 mol%. preferable.
  • active materials for secondary batteries examples include a positive electrode active material and a negative electrode active material.
  • the positive electrode active material is not particularly limited, and examples thereof include a composite oxide of lithium and a transition metal, a transition metal oxide, a transition metal sulfide, and a conductive polymer.
  • Specific examples of the composite oxide of lithium and a transition metal include LiCoO 2 , LiNiO 2 , LiFePO 4 , LiMnO 2, and LiMn 2 O 4 , but are not limited thereto.
  • Specific examples of the transition metal oxide are MnO 2 and V 2 O 5 , but are not limited thereto.
  • Specific examples of the transition metal sulfide are MoS 2 and TiS 2 , but are not limited thereto.
  • Specific examples of the conductive polymer include, but are not limited to, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole.
  • the negative electrode active material is not particularly limited, and examples thereof include graphite, amorphous carbon, a fired polymer compound, coke, carbon fiber, conductive polymer, tin, silicon, and metal alloy.
  • a specific example of the polymer compound fired body is obtained by firing and carbonizing a phenol resin or a furan resin, but is not limited thereto.
  • Specific examples of the cokes include pitch coke, needle coke, and petroleum coke, but are not limited thereto.
  • Specific examples of the conductive polymer include, but are not limited to, polyacetylene and polypyrrole.
  • Specific examples of the metal alloy include, but are not limited to, a lithium-tin alloy, a lithium-silicon alloy, a lithium-aluminum alloy, and a lithium-aluminum-manganese alloy.
  • Examples of the negative electrode active material include a carbonaceous material such as amorphous hard carbon in addition to a graphite material. Among these, a graphite material is preferable because of its excellent charge / discharge characteristics, high discharge capacity and potential flatness.
  • Examples of graphite (graphite particles) used as the negative electrode active material include graphite particles such as natural graphite and artificial graphite; bulk mesophase graphite particles obtained by heat-treating mesophase pitch and mesophase spherules using tar and pitch as raw materials.
  • a composite carbon material composed of a graphite material composed of spherical particles and carbon fiber; a negative electrode material formed by mixing and granulating granular graphite, petroleum pitch, and flaky graphite; and attaching flaky graphite to the surface of the granular graphite Negative electrode material obtained by crushing and pulverizing.
  • the aqueous medium is a medium containing water as a main component.
  • water ion exchange water, distilled water, deionized distilled water, RO (Reverse Osmosis; reverse osmosis) water, or the like can be used.
  • RO Reverse Osmosis; reverse osmosis
  • the term "mainly composed of water” means that water is contained in an amount of 60% by mass or more, preferably 75% by mass or more, and more preferably 90% by mass or more.
  • Use of an aqueous medium can contribute to reduction of environmental load.
  • the aqueous medium has a low environmental load and has a low volatility of water.
  • An alcohol or ether that does not adversely affect the drying property may be contained. Examples of the alcohol include methanol, ethanol, n-propanol, 2-propanol (isopropyl alcohol), n-butanol, isobutanol, t-butanol, ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
  • Examples include, but are not limited to, butyl cellosolve, propylene glycol monomethyl ether, and 1- (2-hydroxyethyl) -2-pyrrolidone. These alcohols or ethers can be used alone or in combination of two or more.
  • the content of the alcohol in the aqueous medium is preferably 1% by mass to 40% by mass, and more preferably 3% by mass to 25% by mass, based on the total mass of the aqueous medium. Is more preferable.
  • the content of the alcohol is 1% by mass or more, the effect of improving the wettability of the paste composition with respect to the substrate is more exerted, and cissing of the paste composition on the substrate is suppressed.
  • the alcohol content is 40% by mass or less, crystals do not precipitate in the paste composition, and it is easy to arrange the paste composition on the substrate in a film form.
  • the improvement effect by adding the alcohol may be insufficient. If the content of the alcohol is more than 40% by mass, crystals may be precipitated in the paste composition, and it may be difficult to arrange the paste composition in a film on a substrate.
  • the paste composition of the present invention may contain other components other than the above components, as long as the effects of the present invention are not impaired.
  • examples of such other components include, but are not limited to, volatile amines, polymer components, additives, and organic solvents.
  • a volatile amine may be added.
