TW201921790A - Composition for current collector - Google Patents

Composition for current collector

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Publication number
TW201921790A
TW201921790A TW107119739A TW107119739A TW201921790A TW 201921790 A TW201921790 A TW 201921790A TW 107119739 A TW107119739 A TW 107119739A TW 107119739 A TW107119739 A TW 107119739A TW 201921790 A TW201921790 A TW 201921790A
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TW
Taiwan
Prior art keywords
composition
current collector
acid
group
battery
Prior art date
Application number
TW107119739A
Other languages
Chinese (zh)
Inventor
馬場健
Original Assignee
日商協立化學產業股份有限公司
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Publication of TW201921790A publication Critical patent/TW201921790A/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention can improve adhesive property between a current collector and an active material or an active material layer and can improve a cycle life. The present invention pertains to: a composition for a current collector of a battery or an electric double layer capacitor, the composition comprising polyacrylamide and at least one selected from the group consisting of an organic acid, an organic acid anhydride, an inorganic acid, a metal salt of an organic acid, and a metal salt of an inorganic acid; a composition for forming an undercoat layer, said composition comprising the composition for a current collector; a binder composition comprising the composition for a current collector; a composition for forming an electrode, said composition comprising the binder composition and an active material; a current collector of a battery or an electric double layer capacitor, the current collector being coated with the composition for a current collector; and a battery or an electric double layer capacitor comprising the current collector of a battery or an electric double layer capacitor.

Description

集電體用組成物Composition for current collector

本發明係關於電池或電雙層電容器之集電體用組成物、經其塗佈之電池或電雙層電容器之集電體，及含有該電池或電雙層電容器之集電體的電池或電雙層電容器。The present invention relates to a composition for a current collector of a battery or an electric double-layer capacitor, a coated current collector of the battery or an electric double-layer capacitor, and a battery or a battery containing the current collector of the battery or the electric double-layer capacitor. Electric double-layer capacitor.

輕量且電壓高，容量亦大之鋰離子蓄電池，或充放電速率特性良好的電雙層電容器，係作為行動電話或筆記型電腦等之行動機器、數位相機等之攜帶式機器、車輛或家庭用的電源而廣為實用化，成為生活不可缺的電能儲存裝置。Light-weight, high-voltage, large-capacity lithium-ion batteries, or electric double-layer capacitors with good charge-discharge rate characteristics, are used as mobile devices such as mobile phones or notebook computers, portable devices such as digital cameras, vehicles, or homes The power supply used is widely practical and has become an indispensable power storage device for life.

以鋰離子蓄電池為代表之蓄電池，具有以隔離膜隔離之正極片與負極片的組合之構造，作為基本構造。於蓄電池，係要求如充放電之效率、循環壽命的電池特性。為了充分發揮作為如此之電池的特性，為了提高電池集電體與活性物質層間之密合性，已知有於電池集電體設置導電性的底塗層，且於該導電性底塗層之表面形成活性物質層的方法(專利文獻1)。作為提高蓄電池之循環特性的方法，另一方面，為了提高電池集電體與活性物質之間的密合性，已知有使用由含有合成橡膠系乳膠型黏合劑、纖維素系黏合劑及丙烯醯胺系水溶性高分子之黏合劑，與活性物質所構成之混合物，來形成活性物質層的方法(專利文獻2)。Lithium-ion batteries, represented by lithium-ion batteries, have a combination of a positive electrode sheet and a negative electrode sheet separated by a separator, as a basic structure. For batteries, battery characteristics such as charge and discharge efficiency and cycle life are required. In order to give full play to the characteristics of such a battery and to improve the adhesion between the battery current collector and the active material layer, it is known to provide a conductive undercoat layer on the battery current collector, A method of forming an active material layer on the surface (Patent Document 1). As a method for improving the cycle characteristics of a storage battery, on the other hand, in order to improve the adhesion between a battery current collector and an active material, it is known to use a synthetic rubber-based latex-based adhesive, a cellulose-based adhesive, and propylene. Method for forming an active material layer by mixing a binder of an ammonium-based water-soluble polymer with an active material (Patent Document 2).

於正極片及負極片，係存在有於集電體形成有活性物質層的塗佈部，與為了連接電極端子而未塗佈有活性物質層的未塗佈部。於未塗佈部，係露出有鋁或銅等之集電體，但此係因施加外力等之要因而於電池內部產生短路時，在安全性方面係有問題。由於伴隨電池之大容量化，發熱量亦增加，故例如於適於車載用等之電源用途的電池中，該問題係嚴重的。對此問題，揭示有於層合於集電體之活性物質層與未塗佈部的交界，藉由含有固體絕緣物之絕緣性溶液而形成絕緣構件的方法(專利文獻3)。 [先前技術文獻] [專利文獻]In the positive electrode sheet and the negative electrode sheet, there are a coated portion where an active material layer is formed on a current collector, and an uncoated portion which is not coated with an active material layer to connect an electrode terminal. In the uncoated portion, a current collector such as aluminum or copper is exposed, but this is a problem in terms of safety when a short circuit occurs inside the battery due to an external force or the like. As the capacity of the battery increases, the amount of heat generation also increases. This problem is serious, for example, in batteries suitable for power supply applications such as automotive applications. In response to this problem, a method for forming an insulating member by using an insulating solution containing a solid insulator at the interface between the active material layer laminated on the current collector and the uncoated portion is disclosed (Patent Document 3). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開昭63-121265公報 　　[專利文獻2]日本特開2005-203370號公報 　　[專利文獻3]國際公開第2016/067706號[Patent Document 1] Japanese Patent Laid-Open No. 63-121265 [Patent Document 2] Japanese Patent Laid-Open No. 2005-203370 [Patent Document 3] International Publication No. 2016/067706

[發明所欲解決之課題][Problems to be Solved by the Invention]

但是，專利文獻2所揭示之混合物中，集電體與活性物質層或活性物質之密合性並不充分。又，專利文獻3之方法中，僅於集電體與活性物質層之交界附著絕緣性溶液，於密合性方面尚存有課題。又，對絕緣材料係要求絕緣性之提高、於密合性方面的進一步改善。另一方面，於集電體上形成絕緣性之構件時，於集電體與活性物質層之電子的交換受到阻礙，因此通常無法避免作為電池之特性，特別是循環壽命性受到妨礙。However, in the mixture disclosed in Patent Document 2, the adhesion between the current collector and the active material layer or the active material is insufficient. Further, in the method of Patent Document 3, an insulating solution is adhered only at the interface between the current collector and the active material layer, and there is still a problem in terms of adhesion. In addition, insulation materials are required to have improved insulation properties and further improved adhesion. On the other hand, when an insulating member is formed on the current collector, the exchange of electrons between the current collector and the active material layer is hindered. Therefore, it is generally unavoidable that the characteristics as a battery, particularly the cycle life, are hindered.

本發明之課題係提供可提高集電體與活性物質層或活性物質之密合性，且提高循環壽命性之電池或電雙層電容器之集電體用組成物。 [用以解決課題之手段]An object of the present invention is to provide a composition for a current collector of a battery or an electric double-layer capacitor, which can improve the adhesion between the current collector and the active material layer or the active material and improve the cycle life. [Means to solve the problem]

本發明係關於以下者。 　　[1]一種電池或電雙層電容器之集電體用組成物，其含有聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種。 　　[2]如[1]之集電體用組成物，其中聚丙烯醯胺之重量平均分子量，為1,000,000～100,000,000。 　　[3]如[1]或[2]之集電體用組成物，其中有機酸，為選自由苯均四酸、1,2,3-丙烷三羧酸、天門冬胺酸、蜜石酸及聚丙烯酸所成之群的至少1種；有機酸之無水物，為選自由前述有機酸之無水物所成之群的至少1種；無機酸，為選自由鹽酸、氫氟酸、6氟化磷酸及4氟化硼酸所成之群的至少1種；有機酸之金屬鹽，為選自由前述有機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種；且無機酸之金屬鹽，為選自由前述無機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種。 　　[4]如[1]～[3]中任一項之集電體用組成物，其進一步含有選自由合成橡膠系乳膠型黏合劑、苯乙烯丁二烯橡膠乳膠及腈丁二烯橡膠乳膠所成之群的至少1種。 　　[5]如[1]～[4]中任一項之集電體用組成物，其進一步含有選自由碳黑、鎳粉、鐵粉、氧化鋁、二氧化矽、氧化鈦及氧化鋯所成之群的至少1種。 　　[6]一種底塗層形成用組成物，其係由如[1]～[5]中任一項之集電體用組成物所構成。 　　[7]一種黏合劑組成物，其係由如[1]～[5]中任一項之集電體用組成物所構成。 　　[8]一種電極形成用組成物，其含有如[7]之黏合劑組成物與活性物質。 　　[9]一種電池或電雙層電容器之集電體之製造方法，其包含 　　將如[6]之底塗層形成用組成物塗佈於集電體上，而形成底塗層形成用組成物之塗膜之步驟，及 　　於塗佈有前述底塗層形成用組成物的集電體上，塗佈導電性之活性物質之步驟。 　　[10]一種電池或電雙層電容器之集電體之製造方法，其包含 　　將如[8]之電極形成用組成物塗佈於集電體上，而形成電極形成用組成物之塗膜之步驟。 　　[11]一種電池或電雙層電容器之集電體，其係經如[1]～[8]中任一項之組成物塗覆。 　　[12]一種電池或電雙層電容器，其包含如[11]之電池或電雙層電容器之集電體。 [發明之效果]The present invention relates to the following. [1] A composition for a current collector of a battery or an electric double-layer capacitor, comprising polyacrylamide, and a metal selected from the group consisting of an organic acid, an anhydrous organic acid, an inorganic acid, a metal salt of an organic acid, and a metal of an inorganic acid At least one species of salt group. [2] The composition for a current collector according to [1], wherein the weight average molecular weight of the polypropylene amidamine is 1,000,000 to 100,000,000. [3] The composition for a current collector according to [1] or [2], wherein the organic acid is selected from the group consisting of pyromellitic acid, 1,2,3-propanetricarboxylic acid, aspartic acid, and tartaric acid And at least one of the group consisting of polyacrylic acid; the anhydrous form of the organic acid is at least one kind selected from the group consisting of the aforementioned anhydrous form of the organic acid; the inorganic acid is selected from the group consisting of hydrochloric acid, hydrofluoric acid, and 6 fluorine At least one kind of group consisting of phosphoric acid and 4-fluorinated boric acid; the metal salt of the organic acid is at least one kind selected from the group consisting of the organic acid and a salt of lithium, sodium, potassium, or calcium; and an inorganic acid The metal salt is at least one selected from the group consisting of the inorganic acid and a salt of lithium, sodium, potassium, or calcium. [4] The composition for a current collector according to any one of [1] to [3], further comprising a compound selected from a synthetic rubber-based latex-type adhesive, a styrene butadiene rubber latex, and a nitrile butadiene rubber latex. At least one of the groups formed. [5] The composition for a current collector according to any one of [1] to [4], further comprising a member selected from the group consisting of carbon black, nickel powder, iron powder, aluminum oxide, silicon dioxide, titanium oxide, and zirconia. Group of at least one. [6] A composition for forming an undercoat layer, comprising the composition for a current collector according to any one of [1] to [5]. [7] An adhesive composition comprising the composition for a current collector according to any one of [1] to [5]. [8] A composition for forming an electrode, which contains a binder composition such as [7] and an active material. [9] A method for manufacturing a current collector for a battery or an electric double-layer capacitor, comprising coating the current collector with the composition for forming an undercoat layer as described in [6] to form the composition for forming an undercoat layer. A step of applying a coating film, and a step of applying a conductive active material to a current collector coated with the aforementioned composition for forming an undercoat layer. [10] A method for manufacturing a current collector for a battery or an electric double-layer capacitor, comprising applying the electrode forming composition as described in [8] on the current collector to form a coating film of the electrode forming composition. step. [11] A current collector for a battery or an electric double-layer capacitor, which is coated with a composition according to any one of [1] to [8]. [12] A battery or an electric double-layer capacitor, which comprises a current collector of the battery or the electric double-layer capacitor as in [11]. [Effect of the invention]

依照本發明，可提供可提高集電體與活性物質層或活性物質之密合性，且提高循環壽命性的電池或電雙層電容器之集電體用組成物。According to the present invention, it is possible to provide a composition for a current collector of a battery or an electric double-layer capacitor that can improve the adhesion between the current collector and the active material layer or the active material and improve the cycle life.

