TW202018047A - Binder for nonaqueous electrolyte batteries, aqueous binder solution and slurry composition each using same, electrode for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery - Google Patents

Binder for nonaqueous electrolyte batteries, aqueous binder solution and slurry composition each using same, electrode for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery Download PDF

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TW202018047A
TW202018047A TW107144468A TW107144468A TW202018047A TW 202018047 A TW202018047 A TW 202018047A TW 107144468 A TW107144468 A TW 107144468A TW 107144468 A TW107144468 A TW 107144468A TW 202018047 A TW202018047 A TW 202018047A
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binder
aqueous electrolyte
copolymer
carboxylic acid
electrolyte battery
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TWI833722B (en
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太田有紀
岩崎秀治
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日商可樂麗股份有限公司
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a binder for nonaqueous electrolyte batteries, which contains a neutralized salt of a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid, and wherein the neutralized salt is a neutralized salt of the copolymer and a basic substance that contains a polyvalent metal.

Description

非水電解質電池用黏合劑、使用其之黏合劑水溶液及漿體組成物、以及非水電解質電池用電極及非水電解質電池 Binder for non-aqueous electrolyte battery, binder aqueous solution and slurry composition using the same, electrode for non-aqueous electrolyte battery and non-aqueous electrolyte battery

本發明係關於一種非水電解質電池用黏合劑、使用其之黏合劑水溶液及漿體組成物、以及非水電解質電池用電極及非水電解質電池。 The present invention relates to a binder for non-aqueous electrolyte batteries, binder aqueous solutions and slurry compositions using the same, and electrodes and non-aqueous electrolyte batteries for non-aqueous electrolyte batteries.

近年來,行動電話、筆記型個人電腦、平板型資訊終端機等行動終端之普及顯著。行動終端追求更舒適的攜帶性,而伴隨小型化、薄型化、輕量化及高性能化之急速發展,使用於行動終端之電池亦要求小型化、薄型化、輕量化及高性能化。作為這樣的行動終端之電源所使用的二次電池,經常使用鋰離子二次電池。鋰離子二次電池等非水電解質電池具有下述結構:隔著隔離材設置正極與負極並與電解液一起收納於容器內之結構,該電解液係使如LiPF6、LiBF4、LiTFSI(雙(三氟甲基磺醯基)醯亞胺鋰)、LiFSI(雙(氟磺醯基)醯亞胺鋰)的鋰鹽溶解於碳酸伸乙酯等有機液體而成者。 In recent years, the popularity of mobile terminals such as mobile phones, notebook personal computers, and tablet-type information terminals has been remarkable. Mobile terminals are pursuing more comfortable portability. With the rapid development of miniaturization, thinness, weight reduction, and high performance, batteries used in mobile terminals also require miniaturization, thinness, weight reduction, and high performance. As a secondary battery used as a power source of such a mobile terminal, a lithium ion secondary battery is often used. A non-aqueous electrolyte battery such as a lithium ion secondary battery has a structure in which a positive electrode and a negative electrode are provided through a separator and stored in a container together with an electrolyte solution such as LiPF 6 , LiBF 4 , LiTFSI (double The lithium salt of (trifluoromethylsulfonyl) lithium imide), LiFSI (lithium bis(fluorosulfonyl) imide) is dissolved in an organic liquid such as ethyl carbonate.

構成非水電解質電池之負極及正極,通常係使黏合劑及增黏劑溶解或分散於水或溶劑,對其混合活性物質和導電助劑(導電賦予劑)等,所得之電極用漿體 (以下有僅稱為「漿體」之情形)在塗布於集電體後,藉由使水或溶劑乾燥而使其結著以形成為混合層。 The negative electrode and positive electrode of a non-aqueous electrolyte battery are usually made by dissolving or dispersing a binder and a thickener in water or a solvent, mixing an active material and a conductive auxiliary agent (conductivity-imparting agent), etc. to obtain a slurry for electrodes (Hereinafter referred to as "slurry") After being coated on the current collector, it is bound by drying with water or solvent to form a mixed layer.

近年來,從降低對環境之負荷和製造裝置之簡便性的觀點來看,對於不使用溶劑而是使用水之漿體作為電極用漿體的關注度提高,尤其在負極之製造上,正轉往使用水媒介之漿體急速發展。作為這樣的水媒介用之黏合劑,已知以工業上最常用之於苯乙烯-丁二烯橡膠(SBR)等二烯系橡膠添加羧甲基纖維素‧鈉鹽(CMC-Na)作為增黏劑之系(例如專利文獻1)為首之各種類型的黏合劑:聚丙烯酸等丙烯酸系黏合劑(例如專利文獻2及3)、聚醯胺/醯亞胺系之黏合劑(例如專利文獻4及5)、聚乙烯醇系黏合劑(例如專利文獻6及7)等。 In recent years, from the viewpoint of reducing the load on the environment and the simplicity of the manufacturing equipment, attention has been paid to the use of a slurry of water instead of a solvent as an electrode slurry, especially in the production of negative electrodes. The rapid development of slurry using water media. As such a binder for an aqueous medium, it is known to add carboxymethyl cellulose‧sodium salt (CMC-Na) as the most commonly used in the industry to diene rubbers such as styrene-butadiene rubber (SBR) Various types of adhesives including adhesives (for example, Patent Document 1): acrylic adhesives such as polyacrylic acid (for example, Patent Documents 2 and 3), polyamidoamine/acrylimide adhesives (for example, Patent Document 4) And 5), polyvinyl alcohol-based adhesives (for example, Patent Documents 6 and 7) and the like.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2014-13693公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2014-13693

[專利文獻2]日本特開2002-260667公報 [Patent Document 2] Japanese Unexamined Patent Publication No. 2002-260667

[專利文獻3]日本特開2003-282061公報 [Patent Document 3] Japanese Unexamined Patent Publication 2003-282061

[專利文獻4]日本特開2001-68115公報 [Patent Document 4] Japanese Unexamined Patent Publication 2001-68115

[專利文獻5]日本特開2015-65164公報 [Patent Document 5] Japanese Patent Laid-Open No. 2015-65164

[專利文獻6]日本特開平11-250915公報 [Patent Document 6] Japanese Laid-Open Patent Publication No. 11-250915

[專利文獻7]日本特開2017-59527公報 [Patent Document 7] Japanese Patent Application Publication No. 2017-59527

然而,以往使用之SBR/CMC-Na添加系之黏 合劑,除了有難以承受充放電時產生的熱,容量維持率低的問題以外,還有因為是2液型所以保存安定性低,漿體製作步驟繁雜之製造上的課題。又,如上述專利文獻2~5所揭示之丙烯酸系黏合劑及聚醯胺/醯亞胺系黏合劑,其柔軟性不足、電極容易破裂且電阻高的問題並未充分解決。再者,聚乙烯醇系黏合劑因活性物質易凝集而有漿體安定性變低的傾向,即使在為了提高安定性而併用如纖維素衍生物之水溶性高分子之情形,其電阻亦高,就作為非水電解質電池之電極所使用的黏合劑而言,尚未充分滿足。 However, the SBR/CMC-Na additive system used in the past In addition to the problems of being difficult to withstand the heat generated during charge and discharge and the low capacity retention rate, the mixture has the problems of manufacturing stability because of the two-liquid type, low storage stability, and complicated slurry preparation steps. In addition, the acrylic adhesives and polyacrylamide/imide adhesives disclosed in Patent Documents 2 to 5 described above have not sufficiently solved the problems of insufficient flexibility, electrodes being easily broken, and high electrical resistance. In addition, the polyvinyl alcohol-based adhesive tends to have a low stability of the slurry due to the easy aggregation of the active material. Even when water-soluble polymers such as cellulose derivatives are used in combination to improve the stability, the resistance is high. As for the binder used as the electrode of the non-aqueous electrolyte battery, it has not been fully satisfied.

因此,本發明之目的係提供一種漿體安定性優異且當使用於非水電解質電池之電極時可實現低電阻化之非水電解質電池用黏合劑,謀求非水電解質電池的電池之高容量化(低電阻化、高效率化)、電池壽命(循環特性)及充電速度(速率特性)等電池特性之提升。 Therefore, an object of the present invention is to provide a binder for a non-aqueous electrolyte battery that is excellent in slurry stability and can be used to reduce resistance when used in an electrode of a non-aqueous electrolyte battery, and to increase the capacity of the battery of the non-aqueous electrolyte battery (Lower resistance, higher efficiency), battery life (cycle characteristics), and charging speed (rate characteristics) are improved.

本發明者等為了解決上述課題而潛心探討,結果完成本發明。亦即,本發明提供下述的理想態樣。 The present inventors have intensively studied to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides the following ideal aspects.

[1]一種非水電解質電池用黏合劑,其係包含乙烯醇與乙烯性不飽和羧酸之共聚物的中和鹽而成,前述中和鹽為前述共聚物與包含多價金屬之鹼性物質的中和鹽。 [1] A binder for non-aqueous electrolyte batteries, which is composed of a neutralized salt containing a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid, and the aforementioned neutralized salt is the basicity of the aforementioned copolymer and containing a polyvalent metal Substance neutralization salt.

[2]如前述[1]所記載之非水電解質電池用黏合劑,其中前述中和鹽為前述共聚物與包含多價金屬之鹼性物質及包含鹼金屬之鹼性物質的中和鹽。 [2] The binder for a non-aqueous electrolyte battery according to the above [1], wherein the neutralizing salt is a neutralizing salt of the copolymer and an alkaline substance containing a polyvalent metal and an alkaline substance containing an alkali metal.

[3]如前述[1]或[2]所記載之非水電解質電池用黏合 劑,其中多價金屬為二價金屬。 [3] Adhesive for non-aqueous electrolyte batteries as described in [1] or [2] above Agent, where the multivalent metal is a divalent metal.

[4]如前述[1]~[3]中任一項所記載之非水電解質電池用黏合劑,其中非水電解質電池用黏合劑中的多價金屬原子之含量係相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元而言小於0.5當量。 [4] The binder for a non-aqueous electrolyte battery as described in any one of the above [1] to [3], wherein the content of polyvalent metal atoms in the binder for a non-aqueous electrolyte battery is relative to vinyl alcohol and ethylene The ethylenically unsaturated carboxylic acid unit in the copolymer of the unsaturated unsaturated carboxylic acid is less than 0.5 equivalent.

[5]如前述[1]~[4]中任一項所記載之非水電解質電池用黏合劑,其中在非水電解質電池用黏合劑中,相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元之多價金屬原子及鹼金屬原子的合計當量比為1以下。 [5] The binder for a non-aqueous electrolyte battery as described in any one of the above [1] to [4], wherein the binder for a non-aqueous electrolyte battery relative to the vinyl alcohol and the ethylenically unsaturated carboxylic acid The total equivalent ratio of the polyvalent metal atom and the alkali metal atom of the ethylenically unsaturated carboxylic acid unit in the copolymer is 1 or less.

[6]如前述[1]~[5]中任一項所記載之非水電解質電池用黏合劑,其中乙烯醇與乙烯性不飽和羧酸之共聚物為接枝共聚物。 [6] The binder for a non-aqueous electrolyte battery as described in any one of the above [1] to [5], wherein the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid is a graft copolymer.

[7]一種非水電解質電池用黏合劑水溶液,其係包含如前述[1]~[6]中任一項所記載之非水電解質電池用黏合劑及水而成。 [7] An aqueous solution of a binder for a non-aqueous electrolyte battery, which comprises the binder for a non-aqueous electrolyte battery as described in any one of [1] to [6] and water.

[8]一種非水電解質電池用漿體組成物,其係包含如前述[1]~[6]中任一項所記載之非水電解質電池用黏合劑、活性物質及水而成。 [8] A slurry composition for a non-aqueous electrolyte battery, which comprises the binder for a non-aqueous electrolyte battery as described in any one of the above [1] to [6], an active material, and water.

[9]一種非水電解質電池用電極,其包含集電體,該集電體具備:包含如前述[1]~[6]中任一項所記載之非水電解質電池用黏合劑及活性物質所成之層。 [9] An electrode for a non-aqueous electrolyte battery, including a current collector including: a binder and an active material for a non-aqueous electrolyte battery as described in any one of the above [1] to [6] The layer formed.

[10]一種非水電解質電池,其具有如前述[9]所記載之非水電解質電池用電極。 [10] A non-aqueous electrolyte battery having the electrode for a non-aqueous electrolyte battery as described in [9] above.

根據本發明,可提供一種漿體安定性優異且當使用於非水電解質電池之電極時可實現低電阻化之非水電解質電池用黏合劑,使用其可提升非水電解質電池之電池特性。 According to the present invention, it is possible to provide a binder for a non-aqueous electrolyte battery which is excellent in slurry stability and which can achieve low resistance when used in an electrode of a non-aqueous electrolyte battery, and which can improve the battery characteristics of the non-aqueous electrolyte battery.

以下針對本發明之實施形態進行詳細說明,惟本發明並未限定於此等。 The embodiments of the present invention will be described in detail below, but the present invention is not limited to these.

本發明之非水電解質電池用黏合劑(以下亦稱為「本發明之黏合劑」)係包含乙烯醇與乙烯性不飽和羧酸之共聚物的中和鹽而成。在本發明中,共聚物的中和鹽係指由乙烯性不飽和羧酸所生成之羰酸的活性氫與鹼性物質反應而形成鹽作為中和物存在者。此外,本發明之黏合劑主要由前述中和鹽所構成,惟共聚物的中和鹽通常藉由在複數的共聚物之存在下與鹼性物質反應而得,因此本發明之黏合劑亦可包含未形成中和鹽而存在之共聚物。 The binder for a non-aqueous electrolyte battery of the present invention (hereinafter also referred to as "binder of the present invention") is made of a neutralized salt containing a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid. In the present invention, the neutralized salt of the copolymer means that the active hydrogen of the carbonyl acid generated from the ethylenically unsaturated carboxylic acid reacts with an alkaline substance to form a salt and exists as a neutralized substance. In addition, the adhesive of the present invention is mainly composed of the aforementioned neutralizing salt, but the neutralizing salt of the copolymer is usually obtained by reacting with a basic substance in the presence of a plurality of copolymers, so the adhesive of the present invention can also Including copolymers that exist without forming a neutralizing salt.