  • the type of volatile amine that can be contained in the paste composition of the present invention is not particularly limited, and examples thereof include ammonia, trimethylamine, triethylamine, tributylamine, and N-methylmorpholine. One of these volatile amines can be used alone, or two or more can be used in combination.
  • the content of the volatile amine that can be contained in the paste composition of the present invention is not particularly limited, but does not exceed the number of moles of carboxy groups that are not used in the addition reaction between the cyclic unsaturated ether compound and the tetracarboxylic acid. Is preferred.
  • the paste composition of the present invention may further contain a polymer component other than polyimide as long as its properties are not impaired.
  • a polymer component other than polyimide for example, an aqueous dispersion of styrene-butadiene rubber (SBR) generally used in the current state of the art can be used in a ratio that does not impair its properties.
  • SBR styrene-butadiene rubber
  • the polymer component is added to the paste composition of the present invention, for example, it is prepared by blending each component by an appropriate mixing method such as roll mixing, Banbury mixing, screw mixing, stirring mixing, orbital rotation type rotation mixing, and the like. can do.
  • the paste composition of the present invention may contain, if necessary, a reinforcing material, a filler, an antioxidant, an antioxidant, a light stabilizer, an anti-scorch agent, other crosslinking retarders, a plasticizer, a preservative, and a processing aid. And one or more additives selected from the group consisting of lubricants, pressure-sensitive adhesives, lubricants, flame retardants, fungicides, antistatic agents, colorants and surfactants.
  • the paste composition of the present invention substantially contains an organic solvent except for an organic solvent such as an alcohol and an ether contained in an aqueous medium, an organic solvent contained in a volatile amine, and a trace amount of an organic solvent unavoidably mixed. Preferably not.
  • substantially contains no organic solvent means that the content of the organic solvent in the paste composition of the present invention is 0.1% by mass or less based on the entire paste composition. .
  • organic solvent examples include, for example, N-methyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N- Organic solvents having a high environmental load, such as dimethylacetamide, N-methylcaprolactam, acetone, ⁇ -butyrolactone, methylethylketone and methylisobutylketone.
  • the viscosity of the paste composition of the present invention is not particularly limited, but is quantitatively grasped using a general viscometer such as a B-type viscometer, an E-type viscometer, or a Zahn cup, and wets the base material or the current collector. A range that does not affect sex may be used.
  • the method for producing the paste composition of the present invention is not particularly limited, and examples thereof include the following method.
  • First, the active material for a secondary battery is put into a rotation-revolution type mixer, and is stirred at 30 to 500 rpm.
  • the composition for coating an active material for a secondary battery prepared by stirring a mixture of the hemiacetal ester derivative (1), the polyamine (2) and the aqueous medium is added to the active material for a secondary battery in this state for 1 to 90 minutes. And mix dropwise. If necessary, a conductive additive is mixed. While stirring, the temperature is raised to 50 to 150 ° C., the pressure is reduced to 0.007 to 0.04 MPa, and the temperature is maintained for 10 to 150 minutes.
  • the electrode material for a secondary battery of the present invention includes a hemiacetal ester derivative (1), a polyamine (2), and an active material for a secondary battery.
  • the hemiacetal ester derivative (1), the polyamine (2), and the active material for a secondary battery are as described above.
  • the secondary battery electrode material of the present invention can be obtained, for example, by drying the paste composition of the present invention to remove the aqueous medium.
  • the dispersion medium is preferably removed.
  • the electrode for a secondary battery of the present invention has the electrode material for a secondary battery of the present invention.
  • the method for producing the electrode for a secondary battery of the present invention is not particularly limited.
  • the paste composition of the present invention is applied to a current collector using a coating device such as a doctor blade, and then dried to remove the aqueous medium, and then pressed by a press machine if necessary.
  • the secondary battery electrode of the present invention is obtained.
  • an electrode having a desired thickness may be produced by coating multiple layers.
  • the binder blending ratio in the vicinity of the separator may be increased for the purpose of achieving the protection of the electrode for a secondary battery of the present invention against overheating on the separator side.
  • the binder blending ratio in the vicinity of the current collector may be increased for the purpose of achieving the protection of the electrode for a secondary battery of the present invention against overheating on the current collector side.
  • the binder means a component such as a hemiacetal ester derivative (1) and a polyamine (2), excluding the active material for a secondary battery, among the components constituting the electrode for a secondary battery of the present invention.