[電池或電雙層電容器之集電體用組成物] 　　電池或電雙層電容器之集電體用組成物(以下亦僅稱為「集電體用組成物」)，含有聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種。[Composition for current collector of battery or electric double-layer capacitor] 组成 Composition for current collector of battery or electric double-layer capacitor (hereinafter also simply referred to as "composition for current collector"), which contains polypropylene amine, At least one selected from the group consisting of an organic acid, an anhydrous substance of an organic acid, an inorganic acid, a metal salt of an organic acid, and a metal salt of an inorganic acid.

[聚丙烯醯胺] 　　聚丙烯醯胺，為對集電體用組成物賦予接著性，造成集電體與活性物質層或活性物質之密合性的高分子化合物。聚丙烯醯胺，為丙烯醯胺之均聚物或共聚物，可列舉非離子系、陰離子系、陽離子系或兩性系之聚丙烯醯胺。[Polyacrylamide] Polyacrylamide is a polymer compound that imparts adhesiveness to a composition for a current collector and causes adhesion between the current collector and the active material layer or the active material. Polyacrylamide is a homopolymer or copolymer of acrylamide, and examples thereof include nonionic, anionic, cationic or amphoteric polyacrylamide.

聚丙烯醯胺之重量平均分子量，較佳為1,000,000～100,000,000、更佳為3,000,000～50,000,000、特佳為5,000,000～30,000,000。聚丙烯醯胺之重量平均分子量若為前述範圍，則可更提高集電體與活性物質層或活性物質之密合性，且更提高循環壽命性。本說明書中，重量平均分子量，意指使用GPC(凝膠滲透層析)所求得之以聚環氧乙烷換算之重量平均分子量。The weight average molecular weight of the polyacrylamide is preferably 1,000,000 to 100,000,000, more preferably 3,000,000 to 50,000,000, and particularly preferably 5,000,000 to 30,000,000. If the weight average molecular weight of the polyacrylamide is in the aforementioned range, the adhesion between the current collector and the active material layer or the active material can be further improved, and the cycle life can be further improved. In this specification, a weight average molecular weight means the weight average molecular weight in terms of polyethylene oxide calculated | required using GPC (gel permeation chromatography).

聚丙烯醯胺之市售品，可列舉Accofloc N-102(MT AQUAPOLYMER股份有限公司製)、Accofloc A-102(MT AQUAPOLYMER股份有限公司製)、Sunfloc NOP(三洋化成工業股份有限公司製)、Sunfloc N-500P(三洋化成工業股份有限公司製)等。 　　聚丙烯醯胺，可為單獨或2種以上之組合。Examples of commercially available products of polyacrylamide include Accofloc N-102 (manufactured by MT AQUAPOLYMER Co., Ltd.), Accofloc A-102 (manufactured by MT AQUAPOLYMER Co., Ltd.), Sunfloc NOP (manufactured by Sanyo Chemical Industry Co., Ltd.), and Sunfloc N-500P (manufactured by Sanyo Chemical Industry Co., Ltd.), etc. Polyacrylamide can be used alone or in combination of two or more.

[有機酸] 　　有機酸，係指具有由碳原子所構成之分子構造，且於其分子中具有至少1個之於中性附近之pH氫離子會解離的官能基(例如羧基、膦酸基或碸基)之酸。[Organic acid] Organic acid refers to a molecular structure composed of carbon atoms and having at least one functional group (such as a carboxyl group, a phosphonic acid group or Amidino).

有機酸較佳為於分子中具有至少2個羧基之酸的多羧酸。多羧酸例如可列舉選自由琥珀酸、己二酸、馬來酸、鄰苯二甲酸、偏苯三甲酸、檸檬酸、1,2,3-丙烷三羧酸、丁烷四羧酸、3,3’,4,4’-聯苯四羧酸、六氫鄰苯二甲酸、3,3’,4,4’-二苯基碸四羧酸、甲基雙環[2.2.1]庚烷-2,3-二羧酸、雙環[2.2.1]庚烷-2,3-二羧酸、天門冬胺酸、苯均四酸、苯六甲酸、含磷酯基四羧酸、苯基乙炔基鄰苯二甲酸、3-氟-1,2-苯二羧酸、2,2-雙(4-羧基苯基)六氟丙烷、4,4’-(六氟異亞丙基)雙(1,2-苯二羧酸)、4,4’-(六氟異亞丙基)二鄰苯二甲酸、4,4’-二羧基二苯基碸、氧基二鄰苯二甲酸及聚丙烯酸所成之群的至少1種。由交聯性之觀點，有機酸特佳為選自由苯均四酸、1,2,3-丙烷三羧酸、天門冬胺酸、蜜石酸及聚丙烯酸所成之群的至少1種。 　　有機酸，可為單獨或2種以上之組合。The organic acid is preferably a polycarboxylic acid having an acid having at least two carboxyl groups in the molecule. Examples of the polycarboxylic acid are selected from the group consisting of succinic acid, adipic acid, maleic acid, phthalic acid, trimellitic acid, citric acid, 1,2,3-propanetricarboxylic acid, butanetetracarboxylic acid, and 3 , 3 ', 4,4'-biphenyltetracarboxylic acid, hexahydrophthalic acid, 3,3', 4,4'-diphenylphosphonium tetracarboxylic acid, methylbicyclo [2.2.1] heptane -2,3-dicarboxylic acid, bicyclic [2.2.1] heptane-2,3-dicarboxylic acid, aspartic acid, pyromellitic acid, pyromellitic acid, phosphorus ester-containing tetracarboxylic acid, phenyl Ethynyl phthalic acid, 3-fluoro-1,2-benzenedicarboxylic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4 '-(hexafluoroisopropylidene) bis (1,2-benzenedicarboxylic acid), 4,4 '-(hexafluoroisopropylidene) diphthalic acid, 4,4'-dicarboxydiphenylphosphonium, oxydiphthalic acid and At least one of the groups made of polyacrylic acid. From the viewpoint of crosslinkability, the organic acid is particularly preferably at least one selected from the group consisting of pyromellitic acid, 1,2,3-propanetricarboxylic acid, aspartic acid, meltaric acid, and polyacrylic acid. Organic acids may be used alone or in combination of two or more.

[有機酸之無水物] 　　有機酸之無水物，係指前述有機酸之酸酐。[Anhydrous substance of organic acid] Anhydrous substance of organic acid means the anhydride of the aforementioned organic acid.

有機酸之無水物，可列舉選自由乙二醇雙偏苯三甲酸酐(酸酐)、1,3,3a,4,5,9b-六氫-5(四氫-2,5-二側氧-3-呋喃基)萘并[1,2-c]呋喃-1,3-二酮(酸酐)、甘油雙偏苯三甲酸酐單乙酸酯(酸酐)、乙二醇雙偏苯三甲酸酐(酸酐)，及前述具體的多羧酸之無水物(例如苯均四酸酐、1,2,3-丙烷三羧酸酐、天門冬胺酸酐、蜜石酸酐、聚丙烯酸酐、馬來酸酐、偏苯三甲酸酐、4,4’-(六氟異亞丙基)二鄰苯二甲酸酐)所成之群的至少1種。由交聯性之觀點，有機酸之無水物，特佳為選自由苯均四酸酐、1,2,3-丙烷三羧酸酐、天門冬胺酸酐、蜜石酸酐及聚丙烯酸酐所成之群的至少1種。 　　有機酸之無水物，可為單獨或2種以上之組合。Anhydrous organic acids may be selected from ethylene glycol bistrimellitic anhydride (anhydride), 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo- 3-furanyl) naphtho [1,2-c] furan-1,3-dione (anhydride), glycerol bistrimellitic anhydride monoacetate (anhydride), ethylene glycol bistrimellitic anhydride (anhydride ), And the anhydrates of the aforementioned specific polycarboxylic acids (e.g. pyromellitic anhydride, 1,2,3-propane tricarboxylic anhydride, aspartic anhydride, tartaric anhydride, polyacrylic anhydride, maleic anhydride, trimellitic acid At least one of the group consisting of acid anhydride and 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride). From the viewpoint of crosslinkability, the anhydrous form of the organic acid is particularly preferably selected from the group consisting of pyromellitic anhydride, 1,2,3-propanetricarboxylic anhydride, aspartic anhydride, tartaric anhydride, and polyacrylic anhydride. At least 1 species. Anhydrous organic acids can be used alone or in combination of two or more.

[有機酸之金屬鹽] 　　有機酸之金屬鹽，為前述有機酸，與金屬(例如鹼金屬、鹼土類金屬、過渡金屬等)之鹽。有機酸之金屬鹽，較佳為選自由前述有機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種；特佳為選自由前述之更佳之有機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種。 　　有機酸之金屬鹽，可為單獨或2種以上之組合。[Metal salt of organic acid] A metal salt of an organic acid is a salt of the aforementioned organic acid and a metal (for example, an alkali metal, an alkaline earth metal, a transition metal, etc.). The metal salt of an organic acid is preferably at least one selected from the group consisting of the aforementioned organic acid and a salt of lithium, sodium, potassium, or calcium; particularly preferably, it is selected from the aforementioned more preferred organic acid and lithium, sodium, potassium Or at least one group of calcium salts.金属 Organic acid metal salts may be used alone or in combination of two or more.

[無機酸] 　　無機酸例如可列舉硝酸、硫酸、氫氟酸、氫氯酸、氫溴酸、6氟化磷酸、4氟化硼酸等。由電化學的安定性之觀點，無機酸更佳為選自由鹽酸、氫氟酸、6氟化磷酸及4氟化硼酸所成之群的至少1種。 　　無機酸，可為單獨或2種以上之組合。[Inorganic Acid] Examples of the osmium inorganic acid include nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, 6-fluorinated phosphoric acid, and 4-fluorinated boric acid. From the viewpoint of electrochemical stability, the inorganic acid is more preferably at least one selected from the group consisting of hydrochloric acid, hydrofluoric acid, 6-fluorinated phosphoric acid, and 4-fluorinated boric acid. Inorganic acid may be used alone or in combination of two or more.

[無機酸之金屬鹽] 　　無機酸之金屬鹽，為前述無機酸，與金屬(例如鹼金屬、鹼土類金屬、過渡金屬等)之鹽。無機酸之金屬鹽，較佳為選自由前述無機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種；特佳為選自由前述之更佳之無機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種。 　　無機酸之金屬鹽，可為單獨或2種以上之組合。[Metal salt of inorganic acid] A metal salt of an inorganic acid is a salt of the aforementioned inorganic acid and a metal (for example, an alkali metal, an alkaline earth metal, a transition metal, etc.). The metal salt of an inorganic acid is preferably at least one selected from the group consisting of the aforementioned inorganic acid and a salt of lithium, sodium, potassium or calcium; particularly preferably, it is selected from the aforementioned more preferred inorganic acid and lithium, sodium, potassium Or at least one group of calcium salts. The metal salt of an inorganic acid may be used alone or in combination of two or more kinds.

[其他成分] 　　集電體用組成物，在發揮本發明之效果的範圍內，可含有其他成分。如此之其他成分，可列舉聚丙烯醯胺以外之樹脂黏合劑、填料、溶劑、偶合劑、安定劑等。其他成分可各為單獨或2種以上之組合。例如，作為其他成分，可為2種以上之填料及單獨之溶劑的組合。[Other components] The composition for a current collector may contain other components within a range in which the effects of the present invention are exhibited. Examples of such other components include resin binders, fillers, solvents, coupling agents, and stabilizers other than polypropylene amidamine. The other components may be each alone or a combination of two or more. For example, the other component may be a combination of two or more fillers and a single solvent.

(聚丙烯醯胺以外之樹脂黏合劑) 　　聚丙烯醯胺以外之樹脂黏合劑(以下亦僅稱為「樹脂黏合劑」)，為對集電體用組成物賦予接著性，造成集電體與活性物質層或活性物質之密合性的高分子。構成樹脂黏合劑之高分子，可為水溶性或非水溶性。(Resin Adhesives Other Than Polyacrylamide) 树脂 Resin adhesives other than polypropylene ammonium (hereinafter also simply referred to as "resin adhesives") impart adhesiveness to the composition for current collectors, causing the current collectors and Adhesive polymer of active material layer or active material. The polymer constituting the resin adhesive may be water-soluble or water-insoluble.