藉由使用乙烯醇與乙烯性不飽和羧酸之共聚物,相較於以往的丙烯酸系黏合劑和聚乙烯醇系黏合劑,可提高電極之柔軟性,在長期使用電極時,即使活性物質反覆膨脹與收縮之情形亦不易破裂,可得到具有經改善之耐久性的電極。在本發明中,作為乙烯性不飽和羧酸,例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸等乙烯性不飽和單羧酸;反丁烯二酸、亞甲基丁二酸、順 丁烯二酸等乙烯性不飽和二羧酸等。其中從取得性、聚合性、生成物之安定性等的觀點來看,又以丙烯酸、甲基丙烯酸及順丁烯二酸為較佳。此等之乙烯性不飽和羧酸酯可單獨使用1種,亦可組合2種以上來使用。 By using a copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid, the flexibility of the electrode can be improved compared to the conventional acrylic adhesive and polyvinyl alcohol adhesive. Even when the electrode is used for a long period of time, even if the active material is repeated The case of expansion and contraction is also not easy to break, and an electrode with improved durability can be obtained. In the present invention, examples of the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; fumaric acid, methylene succinic acid, cis Butyric acid and other ethylenically unsaturated dicarboxylic acids. Among them, acrylic acid, methacrylic acid, and maleic acid are more preferred from the viewpoint of availability, polymerizability, and stability of products. One type of these ethylenically unsaturated carboxylic acid esters may be used alone, or two or more types may be used in combination.

在本發明中,共聚物中相對於乙烯醇之乙烯性不飽和羧酸的含量(乙烯性不飽和羧酸變性量)係以0.1~60莫耳%為較佳,1~50莫耳%為更佳,5~35莫耳%為再佳。若相對於乙烯醇之乙烯性不飽和羧酸的含量在前述範圍內,則作為溶解於水之高分子量體之親水性、水溶性、對於金屬和離子之親和性變得良好。又,當使用於非水電解質電池之電極時,亦有可對電極賦予適度的韌性,降低電阻之優點。此外,乙烯性不飽和羧酸之含量(變性量)例如可藉由核磁共振譜法(NMR)來定量。 In the present invention, the content of the ethylenically unsaturated carboxylic acid in the copolymer relative to the vinyl alcohol (the amount of denaturation of the ethylenically unsaturated carboxylic acid) is preferably 0.1 to 60 mol %, and 1 to 50 mol% Even better, 5 to 35 mol% is the best. When the content of the ethylenically unsaturated carboxylic acid relative to the vinyl alcohol is within the aforementioned range, the hydrophilicity, water solubility, and affinity for metals and ions of the high molecular weight body dissolved in water become good. In addition, when used in the electrode of a non-aqueous electrolyte battery, it also has the advantage of giving moderate toughness to the electrode and reducing resistance. In addition, the content (denaturation amount) of the ethylenically unsaturated carboxylic acid can be quantified by nuclear magnetic resonance spectroscopy (NMR), for example.

在本發明中,乙烯醇與乙烯性不飽和羧酸共聚物之共聚合形態並未特別限定,可為無規共聚物、交互共聚物、嵌段共聚物、接枝共聚物等之任一者。由於藉由規則地排列乙烯醇可提升接著性,因此作為共聚合形態係以嵌段共聚物或接枝共聚物為較佳,由於可在保持高接著性的狀態下得到適度的柔軟性,因此以接枝共聚物為更佳。又,從容易製造,工業生產性優異的觀點來看,亦以接枝共聚物為有利。 In the present invention, the copolymerization form of the vinyl alcohol and ethylenically unsaturated carboxylic acid copolymer is not particularly limited, and may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, etc. . Since the vinyl alcohol can be regularly arranged to improve adhesion, a block copolymer or a graft copolymer is preferred as the copolymerization morphology. Since moderate flexibility can be obtained while maintaining high adhesion, the The graft copolymer is better. In addition, from the viewpoint of easy production and excellent industrial productivity, the graft copolymer is also advantageous.

在本發明中,上述共聚物能以聚乙烯醇與乙烯性不飽和羧酸作為起始原料,藉由以往周知的方法來製造。例如可使用陰離子聚合、陽離子聚合、自由基聚 合等任一聚合起始方法,又,亦可採用溶液聚合、塊狀聚合、懸浮聚合、分散聚合或乳液聚合等任一方法。 In the present invention, the above copolymer can be produced by a conventionally known method using polyvinyl alcohol and an ethylenically unsaturated carboxylic acid as starting materials. For example, anionic polymerization, cationic polymerization, free radical polymerization can be used Any polymerization initiation method, such as solution polymerization, bulk polymerization, suspension polymerization, dispersion polymerization, or emulsion polymerization, can also be used.

在本發明中,乙烯醇與乙烯性不飽和羧酸共聚物之平均分子量係以數量平均分子量而言為5,000~250,000為較佳,10,000以上為更佳,15,000以上為再佳,200,000以下為更佳,150,000以下為再佳。若數量平均分子量為上述下限值以上,則可得到具有良好的機械強度之黏合劑。又,若數量平均分子量為上述上限以下,則當作成漿體組成物時之黏度安定性提升,不易發生漿體之凝集,漿體組成物之操作性優異。此外,本發明之共聚物的數量平均分子量,係意指藉由使用聚環氧乙烷及聚乙二醇作為標準物質,且使用水系管柱作為管柱之凝膠滲透層析(GPC)法來測定之值。 In the present invention, the average molecular weight of the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid is preferably 5,000 to 250,000 in terms of number average molecular weight, more preferably 10,000 or more, even more preferably 15,000 or more, and more preferably 200,000 or less Best, below 150,000 is the best. If the number average molecular weight is equal to or higher than the above lower limit, an adhesive with good mechanical strength can be obtained. In addition, if the number average molecular weight is equal to or lower than the above upper limit, the viscosity stability when used as a slurry composition is improved, and the aggregation of the slurry is unlikely to occur, and the slurry composition is excellent in handleability. In addition, the number average molecular weight of the copolymer of the present invention means a gel permeation chromatography (GPC) method using polyethylene oxide and polyethylene glycol as standard materials and using an aqueous column as the column To determine the value.

在本發明之黏合劑中,前述共聚物的中和鹽係前述共聚物與包含多價金屬之鹼性物質之中和鹽。藉由構成前述共聚物之乙烯性不飽和羧酸中的羧基採取由多價金屬所交聯之結構,當作成漿體組成物時,構成黏合劑之聚合物中的羥基及羧酸的氫鍵所致之凝集可被緩和,可謀求漿體之安定性。又,當將本發明之黏合劑作成水溶液時,亦有可藉由交聯來增加黏度,可藉由抑制凝集來提升漿體安定性之優點。 In the adhesive of the present invention, the neutralizing salt of the aforementioned copolymer is a neutralizing salt of the aforementioned copolymer and an alkaline substance containing a polyvalent metal. When the carboxyl group in the ethylenically unsaturated carboxylic acid constituting the aforementioned copolymer adopts a structure cross-linked by a polyvalent metal, when used as a slurry composition, the hydroxyl group in the polymer constituting the binder and the hydrogen bond of the carboxylic acid The resulting agglutination can be alleviated, and the stability of the slurry can be sought. In addition, when the binder of the present invention is made into an aqueous solution, there is an advantage that the viscosity can be increased by crosslinking, and the stability of the slurry can be improved by suppressing aggregation.

在本發明中,多價金屬係意指價數為二價以上的金屬,例如可列舉:鎂、鈣、鋇等週期表第2族之金屬、鋁等。其中從對於水之溶解性或電安定性的觀點來看,多價金屬又以二價金屬為較佳,鎂及鈣為更佳。 在本發明中,作為為了形成乙烯醇與乙烯性不飽和羧酸之共聚物的中和鹽可使用之包含多價金屬之鹼性物質,例如可列舉:碳酸鈣、碳酸鎂等碳酸鹽;氫氧化鈣、氫氧化鎂、氫氧化鋇、氫氧化鋁等氫氧化物;乙酸鎂、乙酸鈣、乙酸鋁等乙酸鹽;氯化鎂、氯化鈣、氯化鋁等氯化物等。其中從對於水之溶解性的觀點來看,又以乙酸鎂、乙酸鈣為較佳。包含多價金屬之鹼性物質可單獨使用,亦可組合2種以上來使用。 In the present invention, a polyvalent metal means a metal having a valence of more than two valences, and examples thereof include metals of Group 2 of the periodic table, such as magnesium, calcium, and barium, and aluminum. Among them, from the viewpoint of water solubility or electrical stability, bivalent metals are more preferred, and magnesium and calcium are more preferred. In the present invention, an alkaline substance containing a polyvalent metal that can be used as a neutralizing salt for forming a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid includes, for example, carbonates such as calcium carbonate and magnesium carbonate; hydrogen Hydroxides such as calcium oxide, magnesium hydroxide, barium hydroxide, and aluminum hydroxide; acetates such as magnesium acetate, calcium acetate, and aluminum acetate; chlorides such as magnesium chloride, calcium chloride, and aluminum chloride. Among them, magnesium acetate and calcium acetate are more preferable from the viewpoint of solubility in water. The alkaline substance containing polyvalent metals may be used alone or in combination of two or more.

在本發明之黏合劑中,多價金屬原子之含量係以相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元而言小於0.5當量為較佳。在此,在本發明中,相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元之多價金屬原子的當量,係表示相對於1莫耳的該乙烯性不飽和羧酸單元之多價金屬原子的莫耳量。若多價金屬原子之含量小於0.5當量,則可抑制必要以上的黏度上升,作為黏合劑之操作性變佳,電極之製作變得容易。又,茲認為:乙烯醇與乙烯性不飽和羧酸之共聚物的接著效果係在混入經分散之活性物質的狀態下藉由聚合物凝集而顯示高接著性,若與共聚物形成交聯結構之多價金屬原子的量過多,則聚合物之凝集力會因形成之交聯而受到抑制,有接著力降低之傾向,但只要小於0.5當量即可實現高接著性。因此,多價金屬原子之含量係以相對於乙烯性不飽和羧酸單元而言為0.4當量以下為較佳。又,由於可得到鹼殘留少的水溶性共聚物鹽,亦可提升使用該黏合劑之電 極的接著性,因此多價金屬原子之含量係以相對於乙烯性不飽和羧酸單元而言為0.05當量以上為較佳,0.08當量以上為更佳。 In the adhesive of the present invention, the content of the polyvalent metal atom is preferably less than 0.5 equivalent with respect to the ethylenically unsaturated carboxylic acid unit in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid. Here, in the present invention, the equivalent of the polyvalent metal atom of the ethylenically unsaturated carboxylic acid unit in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid means the ethylene property relative to 1 mole The molar amount of polyvalent metal atoms of unsaturated carboxylic acid units. If the content of the polyvalent metal atom is less than 0.5 equivalent, the increase in viscosity necessary for more than necessary can be suppressed, the operability as a binder becomes better, and the production of the electrode becomes easier. In addition, it is believed that the adhesion effect of the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid shows high adhesion by polymer aggregation in the state where the dispersed active material is mixed, and if a cross-linked structure is formed with the copolymer If the amount of polyvalent metal atoms is too large, the cohesive force of the polymer will be suppressed due to the formation of crosslinks, and the adhesion tends to decrease, but as long as it is less than 0.5 equivalents, high adhesion can be achieved. Therefore, the content of the polyvalent metal atom is preferably 0.4 equivalents or less relative to the ethylenically unsaturated carboxylic acid unit. In addition, since a water-soluble copolymer salt with little alkali residue can be obtained, the electricity using the binder can also be improved Since the adhesiveness is extremely high, the content of polyvalent metal atoms is preferably 0.05 equivalents or more relative to the ethylenically unsaturated carboxylic acid unit, and more preferably 0.08 equivalents or more.

又,本發明之黏合劑中的多價金屬原子之含量,係藉由使用之共聚物的乙烯性不飽和羧酸變性量、使用之多價金屬的種類、及相對於乙烯性不飽和羧酸單元之多價金屬原子的量等而適宜決定,並未特別限定,而以相對於黏合劑之總質量(固體成分)而言為0.01~10質量%為較佳,0.05~8質量%為更佳,0.1~5質量%為再佳。若多價金屬原子之含量在上述範圍,則可實現高接著性及漿體安定性。此外,固體成分係意指從構成黏合劑之成分去除溶媒所剩之成分。又,黏合劑中的多價金屬原子之含量可藉由後述之實施例所記載之方法來測定。 In addition, the content of the polyvalent metal atom in the binder of the present invention is determined by the amount of denaturation of the ethylenically unsaturated carboxylic acid of the copolymer used, the type of polyvalent metal used, and the relative amount of the ethylenically unsaturated carboxylic acid The amount of polyvalent metal atoms in the unit is appropriately determined, and is not particularly limited, but it is preferably 0.01 to 10% by mass relative to the total mass (solid content) of the binder, and more preferably 0.05 to 8% by mass Good, 0.1 to 5 mass% is the best. If the content of polyvalent metal atoms is within the above range, high adhesion and paste stability can be achieved. In addition, the solid content means the component remaining after removing the solvent from the component constituting the binder. In addition, the content of polyvalent metal atoms in the binder can be measured by the method described in the examples described later.