  • the paste composition of the present invention contains a positive electrode active material as a secondary battery active material, a positive electrode for a secondary battery is obtained, and when the paste composition contains a negative electrode active material, a negative electrode for a secondary battery is obtained.
  • various known additives such as a conductive agent and a binder can be appropriately used.
  • the conductive agent include a graphitized product and carbon black.
  • the binder include polymer compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, tetrafluoroethylene, styrene butadiene rubber, polyethylene, and polypropylene.
  • a conductive agent examples include a graphitized product and carbon black.
  • the binder those exhibiting chemical and electrochemical stability to the electrolyte are preferable.
  • fluorine-based resin powders such as polytetrafluoroethylene and polyvinylidene fluoride; resin powders such as polyethylene and polyvinyl alcohol Carboxymethyl cellulose; and the like.
  • the secondary battery of the present invention has the secondary battery electrode of the present invention. That is, the structure of the secondary battery of the present invention is the same as that of the conventional secondary battery, except that the secondary battery electrode of the present invention is used as the positive electrode and / or the negative electrode.
  • the secondary battery of the present invention is obtained by combining electrodes serving as counter electrodes, storing the battery together with the separator in a cell container, injecting an electrolytic solution, and sealing the cell container.
  • a positive electrode is formed on one surface of the current collector, and a negative electrode is formed on the other surface to produce a bipolar electrode.
  • the bipolar electrode is laminated with a separator, stored in a cell container, and injected with an electrolyte. It can also be obtained by sealing the cell container.
  • Both the positive electrode and the negative electrode may be used as a secondary battery electrode of the present invention to form a secondary battery.
  • the secondary battery of the present invention may be an all-solid-state battery or an all-resin battery in which the electrolyte is reduced or does not contain the electrolyte.
  • ⁇ Separator> As the separator, a microporous film of a polyethylene or polypropylene film; a multilayer film of a porous polyethylene film and polypropylene; a nonwoven fabric of porous polyimide, polyester fiber, aramid fiber, glass fiber, and the like; and silica on the surface thereof , Alumina, titania and other fine ceramic particles attached thereto.
  • ⁇ Current collector> examples include copper, aluminum, titanium, stainless steel, nickel, calcined carbon, a conductive polymer, and a conductive glass.
  • an electrolyte containing an electrolyte and a non-aqueous solvent, which is used for manufacturing a secondary battery, can be used.
  • Electrodes As the electrolyte, those used in ordinary electrolytic solutions can be used. For example, lithium salts of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 or LiClO 4 , or LiN (CF 3 SO 2) ) 2 , lithium salts of organic acids such as LiN (C 2 F 5 SO 2 ) 2 or LiC (CF 3 SO 2 ) 3 . Of these, LiPF 6 is preferred from the viewpoint of battery output and charge / discharge cycle characteristics.
  • Non-aqueous solvent those used in ordinary electrolytic solutions and the like can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylate esters, cyclic or chain ethers, phosphate esters, nitriles Compounds, amide compounds, sulfones, sulfolanes and the like and mixtures thereof can be used.
  • One type of non-aqueous solvent may be used alone, or two or more types may be used in combination.
  • lactone compound examples include, for example, a 5-membered ring (such as ⁇ -butyrolactone and ⁇ -valerolactone) and a 6-membered lactone compound (such as ⁇ -valerolactone).
  • Examples of the cyclic carbonate include propylene carbonate, ethylene carbonate, butylene carbonate and the like.
  • Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, di-n-propyl carbonate and the like.
  • Examples of the chain carboxylate include methyl acetate, ethyl acetate, propyl acetate and methyl propionate.
  • Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, 1,3-dioxolan, 1,4-dioxane and the like.
  • Examples of the chain ether include dimethoxymethane and 1,2-dimethoxyethane.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, and tri (trichloromethyl phosphate).
  • Tri (trifluoroethyl) phosphate tri (tripperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphosphoran-2-one, 2-trifluoroethoxy-1,3,3 Examples include 2-dioxaphospholane-2-one and 2-methoxyethoxy-1,3,2-dioxaphospholane-2-one.
  • Examples of the nitrile compound include acetonitrile.
  • Examples of the amide compound include DMF.
  • Examples of the sulfone include dimethyl sulfone and diethyl sulfone.