水溶性之高分子的樹脂黏合劑之具體例子，可列舉完全皂化聚乙烯醇(Kuraray股份有限公司製；Kuraray Poval PVA-124、Japan VAM & Poval股份有限公司製；JC-25等)、部分皂化聚乙烯醇(Kuraray股份有限公司製；Kuraray Poval PVA-235、Japan VAM & Poval股份有限公司製；JP-33等)、改質聚乙烯醇(Kuraray股份有限公司製；Kuraray K Polymer KL-118、Kuraray C Polymer CM-318、Kuraray R Polymer R-1130、Kuraray LM Polymer LM-10HD、Japan VAM & Poval股份有限公司製；D Polymer DF-20、陰離子改質PVA AF-17、烷基改質PVA ZF-15)、羧基甲基纖維素(Daicel工業股份有限公司製；H-CMC、DN-100L、1120、2200、日本製紙Chemical股份有限公司製；MAC200HC等)、合成橡膠系乳膠型黏合劑、苯乙烯丁二烯橡膠(SBR)乳膠、腈丁二烯橡膠乳膠、聚四氟乙烯(PTFE)、羥基乙基纖維素(Daicel工業股份有限公司製；SP-400等)、聚氧乙烯(明成化學工業股份有限公司製；Alkox E-300)、環氧樹脂(Nagase ChemteX股份有限公司製；EX-614、Japan Chemtech股份有限公司製；Epikote 5003-W55等)、聚伸乙亞胺(日本觸媒股份有限公司製；Epomin P-1000)、聚丙烯酸酯(MT AQUAPOLYMER股份有限公司製；Accofloc C-502等)、以及糖類及其衍生物(和光純藥工業股份有限公司；Chitosan 5、日澱化學股份有限公司製；酯化澱粉乳華、Glico股份有限公司製；高分支環狀糊精(cluster dextrin))、聚苯乙烯磺酸(東曹有機化學股份有限公司製；PolyNaSS PS-100等)等之水溶性高分子，此等可於溶解於水的狀態使用。Specific examples of water-soluble polymer resin adhesives include fully saponified polyvinyl alcohol (Kuraray Co., Ltd .; Kuraray Poval PVA-124, Japan VAM & Poval Co., Ltd .; JC-25, etc.), and partially saponification. Polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-235, Japan VAM & Poval Co., Ltd .; JP-33, etc.), modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray K Polymer KL-118, Kuraray C Polymer CM-318, Kuraray R Polymer R-1130, Kuraray LM Polymer LM-10HD, Japan VAM & Poval Co., Ltd .; D Polymer DF-20, anionic modified PVA AF-17, alkyl modified PVA ZF -15), carboxymethyl cellulose (manufactured by Daicel Industries Co., Ltd .; H-CMC, DN-100L, 1120, 2200, Japan Paper Chemical Co., Ltd .; MAC200HC, etc.), synthetic rubber latex adhesives, Ethylene butadiene rubber (SBR) latex, nitrile butadiene rubber latex, polytetrafluoroethylene (PTFE), hydroxyethyl cellulose (manufactured by Daicel Industrial Co., Ltd .; SP-400, etc.), polyoxyethylene (Mingcheng Chemical Industry Co., Ltd. ; Alkox E-300), epoxy resin (made by Nagase ChemteX Co., Ltd .; EX-614, made by Japan Chemtech Co., Ltd .; Epikote 5003-W55, etc.), polyethyleneimine (made by Japan Catalyst Co., Ltd .; Epomin P-1000), polyacrylates (manufactured by MT AQUAPOLYMER Co., Ltd .; Accofloc C-502, etc.), and sugars and their derivatives (Wako Pure Chemical Industries, Ltd .; Chitosan 5, manufactured by Nitto Chemical Co., Ltd .; Esterified starch lactam, manufactured by Glico Co., Ltd .; highly branched cyclodextrin (cluster dextrin), polystyrene sulfonic acid (manufactured by Tosoh Organic Chemical Co., Ltd .; PolyNaSS PS-100, etc.) These molecules can be used in a state of being dissolved in water.

非水溶性之高分子的樹脂黏合劑之進一步的具體例子，可列舉丙烯酸酯聚合乳化液(昭和電工股份有限公司製；Polysol F-361、F-417、S-65、SH-502)，及乙烯/乙酸乙烯基共聚合乳化液(Kuraray股份有限公司製；Panflex OM-4000NT、OM-4200NT、OM-28NT、OM-5010NT)等之乳化液，此等可於懸浮於水的狀態使用。Further specific examples of the water-insoluble polymer resin adhesive include acrylate polymerization emulsion (manufactured by Showa Denko Corporation; Polysol F-361, F-417, S-65, and SH-502), and Emulsions of ethylene / vinyl acetate copolymerization emulsions (manufactured by Kuraray Co., Ltd .; Panflex OM-4000NT, OM-4200NT, OM-28NT, OM-5010NT) can be used in the state of being suspended in water.

非水溶性之高分子的樹脂黏合劑之進一步的具體例子，可列舉改質聚乙烯醇(信越化學工業股份有限公司製；Cyanoresin CR-V)、改質普魯蘭多糖(信越化學工業股份有限公司製；Cyanoresin CR-S)、乙烯/丙烯/二烯共聚物等之含烯烴性不飽和鍵聚合物、聚偏二氟乙烯(PVdF)、聚偏二氟乙烯-六氟丙烯共聚物(PVdF-HFP)等之高分子，此等可於溶解於N-甲基吡咯啶酮的狀態使用。Further specific examples of the water-insoluble polymer resin adhesive include modified polyvinyl alcohol (Cyanoresin CR-V, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and pullulan, a modified polysaccharide (Shin-Etsu Chemical Industry Co., Ltd. Manufactured by the company; Cyanoresin CR-S), polymers containing olefinic unsaturated bonds such as ethylene / propylene / diene copolymers, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF -HFP) and other polymers which can be used in a state of being dissolved in N-methylpyrrolidone.

就獲得之容易性的觀點，樹脂黏合劑較佳為合成橡膠系乳膠型黏合劑、苯乙烯丁二烯橡膠乳膠及腈丁二烯橡膠乳膠。 　　樹脂黏合劑，可為單獨或2種以上之組合。From the standpoint of availability, the resin adhesive is preferably a synthetic rubber-based latex-type adhesive, a styrene butadiene rubber latex, and a nitrile butadiene rubber latex. Resin adhesive can be used alone or in combination of two or more.

(填料) 　　填料可列舉導電性填料、絕緣性填料。導電性填料，係發揮對集電體用組成物賦予導電性，提高集電體之導電性的角色。絕緣性填料，係發揮對集電體用組成物賦予絕緣性，防止集電體上之活性物質塗佈部與未塗佈部之間的短路之角色。(Filler) The filler includes conductive fillers and insulating fillers. The conductive filler plays a role of imparting conductivity to a composition for a current collector and improving the conductivity of the current collector. The insulating filler plays a role of imparting insulation to the composition for a current collector and preventing a short circuit between an active material coated portion and an uncoated portion on the current collector.

＜導電性填料＞ 　　導電性填料，為導電性材料之各種公知的無機粒子或有機粒子，可列舉Ag、Cu、Au、Al、Mg、Rh、W、Mo、Co、Ni、Pt、Pd、Cr、Ta、Pb、V、Zr、Ti、In、Fe、Zn等之金屬的粉末、薄片或膠體；Sn-Pb系、Sn-In系、Sn-Bi系、Sn-Ag系、Sn-Zn系之合金粉末或薄片；乙炔黑、爐黑、槽黑等之碳黑，或石墨、石墨纖維、石墨原纖維、碳纖維、活性碳、木炭、碳奈米管、富勒烯等之導電性碳系材料；氧化鋅、氧化錫、氧化銦、氧化鈦(亦即二氧化鈦、一氧化鈦等之氧化鈦)等當中因存在有晶格缺陷而生成多餘電子，顯示出導電性的金屬氧化物等。此處，導電性碳系材料，亦可作為後述之活性物質而發揮功能。<Conductive filler> Conductive fillers are various known inorganic particles or organic particles of conductive materials, and examples include Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr , Ta, Pb, V, Zr, Ti, In, Fe, Zn and other metal powders, flakes or colloids; Sn-Pb-based, Sn-In-based, Sn-Bi-based, Sn-Ag-based, Sn-Zn-based Alloy powder or flakes; carbon black such as acetylene black, furnace black, groove black, or conductive carbon based on graphite, graphite fiber, graphite fibril, carbon fiber, activated carbon, charcoal, carbon nanotube, fullerene, etc. Materials; zinc oxide, tin oxide, indium oxide, titanium oxide (that is, titanium dioxide such as titanium dioxide, titanium oxide, etc.), etc., due to the presence of lattice defects, generate extra electrons, and metal oxides that exhibit conductivity. Here, the conductive carbon-based material can also function as an active material described later.

＜絕緣性填料＞ 　　絕緣性填料，為絕緣性材料之各種公知的無機粒子或有機粒子，可列舉氧化鋁、水鋁石、二氧化矽、氧化鋯、氧化鈦等之氧化物的粉末；膠體二氧化矽、氧化鈦溶膠、氧化鋁溶膠等之氧化物的溶膠；滑石、高嶺土、膨潤石等之黏土礦物；碳化矽、碳化鈦等之碳化物；氮化矽、氮化鋁、氮化鈦等之氮化物(惟，氮化硼除外)；氮化硼、硼化鈦、氧化硼等之硼化物；莫來石等之複合氧化物；氫氧化鋁、氫氧化鎂等之氫氧化物；如苯乙烯丁二烯或腈橡膠之橡膠微粒子、壓克力粒子、胺基甲酸酯粒子、聚丙烯粒子、鐵氟龍(註冊商標)粒子、聚乙烯等之有機粒子；及鈦酸鋇等。<Insulating fillers> Insulating fillers are various well-known inorganic particles or organic particles of insulating materials, and examples thereof include powders of oxides of alumina, gibbsite, silica, zirconia, and titanium oxide; colloid two Sol sols of oxides of silicon oxide, titania sol, alumina sol, etc .; clay minerals such as talc, kaolin, bentonite, etc .; carbides of silicon carbide, titanium carbide, etc .; silicon nitride, aluminum nitride, titanium nitride, etc. Nitrides (except boron nitride); boron nitride, titanium boride, boron oxide, etc .; composite oxides such as mullite; hydroxides such as aluminum hydroxide, magnesium hydroxide; Organic fine particles of styrene butadiene or nitrile rubber, acrylic particles, urethane particles, polypropylene particles, Teflon (registered trademark) particles, polyethylene and other organic particles; and barium titanate.

由獲得之容易性等之方面，填料較佳為選自由碳黑、鎳粉、鐵粉、氧化鋁、二氧化矽、氧化鈦及氧化鋯所成之群的至少1種。又，導電性填料特佳為碳黑，絕緣性填料特佳為氧化鋁。填料可使用粉狀，亦能夠以如二氧化矽溶膠或鋁溶膠之水分散膠體的形態使用。填料粒子之大小並無特殊限制，較佳為0.001～1μm之範圍、更佳為0.005～0.5μm之範圍。填料粒子之大小，例如係以雷射繞射/散射式粒度分布測定裝置所測定的平均粒子徑。 　　填料，可為單獨或2種以上之組合。In terms of availability, etc., the filler is preferably at least one selected from the group consisting of carbon black, nickel powder, iron powder, aluminum oxide, silicon dioxide, titanium oxide, and zirconia. The conductive filler is particularly preferably carbon black, and the insulating filler is particularly preferably alumina. The filler can be used in a powder form, and can also be used in the form of a water-dispersed colloid such as silica sol or aluminum sol. The size of the filler particles is not particularly limited, but is preferably in the range of 0.001 to 1 μm, and more preferably in the range of 0.005 to 0.5 μm. The size of the filler particles is, for example, an average particle diameter measured by a laser diffraction / scattering type particle size distribution measurement device. Fillers may be used alone or in combination of two or more.