在本發明之黏合劑中,前述共聚物的中和鹽,係以前述共聚物與包含多價金屬之鹼性物質及包含鹼金屬之鹼性物質的中和鹽為較佳。共聚物的中和鹽藉由除了由多價金屬所構成以外還由鹼金屬所構成,可提升接著性及漿體安定性,同時藉由多價金屬與共聚物形成之交聯結構而形成金屬離子(電子)之導電通路,藉此降低電阻,可得到高效率的電池。又,可確保對於水之高溶解性,變得可不使用增黏劑而調整為適度的黏度。 In the adhesive of the present invention, the neutralizing salt of the copolymer is preferably a neutralizing salt of the copolymer and an alkaline substance containing a polyvalent metal and an alkaline substance containing an alkali metal. The neutralizing salt of the copolymer is composed of an alkali metal in addition to the polyvalent metal, which can improve the adhesion and the stability of the slurry. At the same time, the metal is formed by the cross-linked structure formed by the polyvalent metal and the copolymer The conductive path of ions (electrons), thereby reducing resistance, can obtain a high-efficiency battery. In addition, high solubility in water can be ensured, and the viscosity can be adjusted to an appropriate viscosity without using a thickener.

作為在本發明中可使用之包含鹼金屬之鹼性物質,例如可列舉:氫氧化鈉、氫氧化鉀、氫氧化鋰等鹼金屬之氫氧化物;碳酸鈉、碳酸鉀等鹼金屬之碳酸鹽; 乙酸鈉、乙酸鉀等鹼金屬之乙酸鹽;磷酸三鈉等鹼金屬之磷酸鹽等。包含鹼金屬之鹼性物質可單獨使用,亦可組合2種以上來使用。此等之中,從對於水之溶解性、取得性的觀點來看,又以氫氧化鋰及氫氧化鈉為較佳。 Examples of alkali substances containing alkali metals that can be used in the present invention include: hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate ; Acetates of alkali metals such as sodium acetate and potassium acetate; phosphates of alkali metals such as trisodium phosphate. The alkaline substance containing alkali metal may be used alone or in combination of two or more. Among these, lithium hydroxide and sodium hydroxide are more preferable from the viewpoint of solubility in water and availability.

在本發明之黏合劑中,鹼金屬原子之含量可藉由黏合劑之用途等而適宜選擇,而通常以相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元而言為0.1~0.9當量為較佳,更佳為0.3~0.8當量。在此,在本發明中,相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元之鹼金屬原子的當量,係表示相對於1莫耳的該乙烯性不飽和羧酸單元之鹼金屬原子的莫耳量。若鹼金屬原子之含量在上述範圍內,則可確保使用該黏合劑組成物之電極的高接著性,可將電阻抑制為低。 In the adhesive of the present invention, the content of alkali metal atoms can be appropriately selected according to the use of the adhesive, etc., and usually relative to the ethylenically unsaturated carboxylic acid in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid The unit is preferably 0.1 to 0.9 equivalents, more preferably 0.3 to 0.8 equivalents. Here, in the present invention, the equivalent of the alkali metal atom of the ethylenically unsaturated carboxylic acid unit in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid means that the ethylenic property is not more than 1 mole. The molar amount of alkali metal atoms in saturated carboxylic acid units. If the content of the alkali metal atoms is within the above range, the high adhesion of the electrode using the binder composition can be ensured, and the resistance can be suppressed low.

在本發明之黏合劑中,相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元之多價金屬原子及鹼金屬原子的合計當量比(中和度),較佳為1以下,更佳為0.9以下,再佳為0.8以下。在本發明中,在由構成黏合劑之乙烯性不飽和羧酸所生成之羰酸的活性氫,與包含多價金屬之鹼性物質及包含鹼金屬之鹼性物質不多不少地反應而形成鹽作為中和物時,上述多價金屬原子及鹼金屬原子之合計當量比係成為1。另一方面,若多價金屬原子及鹼金屬原子之量係相對於乙烯性不飽和羧酸單元而言為過量,則合計當量比大於1。若相對於乙烯性不飽和羧酸單元之多價金屬原子及鹼金 屬的合計當量比為上述上限以下,則可對黏合劑賦予高接著性,且使用該黏合劑所製作之電極亦因黏合劑對於集電體之親和力變高而變得不易剝離,不易發生剝離所致之電池性能的降低。茲認為這是因為:若多價金屬原子及鹼金屬原子之合計當量比為上述上限以下,則黏合劑中所包含之實質上全部的多價金屬原子及鹼金屬原子會與上述共聚物形成鹽,因此包含游離於黏合劑中之金屬和未被使用於形成中和鹽之金屬的鹼性物質會發揮如潤滑劑般的作用,藉此可防止接著性降低。又,多價金屬原子與鹼金屬原子之合計當量比的下限較佳為0.1以上,更佳為0.3以上。若合計當量比為上述下限以上,則有酸性度低且可抑制電解液之分解的優點。 In the adhesive of the present invention, the total equivalent ratio (neutralization degree) of the polyvalent metal atoms and alkali metal atoms of the ethylenically unsaturated carboxylic acid unit in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid, It is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less. In the present invention, the active hydrogen of the carbonyl acid generated from the ethylenically unsaturated carboxylic acid constituting the binder reacts with the alkaline substance containing polyvalent metal and the alkaline substance containing alkali metal no more When a salt is formed as a neutralized product, the total equivalent ratio of the polyvalent metal atoms and alkali metal atoms becomes 1. On the other hand, if the amount of polyvalent metal atoms and alkali metal atoms is excessive relative to the ethylenically unsaturated carboxylic acid unit, the total equivalent ratio is greater than 1. If relative to the polyvalent metal atom and alkali gold of the ethylenically unsaturated carboxylic acid unit If the total equivalent ratio of the genus is below the above upper limit, high adhesiveness can be imparted to the adhesive, and the electrode made using the adhesive also becomes difficult to peel off due to the high affinity of the adhesive for the current collector, and peeling does not occur easily. The resulting decrease in battery performance. It is believed that this is because if the total equivalent ratio of polyvalent metal atoms and alkali metal atoms is below the upper limit, substantially all of the polyvalent metal atoms and alkali metal atoms contained in the binder will form a salt with the copolymer Therefore, the alkaline substance containing the metal that is free in the binder and the metal that is not used to form the neutralizing salt will play a role like a lubricant, thereby preventing the decrease in adhesion. In addition, the lower limit of the total equivalent ratio of the polyvalent metal atom and the alkali metal atom is preferably 0.1 or more, and more preferably 0.3 or more. If the total equivalent ratio is more than the above lower limit, there is an advantage that the acidity is low and decomposition of the electrolyte can be suppressed.

又,本發明之黏合劑中的多價金屬原子及鹼金屬原子之合計含量,係藉由使用之共聚物的乙烯性不飽和羧酸變性量、使用之金屬的種類、及相對於乙烯性不飽和羧酸單元之金屬原子的量等而適宜決定,並未特別限定,而以相對於黏合劑之總質量(固體成分)而言為0.02~40質量%為較佳,0.1~28質量%為更佳,0.2~15質量%為再佳。若多價金屬原子及鹼金屬原子之合計含量在上述範圍,則可實現高接著性及漿體安定性。此外,黏合劑中的鹼金屬之含量可藉由後述之實施例所記載之方法來測定。 In addition, the total content of polyvalent metal atoms and alkali metal atoms in the binder of the present invention is determined by the amount of denaturation of the ethylenically unsaturated carboxylic acid of the copolymer used, the type of metal used, and the relative The amount of metal atoms of the saturated carboxylic acid unit is appropriately determined, and is not particularly limited, but it is preferably 0.02 to 40% by mass relative to the total mass (solid content) of the binder, and 0.1 to 28% by mass Even better, 0.2 to 15% by mass is the best. If the total content of polyvalent metal atoms and alkali metal atoms is within the above range, high adhesion and paste stability can be achieved. In addition, the content of the alkali metal in the binder can be measured by the method described in the examples described later.

在本發明之黏合劑中,尤其當多價金屬原子及鹼金屬原子的相對於乙烯性不飽和羧酸單元之合計當量比在上述範圍,且多價金屬原子之含量在先前記載之 規定範圍時,可在藉由因多價金屬所形成之交聯結構維持高漿體安定性的狀態下,確保高接著性及低電阻性。 In the adhesive of the present invention, especially when the total equivalent ratio of the polyvalent metal atom and the alkali metal atom to the ethylenically unsaturated carboxylic acid unit is within the above range, and the content of the polyvalent metal atom is as previously described When the range is specified, high adhesion and low resistance can be ensured while maintaining a high slurry stability by a cross-linked structure formed by polyvalent metals.

本發明之黏合劑的上述多價金屬原子及鹼金屬原子之合計當量比,在由乙烯性不飽和羧酸所生成之羰酸的活性氫,與包含多價金屬之鹼性物質及包含鹼金屬之鹼性物質不多不少地反應而形成鹽作為中和物時,亦即在中和點時,係成為1。中和點可使用利用鹼之滴定、紅外線光譜、NMR光譜等方法來決定,而為了簡便且正確地測定,係以進行利用鹼之滴定為較佳。作為具體的滴定之方法,並未特別限定,可藉由溶解於離子交換水等雜質少的水,藉由氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼性物質進行中和來實施。作為中和點之指示劑,並未特別限定,可使用藉由鹼來指示pH之酚酞等指示劑。 The total equivalent ratio of the above polyvalent metal atoms and alkali metal atoms of the binder of the present invention, the active hydrogen of carbonyl acid generated from an ethylenically unsaturated carboxylic acid, and the alkaline substance containing polyvalent metal and containing alkali metal When the alkaline substance reacts more or more to form a salt as a neutralized substance, that is, at the neutralization point, it becomes 1. The neutralization point can be determined by methods such as titration using an alkali, infrared spectroscopy, and NMR spectroscopy. For simple and accurate measurement, it is preferable to perform titration using an alkali. The specific titration method is not particularly limited, and it can be carried out by neutralizing alkaline materials such as lithium hydroxide, sodium hydroxide, and potassium hydroxide by dissolving in water with few impurities such as ion-exchanged water. The indicator of the neutralization point is not particularly limited, and an indicator such as phenolphthalein that indicates pH with a base can be used.

在本發明中,乙烯醇與乙烯性不飽和羧酸共聚物與包含多價金屬之鹼性物質及因應需要的包含鹼金屬之鹼性物質的中和鹽,可根據周知的方法藉由使上述共聚物與鹼性物質反應而得到,其中以在水的存在下實施反應,且以水溶液之形式得到中和物之方法為簡便而較佳。 In the present invention, the neutralization salt of the vinyl alcohol and ethylenically unsaturated carboxylic acid copolymer and the alkaline substance containing polyvalent metal and the alkaline substance containing alkali metal as required can be obtained by using the above method according to well-known methods. The copolymer is obtained by reacting with a basic substance. Among them, the method of performing the reaction in the presence of water and obtaining the neutralized substance in the form of an aqueous solution is simple and preferable.

在本發明中,前述黏合劑亦可因應需要而進一步包含增黏劑和界面活性劑等在該領域中以往所使用之添加劑。作為這樣的添加劑,例如可包含:各種醇類、聚醚類、纖維素類、澱粉等多醣類。尤其藉由包含聚乙烯醇及/或其變性物,可期待羧基所致之黏合劑的凝集性 及與集電極的親和性提高,接著性提升之效果。又,藉由混合不同的聚合物,以表面上而言分子量分布變廣,再者,聚合物之結晶性降低,因此可期待柔軟性提升之效果。除此之外,藉由與異種聚合物之分子間相互作用來抑制均聚物之凝集,藉此可期待漿體安定性提升之效果。因此,係以包含此等為有利。 In the present invention, the aforementioned adhesive may further contain additives such as tackifiers and surfactants, which have been conventionally used in this field, as needed. Examples of such additives include various alcohols, polyethers, celluloses, starches, and other polysaccharides. Especially by including polyvinyl alcohol and/or its denatured substance, the cohesiveness of the adhesive due to the carboxyl group can be expected And the affinity with the collector is improved, and the effect of the adhesion is improved. In addition, by mixing different polymers, the molecular weight distribution is broadened on the surface, and further, the crystallinity of the polymer is lowered, so the effect of improving flexibility can be expected. In addition, the intermolecular interactions with heterogeneous polymers are used to suppress the aggregation of homopolymers, and the effect of improving the stability of the slurry can be expected. Therefore, it is advantageous to include these.

當本發明之黏合劑包含聚乙烯醇時,聚乙烯醇之皂化度較佳為50莫耳%以上,更佳為80莫耳%以上,再佳為95莫耳%以上。若皂化度在上述範圍,則不易因黏合劑中所包含之金屬而水解,可保持安定性而較佳。 When the binder of the present invention contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 95 mol% or more. If the degree of saponification is in the above range, it is less likely to be hydrolyzed by the metal contained in the binder, and it is preferable to maintain stability.

當本發明之黏合劑包含聚乙烯醇時,黏合劑中所包含之聚乙烯醇的量係相對於黏合劑之總質量而言較佳為40質量%以下,更佳為30質量%以下,再佳為20質量%以下。若聚乙烯醇之含量為上述上限以下,則可確保低電阻性,實現高充放電效率。 When the binder of the present invention contains polyvinyl alcohol, the amount of polyvinyl alcohol contained in the binder is preferably 40% by mass or less, more preferably 30% by mass or less, relative to the total mass of the binder. It is preferably 20% by mass or less. If the content of polyvinyl alcohol is below the above upper limit, low resistance can be ensured, and high charge and discharge efficiency can be achieved.