  • Non-aqueous solvent (Preferred non-aqueous solvent)
  • lactone compounds, cyclic carbonates, chain carbonates or phosphates are preferable, and lactone compounds, cyclic carbonates or chain carbonates are more preferable,
  • a mixture of a cyclic carbonate and a chain carbonate is more preferred.
  • the mixture of the cyclic carbonate and the chain carbonate a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) is preferable.
  • Example 1 Preparation of paste composition (negative electrode mixture paste) In a separable flask (300 mL; cylindrical) equipped with a stirrer, 1,2,4,5-benzenetetracarboxylic acid (11.1 g) and water (45.9 g) were added. ) was added and stirred and mixed at 25 ° C. for 10 minutes. Thereafter, 2,3-dihydrofuran (3.8 g) was added, and the mixture was further stirred and mixed at 40 ° C. for 90 minutes to obtain an aqueous dispersion of a dihydrofuran derivative.
  • aqueous dispersion of the dihydrofuran derivative 71.6 g
  • water (72.4 g) were added and mixed by stirring at 40 ° C. for 3 hours to obtain an aqueous dispersion containing a dihydrofuran derivative and a polyamine.
  • a negative electrode material powder (graphitized mesophase sphere, average particle diameter 19 ⁇ m, specific surface area 2.1 m 2 / g) (98 parts by mass) and a binder (carboxymethyl cellulose) (1 part by mass) were prepared as described above.
  • the prepared negative electrode mixture paste was applied on a copper foil so as to have a uniform thickness, and the solvent was evaporated and dried at 90 ° C. in vacuum to form a negative electrode mixture layer.
  • the negative electrode mixture layer was pressed by a hand press.
  • the working electrode (negative electrode) closely adhered to the current collector made of the copper foil was produced by punching the copper foil and the negative electrode mixture layer into a circular shape having a diameter of 15.5 mm.
  • the electrode density was determined from the mass and thickness of the negative electrode. Since the heating temperature was 90 ° C., the hemiacetal ester derivative did not react with the polyamine, and was in a mixture state.
  • FIG. 1 is a sectional view showing an evaluation battery.
  • the peripheral edges of the outer cup 1 and the outer can 3 are caulked via an insulating gasket 6 to form a sealed structure.
  • a current collector 7 a, a counter electrode 4, a separator 5, a working electrode (negative electrode) 2, and The current collector 7b is stacked.
  • Such an evaluation battery was manufactured as follows.
  • the separator 5 impregnated with the electrolyte was laminated between the working electrode 2 closely contacted with the current collector 7b and the counter electrode 4 closely adhered to the current collector 7a. Thereafter, the working electrode 2 was accommodated in the outer cup 1, and the counter electrode 4 was accommodated in the outer can 3. The outer cup 1 and the outer can 3 were put together, and the peripheral edge of the outer cup 1 and the outer can 3 was caulked via an insulating gasket 6 and sealed.
  • the electrolyte and separator used at the time of battery production were those produced under the following conditions.
  • Electrolyte Solution and Separator LiPF 6 was dissolved in a mixed solvent of ethylene carbonate (30% by volume) and propylene carbonate (70% by volume) at a concentration of 1 mol / L to obtain a non-aqueous electrolyte.
  • the prepared non-aqueous electrolyte was impregnated into a porous polypropylene body (thickness: 20 ⁇ m) to obtain an electrolyte-impregnated separator.
  • Charge / discharge test Using the produced evaluation battery, a charge / discharge test was performed as follows to evaluate various characteristics. After constant current charging of 0.9 mA was performed until the circuit voltage reached 0 mV, switching to constant voltage charging was performed when the circuit voltage reached 0 mV. : MAh / g). Thereafter, the operation was suspended for 10 minutes. Next, constant current discharge was performed at a current value of 0.9 mA until the circuit voltage reached 1.5 V, and the discharge capacity (unit: mAh / g) was determined from the amount of current supplied during this time. This was the first cycle. Next, charging and discharging were performed in the same manner as in the first cycle, except that the charging current was 1 C and the discharging current was 2 C. Thereafter, charging and discharging were performed in the same manner as in the first cycle, with the charging current being 0.5 C and the discharging current being 2.5 C.
  • the irreversible capacity (initial charge / discharge loss) (unit: mAh / g) was calculated from the following equation (1).
  • Irreversible capacity charge capacity in first cycle-discharge capacity in first cycle (1)
  • the 1C charging rate (unit:%) was calculated from the following equation (2).