(溶劑) 　　為了調整液性，集電體用組成物可含有溶劑。溶劑可例示烴(丙烷、n-丁烷、n-戊烷、異己烷、環己烷、n-辛烷、異辛烷、苯、甲苯、二甲苯、乙苯、戊苯、松節油、蒎烯等)；鹵素系烴(氯甲烷、氯仿、四氯化碳、二氯乙烷、溴甲烷、溴乙烷、氯苯、氯溴甲烷、溴苯、氟二氯甲烷、二氯二氟甲烷、二氟氯乙烷等)；一元醇(甲醇、乙醇、n-丙醇、異丙醇、n-戊醇、異戊醇、n-己醇、n-庚醇、2-辛醇、n-十二醇、壬醇、環己醇、去水甘油等)；醚及縮醛(乙基醚、二氯乙基醚、異丙基醚、n-丁基醚、二異戊基醚、甲基苯基醚、乙基苯甲基醚、呋喃、糠醛、2-甲基呋喃、桉樹腦、甲縮醛等)(惟，具有羥基之醚除外)；酮(丙酮、甲基乙基酮、甲基-n-丙基酮、甲基-n-戊基酮、二異丁基酮、佛爾酮、異佛爾酮、環己酮、苯乙酮等)；酯(甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸-n-戊酯、乙酸甲基環己酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、硬脂酸丁酯等)(惟，碳酸酯除外)；碳酸酯(碳酸二乙酯、碳酸伸乙酯等)；多元醇及其衍生物(乙二醇、乙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚、甲氧基甲氧基乙醇、乙二醇單乙酸酯、二乙二醇、二乙二醇單甲基醚、丙二醇、丙二醇單乙基醚等)；脂肪酸(甲酸、乙酸、乙酸酐、丙酸、丙酸酐、丁酸、異戊酸)；酚類(酚、甲酚、o-甲酚、二甲酚等)；有機氮化合物(硝基甲烷、硝基乙烷、1-硝基丙烷、硝基苯、單甲胺、二甲胺、三甲胺、單乙胺、二戊胺、苯胺、單甲基苯胺、o-甲苯胺、o-氯苯胺、二氯己胺、二環己胺、單乙醇胺、甲醯胺、N,N-二甲基甲醯胺、乙醯胺、乙腈、吡啶、α-甲基吡啶、2,4-二甲基吡啶、喹啉、嗎啉等)；有機硫化合物、有機磷化合物、有機硼化合物及其他化合物(二硫化碳、二甲基亞碸、4,4-二乙基-1,2-二硫代環戊烷、二甲基硫醚、二甲基二硫醚、甲烷硫醇、丙烷磺內酯、磷酸三乙酯、磷酸三苯酯、硼酸戊酯等)；無機溶劑(液體氨、聚矽氧油、水等)等之液體。 　　溶劑，可為單獨或2種以上之組合。(Solvent) In order to adjust the liquidity, the composition for a current collector may contain a solvent. Examples of the solvent include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, pentylbenzene, turpentine, pinene Etc.); Halogen-based hydrocarbons (chloromethane, chloroform, carbon tetrachloride, dichloroethane, bromomethane, bromoethane, chlorobenzene, chlorobromomethane, bromobenzene, chloromethane, dichlorodifluoromethane, difluoro Ethyl chloride, etc.); Monohydric alcohols (methanol, ethanol, n-propanol, isopropanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-twelve Alcohol, nonanol, cyclohexanol, dehydrated glycerol, etc.); ethers and acetals (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisopentyl ether, methylbenzene Ether, ethyl benzyl ether, furan, furfural, 2-methylfuran, eucalyptol, methylal, etc. (except for ethers with hydroxyl groups); ketones (acetone, methyl ethyl ketone, methyl -n-propyl ketone, methyl-n-pentyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.); esters (methyl formate, ethyl formate , Propyl formate, methyl acetate, ethyl acetate, propyl acetate, -n-pentyl acetate, acetic acid Cyclohexyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, etc.) (except carbonates); carbonates (diethyl carbonate, ethylene carbonate, etc.); Polyols and their derivatives (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol mono Acetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, etc.); fatty acids (formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid) ; Phenols (phenol, cresol, o-cresol, xylenol, etc.); organic nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethylamine , Trimethylamine, monoethylamine, dipentylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, dichlorohexylamine, dicyclohexylamine, monoethanolamine, formamidine, N, N- Dimethylformamide, acetamide, acetonitrile, pyridine, α-methylpyridine, 2,4-dimethylpyridine, quinoline, morpholine, etc.); organic sulfur compounds, organic phosphorus compounds, organic boron compounds, and Other compounds (carbon disulfide, Dimethyl sulfene, 4,4-diethyl-1,2-dithiocyclopentane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate Esters, triphenyl phosphate, amyl borate, etc.); inorganic solvents (liquid ammonia, silicone oil, water, etc.). The rhenium solvent may be used alone or in combination of two or more.

(偶合劑) 　　偶合劑，為與集電體用組成物中所含之具有活性氫(例如氫鍵性官能基)的取代基反應，提高交聯密度，且可更加提高集電體與活性物質層或活性物質之密合性的成分。(Coupling agent) Coupling agent reacts with a substituent having an active hydrogen (for example, a hydrogen-bonding functional group) contained in the composition for a current collector to increase the crosslink density and further increase the current collector and the active material. Adhesive component of layer or active material.

偶合劑較佳為矽烷偶合劑及鈦系偶合劑。氟系之矽烷偶合劑，可列舉(十三氟-1,1,2,2-四氫辛基)三乙氧基矽烷；環氧基改質矽烷偶合劑，可列舉信越化學工業股份有限公司製偶合劑(商品名：KBM-403)；氧雜環丁烷改質矽烷偶合劑，可列舉東亞合成股份有限公司製偶合劑(商品名：TESOX電池集電體用組成物)；及含有不飽和基之矽烷偶合劑，可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷。鈦系偶合劑，可列舉鈦酸四-i-丙酯、鈦酸四-n-丁酯、鈦酸二異硬脂醯基伸乙酯等。 　　偶合劑，可為單獨或2種以上之組合。The coupling agent is preferably a silane coupling agent and a titanium-based coupling agent. Examples of fluorine-based silane coupling agents include tridecylfluoro-1,1,2,2-tetrahydrooctyl triethoxysilane; epoxy-modified silane coupling agents include Shin-Etsu Chemical Industry Co., Ltd. Coupling agent (trade name: KBM-403); oxetane modified silane coupling agent, including coupling agents manufactured by Toa Synthesis Co., Ltd. (trade name: TESOX battery current collector composition); Examples of the saturated silane coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of the titanium-based coupling agent include tetra-i-propyl titanate, tetra-n-butyl titanate, and diisostearylfluorenyl titanate. Coupling agents may be used alone or in combination of two or more.

(安定劑) 　　集電體用組成物，可依需要，適當選擇而含有安定劑。如此之安定劑，具體而言可列舉2,6-二-tert-丁基-酚、2,4-二-tert-丁基-酚、2,6-二-tert-丁基-4-乙基-酚、2,4-雙-(n-辛硫基)-6-(4-羥基-3,5-二-tert-丁基-苯胺基)-1,3,5-三嗪等之酚系抗氧化劑；烷基二苯胺、N,N’-二苯基-p-苯二胺、6-乙氧基-2,2,4-三甲基-1,2-二氫喹啉、N-苯基-N’-異丙基-p-苯二胺等之芳香族胺系抗氧化劑；二月桂基-3,3’-硫代二丙酸酯、二-十三烷基-3,3’-硫代二丙酸酯、雙[2-甲基-4-{3-n-烷硫基丙醯氧基}-5-tert-丁基-苯基]硫醚、2-巰基-5-甲基-苯并咪唑等之硫醚系氫過氧化物分解劑；亞磷酸參(異癸基)酯、亞磷酸苯基二異辛酯、亞磷酸二苯基異辛酯、二(壬基苯基)季戊四醇二亞磷酸酯、3,5-二-tert-丁基-4-羥基-苯甲基磷酸酯二乙酯、鈉雙(4-tert-丁基苯基)磷酸酯等之磷系氫過氧化物分解劑；水楊酸苯酯、水楊酸4-tert-辛基苯酯等之水楊酸酯系光安定劑；2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮-5-磺酸等之二苯甲酮系光安定劑；2-(2’-羥基-5’-甲基苯基)苯并三唑、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2N-苯并三唑-2-基)酚]等之苯并三唑系光安定劑；碳酸苯基-4-哌啶酯、癸二酸雙-[2,2,6,6-四甲基-4-哌啶基]等之受阻胺系光安定劑；[2,2’-硫代-雙(4-t-辛基酚化物)]-2-乙基己胺-鎳-(II)等之Ni系光安定劑；氰基丙烯酸酯系光安定劑；及草酸苯胺化物系光安定劑等。 　　安定劑，可為單獨或2種以上之組合。(Stabilizer) The composition for a current collector may be appropriately selected and contains a stabilizer as needed. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, and 2,6-di-tert-butyl-4-ethyl -Phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-aniline) -1,3,5-triazine, etc. Phenolic antioxidants; alkyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, Aromatic amine antioxidants such as N-phenyl-N'-isopropyl-p-phenylenediamine; dilauryl-3,3'-thiodipropionate, di-tridecyl-3 3'-thiodipropionate, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto -5-methyl-benzimidazole and other thioether-based hydroperoxide decomposition agents; ginseng (isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (Nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl, sodium bis (4-tert-butylphenyl) phosphate Phosphorus-based hydroperoxide decomposition agent; salicylic acid-based light stabilizers such as phenyl salicylate, 4-tert-octyl phenyl salicylate; 2,4-dihydroxydi Benzophenone-based light stabilizers such as ketone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid; 2- (2'-hydroxy-5'-methylphenyl) benzo Triazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], etc. Benzotriazole light stabilizers; hindered amine light stabilizers such as phenyl-4-piperidine carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate, etc. ; [2,2'-thio-bis (4-t-octylphenolate)] 2-ethylhexylamine-nickel- (II) and other Ni-based light stabilizers; cyanoacrylate-based light stabilizers Agents; and anilide oxalate light stabilizers. Rhenium stabilizers can be used alone or in combination of two or more.

(界面活性劑) 　　為了調節濕潤性，集電體用組成物可含有界面活性劑。如此之界面活性劑，可列舉陰離子界面活性劑、兩性界面活性劑及非離子(非離子)型界面活性劑。 　　陰離子界面活性劑，可列舉肥皂、月桂基硫酸鹽、聚氧乙烯烷基醚硫酸鹽、烷基苯磺酸鹽、聚氧乙烯烷基醚磷酸、聚氧乙烯烷基苯基醚磷酸、N-醯基胺基酸鹽、α-烯烴磺酸鹽、烷基硫酸酯鹽、烷基苯基醚硫酸酯鹽、甲基牛磺酸鹽等。陰離子界面活性劑之對陽離子，可使用鈉離子及鋰離子等。集電體用組成物使用於鋰離子蓄電池時，界面活性劑較佳為鋰離子型。 　　兩性界面活性劑，可列舉鹽酸烷基二胺基乙基甘胺酸、2-烷基-N-羧基甲基-N-羥基乙基咪唑鎓甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、椰子油脂肪酸醯胺丙基甜菜鹼、脂肪酸烷基甜菜鹼、磺甜菜鹼、氧化胺等。 　　非離子(非離子)型界面活性劑，可列舉聚乙二醇之烷基酯型化合物、三乙二醇單丁基醚等之烷基醚型化合物、聚氧山梨醇酐酯等之酯型化合物、烷基酚型化合物、氟型化合物、聚矽氧型化合物等。 　　界面活性劑，可為單獨或2種以上之組合。(Surfactant) In order to adjust the wettability, the composition for a current collector may contain a surfactant. Examples of such a surfactant include an anionic surfactant, an amphoteric surfactant, and a nonionic (nonionic) surfactant. Examples of the anionic surfactant include soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkylphenyl ether phosphoric acid, and N- Fluorenylamino acid salts, α-olefin sulfonates, alkyl sulfate salts, alkylphenyl ether sulfate salts, methyl taurine, and the like. As the counter-cation of the anionic surfactant, sodium ion and lithium ion can be used. When the composition for a current collector is used in a lithium ion battery, the surfactant is preferably a lithium ion type. Amphoteric surfactants include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, and lauryldimethylaminoacetic acid betaine , Coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amine oxide, etc. Non-ionic (non-ionic) surfactants include alkyl ester compounds such as polyethylene glycol, alkyl ether compounds such as triethylene glycol monobutyl ether, and ester types such as polyoxysorbate Compounds, alkylphenol compounds, fluorine compounds, polysiloxane compounds, and the like. Surfactants can be used alone or in combination of two or more.