本發明之黏合劑,可為包含乙烯醇與乙烯性不飽和羧酸共聚物與包含多價金屬之鹼性物質及因應需要的包含鹼金屬之鹼性物質的中和鹽而成,但當包含如上述的添加劑等不同於上述中和鹽、及其存在時為前述未形成中和鹽而存在之上述共聚物的成分(以下亦稱為「其它成分」)時,其它成分之含量係相對於黏合劑之總質量而言,以合計而言較佳為40質量%以下,更佳為30質量%以下。 The adhesive of the present invention may be a neutralizing salt containing a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid, an alkaline substance containing a polyvalent metal, and an alkaline substance containing an alkali metal as needed, but when included When the additives mentioned above are different from the above-mentioned neutralized salt and the components of the above-mentioned copolymer (hereinafter also referred to as "other components") that exist when the above-mentioned neutralized salt is not formed, the content of other components is relative to The total mass of the binder is preferably 40% by mass or less, and more preferably 30% by mass or less.

本發明之黏合劑,通常以包含上述黏合劑與 水之黏合劑水溶液之形式使用。因此,本發明係以包含本發明之黏合劑及水而成之非水電解質電池用黏合劑水溶液作為對象。 The adhesive of the present invention usually contains the above adhesive and Use in the form of an aqueous solution of water binder. Therefore, the present invention is directed to an aqueous binder solution for a non-aqueous electrolyte battery containing the binder of the present invention and water.

本發明之黏合劑水溶液的黏合劑之含量,只要因應其用途、所欲之黏度等而適宜決定即可,例如可為相對於黏合劑水溶液之總質量而言為1~50質量%,較佳為3~30質量%,更佳為5~20質量%。換言之,本發明之黏合劑水溶液的水之含量係相對於黏合劑水溶液之總質量,例如可為50~99質量%,較佳為70~97質量%,更佳為80~95質量%。若黏合劑或水之含量在上述範圍,則以適度的黏度之水溶液而言操作性變得良好。 The content of the adhesive in the aqueous solution of the adhesive of the present invention may be appropriately determined according to its use, desired viscosity, etc., for example, it may be 1 to 50% by mass relative to the total mass of the aqueous solution of the adhesive, preferably 3 to 30% by mass, more preferably 5 to 20% by mass. In other words, the water content of the binder aqueous solution of the present invention is relative to the total mass of the binder aqueous solution, and may be, for example, 50 to 99% by mass, preferably 70 to 97% by mass, and more preferably 80 to 95% by mass. If the content of the binder or water is within the above range, the handleability becomes good with an aqueous solution of moderate viscosity.

再者,本發明之黏合劑,亦能以含有上述黏合劑還有水及活性物質之漿體組成物之形式使用。因此,本發明亦以包含本發明之黏合劑、水及活性物質而成之非水電解質電池用漿體組成物作為對象。 Furthermore, the adhesive of the present invention can also be used in the form of a slurry composition containing the above adhesive and water and active substances. Therefore, the present invention also targets a slurry composition for a non-aqueous electrolyte battery including the binder of the present invention, water, and an active material.

本發明之漿體組成物的黏合劑之含量,係當漿體組成物中所包含之活性物質的總質量為100時,通常以0.1~15質量%為較佳,更佳為0.5~10質量%,再佳為1~8質量%。若黏合劑之含量在上述範圍,則成為適度的黏度之漿體組成物,易於將塗布於集電體時之層厚控制於所欲之範圍,又,可抑制放電容量之降低。 The content of the binder of the slurry composition of the present invention is when the total mass of the active material contained in the slurry composition is 100, usually 0.1 to 15% by mass is preferred, and more preferably 0.5 to 10 by mass %, the best is 1~8 mass%. If the content of the binder is in the above-mentioned range, it becomes a slurry composition of moderate viscosity, and it is easy to control the layer thickness when applied to the current collector to the desired range, and it is also possible to suppress the decrease in discharge capacity.

又,本發明之漿體組成物的水之量,係當漿體組成物中所包含之活性物質的總質量為100時,通常以30~150質量%為較佳,更佳為70~120質量%。 In addition, the amount of water in the slurry composition of the present invention is when the total mass of the active material contained in the slurry composition is 100, usually 30 to 150% by mass is preferred, and more preferably 70 to 120 quality%.

在本發明中,作為用來溶解黏合劑之溶媒, 取代水或除了水以外,例如可使用:甲醇、乙醇、丙醇、2-丙醇等醇類、四氫呋喃、1,4-二

Figure 107144468-A0202-12-0015-3
烷等環狀醚類、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類、N-甲基吡咯啶酮、N-乙基吡咯啶酮等環狀醯胺類、二甲基亞碸等亞碸類等,而從安全性及環保等的觀點來看,以溶媒而言係以至少包含水為較佳。 In the present invention, as a solvent for dissolving the binder, in place of or in addition to water, for example, alcohols such as methanol, ethanol, propanol, 2-propanol, tetrahydrofuran, 1,4-bis
Figure 107144468-A0202-12-0015-3
Cyclic ethers such as alkanes, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and rings such as N-methylpyrrolidone and N-ethylpyrrolidone Substantial amides, dimethyl sulfoxides, etc., and from the viewpoint of safety, environmental protection, etc., it is preferable to include at least water as the solvent.

又,在本發明之漿體組成物中,除了上述溶媒以外,亦可併用例如在常壓下沸點為100℃以上300℃以下的有機溶媒等。作為這樣的有機溶媒,具體而言例如可列舉:正十二烷等烴類;2-乙基-1-己醇、1-壬醇等醇類;γ-丁內酯、乳酸甲酯等酯類;N-甲基吡咯啶酮、N,N-二甲基乙醯胺、二甲基甲醯胺等醯胺類;二甲基亞碸、環丁碸等亞碸‧碸類等有機分散媒等。當包含此等有機溶媒時,其含量係以成為溶媒全體之20質量%以下的範圍為較佳。 In addition, in the slurry composition of the present invention, in addition to the above-mentioned solvents, for example, an organic solvent having a boiling point of 100° C. or more and 300° C. or less under normal pressure may be used in combination. Specific examples of such organic solvents include hydrocarbons such as n-dodecane; alcohols such as 2-ethyl-1-hexanol and 1-nonanol; and esters such as γ-butyrolactone and methyl lactate Types; N-methylpyrrolidone, N,N-dimethylacetamide, dimethylformamide and other amidamines; dimethyl sulfoxide, cyclobutane and other sulfonamides and other organic dispersions Media, etc. When such an organic solvent is included, its content is preferably within a range of 20% by mass or less of the entire solvent.

當為了製作非水電解質電池之負極而使用本發明之漿體組成物時,作為負極活性物質,例如可例示:無定形碳、石墨、天然石墨、中間相碳微珠(MCMB)、瀝青系碳纖維等碳質材料;聚并苯等導電性高分子;Sn、Si;SiOx、SnOx、LiTiOx所代表之複合金屬氧化物和其它金屬氧化物和鋰金屬、鋰合金等鋰系金屬;TiS2、LiTiS2等金屬化合物等。 When the slurry composition of the present invention is used to make a negative electrode of a non-aqueous electrolyte battery, examples of the negative electrode active material include amorphous carbon, graphite, natural graphite, mesophase carbon microbeads (MCMB), and pitch-based carbon fibers. Carbon materials such as polyacene; conductive polymers such as polyacene; Sn, Si; composite metal oxides and other metal oxides represented by SiO x , SnO x , LiTiO x and lithium-based metals such as lithium metal and lithium alloy; TiS 2. Metal compounds such as LiTiS 2 etc.

又,當為了製作非水電解質電池之正極時,作為正極活性物質,例如可例示:磷酸鐵鋰(LiFePO4)、磷酸錳鋰(LiMnPO4)、磷酸鈷鋰(LiCoPO4)、焦磷酸鐵 (Li2FeP2O7)、鈷酸鋰複合氧化物(LiCoO2)、尖晶石型錳酸鋰複合氧化物(LiMn2O4)、錳酸鋰複合氧化物(LiMnO2)、鎳酸鋰複合氧化物(LiNiO2)、鈮酸鋰複合氧化物(LiNbO2)、鐵酸鋰複合氧化物(LiFeO2)、鎂酸鋰複合氧化物(LiMgO2)、鈣酸鋰複合氧化物(LiCaO2)、銅酸鋰複合氧化物(LiCuO2)、鋅酸鋰複合氧化物(LiZnO2)、鉬酸鋰複合氧化物(LiMoO2)、鉭酸鋰複合氧化物(LiTaO2)、鎢酸鋰複合氧化物(LiWO2)、鋰-鎳-鈷-鋁複合氧化物(LiNi0.8Co0.15Al0.05O2)、鋰-鎳-鈷-錳複合氧化物(LiNi0.33Co0.33Mn0.33O2)、Li過剩系鎳-鈷-錳複合氧化物(LixNiACoBMnCO2固溶體)、氧化錳鎳(LiNi0.5Mn1.5O4)、氧化錳(MnO2)、釩系氧化物、硫系氧化物、矽酸鹽系氧化物等。 In addition, when manufacturing a positive electrode of a non-aqueous electrolyte battery, examples of the positive electrode active material include lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium cobalt phosphate (LiCoPO 4 ), and iron pyrophosphate ( Li 2 FeP 2 O 7 ), lithium cobaltate composite oxide (LiCoO 2 ), spinel-type lithium manganate composite oxide (LiMn 2 O 4 ), lithium manganate composite oxide (LiMnO 2 ), lithium nickelate composite oxide (LiNiO 2), lithium composite oxide niobate (LiNbO 2), lithium iron composite oxides (LiFeO 2), magnesium, lithium composite oxide (LiMgO 2), calcium, lithium composite oxide (LiCaO 2 ), lithium copperate composite oxide (LiCuO 2 ), lithium zincate composite oxide (LiZnO 2 ), lithium molybdate composite oxide (LiMoO 2 ), lithium tantalate composite oxide (LiTaO 2 ), lithium tungstate composite Oxide (LiWO 2 ), lithium-nickel-cobalt-aluminum composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), lithium-nickel-cobalt-manganese composite oxide (LiNi 0.33 Co 0.33 Mn 0.33 O 2 ), Li Excess nickel-cobalt-manganese composite oxide (LixNiACoBMnCO 2 solid solution), manganese oxide nickel (LiNi 0.5 Mn 1.5 O 4 ), manganese oxide (MnO 2 ), vanadium oxide, sulfur oxide, silicate Department of oxides.

在本發明中,前述漿體組成物亦可因應需要而進一步含有增黏劑。作為增黏劑,並未特別限定而可使用該領域中周知的增黏劑,例如可列舉:各種醇類、不飽和羧酸類及其變性物、α-烯烴-順丁烯二酸類及其變性物、纖維素類、澱粉等多醣類等。 In the present invention, the aforementioned slurry composition may further contain a thickener as needed. The tackifier is not particularly limited, and a tackifier known in the art can be used, and examples thereof include various alcohols, unsaturated carboxylic acids and their denatures, α-olefin-maleic acid and their denatures Polysaccharides such as cellulose, cellulose and starch.

當本發明之漿體組成物包含增黏劑時,其含量係當漿體組成物中所包含之活性物質的總質量為100時,以0.1~4質量%為較佳,更佳為0.3~3質量%,再佳為0.5~2質量%。若增黏劑之含量在上述範圍內,可對漿體組成物賦予適度的黏度,同時易於將塗布於集電體時之層厚控制於所欲之範圍,又,可抑制放電容量之降低。 When the slurry composition of the present invention contains a thickener, its content is when the total mass of the active material contained in the slurry composition is 100, preferably 0.1 to 4% by mass, more preferably 0.3 to 3% by mass, the best is 0.5~2% by mass. If the content of the tackifier is within the above range, the slurry composition can be given a moderate viscosity, and at the same time, the layer thickness when applied to the current collector can be easily controlled to a desired range, and the reduction in discharge capacity can be suppressed.

又,漿體組成物亦可因應需要而進一步含有導電助劑。作為導電助劑,例如可列舉:金屬粉、導電性聚合物、乙炔黑等。當漿體組成物包含導電助劑時,其含量係當漿體組成物所包含之活性物質的總質量為100時,通常以0.1~10質量%為較佳,更佳為0.8~7質量%。 In addition, the slurry composition may further contain a conductive aid as needed. Examples of the conductive auxiliary agent include metal powder, conductive polymer, and acetylene black. When the slurry composition contains a conductive aid, its content is when the total mass of the active material contained in the slurry composition is 100, usually 0.1 to 10% by mass is preferred, and more preferably 0.8 to 7% by mass .

本發明之黏合劑由於當使用於非水電解質電池之電極時可實現低電阻化,因此適合作為非水電解質電池用電極之構成材料。因此,本發明亦以包含集電體之非水電解質電池用電極作為對象,該集電體具備包含本發明之黏合劑及活性物質而成之層。本發明之非水電解質電池用電極,例如可藉由下述方法來製作:將包含本發明之黏合劑、活性物質及水之漿體組成物塗布於集電體後,藉由乾燥等方法來去除水等溶媒,藉此使包含本發明之黏合劑及活性物質而成之層(以下亦稱為「混合層」)結著於集電體。 The adhesive of the present invention can be used as an electrode material for a non-aqueous electrolyte battery because it can achieve low resistance when used in an electrode of a non-aqueous electrolyte battery. Therefore, the present invention also targets an electrode for a non-aqueous electrolyte battery including a current collector including a layer including the binder and the active material of the present invention. The electrode for a non-aqueous electrolyte battery of the present invention can be produced by, for example, the following method: applying a slurry composition containing the binder of the present invention, an active material, and water to a current collector, and then drying or the like By removing the solvent such as water, the layer containing the binder and the active material of the present invention (hereinafter also referred to as "mixed layer") is bonded to the current collector.

作為構成本發明之非水電解質電池用電極的集電體,只要是包含導電性材料者則未特別限制,而例如可使用:鐵、銅、鋁、鎳、不鏽鋼、鈦、鉭、金、鉑等金屬材料。此等可單獨使用,亦能以任意的比率組合2種以上來使用。 The current collector constituting the electrode for the non-aqueous electrolyte battery of the present invention is not particularly limited as long as it contains a conductive material, and for example, iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum can be used And other metal materials. These can be used singly or in combination of two or more at any ratio.