  • 1C charge rate 100 ⁇ (charge capacity of CC portion at 1C current value / discharge capacity of first cycle) (2)
  • the 2C discharge rate (unit:%) was calculated from the following equation (3).
  • 2C discharge rate 100 ⁇ (discharge capacity at 2C current value / discharge capacity in first cycle) (3)
  • Electrode expansion coefficient 100 ⁇ ⁇ (thickness of collected negative electrode) ⁇ (thickness of copper foil) ⁇ / ⁇ (thickness of negative electrode before starting charge / discharge test) ⁇ (thickness of copper foil) ⁇
  • Electrode heat breakdown test The negative electrode mixture paste prepared as described above was applied on a copper foil so as to have a uniform thickness, and the solvent was evaporated and dried at 90 ° C in vacuum to form a negative electrode mixture layer. Next, the negative electrode mixture layer was pressed by a hand press. Further, the copper foil and the negative electrode mixture layer were cut into a square of 5.0 cm, and a negative electrode in close contact with a current collector made of the copper foil was produced. The prepared negative electrode in close contact with the current collector was fixed to a glass plate with a polyimide tape, and was subjected to a heat treatment for 20 minutes in a muffle furnace set at 350 ° C. in advance.
  • the state of the electrode (negative electrode) after the heat treatment was evaluated from the viewpoint of damage to the electrode, damage to the current collector, and adhesion between the electrode and the current collector.
  • the evaluation criteria were as follows. The results are shown in Table 2 below. A: The electrode and the current collector were not damaged, and the electrode and the current collector were not separated. B: The electrode and the current collector were not damaged, and the electrode and the current collector were not separated. However, the electrode showed signs of carbonization. C: The electrode was damaged, the current collector was damaged, or the electrode was separated from the current collector.
  • Example 2 Preparation of paste composition (negative electrode mixture paste) In a separable flask (300 mL; cylindrical) equipped with a stirrer, 2,3,3,4-biphenyltetracarboxylic acid (8.7 g) and water (105.0 g) ) was added and stirred and mixed at 25 ° C. for 10 minutes. Thereafter, 2,3-benzofuran (3.0 g) was added, and the mixture was further stirred and mixed at 25 ° C. for 45 minutes to obtain an aqueous dispersion of a benzofuran derivative.
  • a negative electrode material powder (graphitized mesophase sphere, average particle diameter 19 ⁇ m, specific surface area 2.1 m 2 / g) (98 parts by mass) and a binder (carboxymethyl cellulose) (1 part by mass) were prepared as described above.
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 2 below.
  • Example 3 Preparation of Paste Composition (Negative Electrode Mixing Paste) In a separable flask (300 mL; cylindrical) equipped with a stirrer, dicyclohexylmethane 4,4′-diisocyanate (23.7 g: isomer mixture), polytetramethylene Ether glycol (49.0 g: average molecular weight 2000) and dimethylolbutanoic acid (5.9 g) were added and mixed at 90 ° C. for 90 minutes. Thereafter, 2-hydroxyethyl methacrylate (3.4 g) was added as a hydroxyl group-containing acrylic raw material, and the mixture was further stirred for 90 minutes to obtain a urethane polymer. Butyl methacrylate (18.1 g) was added to the obtained urethane-based polymer to obtain a mixture of the urethane-based polymer and butyl methacrylate.
  • a mixture of the urethane-based polymer and butyl methacrylate, and a mixture of a dihydropyran derivative, triethylamine, and adipic dihydrazide were mixed, and warm water was added to obtain a mixed solution.
  • the mixed solution was prepared such that the amount of the residual residue upon drying was 37% by mass.
  • Dimethyl 2,2'-azobis (isobutyrate) was added as a polymerization initiator to the prepared mixed solution, and stirring was continued for 120 minutes while heating to 80 ° C.
  • the dihydropyran derivative was also dispersed in the obtained aqueous solution.
  • a negative electrode material powder (graphitized mesophase sphere, average particle diameter 19 ⁇ m, specific surface area 2.1 m 2 / g) (98 parts by mass) and a binder (carboxymethyl cellulose) (1 part by mass) were prepared as described above.
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 2 below.