[組成] 　　就更加提高集電體與活性物質層或活性物質之密合性的觀點，以固體成分基準計，相對於聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種之合計量100重量份而言，集電體用組成物，較佳含有聚丙烯醯胺0.01～99重量份、更佳含有1～95重量份、特佳含有5～90重量份。[Composition] From the viewpoint of further improving the adhesion between the current collector and the active material layer or active material, based on the solid content, it is selected from the group consisting of organic acids, anhydrous organic acids, and inorganic acids relative to polypropylene amidamine. In terms of 100 parts by weight of the total amount of at least one of the group consisting of a metal salt of an organic acid and a metal salt of an inorganic acid, the composition for a current collector preferably contains 0.01 to 99 parts by weight of polyacrylamide, more It preferably contains 1 to 95 parts by weight, and particularly preferably contains 5 to 90 parts by weight.

就確保絕緣性，容易防止短路之觀點，相對於聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種之合計量100重量份而言，集電體用組成物，較佳含有填料1～1,000重量份、更佳含有10～700重量份、特佳含有15～500重量份。From the viewpoint of ensuring insulation and easy prevention of short circuits, it is at least at least one selected from the group consisting of organic acids, anhydrous organic acids, inorganic acids, metal salts of organic acids, and metal salts of inorganic acids. The total amount of one kind is 100 parts by weight. The composition for a current collector preferably contains 1 to 1,000 parts by weight of a filler, more preferably 10 to 700 parts by weight, and particularly preferably 15 to 500 parts by weight.

就更加提高集電體與活性物質層或活性物質之密合性的觀點，相對於聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種之合計量100重量份而言，集電體用組成物，較佳含有樹脂黏合劑0.1～200重量份、更佳含有1～100重量份、特佳含有2～75重量份。From the viewpoint of further improving the adhesion between the current collector and the active material layer or the active material, compared with polypropylene amidamide, it is selected from the group consisting of organic acids, anhydrous organic acids, inorganic acids, metal salts of organic acids, and inorganic acids. In terms of 100 parts by weight of the total amount of at least one group of metal salts, the composition for a current collector preferably contains 0.1 to 200 parts by weight of a resin binder, more preferably 1 to 100 parts by weight, and is particularly preferred. Contains 2 to 75 parts by weight.

相對於聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種之合計量100重量份而言，集電體用組成物，前述填料及樹脂黏合劑以外之其他成分的含量，並無特殊限定，較佳含有0.01～50重量份、更佳含有0.05～40重量份。With respect to polypropylene amidamide, 100 parts by weight of the total amount of at least one selected from the group consisting of an organic acid, an anhydrous substance of an organic acid, an inorganic acid, a metal salt of an organic acid, and a metal salt of an inorganic acid, The content of the composition for a current collector, other than the filler and the resin binder, is not particularly limited, but it is preferably 0.01 to 50 parts by weight, and more preferably 0.05 to 40 parts by weight.

集電體用組成物，可配合塗覆裝置，為了調整黏度，以任意比率添加溶劑。就塗覆性之觀點，集電體用組成物之黏度，較佳為1～20,000mPa･s、更佳為10～5,000mPa･s、特佳為100～2,000mPa･s。The composition for the current collector can be combined with a coating device. In order to adjust the viscosity, a solvent is added at an arbitrary ratio. From the viewpoint of coatability, the viscosity of the composition for a current collector is preferably 1 to 20,000 mPa ･ s, more preferably 10 to 5,000 mPa ･ s, and particularly preferably 100 to 2,000 mPa ･ s.

[集電體用組成物之製造方法] 　　可藉由將上述成分混合並攪拌，以溶液或懸浮液等的形態得到集電體用組成物。攪拌可適當選擇螺槳式混合機、行星式混合機、複合式混合機(hybrid mixer)、捏合機、乳化用均質機、超音波均質機等之各種攪拌裝置來進行。又，亦可依需要一邊加熱或冷卻一邊攪拌。[Manufacturing method of composition for current collector] The composition for current collector can be obtained in the form of a solution or a suspension by mixing and stirring the above-mentioned components. The stirring can be performed by appropriately selecting various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. Moreover, you may stir while heating or cooling as needed.

[用途] 　　集電體用組成物，可使用作為用以將集電體與活性物質層或活性物質接著之組成物。具體而言，可使作為由集電體用組成物所構成之底塗層形成用組成物(以下亦僅稱為「底塗層形成用組成物」)及由集電體用組成物所構成之黏合劑組成物(以下亦僅稱為「黏合劑組成物」)。此處，由集電體用組成物所構成之底塗層形成用組成物，係用以形成用以將集電體與活性物質層接著之集電體用的底塗層之組成物。又，由集電體用組成物所構成之黏合劑組成物，係用以形成集電體之活性物質層之黏合劑組成物。[Application] (1) The composition for a current collector can be used as a composition for adhering a current collector to an active material layer or an active material. Specifically, a composition for forming an undercoat layer composed of a composition for a current collector (hereinafter also simply referred to as a "composition for forming an undercoat layer") and a composition for a current collector can be used. Adhesive composition (hereinafter also simply referred to as "adhesive composition"). Here, the composition for forming an undercoat layer composed of the composition for a current collector is a composition for forming an undercoat layer for a current collector in which a current collector and an active material layer are bonded. The adhesive composition composed of the composition for a current collector is an adhesive composition for forming an active material layer of a current collector.

(電極形成用組成物) 　　電極形成用組成物，含有黏合劑組成物與活性物質。由於電極形成用組成物含有活性物質，故可使用作為用以於集電體上形成活性物質層之組成物。黏合劑組成物含有溶劑時，電極形成用組成物，亦稱作負極漿料或正極漿料等之電極漿料。由電極形成用組成物所形成之活性物質層，對集電體之密合性優良，活性物質彼此之密合性亦優良。再者，黏合劑組成物係規定為不含有導電性碳系材料者。(Composition for electrode formation) The composition for electrode formation contains a binder composition and an active material. Since the composition for electrode formation contains an active material, it can be used as a composition for forming an active material layer on a current collector. When the binder composition contains a solvent, the electrode forming composition is also referred to as an electrode slurry such as a negative electrode slurry or a positive electrode slurry. The active material layer formed of the electrode-forming composition has excellent adhesion to the current collector, and also has excellent adhesion between the active materials. The adhesive composition is defined as one that does not contain a conductive carbon-based material.

活性物質，只要係使用作為電池或電雙層電容器之活性物質者則無特殊限定。正極活性物質，例如可列舉LiCoO2 、LiNiO2 、LiMnO4 等之含有鋰之過渡金屬氧化物；MoS2 等之氧族元素(chalcogen)化合物。負極活性物質，例如可列舉天然石墨、人造石墨、焦碳、碳纖維等之碳材料(導電性填料中含有前述導電性碳系材料)；含有Al、Si、Sn、Ag、Bi、Mg、Zn、P、Ge、Pb或Ti之鋰合金；前述碳材料與前述鋰合金之複合物；以及鋰氮化物等。 　　活性物質，可為單獨或2種以上之組合。The active material is not particularly limited as long as it is used as an active material for a battery or an electric double-layer capacitor. Examples of the positive electrode active material include lithium-containing transition metal oxides such as LiCoO 2 , LiNiO 2 , and LiMnO 4 ; and chalcogen compounds such as MoS 2 . Examples of the negative electrode active material include carbon materials such as natural graphite, artificial graphite, coke, and carbon fiber (the conductive filler contains the above-mentioned conductive carbon-based material); Al, Si, Sn, Ag, Bi, Mg, Zn, A lithium alloy of P, Ge, Pb, or Ti; a composite of the foregoing carbon material and the foregoing lithium alloy; and a lithium nitride. The active material may be used alone or in combination of two or more.

相對於黏合劑組成物100重量份而言，電極形成用組成物，較佳含有活性物質0.1～20,000重量份、更佳含有1～10,000重量份、特佳含有2～7,500重量份。The electrode forming composition preferably contains 0.1 to 20,000 parts by weight of the active material, more preferably 1 to 10,000 parts by weight, and particularly preferably 2 to 7,500 parts by weight based on 100 parts by weight of the binder composition.

[電池或電雙層電容器之集電體之製造方法] 　　使用了集電體用組成物的電池或電雙層電容器之集電體之製造方法，只要係可得到所期望之集電體的方法則無特殊限制，例如可列舉以下之製造方法。[Method for manufacturing current collector of battery or electric double-layer capacitor] A method for manufacturing current collector of a battery or electric double-layer capacitor using a composition for a current collector, as long as the method can obtain a desired current collector It is not particularly limited, and examples thereof include the following production methods.

(第一製造方法) 　　使用了集電體用組成物的電池或電雙層電容器之集電體之第一製造方法(以下亦稱為「第一製造方法」)，為使用集電體用組成物作為底塗層形成用組成物的製造方法。(First manufacturing method) (1) A first manufacturing method for a current collector of a battery or an electric double-layer capacitor using a composition for a current collector (hereinafter also referred to as a "first manufacturing method") is to use a composition for a current collector A method for producing an undercoat layer-forming composition.

第一製造方法，包含將底塗層形成用組成物塗佈於集電體上，而形成底塗層形成用組成物塗膜之步驟，及於塗佈有前述底塗層形成用組成物的集電體上，塗佈導電性之活性物質之步驟。藉由第一製造方法，集電體上之塗佈有活性物質的部分與未塗佈的部分被隔離，可得到不易產生短路的電極。又，底塗層形成用組成物之電阻大，因此即使有伴隨外力等之衝擊的變形等，集電體上之電性地塗佈有活性物質的部分與未塗佈的部分亦被隔離，可發揮高的安全性。A first manufacturing method includes the steps of applying a composition for forming an undercoat layer to a current collector to form a coating film of the composition for forming an undercoat layer, and applying the composition for forming the undercoat layer. A step of applying a conductive active material to a current collector. According to the first manufacturing method, an active material-coated portion and an uncoated portion on the current collector are separated, and an electrode that is unlikely to cause a short circuit can be obtained. In addition, since the composition for forming the undercoat layer has a large electrical resistance, even if there is deformation or the like accompanying the impact of an external force, the portion where the active material is electrically coated on the current collector is separated from the uncoated portion. High security is available.

將底塗層形成用組成物塗佈於集電體上而形成塗膜之方法，只要係旋轉塗佈、噴霧塗佈等，可塗覆為平面狀者，則無特殊限制，可採用所屬技術領域中具有通常知識者公知之方法。塗覆之後，可藉由吹溫風等之加熱來乾燥，而形成塗膜。底塗層形成用組成物含有溶劑時，加熱溫度例如可為溶劑之沸點左右的溫度。又，亦可藉由於減壓下將溶劑蒸發來形成塗膜。塗膜形成後，亦可依需要藉由輥壓等之方法來進行壓製。The method for applying a composition for forming an undercoat layer to a current collector to form a coating film is not particularly limited as long as it can be applied in a planar state by spin coating, spray coating, or the like, and the technology can be adopted. There are methods known in the art to those of ordinary knowledge. After coating, it can be dried by heating with hot air or the like to form a coating film. When the composition for forming an undercoat layer contains a solvent, the heating temperature may be, for example, a temperature around the boiling point of the solvent. Moreover, a coating film can also be formed by evaporating a solvent under reduced pressure. After the coating film is formed, it can also be pressed by a method such as rolling.

接著，將活性物質層塗佈於將底塗層形成用組成物塗佈於集電體上所得的集電體用之層合薄片上，藉此可得到電極片。活性物質層之塗覆方法，與底塗層形成用組成物之塗佈方法同樣地，可採用所屬技術領域中具有通常知識者公知者。藉由將活性物質層之塗佈區域，以底塗層形成用組成物之塗佈區域出現於電極片上的方式進行塗覆，可得到防止短路，且密合性優良的電極片。Next, an electrode sheet can be obtained by applying an active material layer to a laminated sheet for a current collector obtained by applying a composition for forming an undercoat layer to a current collector. The coating method of the active material layer is the same as the coating method of the undercoat layer-forming composition, and a method known to those skilled in the art can be used. By coating the coated region of the active material layer so that the coated region of the composition for forming the undercoat layer appears on the electrode sheet, an electrode sheet with short-circuit prevention and excellent adhesion can be obtained.