從最能顯現本發明之非水電解質電池負極用漿體的效果來看,係以使用銅作為負極用集電體為較佳。這是因為本發明之黏合劑與銅箔之親和性高,可製作具有高接著性之負極。負極用集電體之形狀並未特別 限制,而通常以厚度0.001~0.5mm左右的薄片狀為較佳。 From the point of view of the effects of the slurry for the negative electrode of the non-aqueous electrolyte battery of the present invention, it is preferable to use copper as the current collector for the negative electrode. This is because the binder of the present invention has a high affinity with copper foil, and a negative electrode with high adhesion can be produced. The shape of the current collector for the negative electrode is not special It is usually limited to a sheet shape with a thickness of about 0.001 to 0.5 mm.

又,從最能顯現本發明之非水電解質電池負極用漿體的效果來看,係以使用鋁作為正極用集電體為較佳。這是因為本發明之黏合劑與鋁箔之親和性高,可製作具有高接著性之正極。正極用集電體之形狀並未特別限制,而通常以厚度0.001~0.5mm左右的薄片狀為較佳。 In addition, from the point of view that can best show the effect of the slurry for a negative electrode of a non-aqueous electrolyte battery of the present invention, it is preferable to use aluminum as a current collector for a positive electrode. This is because the binder of the present invention has high affinity with aluminum foil, and a positive electrode with high adhesion can be produced. The shape of the current collector for a positive electrode is not particularly limited, but usually a thin sheet having a thickness of about 0.001 to 0.5 mm is preferable.

將漿體組成物塗布至集電體之方法並未特別限制,例如可使用:刮刀法、浸塗法、逆輥法、直接輥塗法、凹版印刷法、擠製法、浸漬法、刷毛塗布法等方法。塗布量亦未特別限制,而以藉由乾燥等方法來去除溶媒或分散媒後所形成之包含黏合劑及活性物質之混合層的厚度成為較佳為0.005~5mm,更佳為0.01~2mm的量為佳。 The method of applying the slurry composition to the current collector is not particularly limited, and for example, a doctor blade method, a dip coating method, a reverse roll method, a direct roll coating method, a gravure printing method, an extrusion method, a dipping method, a brush coating method And other methods. The coating amount is also not particularly limited, but the thickness of the mixed layer containing the binder and the active material formed by removing the solvent or dispersion medium by drying or the like becomes preferably 0.005 to 5 mm, more preferably 0.01 to 2 mm. The amount is better.

用來去除漿體組成物所包含之水等溶媒之乾燥方法並未特別限制,例如可列舉:藉由溫風、熱風、低濕風之通風乾燥;真空乾燥;紅外線、遠紅外線、電子束等照射線乾燥等。乾燥條件係以混合層不會因應力集中而發生龜裂、或自集電體剝離之程度的速度範圍下可盡可能迅速地去除溶媒的方式進行調整為較佳。再者,為了提高電極之活性物質的密度,壓製乾燥後的集電體亦為有效。作為壓製方法,可列舉模壓和輥壓等方法。 The drying method for removing the water and other solvents contained in the slurry composition is not particularly limited, for example: ventilation drying by warm air, hot air, low humidity wind; vacuum drying; infrared, far infrared, electron beam, etc. Irradiation drying, etc. The drying condition is preferably adjusted so that the solvent can be removed as quickly as possible within a speed range where the mixed layer does not crack due to stress concentration or peel off from the current collector. In addition, in order to increase the density of the active material of the electrode, it is also effective to suppress the current collector after drying. Examples of the pressing method include methods such as molding and rolling.

再者,本發明亦包含具有上述電極之非水電 解質電池。非水電解質電池通常包含負極、正極及電解液。作為本發明之非水電解質電池,例如可列舉:鋰離子電池、鈉離子電池、鋰硫電池、全固態電池等。 Furthermore, the present invention also includes non-hydroelectric power with the above electrodes Dissolve the battery. Non-aqueous electrolyte batteries usually include a negative electrode, a positive electrode, and an electrolyte. Examples of the non-aqueous electrolyte battery of the present invention include lithium ion batteries, sodium ion batteries, lithium sulfur batteries, and all-solid-state batteries.

當於正極使用本發明之黏合劑時,作為負極,可無特別限制地採用通常使用於鋰離子二次電池等非水電解質電池之負極。例如,作為負極活性物質,可列舉:石墨、硬碳、Si系氧化物等。又,可把將負極活性物質、先前記載之導電助劑、SBR、NBR、丙烯酸橡膠、羥基乙基纖維素、羧甲基纖維素與聚偏二氟乙烯等黏合劑,混合於水或上述在常壓下沸點為100℃以上300℃以下的溶媒等所製備之負極用漿體,塗布於例如銅箔等負極集電體後,藉由乾燥等來去除溶媒而作成負極。 When the binder of the present invention is used for the positive electrode, as the negative electrode, the negative electrode generally used for non-aqueous electrolyte batteries such as lithium ion secondary batteries can be used without particular limitation. For example, examples of the negative electrode active material include graphite, hard carbon, and Si-based oxides. In addition, the negative electrode active material, the previously described conductive auxiliary agent, SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylidene fluoride, and other binders can be mixed in water or the above A slurry for a negative electrode prepared by a solvent having a boiling point of 100° C. or higher and 300° C. or lower at normal pressure is applied to a negative electrode current collector such as copper foil, and the solvent is removed by drying to prepare a negative electrode.

又,當於負極使用本發明之黏合劑時,作為正極,可無特別限制地採用通常使用於鋰離子二次電池等非水電解質電池之正極。例如,作為正極活性物質,可列舉:TiS2、TiS3、非晶質MoS3、Cu2V2O3、非晶質V2O-P2O5、MoO3、V2O5、V6O13等過渡金屬氧化物和LiCoO2、LiNiO2、LiMnO2、LiMn2O4等含有鋰之複合金屬氧化物等。又,可把將正極活性物質、先前記載之導電助劑、SBR、NBR、丙烯酸橡膠、羥基乙基纖維素、羧甲基纖維素與聚偏二氟乙烯等黏合劑,混合於水或上述沸點為100℃以上300℃以下的溶媒等所製備之正極用漿體,塗布於例如鋁等正極集電體後,藉由乾燥等來去除溶媒而作成正極。 In addition, when the binder of the present invention is used as a negative electrode, as the positive electrode, a positive electrode generally used in a non-aqueous electrolyte battery such as a lithium ion secondary battery can be used without particular limitation. For example, examples of the positive electrode active material include TiS 2 , TiS 3 , amorphous MoS 3 , Cu 2 V 2 O 3 , amorphous V 2 OP 2 O 5 , MoO 3 , V 2 O 5 , and V 6 O Transition metal oxides such as 13 and lithium-containing composite metal oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 . Also, a binder such as a positive electrode active material, the previously described conductive auxiliary agent, SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride can be mixed in water or the above boiling point A slurry for a positive electrode prepared by a solvent such as 100°C or higher and 300°C or lower is applied to a positive electrode current collector such as aluminum, and the solvent is removed by drying to prepare a positive electrode.

又,正極及負極亦可皆為包含本發明之黏合 劑的電極。 In addition, both the positive electrode and the negative electrode may include the bonding of the present invention Electrode.

又,本發明之非水電解質電池可使用使電解質溶解於溶媒之電解液。電解液只要是使用於通常的鋰離子二次電池等非水電解質電池者,則可為液狀亦可為凝膠狀,只要適宜選擇可因應負極活性物質、正極活性物質之種類而發揮作為電池之功能者即可。作為具體的電解質,例如可使用任何以往周知的鋰鹽,例如可列舉:LiClO4、LiBF6、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlC14、LiCl、LiBr、LiB(C2H5)4、CF3SO3Li、CH3SO3Li、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、低級脂肪族羧酸鋰等。 In addition, the non-aqueous electrolyte battery of the present invention can use an electrolytic solution in which an electrolyte is dissolved in a solvent. As long as the electrolyte is used in a non-aqueous electrolyte battery such as a general lithium ion secondary battery, it may be in a liquid or gel form, as long as it is appropriately selected and can be used as a battery according to the type of negative electrode active material and positive electrode active material Function. As a specific electrolyte, for example, any conventionally known lithium salt can be used, and examples include LiClO 4 , LiBF 6 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiB 10 Cl 10 , and LiAlC 14 , LiCl, LiBr, LiB(C 2 H 5 ) 4 , CF 3 SO 3 Li, CH 3 SO 3 Li, LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li(CF 3 SO 2 ) 2 N, low grade Aliphatic lithium carboxylate, etc.

這樣的使電解質溶解之溶媒(電解液溶媒)並未特別限定。作為具體例,可列舉:碳酸伸丙酯、碳酸伸乙酯、碳酸伸丁酯、碳酸二甲酯、碳酸二乙酯等碳酸酯類;γ-丁內酯等內酯類;三甲氧基甲烷、1,2-二甲氧基乙烷、二乙基醚、2-乙氧基乙烷、四氫呋喃、2-甲基四氫呋喃等醚類;二甲基亞碸等亞碸類;1,3-二氧戊環、4-甲基-1,3-二氧戊環等氧戊環類;乙腈和硝基甲烷等含氮化合物類;甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯等有機酸酯類;磷酸三乙酯、碳酸二甲酯、碳酸二乙酯等無機酸酯類;二甘二甲醚類;三甘二甲醚類;環丁碸類;3-甲基-2-

Figure 107144468-A0202-12-0020-4
唑啶酮等
Figure 107144468-A0202-12-0020-5
唑啶酮類;1,3-丙磺酸內酯、1,4-丁磺酸內酯、萘磺內酯等磺內酯類等,此等可單獨或混合二種以上來使用。使用凝膠狀的電解液時,可添加腈系聚合物、丙烯酸系聚合物、 氟系聚合物、環氧烷系聚合物等作為凝膠化劑。 Such a solvent for dissolving the electrolyte (electrolyte solvent) is not particularly limited. Specific examples include carbonates such as propyl carbonate, ethyl carbonate, butyl carbonate, dimethyl carbonate, and diethyl carbonate; lactones such as γ-butyrolactone; and trimethoxymethane , 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and other ethers; dimethyl sulfoxide and other sulfoxide; 1,3- Dioxolane, 4-methyl-1,3-dioxolane and other oxypentanes; acetonitrile and nitromethane and other nitrogen-containing compounds; methyl formate, methyl acetate, ethyl acetate, butyl acetate , Methyl propionate, ethyl propionate and other organic acid esters; triethyl phosphate, dimethyl carbonate, diethyl carbonate and other inorganic acid esters; diglyme; triglyme; Cyclodime; 3-methyl-2-
Figure 107144468-A0202-12-0020-4
Oxazolidone
Figure 107144468-A0202-12-0020-5
Zolidone; sultones such as 1,3-propane sultone, 1,4-butane sultone, naphthalene sultone, etc. These can be used alone or in combination of two or more. When a gel-like electrolyte is used, a nitrile polymer, an acrylic polymer, a fluorine polymer, an alkylene oxide polymer, or the like can be added as a gelling agent.

作為製造本發明之非水電解質電池之方法,並未特別限定,而例如可例示下述製造方法。亦即,隔著聚丙烯多孔膜等隔離材來疊合負極與正極,因應電池形狀而捲繞或彎折等,放入電池容器,注入電解液並封口。電池之形狀可為周知的硬幣型、鈕扣型、薄片型、圓筒型、方型、扁平型等任一者。 The method for manufacturing the non-aqueous electrolyte battery of the present invention is not particularly limited, and for example, the following manufacturing method can be exemplified. That is, the negative electrode and the positive electrode are laminated through a separator such as a polypropylene porous membrane, wound or bent according to the shape of the battery, put into the battery container, and the electrolyte is injected and sealed. The shape of the battery may be any of the well-known coin type, button type, sheet type, cylindrical type, square type, and flat type.

本發明之非水電解質電池係兼具接著性與電池特性之提升的電池,對各種用途有用。例如以使用於要求小型化、薄型化、輕量化、高性能化之行動終端的電池而言亦非常有用。 The non-aqueous electrolyte battery of the present invention is a battery having both adhesion and improved battery characteristics, and is useful for various applications. For example, it is also very useful for batteries used in mobile terminals that require miniaturization, thinness, weight reduction, and high performance.

[實施例] [Example]

以下針對本發明之實施例進行說明,惟本發明不限定於此等。 The following describes the embodiments of the present invention, but the present invention is not limited to these.

(實施例1) (Example 1) <乙烯醇與乙烯性不飽和羧酸共聚物之合成> <Synthesis of vinyl alcohol and ethylenically unsaturated carboxylic acid copolymer>

對100g的市售之聚乙烯醇(Kuraray股份有限公司製,28-98s)照射電子束(30kGy)。其次,於具備攪拌機、迴流冷卻管、氮氣導入管及粒子添加口的反應器中,投入33.4g的丙烯酸、466.6g的甲醇,一邊進行氮氣發泡一邊對系統內進行30分鐘的氮氣取代。在此添加100g的經電子束照射之聚乙烯醇,攪拌而在使粒子分散於溶液中之狀態下進行300分鐘的加熱迴流以進行接枝聚 合。此後,進行過濾以回收粒子,藉由在40℃下進行整夜的真空乾燥,得到目的之共聚物(數量平均分子量:25100)。所得之共聚物的乙烯性不飽和羧酸變性量為7.3莫耳%。此外,共聚物之上述數量平均分子量及變性量係根據以下的條件,利用凝膠滲透層析法來測定。 100 g of commercially available polyvinyl alcohol (manufactured by Kuraray Co., Ltd., 28-98s) was irradiated with an electron beam (30 kGy). Next, in a reactor equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a particle addition port, 33.4 g of acrylic acid and 466.6 g of methanol were introduced, and nitrogen substitution was performed in the system for 30 minutes while performing nitrogen foaming. Here, 100 g of polyvinyl alcohol irradiated with electron beams was added, stirred, and the particles were dispersed in the solution, and heated and refluxed for 300 minutes to carry out graft polymerization. Together. After that, filtration was performed to recover the particles, and vacuum drying was performed at 40°C overnight to obtain the intended copolymer (number average molecular weight: 25100). The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 7.3 mol%. In addition, the above-mentioned number average molecular weight and denaturation amount of the copolymer are measured by gel permeation chromatography under the following conditions.