  • paste composition (negative electrode mixture paste) 98 parts by mass of negative electrode material powder (graphitized mesophase spheres, average particle diameter 19 ⁇ m, specific surface area 2.1 m 2 / g), and 1 part of binder (carboxymethyl cellulose) 1 part by mass of styrene butadiene rubber (EQ-Lib-SBR, manufactured by MTI, USA) and water were added, and the mixture was stirred for 5 minutes to prepare a negative electrode mixture paste. The amount of water was adjusted such that the solid content (solute) content in the negative electrode mixture paste became 50% by mass.
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 2 below.
  • Comparative Example 1 uses a widely used styrene-butadiene rubber (SBR) as a typical material of an active material-coated resin that can be used in an aqueous environment.
  • SBR styrene-butadiene rubber
  • Example 4 Preparation of Paste Composition (Positive Electrode Mix Paste) Positive electrode material powder (carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g) (97 parts by mass) and Example The aqueous dispersion containing the dihydrofuran derivative and the polyamine obtained in 1 (3 parts by mass in solid content excluding the aqueous medium) was added with water, and stirred for 5 minutes to prepare a positive electrode mixture paste. The amount of water was adjusted so that the solid content (solute) content in the positive electrode mixture paste became 50% by mass.
  • Positive electrode material powder carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g
  • Example 4 The aqueous dispersion containing the dihydrofuran derivative and the polyamine obtained in 1 (3 parts by mass in solid content excluding the aqueous medium
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 3 below.
  • Example 5 Preparation of Paste Composition (Positive Electrode Mix Paste) Positive electrode material powder (carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g) (97 parts by mass) and Example Water was added to the aqueous dispersion containing the benzofuran derivative and polyamine obtained in 2 (3 parts by mass in terms of solid content excluding the aqueous medium), and the mixture was stirred for 5 minutes to prepare a positive electrode mixture paste. The amount of water was adjusted so that the solid content (solute) content in the positive electrode mixture paste became 50% by mass.
  • Positive electrode material powder carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g
  • Example Water was added to the aqueous dispersion containing the benzofuran derivative and polyamine obtained in 2 (3 parts by mass in terms of solid content excluding the
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 3 below.
  • Example 6 Preparation of Paste Composition (Positive Electrode Mix Paste) Positive electrode material powder (carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g) (97 parts by mass) and Example An acrylic copolymer urethane-based polyamine aqueous solution in which the dihydropyran derivative obtained in 3 was dispersed (3 parts by mass in solid content excluding the aqueous medium) and water were added, and the mixture was stirred for 5 minutes to prepare a positive electrode mixture paste. The amount of water was adjusted so that the solid content (solute) content in the positive electrode mixture paste became 50% by mass.
  • Positive electrode material powder carbon-coated LiFePO 4 , GN-198-S manufactured by BTR, average particle diameter 4 ⁇ m, specific surface area 11 m 2 / g
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 3 below.
  • the electrode was subjected to a heat-resistant breakdown test in the same manner as in Example 1. The test results are shown in Table 3 below.
  • the electrodes (positive electrodes) of Examples 4 to 6 were not broken even by heating at 350 ° C.
  • the electrode of Comparative Example 2 was broken by heating at 350 ° C.
  • Comparative Example 2 uses styrene-butadiene rubber (SBR), which is widely used as a typical material of an active material-coated resin that can be used in an aqueous environment. could not.
  • SBR styrene-butadiene rubber

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Abstract

La présente invention concerne une composition de pâte qui permet la production d'une batterie secondaire qui présente une sécurité élevée contre la chaleur. Cette composition de pâte contient : un dérivé d'ester d'hémiacétal représenté par la formule (1) ; une polyamine représentée par la formule (2) ; un matériau actif pour des batteries secondaires ; et un milieu aqueux.
PCT/JP2019/035239 2018-10-03 2019-09-06 Composition de pâte, matériau d'électrode pour batteries secondaires, électrode pour batteries secondaires et batterie secondaire Ceased WO2020071056A1 (fr)

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JP2020505930A JP7011039B2 (ja) 2018-10-03 2019-09-06 ペースト組成物、二次電池用電極材料、二次電池用電極および二次電池

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TWI848743B (zh) * 2022-06-23 2024-07-11 恆越綠能實業有限公司 降溫滅火材料及鋰電池模組

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JP2023010166A (ja) * 2021-07-09 2023-01-20 Ａｐｂ株式会社 二次電池モジュール、およびそれによって実行する方法
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