藉由第一製造方法，例如可得到如圖1所示之於集電體之上依序層合有使用了底塗層形成用組成物之底塗層、活性物質層的電極片。According to the first manufacturing method, for example, as shown in FIG. 1, an electrode sheet in which an undercoat layer using an undercoat layer-forming composition and an active material layer are sequentially laminated on a current collector can be obtained.

(第二製造方法) 　　使用了集電體用組成物的電池或電雙層電容器之集電體之第二製造方法(以下，亦稱為「第二製造方法」)，為使用集電體用組成物作為黏合劑組成物之製造方法。(Second manufacturing method) (2) A second manufacturing method of a current collector of a battery or an electric double-layer capacitor using a composition for a current collector (hereinafter, also referred to as a "second manufacturing method") is used for a current collector. The composition is a method for producing an adhesive composition.

第二製造方法，包含將電極形成用組成物塗佈於集電體上，而形成電極形成用組成物之塗膜之步驟，此處，前述電極形成用組成物，含有由集電體用組成物所構成之黏合劑組成物與活性物質。The second manufacturing method includes a step of applying a composition for forming an electrode to a current collector to form a coating film of the composition for forming an electrode. Here, the composition for forming an electrode includes a composition for a current collector. Adhesive composition and active substance composed of substances.

第二製造方法，亦可包含設置底塗層之步驟。設置底塗層之步驟，可由公知方法中適當選擇，亦可為將前述底塗層形成用組成物塗佈於集電體上而形成塗膜的步驟。The second manufacturing method may further include a step of providing an undercoat layer. The step of providing the undercoat layer may be appropriately selected from known methods, or may be a step of applying the aforementioned undercoat layer-forming composition to a current collector to form a coating film.

其他條件，係如第一製造方法所述，係依所得之電池或電雙層電容器之集電體來適當選擇。The other conditions are appropriately selected according to the current collector of the obtained battery or electric double-layer capacitor as described in the first manufacturing method.

藉由第二製造方法，例如可得到如圖2所示之於集電體之上依序層合有由電極形成用組成物所形成的活性物質層之電極片。再者，圖2中雖未圖示，但以第二製造方法所製造的電極片，於集電體與由電極形成用組成物所形成的活性物質層之間，亦可具有底塗層。According to the second manufacturing method, for example, as shown in FIG. 2, an electrode sheet in which an active material layer formed of a composition for electrode formation is sequentially laminated on a current collector can be obtained. Although not shown in FIG. 2, the electrode sheet manufactured by the second manufacturing method may have an undercoat layer between the current collector and the active material layer formed of the electrode-forming composition.

[集電體] 　　經集電體用組成物塗覆之集電體，可藉由將集電體用組成物塗覆於電池或電雙層電容器之集電體來製造。亦即，經集電體用組成物塗覆之集電體，具有集電體用組成物之塗覆層。[Current Collector] A current collector coated with a composition for a current collector can be manufactured by coating the current collector with a composition for a battery or an electric double-layer capacitor. That is, the current collector coated with the composition for a current collector has a coating layer of the composition for a current collector.

電池或電雙層電容器之集電體，可例示金、銀、銅、鋁、鎳、鐵、鈷等之金屬或碳纖維不織布、金屬複合材料等之具有導電性的複合材料。鋰離子蓄電池中，正極用係使用鋁箔、負極用係使用銅箔，電雙層電容器中，係使用鋁箔或鋁的蝕刻箔。塗覆可利用凹版塗佈器或縫模塗佈器、噴霧塗佈器、浸漬等。塗覆層之厚度較佳為0.01～100μm之範圍，就電特性及密合性之觀點，更佳為0.05～5μm之範圍。塗覆層之厚度為0.01μm以上時，可發揮充分的電阻。塗覆層之厚度為100μm以下時，對作為電池時的體積不易造成影響。Examples of the current collector of a battery or an electric double-layer capacitor include metals such as gold, silver, copper, aluminum, nickel, iron, and cobalt, or carbon fiber nonwoven fabrics, metal composite materials, and other conductive composite materials. In lithium-ion batteries, aluminum foil is used for the positive electrode, copper foil is used for the negative electrode, and aluminum foil or aluminum etched foil is used for electric double-layer capacitors. For coating, a gravure coater or a slot die coater, a spray coater, or dipping can be used. The thickness of the coating layer is preferably in the range of 0.01 to 100 μm, and more preferably in the range of 0.05 to 5 μm from the viewpoint of electrical characteristics and adhesion. When the thickness of the coating layer is 0.01 μm or more, sufficient resistance can be exhibited. When the thickness of the coating layer is 100 μm or less, it does not easily affect the volume when used as a battery.

[電池或電雙層電容器] 　　包含經集電體用組成物塗覆之電池或電雙層電容器之集電體的電池或電雙層電容器中，電池或電雙層電容器，可藉由公知之方法製造。 [實施例][Battery or electric double-layer capacitor] 中 Among batteries or electric double-layer capacitors that include a battery coated with a composition of a current collector or a collector of an electric double-layer capacitor, the battery or the electric double-layer capacitor may be a known one. Method manufacturing. [Example]

以下使用實施例以具體說明本發明，但本發明不限定於此等。添加量之表示，若無指明，係為質量份。Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these. The amount of addition, if not specified, is part by mass.

[實施例1～28、比較例1～2：作為底塗層形成用組成物之集電體用組成物] [製造例1]底塗層形成用組成物之製造 　　於10L燒杯中，以表1所示之對應各實施例的各材料與摻合量添加各成分，攪拌至各成分大致均勻分散為止，得到底塗層形成用組成物之塗覆液。[Examples 1 to 28, Comparative Examples 1 to 2: Compositions for current collectors as a composition for forming an undercoat layer] [Manufacturing Example 1] The composition for forming an undercoat layer was produced in a 10L beaker. Each component shown in 1 corresponding to each material and blending amount of each example is added, and the components are stirred until the components are substantially uniformly dispersed to obtain a coating liquid for a composition for forming an undercoat layer.

※表1中之各材料係如以下所示。 (1)聚丙烯醯胺 　　聚丙烯醯胺(重量平均分子量600萬)：三洋化成工業股份有限公司製；Sunfloc NOP 　　聚丙烯醯胺(重量平均分子量1200萬)：三洋化成工業股份有限公司製；Sunfloc N-500P 　　聚丙烯醯胺(重量平均分子量1600萬)：MT AQUAPOLYMER股份有限公司製；Accofloc N-102 (2)有機酸、無機酸、有機酸之金屬鹽、無機酸之金屬鹽 　　聚丙烯酸：東亞合成股份有限公司製；20重量%水溶液、AC10H 　　天門冬胺酸：和光純藥工業股份有限公司製；100重量%、L-天門冬胺酸 　　苯均四酸：東京化成工業股份有限公司；100重量% 　　蜜石酸：東京化成工業股份有限公司製；100重量% 　　氫氟酸：和光純藥工業股份有限公司製；49.5重量%氫氟酸 　　6氟化磷酸：和光純藥工業股份有限公司製；60重量%六氟磷酸水溶液 　　4氟化硼酸：和光純藥工業股份有限公司製；42重量%四氟硼酸水溶液 (3)樹脂黏合劑 　　苯乙烯丁二烯橡膠(SBR)：日本A&L股份有限公司製；48重量%乳膠、Nalstar SR-115 (4)填料 　　氧化鋁：大明化學工業股份有限公司製；θ-氧化鋁TM-100(平均粒子徑：0.1μm) 　　碳：電氣化學工業股份有限公司製；Denka Black HS-100(平均粒子徑：0.4μm) (5)溶劑 　　水：離子交換水※ The materials in Table 1 are shown below. (1) Polyacrylamide Polyacrylamide (weight average molecular weight 6 million): manufactured by Sanyo Chemical Industry Co., Ltd .; Sunfloc NOP (polyacrylamide) (weight average molecular weight 12 million): manufactured by Sanyo Chemical Industry Co., Ltd .; Sunfloc N-500P Polyacrylamide (weight average molecular weight 16 million): made by MT AQUAPOLYMER Co., Ltd .; Accofloc N-102 (2) organic acid, inorganic acid, metal salt of organic acid, metal salt of inorganic acid polyacrylic acid: East Asia Synthetic Co., Ltd .; 20% by weight aqueous solution, AC10H Aspartic acid: manufactured by Wako Pure Chemical Industries, Ltd .; 100% by weight, L-aspartic acid pyromellitic acid: Tokyo Chemical Industry Co., Ltd .; 100% % Melanic acid: manufactured by Tokyo Chemical Industry Co., Ltd .; 100% by weight fluorinated hydrofluoric acid: manufactured by Wako Pure Chemical Industries Co., Ltd .; 49.5% by weight hydrofluoric acid 6 fluorinated phosphoric acid: manufactured by Wako Pure Chemical Industries Co., Ltd .; 60 4 wt% hexafluorophosphoric acid aqueous solution 4 boron fluoride: Wako Pure Chemical Industries, Ltd. Co., Ltd .; 42% by weight tetrafluoroborate aqueous solution (3) resin adhesive styrene butadiene rubber (SBR): made by Japan A & L Co., Ltd .; 48% by weight latex, Nalstar SR-115 (4) filler alumina: Manufactured by Daming Chemical Industry Co., Ltd .; θ-alumina TM-100 (average particle diameter: 0.1 μm) Carbon: manufactured by Denki Chemical Industry Co., Ltd .; Denka Black HS-100 (average particle diameter: 0.4 μm) (5) Solvent Water: ion-exchanged water

[製造例2]蓄電裝置用電極片 　　各於集電體1(寬度300mm、厚度20μm之壓延鋁箔)及集電體2(寬度300mm、厚度15μm之壓延銅箔)上以寬度200mm塗佈製造例1中所得之底塗層形成用組成物之塗覆液，於150℃溫風爐中乾燥30秒，製作使用乾燥後之塗覆膜厚1μm之集電體1的集電體層合薄片1，與使用集電體2的集電體層合薄片2。[Manufacturing example 2] Each of the electrode sheets for power storage devices was coated with a width of 200 mm on current collector 1 (rolled aluminum foil with a width of 300 mm and a thickness of 20 μm) and current collector 2 (rolled copper foil with a width of 300 mm and a thickness of 15 μm). The coating liquid of the composition for forming the undercoat layer obtained in 1 is dried in a 150 ° C. hot air oven for 30 seconds to produce a current collector laminated sheet 1 using the current collector 1 with a coating film thickness of 1 μm after drying, The sheet 2 is laminated with a current collector using the current collector 2.

(負極之製造) 　　將作為負極活性物質之石墨(昭和電工股份有限公司製；SCMG-AR)97.5重量%、作為黏合劑之苯乙烯丁二烯橡膠(SBR)(日本A&L股份有限公司製；48重量%乳膠、Nalstar SR-115)1.25重量%與羧基甲基纖維素(CMC)(日本製紙Chemical股份有限公司製；100重量%、Sunrose F-600LC)1.25重量%添加於水溶劑中，製造負極漿料。將該負極漿料以寬度180mm塗覆於集電體層合薄片2之塗覆膜側，於120℃溫風爐乾燥1分鐘後，以線壓300kgf/cm進行輥壓。之後，於100℃恆溫槽中減壓乾燥6小時，得到層合有集電體層合薄片2與負極活性物質之電極片(以下稱為「負極1」)。再者，比較例2之負極1，係使用未塗佈底塗層形成用組成物之壓延銅箔而得到。對於所得之負極1，遵照評估條件之(1)進行試驗。(Manufacture of negative electrode) 负极 Graphite (manufactured by Showa Denko Corporation; SCMG-AR) as a negative electrode active material: 97.5% by weight and styrene butadiene rubber (SBR) (manufactured by Japan A & L Co., Ltd.) as a binder; 48 Latex, Nalstar SR-115) 1.25% by weight and carboxymethyl cellulose (CMC) (manufactured by Nippon Paper Chemical Co., Ltd .; 100% by weight, Sunrose F-600LC) were added to an aqueous solvent to produce a negative electrode Slurry. This negative electrode slurry was coated on the coated film side of the current collector laminated sheet 2 with a width of 180 mm, dried in a hot air oven at 120 ° C. for 1 minute, and then rolled at a linear pressure of 300 kgf / cm. Then, it dried under reduced pressure for 6 hours in a 100 ° C constant temperature bath to obtain an electrode sheet (hereinafter referred to as "negative electrode 1") in which the current collector laminated sheet 2 and the negative electrode active material were laminated. The negative electrode 1 of Comparative Example 2 was obtained by using a rolled copper foil without applying a composition for forming an undercoat layer. The obtained negative electrode 1 was tested in accordance with (1) of the evaluation conditions.