<共聚物的數量平均分子量之測定方法> <Measurement method of number average molecular weight of copolymer>

使用昭和電工股份有限公司製粒徑篩析高效液相層析裝置「GPC-101」,根據以下的條件進行測定。 Using a particle size sieve high-performance liquid chromatography device "GPC-101" manufactured by Showa Denko Co., Ltd., the measurement was performed under the following conditions.

測定條件 Measurement conditions

管柱:將Tosoh股份有限公司製水系管柱「TSKgel GMPWXL」以2根串聯來連接 Tubing: To connect the water system tubing "TSKgel GMPWXL" made by Tosoh Co., Ltd. in series

標準試料:聚環氧乙烷及聚乙二醇 Standard sample: polyethylene oxide and polyethylene glycol

溶媒及移動相:0.1mol/L硝酸鈉水溶液 Solvent and mobile phase: 0.1mol/L sodium nitrate aqueous solution

流量:0.7L/min、溫度:25℃ Flow rate: 0.7L/min, temperature: 25℃

偵檢器:RI Detector: RI

<共聚物的乙烯性不飽和羧酸變性量之測定方法> <Measurement method of denatured amount of ethylene unsaturated carboxylic acid of copolymer>

將進行12小時的40℃減壓乾燥之試料溶解於D2O,製備添加少量的3-(三甲基矽基)-1-丙磺酸鈉之試料以使用於測定。使用1H-NMR(日本電子股份有限公司製;LAMBDA 500),在25℃下進行1H-NMR測定。乙烯醇單元之來自次甲基的波峰係歸屬於3.8~4.2ppm(積分值A),來自羧酸根(CH-COOH)的波峰係歸屬於2.0~2.5ppm(積分值B),利用下式來算出變性量。 A sample that was dried under reduced pressure at 40° C. for 12 hours was dissolved in D 2 O, and a sample added with a small amount of sodium 3-(trimethylsilyl)-1-propanesulfonate was prepared for measurement. 1 H-NMR measurement was performed at 25° C. using 1 H-NMR (manufactured by JEOL Ltd.; LAMBDA 500). The peak of the vinyl alcohol unit derived from methine group is assigned to 3.8~4.2ppm (integral value A), and the peak derived from carboxylate (CH-COOH) is assigned to 2.0~2.5ppm (integrated value B). Calculate the amount of denaturation.

變性量(mol%)=(B/A)×100 Denaturation (mol%)=(B/A)×100

<乙烯醇與乙烯性不飽和羧酸共聚物的中和鹽之製備> <Preparation of Neutralization Salts of Copolymers of Vinyl Alcohol and Ethylene Unsaturated Carboxylic Acid>

於100g的上述所得之乙烯醇與丙烯酸共聚物10質量%水溶液中添加相對於共聚物中的羧酸單元而言為0.5當量的氫氧化鋰,在80℃下加熱攪拌2小時,此後,冷卻至室溫。此後,添加相對於羧酸單元而言為0.1當量的乙酸鎂,一邊餾去乙酸一邊在90℃下加熱攪拌1小時,冷卻至室溫以得到黏合劑水溶液。從1H-NMR之羧酸根的質子位移,算出相對於共聚物中的羧酸單元之鎂及鋰的合計當量比作為中和度,而為0.7。 To 100 g of the 10 mass% aqueous solution of the vinyl alcohol and acrylic acid copolymer obtained above was added 0.5 equivalent of lithium hydroxide relative to the carboxylic acid unit in the copolymer, and the mixture was heated and stirred at 80° C. for 2 hours, and thereafter, cooled to Room temperature. Thereafter, 0.1 equivalents of magnesium acetate relative to the carboxylic acid unit was added, and the acetic acid was distilled off while heating and stirring at 90° C. for 1 hour, and cooled to room temperature to obtain a binder aqueous solution. From the proton shift of the carboxylate group in 1 H-NMR, the total equivalent ratio of magnesium and lithium relative to the carboxylic acid unit in the copolymer was calculated as the degree of neutralization, which was 0.7.

<中和度之算出方法> <Calculation method of neutralization degree>

將進行1小時的80℃熱風乾燥之試料溶解於D2O,製備添加少量的3-(三甲基矽基)-1-丙磺酸鈉之試料以使用於測定。使用1H-NMR(日本電子股份有限公司製;LAMBDA 500),在25℃下進行1H-NMR測定。來自羧酸根(CH-COOH)的波峰係歸屬於2.0~2.5ppm,從伴隨氯化之高磁場位移,製作相對於添加量之位移值的檢量線,藉由使用該檢量線,算出中和度。 A sample subjected to 80° C. hot air drying for 1 hour was dissolved in D 2 O, and a sample added with a small amount of sodium 3-(trimethylsilyl)-1-propanesulfonate was prepared for measurement. 1 H-NMR measurement was performed at 25° C. using 1 H-NMR (manufactured by JEOL Ltd.; LAMBDA 500). The peak derived from carboxylate (CH-COOH) belongs to 2.0 to 2.5 ppm. From the displacement of the high magnetic field accompanying chlorination, a calibration curve for the displacement value relative to the added amount is prepared. Using this calibration curve, the calculation is in progress. And degree.

<多價金屬原子及鹼金屬原子之含量之測定> <Determination of the content of polyvalent metal atoms and alkali metal atoms>

分別根據以下的方法來測定所得之黏合劑水溶液中的多價金屬及鹼金屬之含量(相對於黏合劑水溶液的固體成分之質量%)。將結果示於表1。 The contents of the polyvalent metal and alkali metal in the obtained binder aqueous solution (mass% relative to the solid content of the binder aqueous solution) were respectively measured according to the following methods. The results are shown in Table 1.

使用Thermo Fisher Scientific製微量元素分析裝置「iCAP6500」,作為前處理,於錐形瓶秤量0.01g的試料後,添加1ml的硫酸、5ml的硝酸而加熱分解後,途中添加硝酸(10ml左右)使其完全分解,進行50ml定容(溶媒:水),在RF功率1150W、泵流量50rpm、輔助氣體流量0.5L/分、霧化氣體流量0.7L/分、冷卻氣體流量12L/分之條件下進行測定。 Using a trace element analyzer "iCAP6500" manufactured by Thermo Fisher Scientific, as a pretreatment, after weighing 0.01g of the sample in an Erlenmeyer flask, adding 1ml of sulfuric acid and 5ml of nitric acid and heating to decompose, adding nitric acid (about 10ml) on the way Complete decomposition, 50ml constant volume (solvent: water), measured under conditions of RF power 1150W, pump flow 50rpm, auxiliary gas flow 0.5L/min, atomizing gas flow 0.7L/min, cooling gas flow 12L/min .

<漿體組成物之製作> <Preparation of slurry composition>

電極用漿體組成物之製作係相對於作為負極用活性物質之96質量份的人造石墨(FSN-1,中國杉杉製),將前述黏合劑之10質量%水溶液以固體成分而言為3質量份、及作為導電助劑(導電賦予劑)之Super-P(Timcal公司製)以固體成分而言為1質量份投入專用容器,使用行星攪拌器(ARE-250,Thinky股份有限公司製)進行混練,製作電極塗布用漿體組成物。漿體組成物中的活性物質與黏合劑之組成比係以固體成分而言,石墨粉末:導電助劑:黏合劑=96:1:3(質量比)。 The preparation of the slurry composition for the electrode is based on 96 parts by mass of artificial graphite (FSN-1, manufactured by Chinese fir) as the active material for the negative electrode, and the 10% by mass aqueous solution of the aforementioned binder is 3 in terms of solid content Mass parts and Super-P (manufactured by Timcal Co., Ltd.) as a conductive aid (conductivity imparting agent) are put into a dedicated container with a solid content of 1 mass part, using a planetary stirrer (ARE-250, manufactured by Thinky Co., Ltd.) Kneading was performed to prepare a slurry composition for electrode coating. The composition ratio of the active material and the binder in the slurry composition is based on the solid content, graphite powder: conductive aid: binder = 96: 1: 3 (mass ratio).

<漿體組成物之安定性(目視試驗)> <Stability of slurry composition (visual test)>

為了確認所得之漿體組成物之安定性,以目視確認緊接在漿體組成物製備後之粒子沉降的情況。作為評價基準,將3小時以上未發生沉降之漿體判斷為◎,在3小時~30分發生沉降之漿體判斷為△,在30分以內發生沉降之漿體判斷為×。將結果示於表1。 In order to confirm the stability of the obtained slurry composition, the particle sedimentation immediately after the preparation of the slurry composition was visually confirmed. As an evaluation criterion, the slurry that did not settle for more than 3 hours was judged as ◎, the slurry that settled within 3 hours to 30 minutes was judged as △, and the slurry that settled within 30 minutes was judged as ×. The results are shown in Table 1.

<漿體組成物之安定性(沉降速度)> <Stability of slurry composition (settlement velocity)>

又,使用Nihon Rufuto製分散安定性分析裝置「Lumisizer 610」,將製作之漿體添加於PC製2mm槽,在轉速600rpm、溫度25℃、3小時、Light Factor4之條件下測定所得之漿體組成物的粒子沉降速度(nm/秒),從相對於穿透率20%之時間之移動距離算出沉降速度。將結果示於表1。 Furthermore, using a dispersion stability analyzer "Lumisizer 610" manufactured by Nihon Rufuto, the prepared slurry was added to a 2 mm tank made of PC, and the composition of the obtained slurry was measured under the conditions of 600 rpm, 25°C, 3 hours, and Light Factor 4. The particle sedimentation speed (nm/sec) is calculated from the distance traveled with respect to the penetration rate of 20% of the time. The results are shown in Table 1.

<電池用負極之製作> <Production of negative electrode for battery>

使用棒塗機(T101,松尾產業股份有限公司製)而將所得之前述漿體組成物塗布於集電體之銅箔(CST8G,福田金屬箔粉工業股份有限公司製)上,利用熱風乾燥機在80℃下一次乾燥30分鐘後,使用輥壓機(寶泉股份有限公司製)來進行壓延處理。其次,沖切成電池用電極(φ14mm)後,藉由在140℃下3小時減壓條件之二次乾燥來製作硬幣型電池用電極(負極)。 Using a bar coater (T101, manufactured by Matsuo Industrial Co., Ltd.), the obtained slurry composition was applied to a copper foil of a current collector (CST8G, manufactured by Futian Metal Foil Industrial Co., Ltd.) using a hot air dryer. After drying at 80°C for 30 minutes at a time, a roll press (manufactured by Baoquan Co., Ltd.) was used to perform the rolling treatment. Next, after die-cutting into a battery electrode (φ14 mm), a coin-type battery electrode (negative electrode) was produced by secondary drying at 140° C. for 3 hours under reduced pressure.

<剝離強度、韌性試驗用電極之製作> <Fabrication of electrodes for peel strength and toughness test>

使用棒塗機(T101,松尾產業股份有限公司製)而將所得之前述漿體組成物塗布於集電體之銅箔(CST8G,福田金屬箔粉工業股份有限公司製)上,利用熱風乾燥機在80℃下一次乾燥30分鐘後,使用輥壓機(寶泉股份有限公司製)來進行壓延處理以得到剝離強度及韌性試驗用之電極(膜厚約35μm)。 Using a bar coater (T101, manufactured by Matsuo Industrial Co., Ltd.), the obtained slurry composition was applied to a copper foil of a current collector (CST8G, manufactured by Futian Metal Foil Industrial Co., Ltd.) using a hot air dryer. After drying at 80°C for 30 minutes at a time, a rolling press (manufactured by Baoquan Co., Ltd.) was used to perform rolling treatment to obtain an electrode for peel strength and toughness test (film thickness of about 35 μm).

<電極之剝離強度測定> <Measurement of peel strength of electrode>

測定從集電極的銅箔剝離前述剝離強度試驗用電極時之強度。該剝離強度係使用50N的測力計(Imada股份有限公司製)來測定180°剝離強度。使用雙面膠(Nichiban製雙面膠)來貼合上述所得之電池用塗布電極之漿體塗布面與不鏽鋼板,測定180°剝離強度(剝離寬度10mm,剝離速度100mm/分)。將結果示於表1。 The strength when peeling the electrode for peel strength test from the copper foil of the collector electrode was measured. For this peel strength, a 180N peel strength was measured using a 50N dynamometer (manufactured by Imada Co., Ltd.). A double-sided tape (double-sided tape manufactured by Nichiban) was used to bond the slurry-coated surface of the battery-coated electrode obtained above to a stainless steel plate, and a 180° peel strength (peel width 10 mm, peel speed 100 mm/min) was measured. The results are shown in Table 1.

<電極之韌性試驗> <Toughness Test of Electrode>

電極之韌性的評價係使用JIS K5600-5-1(塗料一般試驗方法-第5部:塗膜之機械性質-第1節:抗彎性(圓筒形心軸法))之Type 1的試驗裝置來進行。以目視進行電極破裂之確認,在本試驗中即使最大徑2mm亦未發生破裂之電極,係準備1.5mm、1.0mm、0.8mm、0.5mm的SUS棒(SUS304Wire,Nilaco製),進行電極捲繞試驗。將未發生破裂之最小的SUS徑示於下述表1。 The evaluation of the toughness of the electrode is a Type 1 test using JIS K5600-5-1 (General test methods for paints-Part 5: Mechanical properties of coating films-Section 1: Bending resistance (cylindrical mandrel method)) Device. Visually confirm the electrode rupture. In this test, the electrode that did not rupture even with a maximum diameter of 2mm was prepared with SUS rods (SUS304Wire, manufactured by Nilaco) of 1.5mm, 1.0mm, 0.8mm, and 0.5mm. test. The smallest SUS diameter without cracking is shown in Table 1 below.

<電池之製作> <Production of battery>

將上述所得之電池用負極移送至氬氣環境下之手套箱(美和製作所股份有限公司製)。於正極使用金屬鋰箔(厚度0.2mm,φ16mm)。又,使用聚丙烯系(Celgard #2400,Polypore股份有限公司製)作為隔離材,電解液係使用六氟化磷酸鋰(LiPF6)之於碳酸伸乙酯(EC)與碳酸乙基甲酯(EMC)添加碳酸伸乙烯酯(VC)之混合溶媒系 (1M-LiPF6,EC/EMC=3/7vol%,VC2重量%)並注入,製作硬幣型電池(2032型)。 The negative electrode for a battery obtained above was transferred to a glove box (made by Miwa Manufacturing Co., Ltd.) under an argon atmosphere. Metal lithium foil (thickness 0.2mm, φ16mm) was used for the positive electrode. In addition, a polypropylene system (Celgard #2400, manufactured by Polypore Co., Ltd.) was used as a separator, and an electrolyte system used lithium hexafluoride phosphate (LiPF 6 ) for ethyl carbonate (EC) and ethyl methyl carbonate ( EMC) Add a mixed solvent system of vinylene carbonate (VC) (1M-LiPF 6 , EC/EMC=3/7vol%, VC2% by weight) and inject to make a coin battery (type 2032).

<充放電特性試驗> <Charge and discharge characteristic test>

針對製作之硬幣型電池,使用市售充放電試驗機(TOSCAT3100,Toyo System股份有限公司製)來實施充放電試驗。將硬幣型電池置於25℃之恆溫槽,充電係對鋰電位進行相對於活性物質量而言為0.1C(約0.5mA/cm2)的定電流充電直到0V為止,進一步對鋰電位實施0V的定電壓充電直到0.02mA的電流為止。將此時之容量作為充電容量(mAh/g)。其次,對鋰電位進行0.1C(約0.5mA/cm2)的定電流放電直到1.5V為止,將此時之容量作為放電容量(mAh/g)。將初期放電容量與充電容量差作為不可逆容量,將放電容量/充電容量之百分率作為充放電效率。將結果示於表1。 For the coin-shaped batteries produced, a commercially available charge and discharge test machine (TOSCAT 3100, manufactured by Toyo System Co., Ltd.) was used to perform charge and discharge tests. The coin-type battery was placed in a constant temperature bath at 25°C. The charging system charged the lithium potential with a constant current of 0.1 C (about 0.5 mA/cm 2 ) relative to the mass of the active material until 0 V, and further applied 0 V to the lithium potential. The constant voltage is charged until the current of 0.02mA. Let the capacity at this time be the charging capacity (mAh/g). Next, the lithium potential was discharged at a constant current of 0.1 C (about 0.5 mA/cm 2 ) until 1.5 V, and the capacity at this time was regarded as the discharge capacity (mAh/g). The difference between the initial discharge capacity and the charge capacity is regarded as the irreversible capacity, and the percentage of the discharge capacity/charge capacity is regarded as the charge-discharge efficiency. The results are shown in Table 1.

(實施例2) (Example 2)

除了將氫氧化鋰及乙酸鎂之添加量設為相對於羧酸單元而言分別為0.3當量以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 1, except that the addition amounts of lithium hydroxide and magnesium acetate were 0.3 equivalents per carboxylic acid unit.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用 電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the peel strength test was prepared by the same method as Example 1. The electrode was measured for peel strength. The results are shown in Table 1.

(實施例3) (Example 3)

除了添加乙酸鈣來取代乙酸鎂以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 1, except that calcium acetate was added instead of magnesium acetate.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例4) (Example 4)

除了於100g的實施例1所製作之乙烯醇與丙烯酸共聚物10重量%水溶液中添加相對於聚合物中的羧酸單元而言為0.2當量的氫氧化鋰、0.3當量的氫氧化鈉、0.1當量的乙酸鎂以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 In addition to adding 100 g of the vinyl alcohol-acrylic acid copolymer 10 wt% aqueous solution prepared in Example 1, 0.2 eq of lithium hydroxide, 0.3 eq of sodium hydroxide, and 0.1 eq relative to the carboxylic acid unit in the polymer Except for magnesium acetate, the same method as in Example 1 was used to prepare a binder aqueous solution.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例5) (Example 5)

除了添加100g的丙烯酸、400g的甲醇以外,與實施例1同樣地進行,合成目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為26.2莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備黏合劑水溶液。 Except that 100 g of acrylic acid and 400 g of methanol were added, it was carried out in the same manner as in Example 1 to synthesize the intended copolymer. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 26.2 mol%. Using this copolymer, the preparation of a neutralization salt was carried out in the same manner as in Example 1, to prepare an aqueous solution of a binder.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例6) (Example 6)

對100g的市售之聚乙烯醇(Kuraray股份有限公司製,Elvanol 71-30)照射電子束(30kGy)。其次,於具備攪拌機、迴流冷卻管、氮氣導入管及粒子添加口的反應器中,投入25g的甲基丙烯酸、475g的甲醇,一邊進行氮氣發泡一邊對系統內進行30分鐘的氮氣取代。在此添加100g的經電子束照射之聚乙烯醇,攪拌而在粒子分散於溶液中之狀態下進行300分鐘的加熱迴流以進行接枝聚合。此後,進行過濾以回收粒子,藉由在40℃下進行整夜的真空乾燥,得到目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為7.0莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備 黏合劑水溶液。 100 g of commercially available polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Elvanol 71-30) was irradiated with an electron beam (30 kGy). Next, in a reactor equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a particle addition port, 25 g of methacrylic acid and 475 g of methanol were introduced, and nitrogen substitution was performed in the system for 30 minutes while performing nitrogen foaming. Here, 100 g of polyvinyl alcohol irradiated with electron beams was added, stirred, and heated and refluxed for 300 minutes with the particles dispersed in the solution to perform graft polymerization. Thereafter, filtration was performed to recover the particles, and the target copolymer was obtained by vacuum drying at 40°C overnight. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 7.0 mole %. Using this copolymer, the preparation of the neutralization salt was carried out in the same manner as in Example 1, and the preparation Aqueous binder solution.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例7) (Example 7)

除了添加100g的甲基丙烯酸、400g的甲醇以外,與實施例5同樣地進行,合成目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為34.0莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備黏合劑水溶液。 Except that 100 g of methacrylic acid and 400 g of methanol were added, it was carried out in the same manner as in Example 5 to synthesize the intended copolymer. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 34.0 mole %. Using this copolymer, the preparation of a neutralization salt was carried out in the same manner as in Example 1, to prepare an aqueous solution of a binder.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例8) (Example 8)

於具備攪拌機、迴流冷卻管、氮氣導入管、起始劑添加口的反應器中,投入370g的水、100g的市售之聚乙烯醇(Kuraray股份有限公司製,M115),在攪拌下以 95℃加熱以溶解該聚乙烯醇後,冷卻至室溫。於所得之水溶液添加0.5當量濃度(N)的硫酸而使pH為3.0。於此,在攪拌下添加9.9g的丙烯酸後,於該水溶液中一邊氮氣發泡一邊加溫至70℃,進一步在70℃之狀態下進行30分鐘的氮氣發泡以進行氮氣取代。氮氣取代後,花費1.5小時於該水溶液滴下80.7g的過硫酸鉀水溶液(濃度2.5質量%)。全量添加後,升溫至75℃進一步攪拌1小時後,冷卻至室溫。將所得之水溶液流延於PET薄膜上,藉由在80℃下熱風乾燥30分鐘來製作薄膜。利用液態氮凍結該薄膜後,使用離心粉碎機來進行粉碎,進一步藉由在40℃下進行整夜的真空乾燥,得到目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為6.0莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備黏合劑水溶液。 In a reactor equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, and a starter addition port, 370 g of water and 100 g of commercially available polyvinyl alcohol (M115 manufactured by Kuraray Co., Ltd.) were put in and stirred under After heating at 95°C to dissolve the polyvinyl alcohol, it was cooled to room temperature. To the resulting aqueous solution, 0.5 equivalent concentration (N) of sulfuric acid was added to make the pH 3.0. Here, after adding 9.9 g of acrylic acid with stirring, the aqueous solution was heated to 70° C. while blowing with nitrogen, and further nitrogen blowing was performed at 70° C. for 30 minutes to perform nitrogen substitution. After nitrogen substitution, 80.7 g of a potassium persulfate aqueous solution (concentration 2.5% by mass) was dropped into this aqueous solution over 1.5 hours. After the total amount was added, the temperature was raised to 75°C and the mixture was further stirred for 1 hour, and then cooled to room temperature. The obtained aqueous solution was cast on a PET film, and the film was produced by drying with hot air at 80°C for 30 minutes. After freezing the film with liquid nitrogen, it was pulverized using a centrifugal pulverizer, and further vacuum dried overnight at 40°C to obtain the intended copolymer. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 6.0 mole %. Using this copolymer, the preparation of a neutralization salt was carried out in the same manner as in Example 1, to prepare an aqueous solution of a binder.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例9) (Example 9)

除了添加20g丙烯酸、150g的過硫酸鉀水溶液(濃度2.5質量%)以外,與實施例8同樣地進行,合成目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為 12.0莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備黏合劑水溶液。 Except that 20 g of acrylic acid and 150 g of potassium persulfate aqueous solution (concentration 2.5% by mass) were added, the same procedure as in Example 8 was carried out to synthesize the intended copolymer. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the resulting copolymer is 12.0 mol%. Using this copolymer, the preparation of a neutralization salt was carried out in the same manner as in Example 1, to prepare an aqueous solution of a binder.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例10) (Example 10)

除了於100g的實施例9所製作之乙烯醇與丙烯酸共聚物10重量%水溶液中添加相對於共聚物中的羧酸單元而言為0.2當量的氫氧化鋰、0.3當量的氫氧化鈉、0.1當量的乙酸鎂以外,利用與實施例9同樣的方法來進行黏合劑水溶液之製備。 Except for adding 100 g of the vinyl alcohol and acrylic acid copolymer 10 wt% aqueous solution prepared in Example 9 to the equivalent of carboxylic acid units in the copolymer, 0.2 equivalent of lithium hydroxide, 0.3 equivalent of sodium hydroxide, and 0.1 equivalent Except for magnesium acetate, the same method as in Example 9 was used to prepare a binder aqueous solution.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例11) (Example 11)

除了於100g的實施例9所製作之乙烯醇與丙烯酸共聚物10重量%水溶液中添加相對於共聚物中的羧酸單元 而言為0.1當量的氫氧化鋰、0.2當量的氫氧化鈉、0.3當量的乙酸鎂以外,利用與實施例9同樣的方法來進行黏合劑水溶液之製備。 In addition to 100 g of the vinyl alcohol and acrylic acid copolymer produced in Example 9 in a 10% by weight aqueous solution relative to the carboxylic acid units in the copolymer In terms of 0.1 equivalents of lithium hydroxide, 0.2 equivalents of sodium hydroxide, and 0.3 equivalents of magnesium acetate, a binder aqueous solution was prepared in the same manner as in Example 9.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例12) (Example 12)

除了將乙酸鎂變更為乙酸鈣以外,利用與實施例10同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 10 except that magnesium acetate was changed to calcium acetate.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例13) (Example 13)

於具備攪拌機、迴流冷卻管、氬氣導入管、起始劑添加口的反應器中,投入640g的乙酸乙烯酯、240.4g的甲醇、0.88g的丙烯酸,一邊進行氮氣發泡一邊對系統內進行30分鐘的氮氣取代。另外製備丙烯酸之甲醇溶液 (濃度20質量%)作為共聚單體之逐次添加溶液(以下記載為延遲溶液),進行30分鐘的氬氣發泡。開始升溫反應器,在內溫成為60℃時,添加0.15g的2,2’-偶氮雙異丁腈以開始聚合。聚合反應之進行中係藉由將製備之延遲溶液滴下於系統內,使聚合溶液中的單體組成(乙酸乙烯酯與丙烯酸之莫耳比率)成為一定的值。在60℃下聚合210分鐘後,冷卻而停止聚合。接著,在30℃、減壓下一邊不時添加甲醇一邊進行未反應的單體之去除,得到丙烯酸所變性之聚乙酸乙烯酯之甲醇溶液。其次,於對該聚乙酸乙烯酯之甲醇溶液追加甲醇而將濃度調整為25質量%之聚乙酸乙烯酯之甲醇溶液400g中,添加20.4g的氫氧化鈉甲醇溶液(濃度18.0質量%)、79.6g的甲醇,在40℃下進行皂化。添加氫氧化鈉甲醇溶液後,會在數分鐘內生成凝膠化物,因此將其利用粉碎機來粉碎,在40℃之狀態下放置60分鐘以進行皂化。利用甲醇來反覆洗淨所得之粉碎凝膠後,藉由在40℃下進行整夜的真空乾燥,合成目的之共聚物。所得之共聚物的乙烯性不飽和羧酸變性量為5.0莫耳%。使用該共聚物而藉由與實施例1同樣的方法來進行中和鹽之製備,製備黏合劑水溶液。 In a reactor equipped with a stirrer, a reflux cooling tube, an argon gas introduction tube, and a starter addition port, 640 g of vinyl acetate, 240.4 g of methanol, and 0.88 g of acrylic acid were charged, and the system was carried out while blowing nitrogen. Replaced by nitrogen for 30 minutes. In addition, prepare methanol solution of acrylic acid (Concentration 20% by mass) As a comonomer, a solution (hereinafter referred to as a delayed solution) was added sequentially, and argon gas foaming was performed for 30 minutes. When the internal temperature became 60°C, 0.15 g of 2,2'-azobisisobutyronitrile was added to start the polymerization. The polymerization reaction is carried out by dropping the prepared delayed solution into the system so that the monomer composition (molar ratio of vinyl acetate to acrylic acid) in the polymerization solution becomes a certain value. After 210 minutes of polymerization at 60°C, the polymerization was stopped by cooling. Next, unreacted monomers were removed while adding methanol from time to time under reduced pressure at 30°C to obtain a methanol solution of acrylic acid-modified polyvinyl acetate. Next, to the methanol solution of polyvinyl acetate, methanol was added to adjust the concentration to 400 g of a methanol solution of polyvinyl acetate with a concentration of 25% by mass, 20.4 g of sodium hydroxide methanol solution (concentration: 18.0% by mass), 79.6 g of methanol was saponified at 40°C. After the sodium hydroxide methanol solution is added, a gelled product will be generated within a few minutes, so it is crushed with a pulverizer and left at 40°C for 60 minutes for saponification. After repeatedly washing the obtained crushed gel with methanol, the target copolymer was synthesized by vacuum drying at 40°C overnight. The amount of denaturation of the ethylenically unsaturated carboxylic acid of the obtained copolymer was 5.0 mole %. Using this copolymer, the preparation of a neutralization salt was carried out in the same manner as in Example 1, to prepare an aqueous solution of a binder.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用 電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the peel strength test was prepared by the same method as Example 1. The electrode was measured for peel strength. The results are shown in Table 1.