(正極之製造) 　　將作為正極活性物質之鈷酸鋰(日本化學工業股份有限公司製；C-5H)94重量%、作為導電助劑之乙炔黑(AB)3重量%，及作為黏合劑之聚偏二氟乙烯(PVdF)(Arkema股份有限公司製；Kynar 761)3重量%，添加於N-甲基吡咯啶酮(NMP)溶劑中，製造正極漿料。將該正極漿料以寬度180mm塗覆於集電體層合薄片1之塗覆膜側，於120℃溫風爐乾燥1分鐘後，以線壓300kgf/cm進行輥壓。之後，於120℃恆溫槽中減壓乾燥6小時，得到層合有集電體層合薄片1與正極活性物質的電極片(以下稱為「正極1」)。(Manufacture of positive electrode) 94% by weight of lithium cobaltate (manufactured by Japan Chemical Industry Co., Ltd .; C-5H) as a positive electrode active material, 3% by weight of acetylene black (AB) as a conductive auxiliary agent, and 3% by weight of polyvinylidene fluoride (PVdF) (manufactured by Arkema Co., Ltd .; Kynar 761) was added to an N-methylpyrrolidone (NMP) solvent to produce a positive electrode slurry. This positive electrode slurry was coated on the coated film side of the current collector laminated sheet 1 with a width of 180 mm, and dried in a hot air oven at 120 ° C. for 1 minute, and then rolled at a linear pressure of 300 kgf / cm. Then, it dried under reduced pressure for 6 hours in a 120 ° C constant temperature bath to obtain an electrode sheet (hereinafter referred to as "positive electrode 1") in which the current collector laminated sheet 1 and the positive electrode active material were laminated.

[製造例3]蓄電裝置 　　將正極1切割為40mm×40mm、負極1切割為44mm×44mm，負極1係將鎳之耳片(tab)、正極1係將鋁之耳片以電阻熔接進行接合。將隔離膜(Celgard股份有限公司製；#2400)切割為寬度46mm、長度140mm，折為3折，其間將正極1及負極1以對向的方式夾入，將其以使寬度50mm長度100mm之鋁層合電池折為二折者夾住，將耳片抵住的部分夾入密封劑後，將密封劑部分與對其直行之邊予以熱層合使成為袋狀。將其置入100℃之真空烘箱中12小時真空乾燥，接著於乾手套箱中注入6氟化磷酸鋰/EC(碳酸伸乙酯)：DEC(碳酸二乙酯)=1：1之1M電解液(Kishida化學股份有限公司製；LBG-96533)，真空含浸之後，將多餘的電解液取出，以真空密封器接合密封，製造鋰離子蓄電池。對於所得之鋰離子蓄電池，遵照評估條件之(2)進行試驗。[Manufacturing Example 3] Power storage device 正极 The positive electrode 1 was cut into 40 mm × 40 mm, the negative electrode 1 was cut into 44 mm × 44 mm, and the negative electrode 1 was made of nickel tabs, and the positive electrode 1 was made of aluminum tabs by resistance welding. Cut the separator (manufactured by Celgard Co., Ltd .; # 2400) into a width of 46mm, a length of 140mm, and a three-fold fold. In the meantime, sandwich the positive electrode 1 and the negative electrode 1 so that they are 50mm wide and 100mm long The aluminum laminate battery is folded in half, and the portion abutting the ears is sandwiched with the sealant, and then the sealant portion is thermally laminated with the straight edge to form a bag shape. Put it into a vacuum oven at 100 ° C for 12 hours to vacuum dry, and then inject into the dry glove box 6 lithium phosphate fluoride / EC (ethylene carbonate): DEC (diethyl carbonate) = 1: 1 1M electrolysis Solution (manufactured by Kishida Chemical Co., Ltd .; LBG-96533). After the vacuum impregnation, the excess electrolyte was removed and sealed with a vacuum sealer to manufacture a lithium ion battery. The obtained lithium ion battery was tested in accordance with (2) of the evaluation conditions.

[評估條件] (1)負極之電阻測定 　　將負極以寬度20mm長度50mm之尺寸切出4枚。將所切出之2枚的塗覆面彼此對合，將其接觸面調整為20mm×20mm，放置於氯乙烯板上。對2枚所接觸的部分施以加重為1kg/cm2 ，將接觸部分固定。使集電體彼此未接觸之各端部結合於AC迷你歐姆計，測定負極之貫通電阻值2次。[Evaluation Conditions] (1) Measurement of Resistance of Negative Electrode The negative electrode was cut into four pieces having a width of 20 mm and a length of 50 mm. The coated surfaces of the two cut out pieces were opposed to each other, and the contact surfaces thereof were adjusted to 20 mm × 20 mm and placed on a vinyl chloride plate. A weight of 1 kg / cm 2 was applied to the two contacted portions to fix the contacted portions. The ends of the current collectors that were not in contact with each other were connected to an AC mini ohmmeter, and the through resistance value of the negative electrode was measured twice.

(2)鋰離子蓄電池之特性 (初期容量) 　　將鋰離子蓄電池以0.01mA之定電流充電至電壓成為4.2V。接著，以4.2V之定電壓充電2小時。之後，以0.01mA之定電流放電至電壓成為3V。重複其2次，由第2次之充電容量與放電容量算出充放電效率。(2) Characteristics of lithium-ion battery (initial capacity) Charge the lithium-ion battery at a constant current of 0.01mA until the voltage becomes 4.2V. Then, it was charged at a constant voltage of 4.2V for 2 hours. After that, it was discharged at a constant current of 0.01 mA until the voltage became 3V. This was repeated twice, and the charge and discharge efficiency was calculated from the second charge capacity and discharge capacity.

(速率特性) 　　由初期容量求得放電速率，測定各放電速率之放電容量。充電係每次花費10小時，以定電流使電壓上昇至4.2V後，以4.2V定電壓充電2小時。之後，花費10小時以定電流放電至成為3V，以此時的放電容量為0.1C之放電容量。接著同樣地充電後，以於12分鐘從由0.1C求得之放電容量結束放電之電流值進行放電，求得此時之放電容量，作為5C時的放電容量。(Rate characteristics) 求 Obtain the discharge rate from the initial capacity, and measure the discharge capacity at each discharge rate. Charging takes 10 hours at a time. After the voltage is increased to 4.2V with a constant current, the battery is charged with a constant voltage of 4.2V for 2 hours. After that, it took 10 hours to discharge at a constant current to 3V, and the discharge capacity at this time was a discharge capacity of 0.1C. Then, after charging in the same manner, discharge was performed at the current value at which discharge was completed at a discharge capacity of 0.1C in 12 minutes, and the discharge capacity at this time was obtained as the discharge capacity at 5C.

(循環壽命) 　　實施以1C充電至4.2V，以4.2V之定電壓充電2小時後，以1C放電之充放電試驗。計算相對於最初第1次之放電而言，於1,000循環後放電容量變為幾%。(Cycle life) A charge-discharge test was performed after charging at 1C to 4.2V, charging at a constant voltage of 4.2V for 2 hours, and then discharging at 1C. Compared with the first discharge, the calculation shows that the discharge capacity becomes several% after 1,000 cycles.

(循環壽命試驗後之電極的剝離試驗) 　　將電池以上述循環壽命條件進行1,000循環耐久充放電試驗，將電池分解，確認耐久試驗後活性物質層有無自負極脫離。評估基準如以下所述。 　　◎：完全未見到脫離 　　○：一部分見到脫離，但集電體未露出 　　△：脫離進行，集電體的一部分露出 　　×：脫離進行，集電體的大半露出(Peel test of electrode after cycle life test) 电池 The battery was subjected to a 1,000-cycle endurance charge-discharge test under the above-mentioned cycle life conditions, and the battery was decomposed to confirm whether the active material layer was detached from the negative electrode after the endurance test. The evaluation criteria are as follows. ◎: No detachment was seen at all ○: A detachment was seen but the current collector was not exposed △: The detachment proceeded and a part of the current collector was exposed ×: The detachment proceeded and most of the current collector was exposed

由表2，顯示出使用實施例之集電體用組成物作為底塗層形成用組成物時，所得之負極相較於未使用集電體用組成物而得之比較例2之負極而言，循環壽命性優良。又，由表2可知，藉由使用實施例之集電體用組成物，可製作初期容量、速率特性均顯示出優良的特性，同時活性物質層未自集電體脫離的鋰離子蓄電池。又，藉由實施例15～17之比較，顯示出聚丙烯醯胺之重量平均分子量為1,000萬以上、較佳為1,500萬以上時，循環壽命性更優良。Table 2 shows that when the composition for a current collector of the example was used as the composition for forming an undercoat layer, the obtained negative electrode was compared with the negative electrode of Comparative Example 2 obtained without using the composition for a current collector. , Excellent cycle life. As can be seen from Table 2, by using the composition for a current collector of the example, a lithium-ion secondary battery having excellent initial capacity and rate characteristics and having an active material layer not detached from the current collector can be produced. In addition, the comparison of Examples 15 to 17 shows that when the weight average molecular weight of polypropylene amidamide is 10 million or more, and preferably 15 million or more, the cycle life is more excellent.

[實施例29～48、比較例3～6：作為黏合劑組成物之集電體用組成物] [製造例4]負極漿料之製造 　　於10L之燒杯中，以表3所示之各實施例及比較例所對應的各材料與摻合量來添加各成分，冷卻至液溫不超過30℃，同時攪拌至各成分成為均勻，得到負極漿料之塗覆液。[Examples 29 to 48, Comparative Examples 3 to 6: Composition for current collector as binder composition] [Production Example 4] Production of negative electrode slurry was carried out in a 10L beaker, and each of the implementations shown in Table 3 was performed. Examples and Comparative Examples correspond to the respective materials and blending amounts to add each component, cool to a liquid temperature of not more than 30 ° C., and stir until the components become uniform to obtain a coating solution for the negative electrode slurry.