(實施例14) (Example 14)

除了將乙酸鎂之量添加為相對於共聚物中的羧酸單元而言為0.5當量以外,與實施例9同樣地進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 9 except that the amount of magnesium acetate was added to 0.5 equivalents relative to the carboxylic acid unit in the copolymer.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例15) (Example 15)

除了未添加氫氧化鋰以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 1, except that lithium hydroxide was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例16) (Example 16)

除了未添加氫氧化鋰以外,利用與實施例2同樣的 方法來進行黏合劑水溶液之製備。 The same as Example 2 was used except that lithium hydroxide was not added Method to prepare the binder aqueous solution.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(實施例17) (Example 17)

除了於100g的實施例1所製作之乙烯醇與丙烯酸共聚物10重量%水溶液未添加氫氧化鋰,添加0.3當量的乙酸鈣以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 1 except that 100 g of the 10% by weight aqueous solution of the vinyl alcohol and acrylic copolymer prepared in Example 1 was not added with lithium hydroxide and 0.3 equivalents of calcium acetate was added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例1) (Comparative example 1)

除了未添加乙酸鎂以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 1, except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成 物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the slurry composition was evaluated Stability of things. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例2) (Comparative example 2)

除了未添加乙酸鎂以外,利用與實施例5同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 5 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例3) (Comparative example 3)

除了未添加乙酸鎂以外,利用與實施例6同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 6 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例4) (Comparative example 4)

除了未添加乙酸鎂以外,利用與實施例7同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 7 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例5) (Comparative example 5)

除了未添加乙酸鎂以外,利用與實施例8同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 8 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例6) (Comparative example 6)

除了未添加乙酸鎂以外,利用與實施例9同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 9 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成 物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the slurry composition was evaluated Stability of things. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例7) (Comparative example 7)

除了未添加乙酸鎂以外,利用與實施例13同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 13 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例8) (Comparative Example 8)

除了未添加乙酸鎂以外,利用與實施例10同樣的方法來進行黏合劑水溶液之製備。 A binder aqueous solution was prepared in the same manner as in Example 10 except that magnesium acetate was not added.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例9) (Comparative Example 9)

使用市售之聚乙烯醇(Kuraray股份有限公司製,28-98s)製備為10質量%水溶液,使用作為黏合劑水溶液。從該水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 A commercially available polyvinyl alcohol (manufactured by Kuraray Co., Ltd., 28-98s) was used to prepare a 10% by mass aqueous solution and used as a binder aqueous solution. From this aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

(比較例10) (Comparative example 10)

除了未添加乙酸鎂,添加5質量%的羧甲基纖維素(Cellogen BSH-6,第一工業製藥股份有限公司製)作為增黏劑以外,利用與實施例1同樣的方法來進行黏合劑水溶液之製備。 Except that magnesium acetate was not added, 5% by mass of carboxymethyl cellulose (Cellogen BSH-6, manufactured by Daiichi Pharmaceutical Co., Ltd.) was added as a thickener, and the binder aqueous solution was carried out in the same manner as in Example 1. Of preparation.

從所得之黏合劑水溶液,藉由與實施例1同樣的方法來製備非水電解質電池用漿體組成物,評價漿體組成物之安定性。又,藉由與實施例1同樣的方法來製作電池用負極,得到硬幣型電池,進行充放電特性試驗。再者,藉由與實施例1同樣的方法來製作剝離強度試驗用電極,進行剝離強度之測定。將結果示於表1。 From the obtained binder aqueous solution, a slurry composition for a non-aqueous electrolyte battery was prepared in the same manner as in Example 1, and the stability of the slurry composition was evaluated. Moreover, the negative electrode for batteries was produced by the same method as Example 1, the coin-type battery was obtained, and the charge-discharge characteristic test was performed. In addition, the electrode for peel strength test was produced by the method similar to Example 1, and the peel strength was measured. The results are shown in Table 1.

Figure 107144468-A0202-12-0041-1
Figure 107144468-A0202-12-0041-1

可清楚得知:使用本發明之黏合劑的實施例1~17可製備安定性非常優異的漿體。又,藉由含有可形成交聯形態之多價金屬,電阻變低,實現了93%以上的高充放電效率。相對於此,未包含多價金屬鹽之比較例1~8雖然顯示高充放電效率,但相較於實施例,漿體安定性並非充分。又,使用增黏劑來增黏之比較例10,其接著性、漿體安定性、充放電效率皆降低,顯示出只有單純的增黏效果並不能達成此等之物性和電池特性之提升。又,可確認到當相對於共聚物中的羧酸單元之多價金屬原子及鹼金屬原子的合計當量比為1以下時,可確保漿體安定性及低電阻性還有高接著性。 It can be clearly seen that Examples 1 to 17 using the adhesive of the present invention can prepare a slurry with excellent stability. In addition, by containing a polyvalent metal that can form a cross-linked form, the resistance becomes low, and a high charge and discharge efficiency of 93% or more is achieved. In contrast, Comparative Examples 1 to 8 that do not contain polyvalent metal salts show high charge and discharge efficiency, but compared with the Examples, the slurry stability is not sufficient. In addition, Comparative Example 10 which uses a thickener to increase the viscosity has reduced adhesion, paste stability, and charge-discharge efficiency, showing that only a simple viscosity-increasing effect cannot achieve these physical properties and battery characteristics. In addition, it can be confirmed that when the total equivalent ratio of the polyvalent metal atom and the alkali metal atom to the carboxylic acid unit in the copolymer is 1 or less, the stability of the slurry, the low resistance, and the high adhesiveness can be ensured.

<拉伸伸長試驗> <Tensile elongation test>

將實施例1及8以及比較例1所製備之黏合劑水溶液(固體成分10質量%),分別以乾燥時之膜厚成為30μm的方式使用棒塗機(T101,松尾產業股份有限公司製)塗布於放置在水平的台上之特夫綸基材(膜厚0.1mm,Esco製)上。其次,在室溫下風乾1天後,剝離特夫綸基材,得到拉伸伸長試驗用之塗膜(薄膜)。將所得之薄膜在25℃、相對濕度45%的環境下放置2天後,利用以下的測定條件來測定該薄膜之拉伸伸長。將結果示於表2。 The adhesive aqueous solutions (solid content 10% by mass) prepared in Examples 1 and 8 and Comparative Example 1 were applied with a bar coater (T101, manufactured by Matsuo Industrial Co., Ltd.) so that the film thickness during drying became 30 μm. On a Teflon substrate (film thickness 0.1mm, made by Esco) placed on a horizontal table. Next, after air-drying at room temperature for 1 day, the Teflon substrate was peeled off to obtain a coating film (film) for tensile elongation test. After the obtained film was left in an environment of 25°C and a relative humidity of 45% for 2 days, the tensile elongation of the film was measured under the following measurement conditions. The results are shown in Table 2.

拉伸伸長測定條件 Tensile elongation measurement conditions

測定裝置:Autograph AG5000B,島津製作所公司製 Measuring device: Autograph AG5000B, manufactured by Shimadzu Corporation

溫度:25℃ Temperature: 25℃

濕度:45%RH Humidity: 45%RH

夾頭間距離:70mm Distance between chucks: 70mm

試驗速度:50mm/分 Test speed: 50mm/min

試驗片:啞鈴型(試驗部之寬度10mm,JIS K 7162-1B之試驗片) Test piece: dumbbell type (width of test part 10 mm, test piece of JIS K 7162-1B)

膜厚:30μm Film thickness: 30μm

Figure 107144468-A0202-12-0043-2
Figure 107144468-A0202-12-0043-2

由乙烯醇與乙烯性不飽和羧酸共聚物為接枝共聚物的實施例1之黏合劑水溶液所得之塗膜,顯示高拉伸伸長,相較於使用嵌段共聚物之情形(實施例8),可確認到可在保持高接著性的同時亦提升柔軟性。另一方面,在未包含多價金屬鹽之情形(比較例1),即使乙烯醇與乙烯性不飽和羧酸共聚物為接枝共聚物,亦未確認到柔軟性之提升。 The coating film obtained from the binder aqueous solution of Example 1 in which vinyl alcohol and an ethylenically unsaturated carboxylic acid copolymer are graft copolymers shows high tensile elongation, as compared with the case of using a block copolymer (Example 8 ), it can be confirmed that softness can be improved while maintaining high adhesiveness. On the other hand, in the case where no polyvalent metal salt is included (Comparative Example 1), even if the vinyl alcohol and ethylenically unsaturated carboxylic acid copolymer is a graft copolymer, no improvement in flexibility is confirmed.

Claims (10)

一種非水電解質電池用黏合劑,其係包含乙烯醇與乙烯性不飽和羧酸之共聚物的中和鹽而成,該中和鹽為該共聚物與包含多價金屬之鹼性物質的中和鹽。 A binder for non-aqueous electrolyte batteries, which is composed of a neutralizing salt of a copolymer of vinyl alcohol and an ethylenically unsaturated carboxylic acid, the neutralizing salt is a neutralization of the copolymer and an alkaline substance containing a polyvalent metal And salt. 如請求項1之非水電解質電池用黏合劑,其中該中和鹽為該共聚物與包含多價金屬之鹼性物質及包含鹼金屬之鹼性物質的中和鹽。 The binder for a non-aqueous electrolyte battery according to claim 1, wherein the neutralizing salt is a neutralizing salt of the copolymer and an alkaline substance containing a polyvalent metal and an alkaline substance containing an alkali metal. 如請求項1之非水電解質電池用黏合劑,其中多價金屬為二價金屬。 The adhesive for non-aqueous electrolyte batteries according to claim 1, wherein the multivalent metal is a divalent metal. 如請求項1之非水電解質電池用黏合劑,其中非水電解質電池用黏合劑中的多價金屬原子之含量係相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元而言小於0.5當量。 The binder for non-aqueous electrolyte batteries as claimed in claim 1, wherein the content of polyvalent metal atoms in the binder for non-aqueous electrolyte batteries is relative to the ethylenic unsaturation in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid The carboxylic acid unit is less than 0.5 equivalent. 如請求項1之非水電解質電池用黏合劑,其中在非水電解質電池用黏合劑中,相對於乙烯醇與乙烯性不飽和羧酸之共聚物中的乙烯性不飽和羧酸單元之多價金屬原子及鹼金屬原子的合計當量比為1以下。 The binder for non-aqueous electrolyte batteries as claimed in claim 1, wherein in the binder for non-aqueous electrolyte batteries, the multivalence relative to the ethylenically unsaturated carboxylic acid unit in the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid The total equivalent ratio of metal atoms and alkali metal atoms is 1 or less. 如請求項1之非水電解質電池用黏合劑,其中乙烯醇與乙烯性不飽和羧酸之共聚物為接枝共聚物。 The adhesive for non-aqueous electrolyte batteries according to claim 1, wherein the copolymer of vinyl alcohol and ethylenically unsaturated carboxylic acid is a graft copolymer. 一種非水電解質電池用黏合劑水溶液,其係包含如請求項1至6中任一項之非水電解質電池用黏合劑及水而成。 An aqueous solution of a binder for a non-aqueous electrolyte battery, which comprises the binder for a non-aqueous electrolyte battery according to any one of claims 1 to 6 and water. 一種非水電解質電池用漿體組成物,其係包含如請求項1至6中任一項之非水電解質電池用黏合劑、活性物質及水而成。 A slurry composition for a non-aqueous electrolyte battery, comprising the binder for a non-aqueous electrolyte battery according to any one of claims 1 to 6, an active material, and water. 一種非水電解質電池用電極,其包含集電體,該集電體具備:包含如請求項1至6中任一項之非水電解質電池用黏合劑及活性物質而成之層。 An electrode for a non-aqueous electrolyte battery includes a current collector including a layer including the binder for a non-aqueous electrolyte battery according to any one of claims 1 to 6 and an active material. 一種非水電解質電池,其具有如請求項9之非水電解質電池用電極。 A non-aqueous electrolyte battery having the electrode for a non-aqueous electrolyte battery according to claim 9.
TW107144468A 2017-12-13 2018-12-11 Binders for non-aqueous electrolyte batteries, aqueous binder solutions and slurry compositions using the same, electrodes for non-aqueous electrolyte batteries and non-aqueous electrolyte batteries TWI833722B (en)

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