※表3中之各材料係如以下所述。 (1)聚丙烯醯胺 　　聚丙烯醯胺(重量平均分子量60萬～100萬)：和光純藥工業股份有限公司；10重量%聚丙烯醯胺水溶液 　　聚丙烯醯胺(重量平均分子量600萬)：三洋化成工業股份有限公司製；Sunfloc NOP 　　聚丙烯醯胺(重量平均分子量1200萬)：三洋化成工業股份有限公司製；Sunfloc N-500P 　　聚丙烯醯胺(重量平均分子量1600萬)：MT AQUAPOLYMER股份有限公司製；Accofloc N-102 (2)有機酸、無機酸、有機酸之金屬鹽、無機酸之金屬鹽 　　聚丙烯酸：東亞合成股份有限公司製；20重量%水溶液、AC10H 　　聚丙烯酸Na：東亞合成股份有限公司製；40重量%水溶液、A-6330 　　天門冬胺酸：和光純藥工業股份有限公司製；100重量%、L-天門冬胺酸 　　苯均四酸：東京化成工業股份有限公司；100重量% 　　氫氟酸：和光純藥工業股份有限公司製；49.5重量%氫氟酸 　　6氟化磷酸：和光純藥工業股份有限公司製；60重量%六氟磷酸水溶液 　　4氟化硼酸：和光純藥工業股份有限公司製；42重量%四氟硼酸水溶液 (3)樹脂黏合劑 　　苯乙烯丁二烯橡膠(SBR)：日本A&L股份有限公司製；48重量%乳膠、Nalstar SR-115 　　羧基甲基纖維素(CMC)：日本製紙Chemical股份有限公司製；100重量%、Sunrose F-600LC (4)負極活性物質 　　石墨：昭和電工股份有限公司製；SCMG-AR※ The materials in Table 3 are as follows. (1) Polyacrylamide Polyacrylamide (weight average molecular weight 600,000 to 1 million): Wako Pure Chemical Industry Co., Ltd .; 10% by weight aqueous solution of polyacrylamide Polyacrylamide (weight average molecular weight 6 million): Made by Sanyo Chemical Industry Co., Ltd .; Sunfloc NOP Polyacrylamide (weight average molecular weight 12 million): Made by Sanyo Chemical Industry Co., Ltd .; Sunfloc N-500P Polypropylene amine (weight average molecular weight 16 million): MT AQUAPOLYMER Limited Made by the company; Accofloc N-102 (2) Organic acid, inorganic acid, metal salt of organic acid, metal salt of inorganic acid Polyacrylic acid: made by Toa Synthetic Co., Ltd .; 20% by weight aqueous solution, AC10H polyacrylic acid Na: Toa synthetic Co., Ltd .; 40% by weight aqueous solution, A-6330 Aspartic acid: manufactured by Wako Pure Chemical Industries, Ltd .; 100% by weight, L-aspartic acid pyromellitic acid: Tokyo Chemical Industry Co., Ltd .; 100% % Hydrofluoric acid: manufactured by Wako Pure Chemical Industries, Ltd .; 49.5 wt% hydrogen Acid 6 fluorinated phosphoric acid: manufactured by Wako Pure Chemical Industries, Ltd .; 60% by weight aqueous solution of hexafluorophosphoric acid 4 fluorinated boric acid: manufactured by Wako Pure Chemical Industries, Ltd .; 42% by weight aqueous solution of tetrafluoroboric acid (3) resin binder benzene Ethylene butadiene rubber (SBR): Japan A & L Co., Ltd .; 48% by weight latex, Nalstar SR-115 carboxymethyl cellulose (CMC): Japan Paper Chemical Co., Ltd .; 100% by weight, Sunrose F-600LC (4) Graphite for negative electrode active material: manufactured by Showa Denko Corporation; SCMG-AR

[製造例5]蓄電裝置用電極片 　　負極之製造(本發明1) 　　使用集電體3(寬度300mm、厚度20μm之壓延銅箔)，作為集電體。將製造例4中所得之負極漿料之塗覆液，以寬度180mm塗覆於集電體3之塗覆膜側，於120℃溫風爐乾燥1分鐘後，以線壓300kgf/cm進行輥壓。之後，於100℃恆溫槽減壓乾燥6小時，得到層合有集電體3與負極活性物質的本發明之電極板(以下稱為「負極2」)。[Production Example 5] Electrode sheet for power storage device 制造 Production of negative electrode (Invention 1) A current collector 3 (rolled copper foil having a width of 300 mm and a thickness of 20 μm) was used as a current collector. The coating liquid of the negative electrode slurry obtained in Manufacturing Example 4 was applied to the coating film side of the current collector 3 with a width of 180 mm, and dried in a hot air oven at 120 ° C for 1 minute, and then rolled with a linear pressure of 300 kgf / cm. Pressure. Then, it dried under reduced pressure for 6 hours in a 100 ° C constant temperature bath to obtain an electrode plate of the present invention (hereinafter referred to as "negative electrode 2") in which a current collector 3 and a negative electrode active material were laminated.

(正極之製造) 　　使用集電體4(寬度300mm、厚度15μm之壓延鋁箔)，作為集電體。將作為正極活性物質之鈷酸鋰(日本化學工業股份有限公司製；C-5H)94重量%、作為導電助劑之乙炔黑(AB)3重量%，及作為黏合劑之聚偏二氟乙烯(PVdF) (Arkema股份有限公司製；Kynar 761)3重量%，添加於N-甲基吡咯啶酮(NMP)溶劑中，製造正極漿料。將該正極漿料，以寬度180mm塗覆於集電體4之塗覆膜側，於120℃溫風爐乾燥1分鐘後，以線壓300kgf/cm進行輥壓。之後，於120℃恆溫槽減壓乾燥6小時，得到層合有集電體4與正極活性物質的本發明之電極板(以下稱為「正極2」)。(Manufacture of positive electrode) A current collector 4 (rolled aluminum foil having a width of 300 mm and a thickness of 15 μm) was used as the current collector. 94% by weight of lithium cobaltate (manufactured by Japan Chemical Industry Co., Ltd .; C-5H) as a positive electrode active material, 3% by weight of acetylene black (AB) as a conductive aid, and polyvinylidene fluoride as a binder (PVdF) (manufactured by Arkema Co., Ltd .; Kynar 761) was added at 3% by weight to an N-methylpyrrolidone (NMP) solvent to produce a positive electrode slurry. This positive electrode slurry was applied to the coating film side of the current collector 4 with a width of 180 mm, and dried in a hot air oven at 120 ° C. for 1 minute, and then rolled at a linear pressure of 300 kgf / cm. Then, it dried under reduced pressure for 6 hours in a 120 ° C thermostatic bath to obtain an electrode plate of the present invention (hereinafter referred to as "positive electrode 2") in which a current collector 4 and a positive electrode active material were laminated.

[製造例6]蓄電裝置 　　除了將負極1取代為負極2、將正極1取代為正極2以外，係以製造例3記載之方法，製造鋰離子蓄電池。對於所得之鋰離子蓄電池，遵照前述評估條件之(2)進行試驗。[Production Example 6] Power storage device A lithium-ion secondary battery was manufactured by the method described in Production Example 3 except that the negative electrode 1 was replaced with the negative electrode 2 and the positive electrode 1 was replaced with the positive electrode 2. The obtained lithium ion battery was tested in accordance with (2) of the aforementioned evaluation conditions.

由表4，顯示出使用實施例之集電體組成物作為黏合劑組成物時，使用所得之負極的蓄電池，循環壽命性優良。又，由表4可知，藉由使用實施例之集電體組成物，可製造初期容量、速率特性均顯示出優良特性，同時活性物質層未自集電體脫離的鋰離子蓄電池。Table 4 shows that when the current collector composition of the example was used as the binder composition, the battery using the obtained negative electrode had excellent cycle life. In addition, it can be seen from Table 4 that by using the current collector composition of the example, a lithium-ion secondary battery having excellent initial capacity and rate characteristics and having no active material layer detached from the current collector can be manufactured.

1‧‧‧活性物質層1‧‧‧active material layer

2‧‧‧使用了底塗層形成用組成物之底塗層2‧‧‧ An undercoat layer using a composition for forming an undercoat layer

3‧‧‧集電體3‧‧‧ current collector

4‧‧‧使用了含有黏合劑組成物與活性物質的電極形成用組成物之活性物質層4‧‧‧ Active material layer using an electrode-forming composition containing a binder composition and an active material

[圖1]表示使用底塗層形成用組成物之電極片的構造之示意圖。 　　[圖2]表示使用電極形成用組成物之電極片的構造之示意圖。FIG. 1 is a schematic diagram showing a structure of an electrode sheet using a composition for forming an undercoat layer. [Fig. 2] A schematic diagram showing a structure of an electrode sheet using a composition for electrode formation.

Claims (13)

一種電池或電雙層電容器之集電體用組成物，其含有聚丙烯醯胺，與選自由有機酸、有機酸之無水物、無機酸、有機酸之金屬鹽及無機酸之金屬鹽所成之群的至少1種。A composition for a current collector of a battery or an electric double-layer capacitor, comprising polypropylene amide, and selected from the group consisting of an organic acid, an anhydrate of an organic acid, an inorganic acid, a metal salt of an organic acid, and a metal salt of an inorganic acid Group of at least one. 如請求項1之集電體用組成物，其中聚丙烯醯胺之重量平均分子量，為1,000,000～100,000,000。For example, the composition for a current collector of claim 1, wherein the weight average molecular weight of the polyacrylamide is 1,000,000 to 100,000,000. 如請求項1或2之集電體用組成物，其中有機酸，為選自由苯均四酸、1,2,3-丙烷三羧酸、天門冬胺酸、蜜石酸及聚丙烯酸所成之群的至少1種；有機酸之無水物，為選自由前述有機酸之無水物所成之群的至少1種；無機酸，為選自由鹽酸、氫氟酸、6氟化磷酸及4氟化硼酸所成之群的至少1種；有機酸之金屬鹽，為選自由前述有機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種；且無機酸之金屬鹽，為選自由前述無機酸與鋰、鈉、鉀或鈣之鹽所成之群的至少1種。The composition for a current collector according to claim 1 or 2, wherein the organic acid is selected from the group consisting of pyromellitic acid, 1,2,3-propanetricarboxylic acid, aspartic acid, tartaric acid, and polyacrylic acid. At least one species of group; an anhydrous substance of an organic acid is at least one substance selected from the group consisting of the anhydrous substance of the organic acid; an inorganic acid is selected from the group consisting of hydrochloric acid, hydrofluoric acid, 6-fluorinated phosphoric acid, and 4 fluorine At least one kind of group formed by boric acid; a metal salt of an organic acid is at least one kind selected from the group consisting of the aforementioned organic acid and a salt of lithium, sodium, potassium, or calcium; and a metal salt of an inorganic acid is At least one selected from the group consisting of the inorganic acid and a salt of lithium, sodium, potassium, or calcium. 如請求項1或2之集電體用組成物，其進一步含有選自由合成橡膠系乳膠型黏合劑、苯乙烯丁二烯橡膠乳膠及腈丁二烯橡膠乳膠所成之群的至少1種。The composition for a current collector according to claim 1 or 2, further comprising at least one selected from the group consisting of a synthetic rubber-based latex-type adhesive, a styrene butadiene rubber latex, and a nitrile butadiene rubber latex. 如請求項1或2之集電體用組成物，其進一步含有選自由碳黑、鎳粉、鐵粉、氧化鋁、二氧化矽、氧化鈦及氧化鋯所成之群的至少1種。The composition for a current collector according to claim 1 or 2, further comprising at least one selected from the group consisting of carbon black, nickel powder, iron powder, aluminum oxide, silicon dioxide, titanium oxide, and zirconia. 如請求項3之集電體用組成物，其進一步含有選自由碳黑、鎳粉、鐵粉、氧化鋁、二氧化矽、氧化鈦及氧化鋯所成之群的至少1種。The composition for a current collector according to claim 3, further comprising at least one selected from the group consisting of carbon black, nickel powder, iron powder, aluminum oxide, silicon dioxide, titanium oxide, and zirconia. 一種底塗層形成用組成物，其係由如請求項1～6中任一項之集電體用組成物所構成。A composition for forming an undercoat layer, comprising the composition for a current collector according to any one of claims 1 to 6. 一種黏合劑組成物，其係由如請求項1～6中任一項之集電體用組成物所構成。An adhesive composition comprising the composition for a current collector according to any one of claims 1 to 6. 一種電極形成用組成物，其含有如請求項8之黏合劑組成物與活性物質。A composition for forming an electrode, comprising the binder composition according to claim 8 and an active material. 一種電池或電雙層電容器之集電體之製造方法，其包含 　　將如請求項7之底塗層形成用組成物塗佈於集電體上，而形成底塗層形成用組成物之塗膜之步驟，及 　　於塗佈有前述底塗層形成用組成物的集電體上，塗佈導電性之活性物質之步驟。A method for manufacturing a current collector of a battery or an electric double-layer capacitor, comprising applying the undercoat layer-forming composition as claimed in claim 7 on the current collector to form a coating film of the undercoat layer-forming composition. A step of applying a conductive active material to a current collector coated with the aforementioned composition for forming an undercoat layer. 一種電池或電雙層電容器之集電體之製造方法，其包含 　　將如請求項9之電極形成用組成物塗佈於集電體上，而形成電極形成用組成物之塗膜之步驟。A method for manufacturing a current collector for a battery or an electric double-layer capacitor, comprising the steps of: (a) coating the current collector with the electrode forming composition as claimed in claim 9 to form a coating film of the electrode forming composition; 一種電池或電雙層電容器之集電體，其係經如請求項1～9中任一項之組成物塗覆。A current collector for a battery or an electric double-layer capacitor, which is coated with the composition according to any one of claims 1 to 9. 一種電池或電雙層電容器，其包含如請求項12之電池或電雙層電容器之集電體。A battery or an electric double-layer capacitor comprising a battery or a current collector of an electric double-layer capacitor as claimed in claim 12.
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